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Chemical Kinetics,
Experimentation
Terence J. Kemp
University of Warwick

I. Introduction
II. Mathematical Manipulation of Rate Data
III. Computer Modeling of Reaction Systems
IV. General Methodology of Reaction Kinetics
V. Flow Systems
VI. Pulse and Shock Methods
VII. Relaxation Methods
VIII. Spectral Line-Broadening Methods
IX. Electrochemical Methods

GLOSSARY Monochromator Optical device based on dispersion of

white light by one or more prisms or diffraction gratings
Chemiluminescence Emission of electromagnetic radia- into its constituent wavelengths, which are utilized in
tion in the ultraviolet, visible, or infrared regions from turn.
the products of a chemical reaction proceeding in the Phosphorescence Spontaneous emission of light by a
dark. molecule from an electronically excited state that has
Fluorescence Spontaneous emission of light by a mole- a different total electronic spin from the ground state.
cule from an electronically excited state that has the Photomultiplier tube Electronic device contained with-
same total electronic spin as the ground state. in an evacuated glass envelope, enabling the photoelec-
Laser Optical device achieving the stimulated emission tric conversion of incident light at a metallic surface
of electromagnetic radiation from a molecule, ion, or into electric current via a number of stages of amplifi-
chemical system following the generation of a non- cation.
Boltzmann “population inversion” between the ground Reaction layer That layer of solution adjacent to an elec-
and an excited state by means of some source of exci- trode within which a stationary distribution of elec-
tation (e.g., an electric discharge or a powerful flash of troactive species is established as the result of homo-
white light (optical pumping)). geneous reaction.

721
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722 Chemical Kinetics, Experimentation

Relaxation Process where by a molecule returns from a etc., indicate the concentrations of the various reactants;
high-energy state to its normal state of lower energy. α, β, etc. are the orders of reaction with respect to [A],
Relaxation time Time for the fraction 1/e of excited [B], etc., respectively; α + β + · · · represents the total re-
molecules to return by relaxation to their normal state. action order; and k is the rate constant. The units of k are
dependent on the total reaction order; from Eq. (3) it can
be seen that they are
EXPERIMENTATION IN CHEMICAL KINETICS is
the methodology of measuring the rates of chemical re- (mol dm−3 sec−1 )/(mol dm−3 )α+β+···
actions to yield rate constants, reaction orders, and acti- and for total reaction orders of zero, one, two, and three the
vation parameters with the ultimate goal of establishing units of k are mol dm−3 sec−1 , sec−1 , dm3 mol−1 sec−1 ,
the mechanism of a particular reaction. It covers classical and dm6 mol−2 sec−1 , respectively.
approaches based on conventional sampling and analyti- It is important to note that while the rate of reaction
cal methods, and the use of high pressures as well as the depends on the concentrations of the reactants, the rate
impressive array of fast reaction methods now available constant is independent of these and is the parameter com-
through developments in magnet technology, electronics, monly referred to in discussion of reaction kinetics. While
lasers, and small dedicated computers. These are grouped for normal reaction systems the rate constant is naturally
under flow systems, pulse and shock methods, relaxation independent of time, for systems featuring an initially in-
methods, analysis of spectroscopic line-broadening, and homogeneous distribution of reactants—as, for example,
electrochemical methods. along the track of an α-particle or laser pulse immediately
after discharge—the rate constant varies with time until
homogeneity is achieved.
I. INTRODUCTION

The task of the experimentalist in dealing with chemical

systems is to determine first the rate of the reaction con- II. MATHEMATICAL MANIPULATION
cerned and then its rate constant before proceeding to the OF RATE DATA
ultimate goal of elucidating the reaction mechanism. Such
a reaction rate will be determined under a set of closely When a reaction is mechanistically simple, it is easy to
specified conditions, particularly reactant concentrations, determine its rate, reaction order, and rate constant. For
catalyst, temperature, solvent, gas pressure, ionic strength, example, if a molecule A is decomposing in an inert sol-
nature of the reactor surface, radiant light intensity, etc., vent in a unimolecular process, then the rate law is
depending on the type of system under investigation. The −d[A]/dt = k[A] (4)
accuracy and precision of the figure arrived at will also
need to be specified. Many investigators will attempt to which can be rearranged to
factorize the rate constant for the reaction into its compo-
nents via the Arrhenius equation, −d[A]/[A] = k dt (5)

k = Ae−E/RT (1) Equation (5) can be integrated:

by measuring rates (and hence k) over as wide a tempera- −ln[A] = kt + constant (6)
ture range as will give reasonable accuracy to the individ-
ual values for A and E, or, in the language of transition- The integration constant is found by noting that at time
state theory, the enthalpy and entropy of activation, H = zero the value of [A] can be regarded as [A]0 ; thus the
and S = , respectively: constant equals ( −ln[A]0 ) and Eq. (6) may be rewritten
as Eq. (7):
kB T S = /R −H = /RT
k= e e (2)
h ln[A] − ln[A]0 = −kt (7)
It should be noted that in translating reaction rates into Thus a graphical plot of [A] versus time will give a
rate constants, the experimentalist needs the rate equation, straight line of slope, −k and an intercept at time zero of
which typically takes the form [A]0 .
v = k[A]α [B]β [C]γ · · · (3) For a second-order reaction, the rate law could take the
form
where v signifies the rate as measured by loss of a reac-
tant, e.g., −d[A]/dt or formation of a product; [A], [B], −d[A]/dt = k[A]2 (8)
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Chemical Kinetics, Experimentation 723

or, where we are dealing with two different reactants, A or

and B,
v = k [A]2 (15)
−d[A]/dt = −d[B]/dt = k[A][B] (9)
where k = k[B]0 [C]20 . Thus Eq. (15) takes the form of
The experimentalist will normally select concentrations Eq. (8) and can be dealt with similarly. It is also possible
such that [A] = [B], and then Eq. (9) becomes identical to determine reaction orders by this approach; thus if [B]0
with Eq. (8). in Eq. (14) is doubled, then k is doubled, indicating a first-
Rearranging Eq. (8), order dependence on [B], while if [C]0 is doubled then k
−d[A]/[A]2 = k dt (10) is quadrupled, indicating a second-order dependence on
[C]. In other examples, of course, the “simplified” rate
and then integrating, equation might take the form

1/[A] = kt + const (11) v = k [A] (16)

As before, the integration constant is determined by not- when the test given by Eq. (7) would apply.
ing that at time zero the concentration of A can be written The other main device for dealing with highly complex
as [A]0 , and the constant therefore equals 1/[A]0 . Equa- reactions is the method of initial rates. When it is impossi-
tion (11) can now be rewritten as ble to investigate a reaction by some simple mathematical
test such as Eq. (7) or (12), which normally depends on
1/[A] − 1/[A]0 = kt (12)
following at least one of the reactants for up to 90% of its
Hence a plot of 1/[A] versus time will give a straight line course of disappearance, then the method of initial rates
with a slope of k. is utilized. This depends on the idea that if a reaction is
Equations (7) and (12) not only provide the vehicle followed for only 5 or 10% of its total course, then a plot
for extracting rate constants from experimental data, they of the concentration of that reactant disappearing most
also provide the test for whether the disappearance of a quickly versus time will approximate to a straight line.
particular reactant follows first- or second-order kinetics. (All reactant–time plots, except for zero-order reactions,
To apply this test with rigor, it is desirable to test the are curved with −d[A]/dt decreasing as [A] decreases;
adherence of the data to a particular mathematical law for however, the graph of first few percent of any such reac-
several half-lives, i.e., for 75–95% of total reaction. (One tion approximates to the tangent to this curve at time zero.)
half-life is the time for the concentration of A to fall from Such a straight line yields an immediate value for k if [A],
[A]0 to [A]0 /2.) [B], and [C] are taken as [A]0 , [B]0 , [C]0 , . . . .
To cope with kinetically more complex reactions, the β γ
experimentalist needs to rely on one or more of several −d[A]/dt = k[A]α0 [B]0 [C]0 · · · (17)
well-tested procedures for simplifying the analysis of data The effect of variation of [B], [C], etc., separately on
by manipulating the starting concentrations of the reac- −d[A]/dt will then yield rate data enabling evaluation of
tants. The best known of these devices is the “isolation β, γ , etc.
method,” due originally to Ostwald. If a reaction involves
several reactants or retardation by a product, then the re-
sulting rate law may be too complex, mathematically, to
test in the normal situation when all the reactant concen- III. COMPUTER MODELING OF
trations are changing simultaneously. However, if every REACTION SYSTEMS
reactant concentration is kept large except for one (say
A), then during the reaction only [A] will change appre- This takes various forms, depending on the complexity of
ciably, the equivalent amounts of B, C, etc., being removed the reaction system. At its simplest, programs are available
representing only a tiny fraction of [B]0 , [C]0 , etc., so that in the principal programming languages for any computer
[B], [C], etc., can be regarded as remaining essentially un- operating system to enable the testing of raw data in terms
changed throughout reaction. For example, if we have a of the simplest types of kinetic rate law, Eqs. (7) and (12),
rate law given by Eq. (13), and it is now universal for microcomputers interfaced with
apparatus to be capable of recording, storing, and process-
v = k[A]2 [B][C]2 (13) ing kinetic data in digital form or after analog-to-digital
then if [B] ≈ [C] [A], conversion. Programs giving complete solutions have also
been written for more complex kinetic situations, of which
v = k[A]2 [B]0 [C]20 (14) the following are well-known examples.
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724 Chemical Kinetics, Experimentation

1. Series first-order reactions: where dozens of processes are involved, some chemical
k1 k2 and others, such as diffusion or turbulence, being physi-
A→B→C (18) cal. Here the task is not to express the situation exactly,
2. Reversible first-order reactions: as in Eqs. (18)–(26), but rather to approximate to the ob-
k1 served state by examining the effects of gradually intro-
A B (19) ducing particular component terms. The computer is used
k−1
to generate a numerical solution from a set of given rate
(A notable example is conformational interchange by equations, rate constants, and reaction concentrations for
NMR line-broadening techniques; see Section VIII.) different reaction times, and a screen graphical presen-
3. Reversible reactions involving second-order steps in tation is often employed. This procedure is illustrated in
both directions. The following examples are taken from Fig. 1 for the concentrations-time profiles for reactants
the many studies based on line-broadening analyses from and products on a photoirradiated mixture of trans-but-2-
nuclear magnetic resonance (NMR) and electron spin res- ene, NO, NO2 , and air. The relevant equations are given
onance (ESR) spectroscopy, respectively. in Fig. 2.
(a) Proton transfer: Computer modeling is also helpful in unravelling the
k1 temperature dependence of complex systems. Fitting to
A + H3 O+ AH+ + H2 O (20) the Arrhenius equation [Eq. (1)] is simple, but the number
k−1
of parameters involved increases, and therefore the pro-
(b) Electron transfer: grams become lengthier, with the complexity of the sys-
k1 tem. Well-known variants of the simple Arrhenius equa-
A + B± A± + B (21) tion to which data can be fitted by computer are as follows:
k−1

4. Parallel second-order reactions occurring in two dif- 1. Two parallel terms:

ferent zones of polymeric solids without mutual interfer-
ence: k = A1 e−E1 /RT + A2 e−E2 /RT (27)

zone 1: R· + R· → RR
k1
(22) This is often recognized from a plot of ln k against
1/T , which, instead of exhibiting a single line as for
Eq. (1), will show two linear regions intersecting in a
k2 particular, narrow temperature range.
zone 2: R· + R· → RR (23)
2. For solution reactions investigated over very wide
5. Relaxation from two excited states in equilibrium temperature ranges, especially cryogenic
(both stages first-order): temperatures when molecular diffusion can be
“frozen” at a limiting temperature T0 :
∗A
k1 ∗B
k −1 k = Ae−[B/(T −T0 )] (28)
k2 k3

A B (24)
IV. GENERAL METHODOLOGY
6. Relaxation from two excited states in equilibrium OF REACTION KINETICS
(one stage second-order):
∗A
k1 ∗AB
In relatively simple systems, where reactants proceed di-
+ B
k −1 rectly to a small number of products without the interven-
k2 k3 tion of intermediate species (and in most cases even when
A A + B these do play some role), the main problem is that of de-
(25)
termining the concentration of one or more reactants or
7. Kinetics of photobleaching of a system of ab- products as a function of time. This becomes essentially
sorbance A under steady illumination (making allowance an exercise in analytical chemistry, in that virtually all
for increased transmission, and therefore reduced rate of methods of chemical and physicochemical analysis have
photolysis, as photoreaction proceeds): been applied at some time in determining reaction rates.
−d A/dt = k(1 − 10−A ) (26)
A. Conventional Methods
Computers prove invaluable in dealing with exceed-
ingly complex kinetic situations such as are found in The design of specialized kinetic apparatus is largely de-
combustion or the chemistry of planetary atmospheres, termined by the magnitude of the reaction rates concerned.
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Chemical Kinetics, Experimentation 725

FIGURE 1 Experimental (upper) and computer predictions (lower) for the photoreaction of a mixture of trans-but-2-
ene, NO, NO2 , and air. [From Kerr, J. A., Calvert, J. G., and Demerjian, K. L. (1972). Chem. Br. 8, 252.]

When reactions are “slow,” i.e., with half-lives of the order of the entire reaction mixture with respect to one or
of minutes, hours, or longer, then conventional sampling more components is monitored throughout the reaction,
methods are very appropriate; thus a thoroughly mixed re- from time to time or even continuously, by some physical
action system is made up after thermostating the separate method such as spectrophotometry, conductivity, poten-
reactants to the desired temperature, and samples are taken tiometry, or NMR. Commercial spectrophotometers and
at suitable, measured time intervals and submitted to anal- magnetic resonance spectrometers are now widely used
ysis for a particular reactant or product. Because reaction in which a kinetic mode is available for automatically de-
continues within the sample while sampling is occurring, termining optical or radiofrequency absorbances at preset
it is usually the case that one needs to “quench” the re- band maxima as a function of time: the resulting data,
action either by cooling the sample rapidly to “freeze” sometimes running to thousands of points, can be stored
reaction or by mixing the sample with another reagents, and analyzed at leisure.
which halts reaction by consuming one reactant virtually Polymerization kinetics can be followed very simply
instantaneously. using a dilatometer (a reaction vessel consisting of a bulb
This type of procedure is still widely used because of its with a capillary side-arm) to measure total reaction vol-
simplicity, particularly when more sophisticated apparatus ume, which decreases gradually but markedly as reaction
is unavailable. The analysis itself is typically by titration, proceeds.
ultraviolet (UV)–visible or infrared (IR) spectrophotom- Many “slow” gas phase reactions have been studied
etry, or gas-liquid chromatography. simply by measuring the total pressure of a “static”
An important variant of this method is to use a non- reaction system at different times. Such an approach
destructive analytical method in which the composition can be dangerously simplistic, however, and it is best
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726 Chemical Kinetics, Experimentation

FIGURE 2 Reaction schemes for the photoxidation of trans-but-2-ene in the presence of NO and NO2 . (Left) Initiation
of O atoms or ozone. (Right) Initiation by hydroxyl radicals. (These are incorporated into the computer model employed
in Fig. 1.) [From Kerr, J. A., Calvert, J. G., and Demerjian, K. L. (1972). Chem. Br. 8, 252.]

supplemented by an in situ analytical method such as spec- Kinetic processes occuring within solids are inherently
troscopy or by sampling tiny quantities into a mass spec- more difficult to monitor, but ESR spectroscopy provides
trometer, if necessary via a gas chromatograph. While the a nondestructive, highly sensitive method for investigating
static system has the advantage that it is well-defined in free radical processes.
terms of temperature, concentration, surface area, and ma- The development in NMR spectroscopy of magic-angle
terial of the containing vessel, it suffers from the compar- spinning (MAS) enables solid-state transformations to be
atively small amounts of material available for analysis. determined, conventional NMR having been limited pre-
Flow systems for gases provide plenty of material but are viously to bulk physical processes such as the transition
less well-defined otherwise. An often useful compromise through the glass temperature of polymers. One nice appli-
is found in the capacity-flow technique, in which reactants cation of MAS-NMR is the kinetics of the hardening of wet
are conducted into the vessel, efficient stirring is provided, cement by following the 29 Si resonances. Optical meth-
and the reacting mixture is withdrawn at such a rate as to ods are most easily applied to thin films of materials—
set up a steady state. for example, the kinetics of polymer degradation can be
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Chemical Kinetics, Experimentation 727

determined from the development of the IR peak of the kF [A∗ ]

ϕF0 = (38)
carbonyl group frequency in degraded polyalkenes. (kF + kNR )[A∗ ]
The ratio of the fluorescence yields, and therefore mea-
B. Steady-State Methods sured fluorescence intensities, IF and IF0 , in the presence
and absence, respectively, of the quencher molecule is
Many complex reactions proceed at a relatively slow rate given by
as measured by the gross disappearance of reactant or
appearance of product, and yet the measured rate, charac- ϕF0 I0 (kF + kNR + kQ [Q])[A∗ ]
= F = (39)
terized by an “experimental” rate constant k, can include ϕF IF (kF + kNR )[A∗ ]
components relating to very fast processes. This is the which can be simplified to
case especially for chain reactions, where the number of
reaction chains existing at a given moment is very small, (kQ [Q])[A∗ ]
IF0 /IF = 1 + (40)
but the individual processes associated with each center (kF + kNR )
occur extremely rapidly. To resolve such a composite rate Thus a plot of IF0 /IF versus [Q] will yield a straight line
constant into its individual components normally requires of slope kQ /(kF + kNR ). This is called the Stern–Volmer
some fast-reactions technique that concentrates on the ini- constant, and it can be measured using a conventional
tiation or termination stages. spectrofluorimeter. Stern–Volmer constants can be mea-
Another such example is given by fluorescence quench- sured for the quenching of a single emitting species by a
ing. If a molecule A yields a fluorescent excited state A∗ range of quenchers and then factorized into their compo-
that is partially quenched by an added material Q, then a nents simply by measuring the lifetime τ0 of the emitting
simple kinetic analysis of the quenching data will reveal state A∗ in the absence of quencher by some fast-reactions
the second-order quenching constant as follows. Consider technique (Section VI). The term τ0 is related to kF and
the reaction scheme: kNR by
Rate τ0 = 1/(kF + kNR ) (41)
hν ∗
A −→ A Ia (29)
Another type of steady-state method is that of line-
kF
A∗ −→ A + hvF kF [A∗ ] (30) broadening of magnetic resonance spectra, covered in de-
kNR
tail in Section VIII.
A∗ −→ A kNR [A∗ ] (31)
kQ
Q + A∗ −→ A + Q kQ [A∗ ][Q] (32) C. High-Pressure Methods

The rate of formation of A∗ is given by The rate of a chemical reaction is sensitive not only to
temperature [Eq. (1)] but also to pressure. Simple thermo-
d[A∗ ]/dt = Ia (33) dynamic arguments lead to Eq. (42):
The rate of disappearance of A∗ is given by ln(k/k0 ) = − pV = /RT (42)
−d[A∗ ]/dt = (kF + kNR + kQ [Q])[A∗ ] (34) Here k and k0 refer to the rate constants of the reaction at
pressures of p and l atm, respectively, and V = denotes
In the steady-state situation, these two rates are equal, i.e., the volume of activation. Accuracy in values of V = re-
Ia = (kF + kNR + kQ [Q])[A∗ ] (35) quires the use of pressures of up to several thousand atmo-
spheres, as the effect is generally rather small (a few cubic
Now the fluorescence quantum yield is given by the ratio centimeters per mole), and the reaction chamber is usually
of the number of photons emitted per second to the number of thick stainless steel. The term V = is considered in the
of photons absorbed per second: case of solution reactions to be composite, i.e., the sum of
kF [A∗ ] (1) the change in volume of the reactants in forming the
ϕF = (36) transition state and (2) the change in volume of the solvat-
Ia
ing molecules during this process; the latter is particularly
Substituting Eq. (36) into Eq. (35) yields Eq. (37): important when ions are involved as the reactants. When
kF [A∗ ] a process of molecular dissociation is involved, V = will
ϕF = (37) be positive, while when molecules associate to form the
(kF + kNR + kQ [Q])[A∗ ]
transition state, V = is negative; these effects have been
In the absence of any quencher, the fluorescence yield, used diagnostically in solution kinetic studies of inorganic
denoted ϕF0 , is given by Eq. (38): complexes, e.g., by Henry Taube.
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728 Chemical Kinetics, Experimentation

Recent technical developments of the method involve are used and observations are needed at different points in
the use of the NMR method (Section VIII) at high pres- the mixed stream. A useful variant of the continuous-flow
sures, both in steady-state and stopped-flow applications. method is that in which the stream of mixed reactants is
The sample is contained in an open glass sample tube sit- conducted into a quenching medium, which terminates
uated within a metallic pressure chamber; the metal has to reaction by eliminating one reactant virtually instanta-
be nonmagnetic in this case, and beryllium–copper alloy neously. An adaptation of this idea is to pass the reacting
or titanium are the favored materials. solution into a Dewar vessel containing liquid nitrogen at
77 K when the reaction is literally frozen, and the extent
of reaction, or the presence of some intermediate, is
V. FLOW SYSTEMS ascertained by a solid-state technique such as ESR spec-
troscopy.
These have been used to great effect in both solution and
gas-phase studies. B. Stopped-Flow Methods
The disadvantages of the continuous-flow method are
A. Continuous Flow (Solutions)
largely overcome in the stopped-flow technique. After the
The first successful use of continuous-flow systems in reactants have been forced from their “drive syringes”
solution was due to Hartridge and Roughton; the principle into the mixing chamber, adjacent to the optical cell
here is that if the reaction time is of the order of a few where an analyzing light beam is situated, the emerg-
milliseconds to a few seconds, then it is impossible to mix ing mixed solution runs into another vertically mounted
the reactants manually and then record optical changes. “stop syringe,” which rises as it fills until it is arrested
Instead, the two reactants are fed by gravity or under by a mechanical stop (Fig. 3). Flow then ceases, but
pressure through narrow-bore tubes to a mixing chamber, the fast reaction occurring in the optical cell continues
after which observations are made at various points re- to completion, normally in a time of between 10 msec
mote from the mixing point in order to ascertain the extent and 10 sec. In recent adaptations the analyzing light, in-
of reaction. Alternatively, the flow rate can be varied to stead of passing into a monochromator–photomultiplier
display varying time domains of the reaction at a fixed ob- tube–oscilloscope–microcomputer assembly, is passed to
servation point. The disadvantage of the continuous-flow a diffraction granting, which disperses the light over the
configuration is that considerable quantities of reactants faces of a series of photomultiplier tubes or photodiodes

FIGURE 3 Schematic diagram of stopped-flow apparatus. A, reservoir syringes; D, drive syringes; R, hydraulic ram;
1–5, valves; S, stopping syringe; L, light source; MO, monochromator; C, quartz windows; M, mixing point; PM,
photomultiplier tube; HT, power supply to PM; MS, microswitch; W, waste; MA, microammeter; CRO, cathode-ray
oscilloscope; TR, transient recorder; CR, computer.
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Chemical Kinetics, Experimentation 729

FIGURE 4 Time-resolved spectra (0–2 sec after mixing, taken at 40 msec intervals) for the reaction of Zn2+ with
2,2 :6 ,2 –terpyridine (L) in methanol:water (80%:20% v/v) at 25◦ C (Zn2+ ] = 10−4 mol dm−3 , [L] = 10 − 5 mol dm−3 ).
[From Priimov, G. U. Ph.D. thesis, University of Warwick, 1999.]

(in the so-called photodiode array), each of which is sepa- with only a small fraction entering the very low pressure
rately powered and from which the individual outputs feed (∼10−6 torr) mass spectrometer. One example of the type
into a multiplexer. The output from the letter is presented of reaction that can be examined is that between ethyl
on an oscilloscope screen as a complete optical spectrum, radical ( C2 H5 ) and oxygen, for which the stages are
x

each data point corresponding to the signal from one of

the photodetectors. The use of electronic delays enables (i) Generate chlorine atoms in microwave discharge:
a complete time-resolution of the spectrum to be built
Cl2 −→ 2Cl x
(43)
up (Fig. 4): An important development in the stopped-
flow technique has been the incorporation of Fourier- (ii) React Cl with ethane:
x

transform NMR spectroscopy as the detection system. An-

Cl + C2 H6 −→ HCl + C2 H5
x x
(44)
other development of stopped-flow spectrophotometry is
the quenched-flow system. Here, two solutions A and B (iii) React the generated ·C2 H5 with oxygen:
are mixed to produce a highly reactive intermediate, which
C2 H5 + O2 −→ C2 H5 O2
x x
(45)
persists until it encounters a third reactant C at a second
mixer. The resulting reacting mixture is analyzed optically
The C2 H5 radicals are ionized in the mass spectrometer
x

by the usual optical train (Fig. 5).

to yield C2 H5 + ions which are detected at a mass/charge
ratio of 29. The moveable injector controls the relative
concentration of ethyl radicals.
C. Gas-Flow Methods
Resonance fluorescence detection is a highly sensitive
The possibility of flowing reactant gases at low pressures method for observing atomic species. A trace of gas such
down long tubes has long been recognized as a means of as hydrogen is mixed with helium and passed into a mi-
controlling a fast reaction. An additional feature is the use crowave discharge in which some hydrogen is dissociated:
of some excitation source, often a microwave discharge,
H2 −→ 2H x
(46)
at a suitable location in order to generate atoms or small
molecules such as ·CN, ·OH, ·Cl, or ·H. Detection systems Some of the H atoms are excited and emit their typical
include optical spectroscopy (especially for chemilumi- fluorescence
nescent species), electron spin resonance spectroscopy, ∗
H −→ H + hvF
x x
(47)
and atomic resonance fluorescence. Figure 6 illustrates
the use of mass spectrometric detection in a gas-flow The so-called resonance emission enters the reaction zone
system. High-capacity pumps remove most of the gas flow, (Fig. 7) where ground-state H atoms become excited
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730 Chemical Kinetics, Experimentation

distribution as possible by means of a velocity selector (a

set of slotted rotating discs). Better velocity selection can
be achieved by using a supersonic nozzle in which the gas
expands from a high pressure through a small nozzle into
a vacuum. A beam of molecular ions can replace one of
the neutral molecular beams. The detection system relies
on the ionization of the scattered fragments as they strike
the surface. Alternatively, the scattered species can be sub-
mitted to electron bombardment followed by mass spec-
trometric examination of the resulting ions. The internal
energy state of the product molecule is often determined
by laserinduced fluorescence, although in some cases in-
frared chemiluminescence can be observed directly from
vibrationally excited states of the products.
The geometry of the experimental arrangement is illus-
trated in Fig. 8.

VI. PULSE AND SHOCK METHODS

These depend on the virtually instantaneous generation

of new chemical species, normally of high reactivity, in
a system by delivery of a burst of energy sufficient to
generate electronically excited states or to break chemical
bonds to generate radical species.

FIGURE 5 (Top) Side and (bottom) plan views of a quenched- A. Flash Photolysis
flow apparatus. Key: RES, reservoirs (three); DS, drive syringes
(three); MS, microswitch; R, rack; P, pinion; M, motor; TI, thermo- In the technique of flash photolysis, later developed to
stating fluid inlet; TO, outlet; M1, first mixer; M2, second mixer; laser flash photolysis, an intense flash of light is absorbed
Q, quartz windows (two); W, waste outlet; BN, brass nut (three); by molecules in the system to give excited states:
PS, motor power supply; L, lamp; MO, monochromator; FL, focus-
hν
ing lens; PM, photomultiplier tube; MA, milliammeter; CB, control
M → M∗ (49)
box; CRO, cathode-ray oscilloscope; DR, data recorder; CR, chart
recorder; 1–6, taps; shaded area, PTFE blocks. [From Goodman, These then lose energy either by light emission [Eq. (50)],
P. D., Kemp, T. J., and Pinot de Moira, P. (1981). J. Chem. Soc.,
by nonradiative decay [Eq. (51)], by dissociation to give
Perkin Trans. 2, 1221.]
radical species [Eq. (52)], or by attacking the solvent, de-
noted SH [Eq. (53)]:
H + hvF −→ ∗ H x
(48)
M∗ → M + hν1 (or hνp ) (50)
The concentration of H atoms in the reaction cell can thus ∗
M → M. (51)
be monitored by their fluorescence in a repeat of Eq. (47),
and their reactions with the various molecules in the reac- M∗ → A· + B· (52)
tion cell determined. ∗ · ·
M + SH → MH + S (53)

D. Crossed Molecular Beams By monitoring the optical or ESR absorption of the species
A· , B· , MH· , or S· , it is possible to determine their kinet-
Extremely detailed kinetic information for gas-phase pro- ics for such processes as dimerization, as in Eqs. (54)
cesses is gained by allowing two streams of molecules and (55).
emanating from small ovens to intersect at right angles
and by examining the scattering intensity and velocity S· + S· → S—S (54)
distribution of the resulting fragments as a function of MH· + MH· → HM—MH (55)
the scattering angle. The experiment is carried out at high
or reaction with oxygen,
vacuum (10 − 6 to 10 − 7 torr), and the molecules in one
or both of the streams are placed in as narrow a velocity S· + O2 → SO·2 (56)
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Chemical Kinetics, Experimentation 731

FIGURE 6 Schematic diagram showing combination of gas-flow tube with mass spectrometric detection. [Repro-
duced with permission from Pilling, M. J., and Seakins, P. W. (1995). “Reaction Kinetics,” Oxford University Press,
Oxford.]

While many types of experimental layout have been into the femtosecond (fs) regime, enabling, for example,
used successfully, that shown in Fig. 9 is quite typical. observation of a transition state in the breaking of the I-C
A pulsed excimer laser generates light at a wavelength bond in ICN. The concept underlying this work is schema-
that can be controlled by using different halogens or rare tized in Fig. 10. The laser system generates a pulse which
gases. The uv pulse, of duration that can also be controlled, is split into two components, a pump pulse which insti-
can be used either directly or to pump a dye laser, giving gates chemical processes and a probe pulse which mon-
extensive control of the wavelength range. The emerging itors them. The probe pulse is delayed behind the pump
pulse is then fed by mirrors, prisms, or an optical fiber to pulse by a few femtoseconds by lengthening its light path
the sample cell where it excites the molecule of interest (Fig. 10). The probe pulse causes fragments generated by
(in fluid solution or in gaseous form). the pump pulse to emit light, the characteristics of which
Species generated by Eq. (49)–(56) are monitored by provide dynamical information. An example of the funda-
means of an analyzing beam from a high-pressure point- mental character of this type of investigation is illustrated
source lamp, the output of which passes through the sam- in Fig. 11. Ion pairs Na+ I− are excited by the pump pulse
ple cell and thence through a preset monochromator to a to the excited form [Na I]∗ . The bond distance is very
photomultiplier tube or spectography or diode array. The short at the moment of formation, and the excited molecule
signal from the former, which is related to the intensity of has a covalent character. As the molecule vibrates, charge
the incident light, is taken to a cathode-ray oscilloscope moves toward the I atom, and at the furthest point of the
where it is displayed and stored as a function of time imme- stretching vibration the nuclei are 10–15 Å apart, with the
diately following the firing of the laser. The stored signal is bonding now becoming fully ionic [Na+ · · ·I− ]. The atoms
then either photographed for manual analysis or taken via continue to vibrate between these two forms:
an analog-to-digital converter to a microcomputer, where
it is stored and subsequently has largely been processed [Na − l]∗ [Na+ . . . l− ]∗ (57)
to yield rate constants.
The other main instrumental development involving At the critical distance of 6.9 Å, the energies of the ex-
lasers has been the evolution of lasers pulsed to picosec- cited and ground states are very close and there is a 20%
ond or even femtosecond time intervals by mode-locking. chance that the excited state will dissociate to give sepa-
These yield rather weak pulses and are normally used rate Na and I atoms. The femtosecond technique detects
in association with devices enabling data accumulation. a decaying signal from the excited state and an increasing
The Nobel prize for chemistry for 1999 was awarded to signal as bursts of Na atoms appear from each vibration
Ahmed Zewail for his work in extending flash photolysis (Fig. 11).
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732 Chemical Kinetics, Experimentation

FIGURE 7 Schematic diagram illustrating the various processes occurring during reaction of H atoms with resonance
fluorescence detection. [Reproduced with permission from Pilling, M. J., and Seakins, P. W. “Reaction Kinetics,” Oxford
University Press, Oxford.]

Lasers are particularly well suited for the time- PM 1 is conducted to a time-to-amplitude converter (TAC),
resolution of light emission [Eq. (50)], especially in the which is triggered or “started” on its arrival. The photon ar-
form of time-correlated single-photon counting (Fig. 9). In riving at the sample cell excites a potentially luminescent
this technique, the weak output from a repetitively pulsed molecule [Eq. (49)], which, after some time, fluoresces
lamp (pulse width ∼1 nsec) or from a sub-nanosecond [Eq. (50)] or phosphoresces [Eq. (50)]. The photons due
pulsed laser is divided such that part of the pulse is taken to luminescence activate the second photodetector (PM 2
directly to one photodetector (PM 1 in Fig. 9) while the in Fig. 9), from which a pulse is fed to the TAC, which
other part is taken to the sample cell. The signal detected by is then “stopped.” The time interval between “start” and
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Chemical Kinetics, Experimentation 733

by discharging a bank of capacitors through a quartz tube

filled with Kr or Xe: this produces a broad-continuum flash
of between a few microseconds and ∼100 µsec duration.
The time-resolution of this apparatus is orders of magni-
tude inferior to that of laser-flash photolysis, but larger
energies are available in view of the greater spectral width
and timespan of the exciting source, i.e., hundreds or thou-
sands of joules rather than fractions of a joule, and so the
microsecond technique still enjoys considerable use for
particular problems.

B. Pulse Radiolysis
The technique of pulse radiolysis is closely related to that
of flash photolysis: the optical monitoring system is the
same, but the source of light activation is replaced by one
of high-energy radiation in the form of a short pulse of a
FIGURE 8 Schematic diagram illustrating laser flash photoly-
sis. Laser pulses pass through the light guide to the sample
few nanoseconds or microseconds of fast electrons (typi-
cell. Optical monitoring of post-pulse events can be kinetic or cally 3 MeV). The effect of such high-energy radiation is
spectrographic. to excite and ionize the material in the sample cell, which
may be in liquid, gaseous, or even (transparent) solid form.
In the case of water, the initial act of radiolysis is given by
“stop” is stored in the multichannel pulse-height analyzer Eqs. (58)–(60):
and the process is repeated for many thousands, if not hun- H 2 O → H 2 O+ + e −
x

(58)
dreds of thousands, of times per second. The accumulated
+ · +
data yield the averaged luminescent response of the sam- H2 O + H2 O → OH + H3 O (59)
ple molecule and, after computer processing, can lead to e− + H2 O → eaq
−
(60)
lifetimes with very small standard deviations.
In the more traditional form of flash photolysis, origi- Optical studies reveal the presence of the solvated electron
−
nated by R. W. Norrish and G. Porter, the flash is generated eaq as a broad, intense absorption maximizing at ∼700 nm.

FIGURE 9 Block diagram of time-correlated single photon counting apparatus. Key: LS, lamp; LH, lamp housing; S,
slits; HRM, high-radiance monochromator; C, sample cell; SH, sample housing; L, lenses; PM 1, PM 2, photomultiplier
tubes; DISC 1, DISC 2, discriminators; TAC, time-to-amplitude converter; MCAPH, multichannel pulse-height analyzer.
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734 Chemical Kinetics, Experimentation

FIGURE 10 Schematic diagram illustrating layout of femtosecond flash photolysis technique. The pump and probe
pulses are separated in time by adjusting the light path of the latter. Beams of molecules in the sample tube are
excited or dissociated by the pump pulse, and the fragments monitored by the probe pulse on its path to the detector.
Reproduced with permission from Scientific American (see Bibliography).

Addition of materials capable of reacting with electrons Other developments include extension of the optical
−
reduces the lifetime of eaq , enabling kinetics of its fast re- range into the near IR and the use of cryogenic equipment
actions to be determined. The powerful oxidant ·OH (the to examine radiolysis at temperatures as low as 4.2 K.
hydroxyl radical) has only a weak absorption in the ultra-
violet, and its reactivity is best measured by a competition
C. Shock Tubes
method based on its very fast oxidation of thiocyanate ion
−
CNS− to yield the intensely absorbing (CNS)2 ion (λmax
x

Shock tubes are applied to the study of gas phase reac-

472 nm). Addition of a second substrate X will provide tions on the microsecond to millisecond timescale at tem-
competition for · OH, and the intensity of the absorption of peratures of several thousand kelvins. The shock wave
− x

(CNS)2 will be systematically reduced as [X] is increased, is generated by breaking a diaphragm that separates the
enabling a rate constant to be derived. “driver” gas, usually H2 or He at several atmospheres pres-
While optical methods remain the favored means of sure, and the reactant gas diluted in argon at a few torr
analysis in both flash photolysis and pulse radiolysis, other (1 torr = 10−6 mm Hg). The normal configuration for the
methods of detection have been used with great effective- apparatus is a hollow tube (Fig. 10), typically measur-
ness from time to time, including conductivity and ESR ing 15 cm diameter and 6 m in length, which contains,
spectroscopy. The latter technique, in association with in the reactant chamber, sensors for measuring the ve-
flash photolysis in particular, has led to the observation locity of the shock wave, and an observation point. The
of ESR signals with anomalous intensities, for example, shock front generated on rupture of the diaphragm travels
appearing totally in emission, a phenomenon described at supersonic speed (several Mach) toward the reactant
as chemically induced dynamic electron polarization or gas zone, compressing this and heating it to very high
CIDEP. temperatures (which can be calculated), in much less than
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Chemical Kinetics, Experimentation 735

FIGURE 11 Femtosecond flash photolysis of gaseous sodium iodide. As the excited ion-pair vibrates, it gradually
decays (lower curve) and the resulting free atoms are detected (upper curve).

1 msec. Detection of the species in the reaction zone is duration of the pulse should be much shorter than the re-
normally optical, especially as many of these emit light laxation time τ of the system and should approximate to
from their excited states, although absorption spectra can a step-function as in Fig. 11. Interestingly, if the relative
also be measured. Strong shocks in CH4 and CH4 − NH3 change in concentrations of the reactants is very small,
yield, respectively, the emission bands of C2 and CN, while then, whatever the rate law, the reaction curve will follow
Al2 O3 dispersed as a dust yields AlO. Alternatively, the first-order kinetics described by the relaxation time τ , the
reaction zone can be sampled by allowing materials to leak time for A (the change in absorbance at time t) to fall to
through a pinhole into a mass spectrometer. a value (l/e)(A0 ) (where A0 is the final total change in
absorbance). The mathematics of rather complex systems
undergoing relaxation have been established and are given
VII. RELAXATION METHODS by Hague.
While the single-pulse methods described above are
These were developed initially by Eigen and depend on widely used, another approach is to apply the perturba-
the application of a small disturbance to a chemical sys- tion as a sine wave, in which the response will be in the
tem at equilibrium, normally by the dissipation of a pulse form of another sine wave lagging consistently behind
of energy in the temperature-jump method but also on oc- the perturbation to a degree related to the relaxation time
casion by a sudden change in pressure (pressure-jump) of the system. The frequency of the applied perturbation
or electric field. The system then adapts (Fig. 11) to its is critical: if it is too slow, then the chemical response
new situation, normally a slightly higher temperature and will “catch up” and no lag will be detected, but if it is
hence a changed equilibrium constant, at a rate that can too fast the chemical response will never attain a mea-
be measured either optically or conductimetrically. The surable amplitude before it must change direction. Only
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736 Chemical Kinetics, Experimentation

in the all-important intermediate situation will the am- (υA ) CH3 H3C 
O O
plitude of the chemical response be sufficient to enable 
N C N C
determination of the phase lag. Perturbations can take the
form of high-frequency oscillating electric fields, but the (υB) CH3 H H3C H (62)
use of sound waves (to give the ultrasonic method) is that
most widely adopted. The attenuation of the sound wave and will resonate at different frequencies νA and νB giv-
at a particular frequency is related to the chemical relax- ing two lines. Rotation about the N C bond is slow at
ation processes occurring in the solution. The excitation room temperature, because of the partial double-bonding
is via a quartz crystal generator, and detection is by mea- [Eq. (62)], but as the temperature is increased rotation
suring optical dispersion of light transmitted through the becomes faster and finally so fast that the signals coa-
sample. lesce to a single line. Between these two extreme situa-
tions (known as slow and fast exchange, respectively) lies
a continuum of intermediate situations with line shapes
VIII. SPECTRAL LINE-BROADENING given by Eq. (63),
METHODS
g(ν) = [(1 + τ π )P + QR]/(4π 2P 2 + R 2 ) (63)
If the lifetime of a molecule is very short, say δt, then the where
uncertainty principle predicts a broadening of its absorp-
tion line δν (in hertz) given by Eq. (61). P = [0.252 − ν 2 + 0.25δν 2 )τ + /4π (64)
δν ≈ 1/(2π δt) (61) Q = [−ν − 0.5( pA − PB )δν]τ (65)
If δt is ∼0.1 sec, then δν is ∼1 Hz, i.e., in the region R = 0.5( pA − pB )δν − ν(1 + 2π τ ) (66)
of NMR spectroscopy. Accordingly, if a molecule is un-
The symbols are defined as follows: τ = τA τB /(τA + τB ),
dergoing rapid (∼0.1 sec) interchange between two con-
and τA and τB are the average lifetimes of the nuclei in
formations, or is participating in a fast exchange reaction
positions A and B, respectively; pA and pB are the mole
such as proton-transfer, then its NMR spectral linewidth
fractions of A and B, respectively; δν = νA − νB ;  is the
provides a unique source of kinetic information.
width (at half-height) of the signal in the absence of ex-
We cannot develop the theory of NMR spectroscopy
change; and ν is the variable frequency. The lineshape
here, but state simply that the nuclei of a sample in a
calculations are exemplified in Fig. 12.
strong magnetic field are excited by radiofrequency radi-
The ESR spectrum of a dilute solution of a radical an-
ation of a particular frequency for each type of nucleus
ion such as naphthalene consists of many lines. Addi-
(called the Larmor frequency) into excited spin states,
tion of further naphthalene results in electron exchange
from which they return to lower spin states on losing spin
[Eq. (67)], which broadens the lines:
energy by nuclear relaxation. Various factors contribute
to such relaxation, especially the motion of surrounding k2
solvent molecules designated (even in liquids) as the “lat- C10 H÷
8 + C10 H8 C10 H8 + C10 H÷
8 (67)
k−2
tice”; this process is called spin–lattice relaxation, and the
time for l/e part of the excited nuclei to relax this way is This is a consequence of reducing the lifetime of a partic-
denoted T1 . The additional process titled “spin–spin re- ular spin state: an analysis of the lineshape yields the rate
laxation” is denoted T2 . Both of these are normally of sev- constant k2 , which equals k−2 . Radicals able to undergo
eral seconds duration in liquids, and, in accordance with conformational change show a spectral phenomenon
Eq. (61). NMR lines are accordingly very narrow in liq- called the alternating linewidth effect. A temperature-
uid samples. Chemical pathways for reducing the lifetime dependence study of this effect will yield activation pa-
reduce T2 and hence broaden the lines. Analysis of such rameters [energy and entropy, Eq. (2)] for this first-order
broadening leads to values for the kinetics of the chemical process.
pathway.
Another factor influencing the appearance of NMR
spectra is the exchange of nuclei (usually protons) be- IX. ELECTROCHEMICAL METHODS
tween positions with different Larmor frequencies. In the
case of dimethylformamide, the protons in the two methyl Electrochemical methods depend on a competition be-
groups in the planar conformation are inequivalent. tween an electrode reaction, e.g., Eq. (68),
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Chemical Kinetics, Experimentation 737

removed from the system. Hence the (measured) cell cur-

rent is proportional to the rate at which species X arrives
at the electrode surface. Motion of X is due to (1) diffu-
sion, (2) convection, and (3) migration, and conditions are
arranged such that diffusion dominates. Diffusion occurs
because of the depletion in the concentration of X near the
electrode, resulting in a concentration gradient.
If X is participating in a dynamic equilibrium in the bulk
electrolyte solution. Eq. (69) where Y is electrochemically
inactive and with the equilibrium far to the right, i.e., k1
k−1 ,
k1
X Y, K = k1 /k−1 (69)
k−1

then the rate of arrival of X at the electrode depends on the

rate of generation of X from Y, i.e., the situation is under
kinetic control.
The mean lifetime τ of X is given by 1/k1 . Species X
will diffuse a distance µ = Dτ during its mean lifetime,
where D is the diffusion coefficient. Thus, a fraction 1/e
of species X within distance µ of the electrode will be
FIGURE 12 Computed nuclear magnetic resonance spectra for removed, while those farther away will be transformed
the exchange process A B as a function of the parame- to Y before they can be removed. The layer of solution
ter τ . [From Günther, H. (1980). “NMR Spectroscopy,” Wiley, of thickness µ is termed the reaction layer (Fig. 13). The
Chichester.] current at the electrode is then determined by the rate at
which species X is generated in the reaction layer.
A forced convection electrode is exemplified in the tech-
X + e− → R (68)
nique of polarography, the cathode consisting of a growing
and the diffusion of the electroactive species X to the elec- mercury drop at the tip of a fine capillary, which provides
trode surface. The potential of the electrode is selected a constantly renewed, reproducible electrode surface. A
so that Eq. (68) is essentially rapid and irreversible, re- steadily increasing potential is applied to the electrode
sulting in all species X encountering the electrode being and the resulting current measured, to give a polarographic

FIGURE 13 Steady-state concentration distribution (reaction layer) in the case of a chemical reaction preceding an
electrode reaction. [Adapted from Koryta, J., and Dvorak, J. (1987), “Principles of Electrochemistry,” Wiley, Chichester,
England.]
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738 Chemical Kinetics, Experimentation

wave. The relation between the diffusion current, i d and and Medicine,” Pergamon, Oxford.
the reaction current i r provides the kinetic information via Billing, G. D., and Mikkelsen, K. V. (1996). “Molecular Dynamics and
Eq. (70) Chemical Kinetics,” Wiley, New York.
Demas, J. N. (1983). “Excited State Lifetime Measurements,” Academic
1/2 Press, New York.
ir Ck1 t 1/2
= (70) Espenson, J. H. (1995). “Chemical Kinetics and Reaction Mechanisms,”
id − ir K 1/2 2nd ed; McGraw-Hill, New York.
where C is a constant of approximately unity and t is the Greef, R., Peat, R., Peter, L. M., Pletcher, D., and Robinson, J.
(1985). “Instrumental Methods in Electrochemistry,” Ellis Horwood,
drop time.
Chichester.
Hammes, G. G., ed. (1974). “Techniques of Chemistry,” 3rd ed., Vol. VI.
Part II, Wiley (Interscience), New York.
SEE ALSO THE FOLLWING ARTICLES House, J. E. (1997). “Principles of Chemical Kinetics,” W. C. Brown,
Dubuque, Iowa.
ELECTROCHEMISTRY • KINETICS (CHEMISTRY) • NU- Lewis, E. S., ed. (1974). “Techniques of Chemistry,” 3rd ed., Vol. VI.
CLEAR MAGNETIC RESONANCE Part I, Wiley (Interscience), New York.
Ng, C.-Y., Baer, T, and Powis, I. (1994). “Unimolecular and Bimolecular
Ion-Molecule Reaction Dynamics,” Wiley, Chichester.
Pilling, M. J., and Seakins, P. W. (1995). “Reaction Kinetics,” Oxford
BIBLIOGRAPHY University Press, Oxford.
Sandström, J. (1982). “Dynamic NMR Spectroscopy,” Academic Press,
Andrews, D. L. (1992). “Lasers in Chemistry,” 2nd ed., Springer–Verlag, New York.
Berlin. Steinfield, J. I., Francisco, J. S., and Hase, W. L. (1989). “Chemical Ki-
Ashfold, M. N. R., and Baggott, J. E. (1989). “Bimolecular Collisions,” netics and Dynamics,” Prentice-Hall, Englewood Cliffs, New Jersey.
Royal Society of Chemistry, London. Wilkins, R. G. (1991). “Kinetics and Mechanism of Reactions of Tran-
Baxendale, J. H., and Busi, F. (1981). “The Study of Fast Pro- sition Metal Complexes,” VCH, Weinheim, Germany.
cesses and Transient Species by Electron Pulse Radiolysis,” Reidel, Wright, M. R. (1999). “Fundamental Chemical Kinetics,” Horwood Pub-
Dordrecht. lishing, Chichester.
Bensasson, R. V., Land, E. J., and Truscott, T. G. (1983). “Flash Photol- Zewail, A. (1990). “The Birth of Molecules,” Scientific American, De-
ysis and Pulse Radiolysis. Contributions to the Chemistry of Biology cember issue, 40–46.
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Chemical Thermodynamics
J. Barthel and R. Neueder
University of Regensburg

I. Fundamentals
II. Fundamental and Caloric
Equations of Thermodynamics
III. Partial Molar Quantities
IV. Fugacities and Activities
V. Thermodynamic Equilibrium

GLOSSARY are homogeneous systems and phase boundaries at

which the intensive properties show discontinuities.
Activity coefficient Ratio of the activity to the mole frac- Homogeneous system System of which all inten-
tion of a component Yi in a mixture or solution; a mea- sive properties are continuous functions of position
sure of the departure from ideal behavior. throughout the system.
Affinity Driving force of chemical reactions; equals zero Ideal mixture or solution Mixture or solution that shows
at the equilibrium state. no change in volume, enthalpy, or heat capacity when
Chemical potential Content in Gibbs energy of 1 mol it is made up from its initially separated components.
of a component Yi of a mixture or solution, that is, Intensive property (variable) Property (variable) of a
the change in the total Gibbs energy of the system system that is independent of mass.
at constant temperature and pressure when 1 mol of Partial molar quantity Increase in any extensive ther-
component Yi is added to an infinite amount of the modynamic property of a system at constant pressure
system. and temperature when 1 mol of component Yi is added
Electrochemical system System consisting of electri- to an infinite amount of the system. The chemical po-
cally conducting phases. The electric potentials of the tential of component Yi is also the partial molar Gibbs
phases are called Galvani potentials. energy of compound Yi .
Excess property Difference between the actual property Phase See Heterogeneous system.
of a system and its hypothetical value calculated for Reversible process Process yielding the maximum of
an ideal mixture or solution at the same temperature, usable work.
pressure, and mole fraction composition. Thermodynamic equilibrium State of a system at which
Extensive property (variable) Property (variable) of a no measurable changes of its intensive properties occur
system that is proportional to mass. and no measurable flow of matter or energy takes place
Heterogeneous system System consisting of phases that during the period of observation.

767
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768 Chemical Thermodynamics

CHEMICAL THERMODYNAMICS is a phenomeno- a homogeneous system (phase) in equilibrium is defined

logical science. The object of investigation is the macro- unequivocally by a set of variables of state such as p (pres-
scopic properties of chemical systems in thermodynamic sure), T (temperature), and n 1 , n 2 , . . . , n k (amount of sub-
equilibrium. Today Gibbs formalism is generally used stance). The mole number n i is a measure of the amount of
to yield the framework of thermodynamic compatibility substance of component Yi . The number of components
throughout the phenomenological sciences and technol- of a system is the minimum number of independent chemi-
ogy. A multitude of methods, partially based on extrather- cal compounds Yi of which the system investigated can be
modynamic assumptions, are applied to rationalize the ob- made up. A system built by k components Y1 , Y2 , . . . , Yk
servations of chemical systems and for the procurement is called a k-component mixture. Pure systems contain
of basic data for chemical thermodynamic calculations. only a single component. The mole number n i relates the
mass wi of component Yi to its molar mass Mi .
I. FUNDAMENTALS n i = wi /Mi (dimension of n i , moles). (1)

A. Thermodynamic Systems and Properties According to the International Union of Pure and Applied
Chemistry (IUPAC) Commission on Symbols, Terminol-
A chemical system is an accumulation of chemical materi- ogy and Units, a mole is the amount of substance of a
als limited by a boundary. The physical world outside this system that contains as many elementary entities as there
boundary constitutes the surroundings of the system. The are carbon atoms in 0.012 kg of 12 C. The elementary enti-
system may (open system) or may not (isolated system) ties must be specified and may be atoms, molecules, ions,
exchange mass and energy with its surroundings. A sys- electrons, other particles, or specified groups of such par-
tem that exchanges energy but not mass is called a closed ticles, as shown in the following tabulation:
system.
A macroscopic property of a system may (for extensive Elementary Mass of
properties) or may not (for intensive properties) depend on entity 1 mol (g)
its mass. Examples of extensive properties are the volume
of the system or its heat capacity; examples of intensive Hg 200.59
properties are permittivity, density, and specific heat. A HgCl 236.04
Hg2+
2 401.18
system is considered homogeneous if all intensive prop- e− (electrons) 5.460 × 10−4
erties are continuous functions of position throughout the Fe0.91 S 82.88
system; otherwise it is considered heterogeneous. In a het- Mixture of 78.09 mol % N2 , 28.964
erogeneous system the discontinuities of properties are sit- 20.95 mol % O2 , 0.93 mol % argon,
uated on surfaces enclosing homogeneous regions, which and 0.03 mol % CO2
are called phases of the heterogeneous system, with the
surfaces being the phase boundaries. Phases are charac- If the complete set of variables ( p, T, n 1 , . . . , n k ) of a
terized throughout this article by Greek superscripts (e.g., k-component mixture is known, every property P of the
V (α) , V (β) ), phase boundaries by symbols such as V (α/β) . system in its equilibrium state is unequivocally defined:
A homogeneous system or a phase of a heterogeneous
P = P( p, T, n 1 , . . . , n k ) (2)
system can be a gaseous, liquid, or solid system.
Systems showing electrical potentials (Galvani poten- that is, an identical system can be prepared with the same
tials) of their phases are called electrochemical systems. properties by the specified set of variables. This statement
Galvani potentials are the result of movable charges (ions, is the basis of analytical chemistry.
electrons, etc.) within the phases. For electrochemical sys- Infinitely small changes in the variables of state entail
tems electrical potential differences are observed between infinitely small changes in properties P:
electrically conducting phases (e.g., batteries).    
A system is in a state of thermodynamic equilibrium ∂P ∂P
dP = dp + dT
if during the period of observation (1) no measurable ∂ p T,ni ∂ T p,ni
changes of its intensive properties occur and (2) no mea-
k 
 
surable flow of matter or energy takes place. The system is ∂P
in a steady state if only the first condition is fulfilled. Elec- + dn i (3)
i=1
∂n i p,T,n j =n i
trochemical systems in equilibrium show constant Galvani
potentials throughout each phase. In Eq. (3) the partial derivatives indicate the changes in
Chemical thermodynamics uses observable quantities P with one of the variables of state, the others being
for the definition of the state of a system. The state of unchanged; dP is an exact differential as a consequence of
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Chemical Thermodynamics 769

the unequivocally defined, continuous, and continuously tional composition variables, molality (m i , moles of so-
differentiable function P( p, T, n 1 , . . . , n k ). lute Yi per kilogram of solvent), demality (also called
Applying to Eq. (3) the cross-differentiation identities molonity, m̃ i , moles of solute Yi per kilogram of solution),
known as Schwarz relations yields the relations and molarity (ci , moles of solute Yi per cubic decimeter
of solvent).
∂ 2 P/∂ T ∂ p = ∂ 2 P/∂ p ∂ T (4a) If in a mixture component Y1 is considered to be the
∂ 2 P/∂ n i ∂ p = ∂ 2 P/∂ p ∂n i solvent, Y1 = S, and Y2 , . . . , Yk are the solutes, the com-
(4b)
position variables of the solutes are defined by the rela-
∂ P/∂ n i ∂ T = ∂ P/∂ T ∂n i
2 2
(4c) tions
m i = n i /n s Ms (8a)
where (i = 1, 2, . . . , k). As a consequence of Eqs. (3) and

(4) every finite change in property P is independent of the k
process applied (path of integration) when passing from m̃ i = n i n i Mi (8b)
an arbitrary intial state I to an arbitrary final state II, i=1

 II ci = n i /V (8c)
dP = PII − PI (5)
I In Eq. (8c) the volume V of the solution is given in cubic
and equals zero for a cyclic process, decimeters. Conversion formulas for the frequently used
  II  I scales of composition variables are given in Table I. If in
a mixture the solvent itself is a mixture of components
dP = dP + dP = 0 (6)
I II (mixed solvent), the quantities n s and Ms can be defined
as “solvent quantities” when using the relations
n s = n s1 + n s2 + · · · ,
B. Composition Variables
(9)
In technological calculations the amounts of substance n i Ms = xs1 Ms1 + xs2 Ms2 + · · · ,
in the basic set defined in the preceding section are often re- where s1, s2 denote the components making up the mixed
placed by other composition variables such as the weights solvent.
of substance wi which are also extensive variables, or Electrochemistry uses mean composition variables
by intensive variables such as weight percent (wt. %), based on the mole numbers of the ions in the solution pro-
volume percent (vol %), or mole percent (mol %). A com- duced by the electrolyte compounds that are the solutes.
monly used intensive composition variable in fundamen- If the set of extensive composition variables (n 1 , . . . ,
tal and applied research on mixed systems is the mole n k ) is replaced by a set of intensive composition variables,
fraction xi : for example, (x1 , . . . , xk ), where xi = 1, only the in-

k k tensive properties of the system investigated are defined;
xi = n i ni ; xi = 1 (7) extensive properties then are converted to appropriate in-
i=1 i=1 tensive properties, which are the corresponding molar
Mixed systems distinguishing solvent and solute compo- quantities (i.e., the amount of the extensive property per
nents are called solutions. Solution chemistry uses addi- mole of substance).

TABLE I Conversion of Concentration Scales in Binary Systemsa

From

To x2 c2 m2 m̃˜ 2

M 1 c2 M1 m 2 M1 m̃ 2
x2 = x2
d + (M1 − M2 )c2 1 + M1 m 2 1 + (M1 − M2 )m̃ 2
d x2 dm 2
c2 = c2 d m̃ 2
M1 + (M2 − M1 )x2 1 + M2 m 2
x2 c2 m̃ 2
m2 = m2
M1 (1 − x2 ) d − M 2 c2 1 − M2 m̃ 2
x2 c2 m2
m̃ 2 = m̃ 2
M1 + (M2 − M1 )x2 d 1 + M2 m 2
a Subscript 1 denotes solvent; subscript 2 denotes solute; d denotes density of the solution;

M1 and M2 denote molar masses.

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770 Chemical Thermodynamics

C. Forms of Energy tion of silver nitrate where silver deposition and zinc dis-
solution are observed. The chemical energy of the same
Energy can be transferred to and from a system and can
process is used to a maximum as electrical energy by the
be stored in a system in different forms:
help of an appropriate galvanic cell if the electrical current
in the cell is kept infinitely small. This example illustrates
1. Mechanical energy, W mech
the following features of reversible processes:
2. Electrical energy, W el
3. Electromagnetic energy, W elm 1. They are ideal limiting cases.
4. Radiant energy, W rad 2. They are infinitely slow, passing from the initial to the
5. Heat, W heat = Q final state through a series of equilibrium states.
6. Latent heat, W lat. heat = Q lat
7. Chemical energy, W chem
D. The Fundamental Laws of Thermodynamics
These can be converted totally or partially from one to
Thermodynamics is an empirical science. The quintes-
another. By definition, any contribution that increases the
sence of all practical knowledge is condensed in three
energy of a system is counted positive.
fundamental laws (axioms), which are valid because so
Any differential element of work, DW, is not an exact
far they have not been found to be false. (Some textbooks
differential; that is, Schwarz relations are not applicable,
quote an additional “zero law” concerning the definition
and integration from the initial to the final state of the sys-
of thermodynamic temperature.)
tem depends on the path of integration (equation defining
the particular process).
If a system is subjected to a uniform, normal pressure 1. First Law
p, the work executed on this system by an infinitesimal
increase dV of its volume is In 1847 Helmholtz formulated his statement concerning
the conservation of energy and the equivalence of work
DW mech = − p d V (10) and heat: “Although energy may be converted from one
form to another, it cannot be created or destroyed.” As a
If in a galvanic cell the infinitesimal increase of charge
consequence,
dq is subject to a Galvani potential , the electrical work
is (dU )isolated system = 0 (14)
DW = el
dq (11) where

The amount of heat passing to a system during a process dU = DW i ; i = mech, el, . . . (15)
is calculated from the change in temperature dT with the
help of the heat capacity C of the system The differential dU of the total or internal energy U is an
exact differential, in contrast to the differential elements
D Q = C dT. (12) DW i of the different forms of energy. The change in in-
Heat applied to a system for a change of phases (e.g., ternal energy depends only on the initial and final states
melting) without an increase in temperature is called latent and not on the process path.
heat. Energy produced in chemical reactions is chemical
energy. Electromagnetic energy, radiant energy, as well as
2. Second Law
nuclear energy will not be discussed here.
Since all forms of energy do not yield exact differen- The second law of thermodynamics as stated by Clausius
tials, balances of energy forms require the specification of in 1854 concerns the spontaneous evolution of a system
the path of the process studied—for example, isothermal subject to processes. It defines the entropy of a system,
process (T = const) or isobaric process ( p = const). which is related to the change in heat during the process
A process in which the maximum of usable work is and the temperature by the relation
produced is called a reversible process, in contrast to irre-
d S = D Q rev /T (16)
versible processes, which waste usable energy. The usable
chemical energy of the reaction Clausius’s formulation
Zn + 2AgNO3 (aq) ←
→ Zn(NO3 )2 (aq) + 2Ag (13) (d S)isolated system ≥ 0 (17)
is wasted by transforming it to heat (unusuable energy) is the most appropriate formulation of the second law for
when a rod of solid zinc is inserted into an aqueous solu- chemical thermodynamics.
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Chemical Thermodynamics 771

3. Third Law All the symbols in Table II have been explained in Sec-
tion I, except µi (i = 1, . . . , k), which is the chemical
The third law is a summary of conclusions concerning
potential of component Yi . In Table II electrical energy
the zero-temperature behavior of systems. Its formula-
is separated from mechanical, heat, and chemical forms
tion, that the zero-point entropy of perfect crystalline sub-
of energy, since its extensive variable q (charge) is not
stances is zero,
independent of mole numbers n i and its introduction as
S0 = 0 (18) a variable of state would require the use of compatibil-
ity equations. To summarize, the set of variables of state
as announced in 1923 by Lewis and Randall, indicates by
( p , T , n 1 , . . . , n k ) or any other set obtained by replacing
simple application of thermodynamic equations that the
one of the variables by its conjugate variable can be used
heat capacity of such systems vanishes at the zero point
to express the internal energy of the system as a function
of the thermodynamic temperature scale. Consequently,
of its state. Only two functions are relevant in thermody-
the zero point of temperature cannot be attained experi-
namics:
mentally since the thermodynamic functions expressing
maximum reversible work of a system also vanish with U = U (S , V , n 1 , . . . , n k ) (fundamental equation)
horizontal tangent. The internal energy and its Legendre
(20)
transforms (see Section II) are not determined at absolute
zero temperature. U = U (T , V , n 1 , . . . , n k ) (caloric equation) (21)
The other functions can be obtained by appropriate trans-
formations of Eqs. (20) and (21).
II. FUNDAMENTAL AND CALORIC
EQUATIONS OF THERMODYNAMICS
B. Fundamental Equation
Thermodynamics generally is based on two equations, the 1. Homogeneous Systems
fundamental and the caloric equations.
Equation (20), in which all variables of state are extensive
variables, can be written using the notation of Table II,
A. Variables of State
U = U (ξi ); ξi = V, S, n i , . . . , n k (22)
The basic set of variables of state can be extended by re-
flecting on the forms of energy, each of which is given by yielding the exact differential of the internal energy
the product of an intensive (η) and an extensive (ξ ) vari- k+2  
 ∂U
able [see Eqs. (10) and (11)]. Forms of energy yield differ- dU = dξi (23)
ential elements DW i that are not exact differentials, but i=1
∂ξi ξ j =ξi
mathematics postulate that for such elements there exists
at least one integrating factor that converts the nonexact which entails the relations
differential form to an exact differential; for example, the (∂U/∂ V ) S,ni = − p (24a)
integrating factor of heat is T −1 , yielding entropy as the ex-
act differential d S, d S = T −1 D Q rev . Using this concept, (∂U/∂ S)V,ni = T (24b)
every differential element DW i can be expressed with the
help of the conjugate intensive and extensive variables of (∂U/∂n i ) S,V,n j =ni = µi (24c)
the corresponding form of energy (see Table II), where
because the combination of Eqs. (15) and (19) yields the
DW i = ηi d ξi . (19) relation

TABLE II Conjugated Extensive and Intensive Variables of Forms of Energy

Energy form

Arbitrary form Mechanical Heat Chemical Electrical

Variable of energy W i energy energy energy energy

Extensive ξi V S n1 , . . . , nk q
Intensive ηi –p T µ1 , . . . , µ k
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772 Chemical Thermodynamics


k +2 TABLE III Partial Derivatives of Energy Functions and
dU = ηi d ξi (25) Maxwell Relations
i =1 (∂U /∂ S)V ,ni (∂G /∂ T ) p,ni
to which Eq. (23) can be compared. = (∂ H /∂ S) p,ni = T = (∂ A /∂ T )V ,ni = −S
Because the internal energy U [Eq. (22)] is a homo- (∂U /∂ V ) S ,ni (∂G /∂ p)T ,ni
= (∂ A /∂ V )T ,ni = − p = (∂ H /∂ p) S ,ni = V
geneous function of degree 1 of the variables ξi , Euler’s
(∂ T /∂ V ) S ,ni = −(∂ p /∂ S)V ,ni (∂ T /∂ p) S ,ni = (∂ V /∂ S) p,ni
theorem of homogeneous functions yields
(∂ S /∂ V )T ,ni = (∂ p /∂ T )V ,ni (∂ S /∂ p)T ,ni = −(∂ V /∂ T ) p,ni
k +2 
  
k +2
∂U
U= ξi = ξi ηi , (26)
i =1
∂ξi ξ j =ξi i =1
which, as compared with Eq. (25), yields the Gibbs– µi = (∂U /∂n i ) S ,V ,n j =ni = (∂ H /∂n i ) S , p,n j =ni
Duhem–Margules equation:
 
k = (∂ A/∂n i )T,V,n j =ni = (∂G/∂n i )T, p,n j =ni (35)
ξi d ηi = −V dp + S dT + n i d µi = 0 (27)
i =1 The exact differentials dU [Eq. (23)] and dU (m) [Eq. (30)]
The replacement of an arbitrary number of extensive vari- entail Schwarz relations. Maxwell relations and Schwarz
ables ξi (i = 1, . . . , m) by their conjugate intensive vari- relations are summarized in Table III.
ables ηi yields new energy functions U (m) of the system
U (m) = U (m) (η1 , . . . , ηm , ξm +1 , . . . , ξk +2 ). (28) 2. Heterogeneous Systems

These functions can be understood as the Legendre trans- The description of the state of a heterogeneous system
forms of Eq. (25): requires a set of variables of the type given in Table II for
every phase α. As a consequence, the internal energy of a

m
U (m) = U (ξi ) − ηi ξi (29) heterogeneous system made up by ν phases is
i =1 
U = U (α) ξi(α) = U (ξ j ) (36)
The exact differential of Eq. (28) is
 m   when numbering the variables ξ either per phase, ξi(α) (i =
∂U (m) 1, . . . , k + 2; α = 1, . . . , ν) or throughout the system,
dU =(m)
d ηi
i =1
∂ηi ξi ,η j =ηi ξ j [ j = 1, . . . , ν(k + 2)]. The exact differential
k +2 
 
∂U (m) 
ν 
k+2 
ν(k+2)
+ d ξi (30) dU = ηi(α) dξi(α) = η j dξ j (37)
i =m +1
∂ξi η j ,ξ j =ξi
α=1 i=1 j=1
and entails the Maxwell relations is of the type given by Eq. (25). Hence, all equations
 (m) 
∂U for homogeneous systems can be used for the phases of
= −ξi (31a)
∂ηi ξ j ,η j =ηi heterogeneous systems. Equations (36) and (37) neglect
 (m)  the contributions of the phase boundaries U (α/β) to the
∂U total energy U of the heterogeneous system.
= ηi (31b)
∂ξi η j ,ξ j =ξi
The Legendre transforms currently used in thermodynam- 3. Electrochemical Systems
ics are enthalpy, Helmholtz energy, and Gibbs energy:
The internal energy of phase α in an electrochemical sys-
H = U + pV ; d H = V dp + T d S + µi dn i (32) tem depending on the charge q (α) of phase α and the Gal-
A = U − T S; d A = − p d V − S dT + µi dn i (33) vani potential (α) ,

G = U + pV − T S; dG = V dp − S dT + µi dn i U (α) = U (α) S (α) , V (α) , n (α) (α)
1 , . . . , nk , q
(α)
(38)

(34) yields the exact differential

The replacement of all extensive by intensive variables dU (α) = − p (α) d V (α) + T (α) d S (α)
again yields the Gibbs–Duhem–Margules equation. + µi(α) dn i(α) + (α)
dq (α) (39)
The chemical potentials µi introduced as the conjugate
variables of mole numbers n i are given by Eqs. (24c) and in which dq (α) is dependent on mole numbers n i(α) and
(31b): charges F z i of the single species Yi . In Eq. (40) F is the
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Chemical Thermodynamics 773

Faraday number (charge of 1 mole of electrons) and z i is intensive variable. The partial derivatives in Eq. (43) are
the electrical valence of particle Yi : material properties such as
dq (α) = F z i dn i(α) (40) (∂U/∂ T )V = Cv (heat capacity at constant volume)

Combining Eqs. (39) and (40) gives (44)


k or functions of material properties [see Eq. (46)],
dU (α) = − p (α) d V (α) + T (α) d S (α) + µ̃i(α) dn i(α) (41)
i=1
(∂U/∂ V )T = (α/β)T − p (45)
where in contrast to the partial derivatives of the fundamental
µ̃i(α) = µi(α) + zi F (α)
(42) equation, which are the positive or negative conjugate vari-
ables, respectively.
is the electrochemical potential of species Yi in the phase Partial derivatives (∂ f /∂ xi )x j =xi can be transformed to
α. (∂ f /∂ yi ) y j = yi with the help of functional determinants
(Jacobi transformation) if the functions xi = xi (y j ) are
C. Caloric Equation known. For practical use all partial derivatives of energy
The function U (T, V, n 1 , . . . , n k ) [Eq. (21)] yields the functions U , H , A, and G and of entropy S are reduced
exact differential to functions of the tabulated material properties α (ther-
    mal expansivity coefficient), β (isothermal compresibility
∂U ∂U coefficient), and C p (heat capacity at constant pressure):
dU = dT + dV
∂ T V,ni ∂ V V,ni
α = (1/V )(∂ V /∂ T ) p (46a)
k 
 
∂U β = −(1/V )(∂ V /∂ p)T (46b)
+ dn i (43)
i=1
∂n i T,V,n j =n i C p = (∂ H/∂ T ) p (46c)
and the related Schwarz relations. The function U (T, V, The results of these calculations are compiled in Table IV
n 1 , . . . , n k ) is not a homogeneous function since T is an for practical use.

TABLE IV Reduction of Frequently Used Partial Derivatives to Material

Propertiesa
(∂U/∂ T )V = C p − T V α 2 /β (∂U/∂ T ) p = C p − V pα
(∂ H/∂ T )V = C p + V α/β − T V α 2 /β (∂ H/∂ T ) p = C p
(∂ A/∂ T )V = −S (∂ A/∂ T ) p = −S − V pα
(∂G/∂ T )V = −S + V α/β (∂G/∂ T ) p = −S
(∂ S/∂ T )V = C p /T − V α 2 /β (∂ S/∂ T ) p = C p /T
(∂ p/∂ T )V = α/β (∂ p/∂ T )s = C p (T V α)
(∂ V /∂ T )s = −C p β/(T α) + V α (∂ V /∂ T ) H = C p β + V α − T V α 2 (1 − T α)
(∂U/∂ p)V = C p β/α − T V α (∂U/∂ p)T = pVβ − T V α
(∂ H/∂ p)V = C p β/α + V − T V α (∂ H/∂ p)T = V − T V α
(∂ A/∂ p)V = −Sβ/α (∂ A/∂ p)T = pVβ
(∂G/∂ p)V = V − Sβ/α (∂G/∂ p)T = V
(∂ S/∂ p)V = C p β/(T α) − V α (∂ S/∂ p)T = −V α
(∂ V /∂ p) S = T V 2 α 2 /C p − Vβ (∂ V /∂ p) H = V 2 α(T α − 1)/C p − Vβ
(∂ T /∂ p) H = V (T α − 1)/C p
(∂U/∂ V ) p = − p + C p /(V α) (∂U/∂ V )T = − p + T α/β
(∂ H/∂ V ) p = C p /(V α) (∂ H/∂ V )T = (T α − 1)/β
(∂ A/∂ V ) p = − p − S/(V α) (∂ A/∂ V )T = − p
(∂G/∂ V ) p = −S/(V α) (∂G/∂ V )T = −1/β
(∂ S/∂ V ) p = C p /(T V α) (∂ S/∂ V )T = α/β
a The material properties here are heat capacity C , thermal expansion coefficient α, and
p
isothermal compressibility β.
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774 Chemical Thermodynamics

The caloric equation does not contain entropy as a vari-

able of state and hence cannot be used for providing infor-
mation either on thermodynamic equilibria or on chemical
potentials, in contrast to the fundamental equation.

III. PARTIAL MOLAR QUANTITIES

A. Definitions
Extensive thermodynamic quantities Z ( p, T, n 1 , . . . , n k )
of the type given by Eq. (47), such as volume V , entropy S, FIGURE 1 Determination of partial molar quantities Z2 and
apparent molar quantities z from measurements of extensive
enthalpy H , heat capacity C p , and Gibbs energy G, yield
thermodynamic quantities Z p,T,n (n2 ) (also Z2 from Z; see
partial molar quantities: Section III.B).

Z i = (∂ Z /∂n i ) p,T,n j =ni . (47)

Figure 1 illustrates the notation; beginning with n 1 moles
Partial molar quantities Z i are the contributions per of pure component Y1 , the system is made up by the addi-
mole of the components Y1 , . . . , Yk to the total quantity tion of arbitrary amounts n 2 of component Y2 . The mea-
Z p,T (n 1 , . . . , n k ) of the phase at constant pressure and surable quantity Z of the phase is given by the relation
temperature:
Z = n1 Z 1 + n2 Z 2 (52)

k
Z p,T (n 1 , . . . , n k ) = ni Z i . (48) From Fig. 1 it follows that Z 2 is given by the slope of the
i=1 tangent at point n 2 , which in turn permits the determination
Equation (48) results from Euler’s theorem, since Z p,T is a of Z 1 via Eq. (52) or (49b).
homogeneous function of degree 1; it entails the relations Solution chemistry also makes use of another type of

k molar quantity, the so-called apparent molar quantity Z
d Z p,T = Z i dn i (49a) of the solute Y, according to
Z = n 1 Z 1∗ + n 2
i=1
(53)

k Z
n i d Z i = 0. (49b) Y1 being the solvent. The apparent molar quantity Z is
i=1
also shown in Fig. 1. The advantage of apparent molar
Equation (49a) is the exact differential of quantity Z quantities is their direct access from experimental data,
∗
[Eq. (3)] at constant pressure and temperature. Equation Z = (Z − n 1 Z 1 )/n 2 Comparison of Eqs. (52) and (53)
(49b) is a Gibbs–Duhem–Margules type of equation, indi- yields the relations
cating the mutual dependence of partial molar quantities.
Z 1 = Z 1∗ + n 2 (∂ Z /∂n 1 ) p,T,n 2 ;
Using the set of variables (x1 , . . . , xk ) entails the rela- (54)
tions Z2 = Z + n 2 (∂ Z /∂n 2 ) p,T,n 1

Z̄ p,T (x1 , . . . , xk ) = xi Z i and the limiting value at infinite dilution

d Z̄ p,T = Z i d xi (50) Z 2∞ = lim Z 2 = lim Z = ∞
(55)
z
xl →1 xs →1
xi d Z i = 0
Figure 2 illustrates the features of mean molar properties
where Z̄ p,T is the mean value of quantity Z p,T per mole Z̄ p,T [Eq. (50)] for a system of completely miscible com-
of phase, Z̄ p,T = Z p,T / n i . ponents Y1 and Y2 . At mole fraction x2 the quantity Z̄ p,T
The following discussion is limited to two-component is given by the relation
systems (binary systems) of components Y1 and Y2 , mix-
Z̄ p,T = x1 Z 1 + x2 Z 2 (56)
tures of Y1 and Y2 , or solutions of Y2 (solute Y) in Y1
(solvent S). The quantity Z per mole of pure component yielding
Yi will be called Z i∗ and that per mole of Y2 (or Y) in
the infinitely diluted solution in solvent Y1 , (or S) will be Z 1 = Z̄ p,T − x2 (∂ Z̄ /∂ x2 ) p,T ;
(57)
called Z 2∞ (or Z Y∞ ): Z 2 = Z̄ p,T + x1 (∂ Z̄ /∂ x2 ) p,T
Z l∗ = lim Z i ; Z 2∞ = lim Z 2 Equation (57) shows that the tangent at Z̄ p,T at point P(x2 )
xi →1 xl →1
 (51) yields intercepts with the axis at x2 = 0 and x2 = 1, which
or Z Y∞ = lim Z Y .
xs →1 produce the partial molar quantities Z 1 and Z 2 .
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Chemical Thermodynamics 775

is the change in Z 2 accompanying the transfer of Y2 from

the pure state to the infinitely dilute solution in Y1 ; Z 2∞
is determined by appropriate extrapolation methods.
Combining Eqs. (60b), (61b), and (62) yields the rela-
tion
 ∞ ∞
mix Z = n 2 relZ + Z 2 ; Z =
rel
Z − Z (63)
where − relZ is the balance for the dilution process from
concentration c2 of Y2 to infinite dilution
∞
dil Z /n 2 = − rel
Z (c2 ) = Z − Z (c2 ) (64)
FIGURE 2 Determination of the partial molar quantities Z1 and
Z2 as a function of mole fraction x2 from mean molar quantities (e.g., heat of dilution). Dilution from concentration c2 , to
Z̄ p,T (x2 ) (also Z1 and Z2 from  Z̄: see Section III.B).
c2 , c2 < c2 is then given by the relation

Besides partial molar and apparent molar quantities, mix Z (c2 )/n 2 − mix Z (c2 )/n 2 = (c2 ) − (c2 ) (65)
thermodynamics makes use of relative quantities such as
(Z i − Z i∗ ), (Z i − Z i∞ ), or ( Z − ∞
Z ), resulting from mix- C. Thermodynamic Relations
ing or solution processes.
Using partial molar quantities Z i , the differential d Z of
the thermodynamic quantity Z at arbitrary pressure and
B. Mixing Processes temperature is
Formally, property Z before and after mixing of the com-     
∂Z ∂Z k
ponents Y1 and Y2 can be written as dZ = dp + dT + Z i dn i (66)
∂ p T,ni ∂ T p,ni i=1
Z init = n 1 Z 1∗ + n 2 Z 2∗
(58) entailing Schwarz relations of the type given by Eqs. (4a)–
Z fin = n 1 Z 1 + n 2 Z 2 (4c), where P ≡ Z . Hence, the relations existing for the
or extensive quantities Z can also be used for their partial
molar quantities: for example,
Z fin = n 1 Z 1∗ + n 2 Z (59)
(∂G i /∂ T ) p = −Si (67a)
yielding the balances for the mixing process
(∂G i /∂ p)T = Vi (67b)
mix Z = n 1 Z 1 + n 2 Z 2 ; Z i = Z i − Z i∗ (60a) 
(∂(G i /T )/∂ T ) p = − Hi /T 2 (67c)
or
 (∂ Hi /∂ T ) p = C pi (67d)
mix Z = n 2 Z − Z 2∗ (60b)
Equations (67a)–(67d) show the particular role of partial
Here, mix Z is the integral effect of mixing: Z i = Z i − molar Gibbs energies G i . By their definition, quantities G i
Z i∗ are the differential effects. For enthalpies and Gibbs are both partial molar quantities and chemical potentials as
energies, Z = H or G, only the differential effects Z i defined by the fundamental equation of thermodynamics:
can be determined by experiments and not the partial molar
G i ( p, T ) = (∂G/∂n i ) p,T,n j =ni = µi ( p, T ) (68)
quantities Z i themselves, in contrast to volumes and heat
capacities, where both quantities are available.
Since the mixing process may be accompanied by a D. Molar Quantities of Pure Compounds
change of state of component Y2 (e.g., solid or gas state and Molar Quantities at Infinite Dilution
of pure Y2 may change to liquid state in the mixture), it is
Molar volumes of pure compounds Vi∗ and their temper-
advantageous to separate the differential effect Z 2 into
ature and pressure dependence are available from density
two steps:
  measurements:
Z 2 = Z 2 − Z 2∞ + Z 2∞ − Z 2∗ (61a)
Vi∗ = Mi di∗ (69a)
and  ∗  
   ∂ Vi ∂ ln di∗
− Z 2∗ = − ∞
+ Z 2∞ − Z 2∗ (61b) = αi∗ Vi∗ = −Vi∗ (69b)
Z Z Z ∂T p ∂T p
In Eqs. (61a) and (61b) the quantity  ∗  ∗
∂ Vi ∂ ln di
= −βi∗ Vi∗ = −Vi∗ (69c)
Z 2∞ = Z 2∞ − Z 2∗ (62) ∂p T ∂p T
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776 Chemical Thermodynamics

Molar heat capacities C ∗pi are known from calorimetric [H+ (aq)] = 0, thus avoiding the ambiguity resulting from
measurements; their temperature and pressure dependence electrolyte dissociation.
is tabulated for practical use.
Molar entropies Si∗ are tabulated at the standard state
◦ ◦
as standard entropies S298 (Yi ), S298 (Yi ) = Si∗ (1 atm, IV. FUGACITIES AND ACTIVITIES
298.15 K). They are defined by the relation (◦ , standard)
 298.15
◦ A. Chemical Potential of Pure Gases
S298 (Yi ) = c∗◦
pi d(ln T ) (70)
0 On the basis of Eq. (68), the chemical potential of an
Molar enthalpies and Gibbs energies cannot be determined ideal pure gas is obtained by integration of Eq. (73b) after
by experiments (third law of thermodynamics); only dif- replacing Vi∗ with the help of the equation of state of an
ferences with respect to some reference state can be de- ideal gas, Vi∗id = RT / p:
fined. The concept of formation reactions is frequently
used to replace molar enthalpies Hi∗ and Gibbs energies µi∗id ( p, T ) = µi∗id ( p + , T ) + RT ln( p/ p + ). (74)
G i∗ in thermodynamic balances by the standard enthalpies In Eq. (74) p + is an arbitrary reference pressure.
and standard Gibbs energies of formation, f H ◦ [Yi ] and The chemical potential of a real gas is obtained when
f G ◦ [Yi ], respectively. using an appropriate equation of state of a real gas. Vi∗real ,
The formation reaction at standard conditions (1 atm, such as the van der Waals, the Redlich–Kwong, or the
298.15 K) of a pure chemical compound Yi (e.g., CH3 OH) virial equation:
requires the formation of Yi from chemical elements in  p 
their most stable state at standard conditions; here, RT
µi∗real ( p, T ) = µi∗id ( p, T ) + Vi∗real − d p (75)
C(graphite) + 2H2 (g) + 0.5 O2 (g) = CH3 OH(1) (71) p+ p
In Eq. (75) the reference pressure p + is chosen so low
According to this definition, the formation of an ele-
( p + → 0) that the reference potentials µi∗ ( p + , T ) of ideal
ment in its most stable state at standard conditions equals
◦ ◦ and real gases are equal. The integral expression in Eq. (75)
zero. Hence, f H298 [H2 (g)] = 0: f H298 [O2 (g)] = 0;
◦ ◦ is related to the so-called fugacity coefficient φi∗ by the
f H298 [C(graphite)] = 0; but f H298 [C(diamond)] =
help of the relation
1.90 kJ mol−1 , this quantity being the heat of phase transi-  p 
tion, C(graphite) → C(diamond), at standard conditions. RT
RT ln φi∗ = Vi∗real − d p, (76)
Standard heats of formation and phase transition are tabu- 0 p
◦
lated as values f H298 (Yi ). They can be determined with permitting Eq. (75) to be written in the form
high precision by combustion of compounds Yi in special 
calorimeters. Tabulated standard Gibbs energies of for- µi∗real ( p, T ) = µi◦ (T ) + RT ln pφi∗ p ◦ . (77)
mation f G ◦298 (Yi ) are based on the same concept of a Fugacity coefficients of numerous pure gases are tabulated
formation, reaction at standard conditions. from low (φi∗ = 1) to high pressures for practical use.
The temperature and pressure dependence of Hi∗ and In Eq. (77) p ◦ is the standard pressure, p ◦ = 1 atm;
∗
G i are given by the relations quantity pφi∗ is called the fugacity of the pure gas Yi .
 ∗
∂ Hi ∂ T p = C ∗pi Comparison of Eqs. (74) and (77) shows that ideal and
 ∗  (72) real gases can be treated as formally equal when pressures
∂ Hi ∂ p T = Vi∗ 1 − αi∗ T are replaced by fugacities. Using an appropriate equation
 of state of a real gas, for example, the virial equation,
∂G i∗ ∂ T = −Si∗ (73a)
pVi∗ = RT + Bi∗ (T ) p + · · ·
p
 ∗ (78)
∂G i ∂ p = Vi∗ (73b)
T
the fugacity coefficient φi∗ can be approximated with the
Quantities Z i∞
at standard conditons as used in solution help of the relation
chemistry are also tubulated. Standard heats of formation 
◦
of ions in aqueous solutions, f H298 [Yi (aq)], include the φi∗ = exp Bi∗ p RT (79)
heat of formation of the pure compound Yi under standard
conditions and the heat of transfer of pure compound
B. Chemical Potential in Gas Mixtures
Yi from its pure state to infinite dilution in solvent S,
that is, the quantity Hi∞ − Hi∗ . The tables of single-ion In a gas mixture of ideal gases Y1 , . . . , Yk , at pressure p
quantities in aqueous solutions are based on the additional and temperature T , component Yi is at partial pressure pi
assumption that f H ◦ [H+ (aq)] = f G ◦ [H+ (aq)] = S◦ (Dalton’s law) and Eq. (74) can be appropriately used to
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Chemical Thermodynamics 777

yield the chemical potential µi ( p, T ) of Yi in this mixture, The superscript “real” is omitted in Eq. (87) because
since µi ( p, T ) = µi∗ ( pi , T ): this equation is also valid for ideal mixtures where
f i = 1 (φi = φi∗ ). The activity coefficient of a pure phase
µiid ( p, T ) = µi∗id ( p, T ) + RT ln( pi / p)
(xi = 1, φi = φi∗ ) equals unity, in contrast to its fugacity
 coefficient [φi∗ ; see Eq. (76)].
= µi◦ (T ) + RT ln pi p ◦ (80)
Equation (80) exhibits the dependence of µi on the phase
composition ( pi = xi p, where xi is the mole fraction): C. Chemical Potentials in Condensed Phases
µiid ( p, T ) = µi∗id ( p, T ) + RT ln xi (81) The knowledge of equations of state for gas phases permits
the calculation of activity coefficients via fugacity coef-
Equations of state of real gas mixtures, for example, the
ficients. Equations of state for general practical use such
virial equation of state of a binary gas mixture,
as the virial equation (and others) are not known for con-
p V̄ = RT + B̄ p + · · · (82a) densed phases (liquids and solids). However, as shown
by Planck and Schottky, the passage from the gaseous
B̄ = x12 B1∗ + x22 B2∗ + 2x1 x2 B12 (82b) to the liquid or solid state does not change the structure
permit the calculation of fugacities φi of components Yi of Eq. (87) and leads to the general formulation for the
in the real mixture chemical potentials,
 p 
RT µi ( p, T ) = µi∗ ( p, T ) + RT ln xi + RT ln f i (88a)
RT ln φi = Vireal − dp (83)
0 p
µi∗ ( p, T ) = lim [µi ( p, T ) − RT ln xi ] (88b)
with the help of Eq. (56), which yields the partial molar xi →1
quantities needed for estimating the integral expression lim f i = 1 (88c)
in Eq. (83). In Eq. (82b) B1∗ and B2∗ are the second virial xi →1

coefficients of the pure gases Y1 and Y2 ; the cross term which can be used in gaseous, liquid, and solid phases.
B12 , resulting from the interaction of unequal particles in For solutions, the chemical potentials of the solutes
the gas phase, can be obtained from statistical models. A (Y2 , . . . , Yk ), when referred to infinite dilution instead
rough approximation is due to Lewis: B12 = (B1∗ + B2∗ )/2. of pure phase, can be written
The chemical potential of component Yi in a real gas
mixture is related to that in the ideal mixture by the relation µi ( p, T ) = µi∞ ( p, T ) + RT ln xi
  ∗ 
µireal ( p, T ) = µiid ( p, T ) + RT ln φi (84) µ − µi∞
+ RT ln f i exp i (89)
Combination of Eqs. (75), (76), (81), and (84) yields the RT
appropriate expression of the chemical potential µi in real entailing the definition of an activity coefficient:
gas mixtures:  
 f 0i = f i exp µi∗ − µi∞ RT . (90)
µireal ( p, T ) = µi∗real ( p, T ) + RT ln xi + RT ln φi φi∗
(85) The superscript (∗ ) in Eqs. (89) and (90) indicates that the
solute Yi and the solution are considered in equal states
for the dependence of the chemical potential on the com- of aggregation, which is not necessarily the stable state of
position and molecular interactions. Equation (85) relates the pure compound Yi with chemical potential µi∗ .
the chemical potential µireal ( p, T ) of component Yi in the The general definition of the chemical potential of a
gas mixture to that of its pure state, µi∗real ( p, T ); the quo- solute Yi in solution (Y1 is the solvent S) is based on the
tient of the fugacities φi and φi∗ is called the activity activity coefficient of the type given by Eq. (90).
coefficient f i ; the product of activity coefficient f i and
mole fraction xi is the activity ai of component Yi in the µi ( p, T ) = µi∞ ( p, T ) + RT ln xi
mixture:
+ RT ln f 0i (i = 2, . . . , k) (91a)
f i = φi φi∗ ; ai = xi f i (86)
µi∞ ( p, T ) = lim [µi ( p, T ) − RT ln xi ] (91b)
xs →1
Combining Eqs. (85) and (86) yields the generally used
expression lim f 0i = 1 (91c)
xs →1
µi ( p, T ) = µi∗ ( p, T ) + RT ln ai
In solutions, Eqs. (88a)–(88c) are used for the solvent and
= µi∗ ( p, T ) + RT ln xi + RT ln f i (87) Eqs. (91a)–(91c) for the solutes. Identity within restricted
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778 Chemical Thermodynamics

concentration ranges for Eqs. (88a)–(88c) if f i = 1 and for Equation (96b) must be integrated from infinite dilution
Eqs. (91a)–(91c) if f 0i = 1: of component Y2 (x2 = 0, f 02 = 1) to the arbitrary com-
position x2 to yield
µiid ( p , T ) = µi ( p , T ) + RT ln xi . (92)  x2
According to IUPAC rules the superscript  indicates an (ln f 02 )x =x2 = d ln f 02
x2 =0
arbitrary reference state, here ∗ or ∞. Quantities  x1 =1−x2
x1
µi ( p , T ) − µiid ( p , T ) = µiE ( p , T ) = RT ln f i (93a) =− d ln f 1 (98)
x1 =1 1 − x1
µi ( p , T ) − µiid ( p , T ) = µiE ( p , T ) = RT ln f 0i (93b) If the activity coefficient of component Y1 is known as
are referred to as excess chemical potentials. a function of composition, the integrals in Eqs. (97) and
According to the Gibbs–Duhem equation the chemical (98) can be evaluated graphically or analytically to yield
potentials and hence the activity coefficients of a mixture the activity coefficients f 2 and f 02 , respectively.
or solution are not independent; for a binary system at
constant pressure and temperature we have D. Conversion of Reference Potentials
and Activity Coefficients
x 1 d µ1 + x 2 d µ2 = 0 (94)
The preceding considerations are based on the use of the
In Eq. (94) the chemical potentials can be expressed mole fraction scale. Chemists and chemical engineers who
with the help of Eqs. (88a)–(88c) for mixtures and with use other scales for the composition of mixtures and so-
Eqs. (91a)–(91c) solutes in solutions. Since lutions, for example, weight percent and mole percent for
d µi∗ = 0, d µi∞ = 0, mixtures or molality, molonity, and molarity for solutions
and (see Section I.A) must convert chemical potentials and
activity coefficients to these scales. Conversion is based
x1 d ln x1 + x2 d ln x2 = 0 (95)
on the fact that changes in composition scales do not
the following equations are obtained for mixtures and so- change the chemical potential, for example, conversion
lutions, respectively: from the mole fraction scale (µi∞ , f 0i ) to the molality scale
x1 (µi∞(m) , γi ):
d ln f 2 = − d ln f 1 (96a)
1 − x1 µi∞ + RT ln xi + RT ln f 0i
and = µi∞(m) +RT ln m i + RT ln γi (99)
x1
d ln f 02 = − d ln f 1 (96b)
1 − x1 Using Eq. (91c) and the conversion formula from xi to m i
Integration of Eq. (96a) from the pure component Y2 (x2 = (Table I) entails
1, f 2 = 1) to an arbitrary composition x2 yields the activity
µi∞(m) = µi∞ + RT ln Ms ; γi = xs f 0i (100)
coefficient at this composition:
 x2
Yi (i = 2, . . .) being the solutes and S the solvent. For
(ln f 2 )x =x2 = d ln f 2
x2 =1 frequently needed conversion formulas of mole fractions
 x1 =1−x2
x, molarities c, molalities m, and molonities m̃ and corre-
x1 sponding activity coefficients v, y, γ , and β, see Tables V
=− d ln f 1 (97)
x1 =0 1 − x1 and VI.

TABLE V Conversion of Reference Chemical Potentials of Binary Systemsa

From

To µ∞
2 µ∞(c)
2 µ∞(m)
2 µ2∞(m̃)

∞(c) d1 ∞(m) ∞(m̃)

µ∞
2 = µ∞
2 µ2 + RT ln µ2 − RT ln M1 µ2 − RT ln M1
M1
∞(c) M1 ∞(c) ∞(m) ∞(m̃)
µ2 = µ∞
2 + RT ln µ2 µ2 − RT ln d1 µ2 − RT ln d1
d1
∞(m) ∞(c) ∞(m) ∞(m̃)
µ2 = µ∞
2 + RT ln M1 µ2 + RT ln d1 µ2 µ2
∞(m̃) ∞(c) ∞(m) ∞(m̃)
µ2 = µ∞
2 + RT ln M1 µ2 + RT ln d1 µ2 µ2
a Subscript 1 denotes solvent; subscript 2 denotes solute; d denotes density of pure solvent; M denotes molar
1 1
mass of solvent.
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Chemical Thermodynamics 779

TABLE VI Conversion of Activity Coefficients of Different Concentration Scales (Binary Systems)a

From

To f 02 y2 γ2 β2

d + (M1 − M2 )c2
f 02 = f 02 y2 (1 + M1 m 2 )γ2 [1 + (M1 − M2 )m̃ 2 ]β2
d1
d1 (M1 x1 + M2 x2 ) (1 + M2 m 2 )d1 d1
y2 = f 02 y2 γ2 β2
d M1 d d
d − M 2 c2
γ2 = x1 f 02 y2 γ2 (1 − M2 m̃ 2 )β2
d1
M1 x 1 + M2 x 2 d
β2 = f 02 y2 (1 + M2 m 2 )γ2 β2
m1 d1
a Subscript 1 denotes solvent; subscript 2 denotes solute; d denotes density of pure solvent; d denotes density of
1
solution; M1 and M2 denote molar masses.

E. Chemical Potentials of In Eq. (103) the symbol δ indicates virtual processes. A

Electrolyte Compounds virtual process is a process that is realizable, not depending
on time, for which entropy is defined in every state of the
Electrochemistry uses chemical potentials of the type
system; δS is an infinitesimally small variation and in this
given by Eqs. (91a)–(91c) for single ions. The link to ther-
respect equivalent to a differential of first order.
modynamics is established by the help of mean mole frac-
tions x± and mean activity coefficients f ± . For a binary
electrolyte as the solute, Y2 = Cv+
z+ z−
Av− (z + , valent cation: B. Generalized Forces and Internal Variables
z − , valent anion), for example, Na2 SO4 (where z + = +2,
Figure 3 illustrates the situation of a system in equilib-
z − = −1, v+ = 2, v− = 1), the chemical potential µ2 ( p, T )
rium; entropy S is represented as a function of an internal
consists of the chemical potentials of cations and anions,
variable ζ . Internal variables ζ and their conjugate quan-
µ+ ( p, T ) and µ− ( p, T )
tities, generalized forces , are produced by the system in
µ2 ( p, T ) = v+ µ+ ( p, T ) + v− µ− ( p, T ) nonequilibrium states. Generalized forces such as gradi-
  ents of concentration, temperature, or pressure or affinities
= v+ µ∞ ∞
+ ( p, T ) + v− µ− ( p, T )
of chemical reactions are the driving forces to equilibrium.
+ v RT ln x± + v RT ln f = (101) Generalized forces are functions of the intensive variables
of state of the system and equal zero at equilibrium,  = 0.
In Eq. (101) the mean quantities are given by the relations
 1/v  1 Their conjugate internal variables ζ are functions of the
x± = x+v+ x−v− ; f ± = f +v+ f −v− ; extensive variables of state and of supplementary condi-
(102) tions characterizing the process studied. An example is
v = v+ + v−
given in Section V.F.1. Neither the generalized forces nor
internal variables are variables of state; the system in its
V. THERMODYNAMIC EQUILIBRIUM equilibrium state does not recognize them.
The use of the notation of internal variables is exem-
A. Equilibrium Conditions plified in Fig. 3 by an equilibrium of the distribution of

According to Gibbs, thermodynamic equilibrium is de-

fined by one of the following conditions:
(δS)U,V,n ≤ 0 (103a)
or
(δU ) S,V,n ≥ 0 (103b)
Equation (103a) refers to closed, Eq. (103b) to open, sys-
tems. Conditions equivalent to Eq. (103b) are obtained
with the help of Legendre transformations of the funda-
mental equation
(δ H ) S, p,n ≥ 0; (δ A)T,V,n ≥ 0;
(103) FIGURE 3 Explanation of Gibbs’ equilibrium condition δS ≤ 0.
(δG)T, p,n ≥ 0 For details see text.
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780 Chemical Thermodynamics

a chemical compound Y in two immiscible solvents in Mathematics provide a general criterion for stability.
contact, S1 and S2 , n (1) (2)
Y and n Y moles of Y being the The quadratic form δ 2 U is positive for all considerable
amounts of Y dissolved in S1 and S2 , respectively. Then variations of the parameters ξi if, and only if, all the roots
the internal variable ζ is represented as the ratio of the λ of the equation
mole numbers, ζ = n (1) (2)  
Y /n Y . If the state of equilibrium  
is attainable from both sides, ζ > ζ eq and ζ < ζ eq , the U11 − λ U12 ... U1,k+2 
 
tangent at ζ eq is horizontal, (∂ S/∂ζ )eq = 0, and δS equals  U21 U22 − λ . . . U2,k+2 
 .
zero, δS = (∂ S/∂ζ )eq δζ = 0. If, however, compound Y is  . ..  = 0 (107)
 . . 
insoluble in one of the two solvents, the tangent at ζ eq is  
 Uk+2,1 ... Uk+2,k+2 − λ
∼
defined only from one side by the limit of (∂ S/∂ζ ), which
is a negative quantity, and δS ≤ 0 (Gibbs’ equilibrium con- are greater than zero (i.e., if the quadratic form is positive
dition). definite). Variations of order higher than 2 generally must
Gibbs criteria of equilibrium, of course, are in agree- not be considered.
ment with the second law of thermodynamics, which gives
evidence of the variation of entropy in spontaneous pro-
D. Equilibria at Phase Boundaries
cesses (entropy increase) but gives no explicit evidence on
the state of equilibrium itself. A heterogeneous system made up of two phases, α and β,
and k components Yi is in equilibrium [Eq. (103b)] if
 
C. Stability of Equilibrium k
(α) (α)
− p δV + T δS +
(α) (α) (α) (α)
µi δn i
Eqs. (103a) and (103b) do not provide information on the i=1
stability of equilibrium. Stability of equilibrium is rec-  

k
(β) (β)
ognized only when taking into account the variations of + − p δV (β) (β)
+T (β)
δS (β)
+ µi δn i ≥0
degrees greater than unity, δ 2 S, δ 3 S, . . . or δ 2 U , δ 3 U , . . . i=1
in the total variations, (108)
S = δS + δ S + δ S + · · ·
2 3
(104a) All variations in Eq. (108) are under the constraints
U = δU + δ U + δ U + · · ·
2 3
(104b) δS = 0; δV = 0; δn i = 0; i = 1, . . . , k (109)
where yielding the relations
 ∂U
δU = dξi (105a) δS (α) = −δS (β) ; δV (α) = −δV (β) ;
i
∂ξi (β)
(110)
δn i(α) = −δn i ; i = 1, . . . , k
1 
δ2U = Ui j dξi dξ j (105b) which permit us to write Eq. (108) in the form
2 i j
 
    − p (α) − p (β) δV (α) + T (α) − T (β) δS (α)
∂ ∂U
Ui j = (105c) 
k

∂ξ j ∂ξi ξ j =ξi + µi(α) − µi
(β)
δn i(α) ≥ 0 (111)
ξi =ξ j
i=1
and so on. The equilibrium position is a position of stable
Equation (111) is the basic equation for the discussion
equilibrium if
of equilibrium conditions at phase boundaries. For this
δ2 S < 0 or δ2U > 0 (106a) purpose, three sets of variations are studied:

of undetermined equilibrium if A: δS (α) = 0; δn i(α) = 0 (112a)

δ2 S = 0 or δ2U = 0 (106b) B: δV (α) = 0; δn i(α) =0 (112b)

or of unstable equilibrium if C: δS (α)

= 0; δV (α)
=0 (112c)
Set A entails the reduction of Eq. (111) to
δ2 S > 0 or δ2U < 0 (106c)

− p (α) − p (β) δV (α) ≥ 0 (113)
Also metastable equilibria can be observed (e.g., super-
cooled liquids). Metastable equilibria are stable only with Equation (113) is fulfilled if the following conditions are
regard to infinitely neighboring states. met:
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Chemical Thermodynamics 781

1. Both variations, δV (α) > 0 and δV (α) < 0, are possible

and p (α) = p (β) (deformable phase boundary).
2. Variation δV (α) is impossible, δV (α) = 0, and
p (α) > p (β) , p (α) = p (β) , or p (α) < p (β) (undeformable
or rigid phase boundary).
3. Variation δV (α) is possible only in one direction,
δV (α) ≥ 0 and p (α) ≤ p (β) (semideformable phase
boundary).
FIGURE 4 Schematic phase diagram of a pure compound. The
Similar considerations concerning sets B and C yield the diagram exhibits a section around a triple point T where solid (s),
conditions for heat-conducting (T (α) = T (β) ), nonconduct- liquid (l), and gaseous phases (g) are in equilibrium; C is the critical
ing (T (α) > T (β) , T (α) = T (β) , or T (α) < T (β) ), and semi- point; 1 ← →g is the vapor pressure curve, s ←→g is the sublimation
(β) →1 is the fusion pressure curve.
conducting (T (α) ≥ T (β) ) and for permeable (µi(α) = µi ), pressure curve, and s ←
(α) (β) (α) (β) (α) (β)
impermeable (µi > µi , µi = µi , or µi < µi ), and
(β)
semipermeable (µi(α) ≥ µi ) phase boundaries. A one-component system k = 1, to begin with, ex-
hibits three types of regions in its phase diagram depend-
ing on the variables of state p and T (Fig. 4): divariant
E. Phase Equilibria (v = 1, f = 2), univariant (v = 2, f = 1), and nonvariant
1. Gibbs Phase Rule (v = 3, f = 0) regions. Divariant regions are the fields of
solid, liquid, and gaseous states. One equation (v = 1) of
Each of the v phases of a heterogeneous system of k com- type Eq. (116) shows that in these fields the chemical
ponents is subjected to a Gibbs–Duhem–Margules equa- potential µ( p, T ) is a function of p and T , a well-known
tion [see Eq. (27)]: feature. Univariant regions, as given by the curves (evapo-

k+2 ration, 1 ←
→ g; sublimation, s ←→ g; fusion, s ←→ 1) in Fig. 4
ξi(α) dηi(α) = 0; α = 1, . . . , v. (114) (for phase transitions s ← → s, see Figs. 5 and 6), indicate
i=1 equilibrium of two phases. These curves are obtained by
Hence the phase diagram of a heterogeneous system is resolution of the appropriate system of two (v = 2) Gibbs–
defined by v equations of the type given by Eq. (114), Duhem–Margules equations:
showing in total v(k + 2) variables. If all phase boundaries −Vi(α) d p + Si(α) dT + dµi = 0 (117a)
are deformable, heat conducting, and permeable for all
(β) (β)
components Yi , the number of independent variables is −Vi d p + Si dT + dµi = 0 (117b)
reduced to
Equations (117a) and (117b), can be transformed to yield
f =k+2−v (115) the Clausius–Clapeyron differential equation,
Number f is the number of degrees of freedom: Eq. (115)
is the Gibbs phase rule. If f = 0, 1, 2, the system is called
nonvariant, univariant, or divariant, respectively.

2. Theory of Phase Diagrams

The Gibbs–Duhem equations [Eq. (114)] for a hetero-
geneous system in which all phase boundaries are de-
formable, heat conducting, and permeable for all com-
pounds can be written

k

xi(α) −Vi(α) d p + Si(α) dT + dµi = 0;
i=1

α = 1, 2, . . . , v. (116)
In Eq. (116) Vi(α) and Si(α) are the partial molar volume and
entropy of component Yi in phase α. The set of v equations FIGURE 5 Stable (solid lines) and metastable (dashed lines)
(116) is the basis for the theory of phase diagrams. phase diagrams of sulfur. For explanation see text.
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782 Chemical Thermodynamics

diagrams, an arbitrary phase (β) is chosen to be the

reference phase: its k + 1 independent variables, p, T ,
(β) (β)
x1 , . . . , xk−1 are spanning the phase-diagram space. In
order to transform the set of k + 2 variables of Eq. (116) to
these reference variables, the chemical potential of com-
ponent Yi in phase β is written
 (β)   (β) 
(β) ∂µi ∂µi
dµi = dp + dT
∂p ∂T
T,x j p,x j
 

k−1 (β)
∂µi
+ (β)
d xs(β)
s=1 ∂ xs p,T,x j =xs
FIGURE 6 Phase diagram of water. Ice modifications: I, II, III,
V, VI, VII. At the scale of this figure, representation is not possi-  (β) 
ble for both the vapor pressure curve, beginning at triple point (β) (β)

k−1
∂µi
= Vi dp − Si dT + d xs(β)
T (273.16 K. 6.03 × 10−6 kbar) and ending at critical point C ∂ xs
(β)
s=1 p,T,x j =xs
(647.2 K. 0.218 kbar), and the sublimation pressure curve.
(119)
(β)
dp
(β)
S − Si(α) Hi
(α→β) and since dµi(α) = dµi , Eq. (119) can be inserted into Eq.
= i(β) (α)
= (α→β)
(118) (116) to yield
dT Vi − Vi T Vi

k
 (β) 
k
 (β)
Nonvariant regions are points in the phase diagram (triple xi(α) Vi − Vi(α) d p − xi(α) Si − Si(α) dT
points T , v = 3) indicating equilibrium of three phases i=1 i=1
(g, 1, s or s, s, 1 or s, s, g, etc.). The vapor pressure 
k−1
curve (equilibrium: 1 ← → g) terminates in a critical point C. + G αβ
s d x s = 0;
(β)
α = 1, . . . , v (120a)
Above the critical temperature, liquid and gaseous states s=1
are indistinguishable (supercritical fluid state). where
Phase diagrams of pure compounds contain these ele-  
ments in various combinations. Figure 5 (phase diagram 
k
∂µi
(β)
G αβ
s = xi(α) (β)
(120b)
of sulfur) and Fig. 6 (phase diagram of water) are exam- i=1 ∂ xs p,T,x j =xs
ples. The phase diagram of sulfur shows the phenomenon
called allotropy, occurring when the compound studied Since Eq. (120a) reduces to identity if α = β, Eq. (120a)
may exist in two different solid states (here monoclinic is a system of v − 1 differential equations in k + 1 vari-
(β) (β)
and rhombic). Starting at state A, very slowly increasing ables ( p, T, x1 , . . . , xk−1 ). All p, T , x diagrams can be
temperature yields the transition from rhombic to mono- reproduced with the help of Eqs. (120a) and (120b).
clinic sulfur at point B and the transition from monoclinic
to liquid sulfur at point C, with every transition being
(α→β) F. Chemical Reactions
accompanied by a change in molar enthalpy (Hi ),
(α→β) (α→β)
volume (Vi ), entropy (Si ), and heat capacity 1. Generalized Forces and Internal Variables
(α→β)
(c pi ). Transitions of this type are called transitions in Chemical Reactions
of first order, in contrast to transitions of second order,
The internal variable of chemical reactions is the “extent
which show changes only in heat capacity (e.g., Curie
of reaction” ζ , defined by the variables of state n i (amount
point transition of iron, etc.).
of substance Yi ) and supplementary conditions, which
The phase diagram of stable equilibrium states (solid
are given by the stoichiometry of the chemical reaction
lines) of sulfur is superimposed by a phase diagram of
investigated,
metastable states (dashed lines) in which direct transition
from rhombic to liquid sulfur can be formed by rapidly ω1 Y1 + ω2 Y2 + · · · ←
→ ω n Yn + · · · + ω k Y k (121)
increasing the temperature from point A to C. This transi-
tion takes place at point D situated on the fusion pressure which in a more condensed form can be written
curve of the metastable rhombic sulfur, the corresponding
ωi Yi = 0 (122)
metastable triple point being Tm (Fig. 5).
Multicomponent heterogeneous systems require rather In Eq. (122) the stoichiometric coefficients ωi are posi-
complex calculations. In a general treatment of their phase tive for the final and negative for the initial products. The
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Chemical Thermodynamics 783

internal variable ζ of chemical reactions is given by the be taken into account with the help of the corresponding
relation transfer quantities, H (α→β) and V (α→β) , respectively.
dζ = dn i /ωi (123)
yielding the expression 3. Heat Balance of Chemical Reactions

dU = − p d V + T d S − A dζ (124) At constant pressure and temperature the Gibbs energy

of reaction  R G equals the negative affinity [Eqs. (125a)
for the internal energy, where and (125b)], yielding the relation

k

k 
k

A=− ωi µi (125a) R G = ωi µi = ωi µi + RT ln xi f i (129)
i=1 i=1 i=1
or
The enthalpy of reaction R H is obtained from the deriva-

v 
k
tive of R G/T with respect to temperature:
A=− ωi µi(α) (125b)
α=1 i=1 k k  
 ∂ ln f i
is the generalized force, called affinity, of a homogeneous R H = ωi Hi − RT 2
ωi (130)
i=1 i=1
∂T p
[Eq. (125a)] or a heterogeneous [Eq. (125b)] reaction.
Replacing Hi at 1 atm by the enthalpy of formation (see
2. Chemical Equilibrium Section III. D) yields the basic equation of thermochem-
istry,
The Gibbs equilibrium condition entails the relations  
k  k
∂ ln f i

k R H ◦ = ωi f H ◦ − RT 2 ωi (131)
A=− ωi µi = 0 i=1 i=1
∂T p
i=1
where in most cases the effect resulting from the temper-
or
ature dependence of the activity coefficients can be ne-

v 
k
glected when compared with the large enthalpies of for-
A=− ωi µi(α) = 0 (126)
mation.
α=1 i=1

if equilibrium of the chemical reaction is attainable from

both sides. G. Equilibrium of Electrochemical Systems
Using the activity concept (Section IV), Eq. (126) is
For electrochemical systems, electrochemical potentials
transformed to
µ̃i ( p, T ) (Section II) are used instead of chemical po-

k
tentials. Under the action of driving forces, both chemi-
ωi µi ( p, T ) = −RT ln K a ;
cal reactions (e.g., reaction in a galvanic cell) and charge
i=1
(127) transport (e.g., electron transport outside the cell from the

k
 eq ωi
Ka = ai anode to the cathode) may take place. The scheme
 
i=1
Cu(1) | Zn(2) | ZnSO4 (aq)(3)  CuSO4 (aq)(4)  Cu(5) (132)

v 
k
ωi µi(α) ( p, T ) = −RT ln K a ; shows an example of a Galvanic cell. The cell reaction
α=1 i=1
(128) Zn(2) + CuSO(4) → (5) + ZnSO(3)
4 ← Cu (133)

v 
k
 (α)eq ωi
4
Ka = ai is accompanied by the transport of two electrons from
α=1 i=1
phase 1 to phase 5, which materially are identical.
In Eqs. (127) and (128) K a is the equilibrium constants of At cell equilibrium the driving force equals zero:
eq (α)eq
the chemical reaction and ai and ai are the activities
at equilibrium concentrations of the reactants. Using the 
v 
k

ωi µi(α) + n µ̃(1)
e − µ̃e
(v)
=0 (134)
concept of standard reaction enthalpies, standard Gibbs
α=1 i=1
reaction energies, and standard entropies (Section III), the
quantities µi ( p, T ) can be calculated with the help of In Eq. (134) µ̃(α)
e are the electrochemical potentials of the
tabulated standard values (at 25◦ C and 1 atm) and c p or Vi electrons, and n is the number of electrons transferred
functions. Phase transitions on the path of integration must from the anode (phase 1) to the cathode (phase 5). Since
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784 Chemical Thermodynamics

the terminal phases are materially identical (here copper) used for the determination of activity coefficients from
they differ only in their Galvani potentials (α) . vapor-pressure measurements:
 (1)
µ̃(1)
e − µ̃e = F
(v)
− (v) = −F E. (135) f i(1) = pi xi(1) pi∗ (140)
In Eq. (135) E is the measured potential difference of the Starting with the equilibrium condition for a solution and
cell at zero current, the electromotive force of the cell. its gaseous phase,
From Eqs. (134) and (135) follows the wellknown   ◦(g)
Nernst equation: d µi∞(1) + RT ln ai(1) = d µi + RT ln pi φi (141)
 

v−1 k
 (α) ωi and equivalent approximations yield the relation
◦ RT
E=E − ln ai (136a)
nF α=1 i=1
f 0i(1) = pi xi(1) K (142)


v−1 
k where K is Henry’s constant.
−n F E ◦ = ωi vi(α) (136b) An ideal mixture ( f i = 1) or dilution ( f 0i = 1) reduces
α=1 i=1 Eqs. (141) and (142) to
pi = xi(1) pi∗ and pi = xi(1) K (143)
H. Use of Equilibria for the Determination
of Activity Coefficients known as Raoult’s and Henry’s laws, respectively.
Figure 7 illustrates the calculation of f i and f 0i according
Fugacity coefficients and hence activity coefficients can
to Eqs. (140) and (142) as the deviations from ideality.
be calculated with the help of appropriate equations of
state (see Section IV). This is possible, however, only for
the gas phase (van der Waals equation, Redlich–Kwong 2. Liquid–Liquid Equilibria
equation, virial equation); for condensed phases no use- In osmotic pressure measurements a solution is separated
ful general equations of state are available. Experimental from the pure solvent S by a nondeformable membrane
determination of activity coefficients in condensed phases permeable only to the solvent. The pressure of the pure
is based on the study of equilibria. There are numerous
methods, but only typical examples will be given.

1. Vapor–Liquid Equilibria
Equilibrium of a gaseous and a liquid phase in contact
(permeable, deformable, and heat-conducting boundary)
entails the conditions
  ◦(g)
d µi∗(1) + RT ln ai(1) = d µi + RT ln pi φi (137)
which at constant temperature can be transformed with
the help of Eq. (67b), showing the pressure dependence
of the chemical potentials, to yield the relation
 
xi(1) f i(1)
RT d ln = −Vi∗(1) d p (138)
pi φi∗

Integration from xi(1) = 1 (where Pi = pi∗ ) to an arbitrary

mole fraction xi(1) (partial pressure in the gas phase pi ) FIGURE 7 Activity coefficients f 1 , f 2 (mixture), and f 02 (solu-
yields the relation tion) from vapor-pressure measurements on binary systems of
 ∗  components Y1 (chloroform) and Y2 (acetone). p id , p1id , p2id : hy-
(1) (1) pi φi pi
Vi∗(1) pothetical total and partial vapor pressures of the ideal system
xi f i = ∗ ∗ exp dp (139) ( piid , Raoult’s law); O1 E1 = p1∗ , O 2 E2 = p2∗ , vapor pressures of
pi φi pi RT
pure compounds Y1 (chloroform) and Y2 (acetone). p real , p1real ,
The exponential term in Eq. (139), commonly called the p2real : measured total and partial vapor pressures of the binary sys-
tem chloroform–acetone. p2id.sol : hypothetical partial vapor pres-
Poynting correction, differs little from unity for temper-
sure of the ideally dilute solution of Y2 (acetone, solute) in Y1
atures not near the critical temperature. Assuming ideal (chloroform, solvent) (Henry’s law); O 2 F = K (Henry’s constant).
behavior of the gas phase, fugacities can be replaced by Activity coefficients [see Eqs. (140) and (142)]: f 1 = AC1 /AB 1 ;
pressures. Then Eq. (139) yields the relation commonly f 2 = AC 2 /AB 2 ; f 02 = AC 2 /AD.
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Chemical Thermodynamics 785

solvent is p, while in osmotic equilibrium the solution is account, and the integral of Eq. (151) can be solved ana-
subject to an additional pressure , the osmotic pressure, lytically to yield the activity coefficients f s from freezing
yielding the equilibrium condition point depressions.
µs ( p + , T ) = µ∗s ( p, T ) (144) Another method using liquid–solid equilibria deter-
mines solute activity coefficients from temperature-
Using the pressure dependence of the chemical potential dependent solubility data. The pure solute Yi is in equi-
and assuming that the partial molar volume is independent librium with the saturated solution. With reference to the
of pressure yields the relation state of the infinitely dilute solution [Eqs. (91a)–(91c)],
 p+
the equilibrium condition is given by the relation
µs ( p + , T ) = µs ( p, T ) + Vs d p
p
µi∗(s) ( p, T ) = µi∞ ( p, T ) + RT ln(xi f 0i )sat (152)
= µs ( p, T ) + Vs (145)
The differential of Eq. (152) can be expressed with the help
By combining Eqs. (144) and (145), one can determine of the temperature dependence of the chemical potentials,
the activity coefficient of the solvent from the osmotic yielding at constant pressure
pressure
xs f s = exp(−Vs /RT ) (146) Hi∞ − Hi∗(s) Hi∞
d ln(xi f 0i )sat = 2
dT = dT (153)
The solvent activity xs f s can be expressed with the help RT RT 2
of the molal osmotic coefficient which is defined as In Eq. (153) the quantity Hi∞ is the change in enthalpy
ln xs f s for the transfer of component Yi from the pure solid state to
=− (147)
m Ms the infinitely dilute solution. This quantity can be obtained
where m is the molality of the solute and Ms is the molar from heat of solution experiments.
mass of the solvent. Using Eq. (146) yields the follow- If the temperature-dependent solubility measurements
ing relationship between the osmotic coefficient and the are started at a temperature T  where the component Yi
osmotic pressure: is very slightly soluble (xi ) and the activity coefficient f 0i
Vs approaches unity, Eq. (153) can be integrated to yield
= (148)    
m Ms RT
xi T
Hi∞
The measurement of osmotic coefficients combined ( f 0i )sat,T = exp 2
dT (154)
with the Gibbs–Duhem–Margules equation is a well- xi sat T  RT
established method for the determination of the activity
coefficients of solutes.
4. Electrochemical System Equilibria
3. Liquid–Solid Equilibria Electromotive force (emf) measurements are frequently
In freezing point experiments an equilibrium between liq- used to determine activity coefficients of electrolyte so-
uid solution and its pure solid solvent S is achieved. The lutions. Equation (136a) relates the emf to the activi-
equilibrium condition at constant pressure is ties of the reacting cell components. From concentration-
    dependent measurements the standard potential E ◦ of the
µ∗(s) ( p, T ) µ ∗(1)
( p, T )
d s
=d s
+ d(R ln xs f s ) cell reaction and the activity coefficients can be obtained.
T T As an example, according to Eq. (136a), the emf of the
(149) Galvanic cell
The temperature dependence of the chemical potential
Pt(s) | K(Hg) | KCl (conc. in S) | AgCl(s) | Ag(s) | Pt(s)
[Eq. (67c)] can be used in Eq. (149) to yield
(155)
Hs∗(1) − Hs∗(s) fus Hs
d(ln xs f s ) dT = dT (150) can be written as
RT 2 RT 2
where fus Hs is the molar enthalpy of fusion of the pure 2RT
E = E ◦ − ln(cy± ) (156a)
solvent at temperature T . Equation (150) is integrated F
from xs = 1, where T = T ∗ (freezing temperature of pure RT
E ◦ = E ◦ + ln aK(Hg) (156b)
solvent) to an arbitrary concentration xs with freezing tem- F
perature T to yield Here, y± is the mean activity coefficient of the electrolyte
 T on the molar scale.
fus Hs
ln xs f s = dT (151) In Eq. (155) K(Hg) is a potassium amalgam electrode
T∗ RT 2 connected to a solution of KCl at concentration c in
Using the appropriate molar heat capacities, the tempera- solvent S; AgCl(s)/Ag(s) is the silver/silver chloride ref-
ture dependence of the enthalpy of fusion can be taken into erence electrode.
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786 Chemical Thermodynamics

Data analysis of emf measurements according to BIBLIOGRAPHY

Eq. (156a) yields the standard potential of the cell re-
action and the activity coefficients at each concentration. Denbigh, K. (1981). “The Principles of Chemical Equilibrium,” 4th ed.,
Suffice it to mention that such measurements could also be Cambridge Univ. Press, London.
used to determine the activity of potassium in the amalgam Gibbs, J. W. (1957). “Collected Works,” Vol. I, Yale Univ. Press, New
Haven, CT.
phase.
Guggenheim, E. A. (1986). “Thermodynamics,” 8th ed., North-Holland,
A final remark: The IUPAC has changed the stan- Amsterdam.
dard pressure from 1 atm to 105 Pa (105 Pa = 1 bar = Haase, R. (1956). “Thermodynamik der Mischphasen,” Springer-Verlag,
0.98692 atm). The numerical values of the tabulated stan- Berlin and New York.
dard data at 1 atm of condensed components generally are Honig, J. M. (1999). “Thermodynamics,” Academic Press, San Diego.
Kirkwood, J. G., and Oppenheim, I. (1961). “Chemical Thermodynam-
not affected, owing to their small pressure dependence in
ics,” McGraw-Hill, New York.
contrast to gases which undergo a slight change. Klotz, I. M., and Rosenberg, R. M. (1994). “Chemical Ther-
modynamics—Basic Theory and Methods,” 5th ed., Benjamin, New
York.
Kondepudi, D., and Prigogine, I. (1998). “Modern Thermodynamics,”
SEE ALSO THE FOLLOWING ARTICLES Wiley, New York.
Lewis, G. N., and Randall, M. (1961). “Thermodynamics,” 2nd ed.,
BATTERIES • CRITICAL DATA IN PHYSICS AND CHEM- McGraw-Hill, New York.
Planck, M. (1964). “Vorlesungen über Thermodynamik,” 11th ed., de
ISTRY • ELECTROCHEMISTRY • ELECTROLYTE SOLU-
Gruyter, Berlin.
TIONS, THERMODYNAMICS • POTENTIAL ENERGY SUR- Pitzer, K. S. (1995). “Thermodynamics,” 3rd ed., McGraw-Hill, New
FACES York.
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Computational Chemistry
Matthias Hofmann Henry F. Schaefer III
Ruprecht-Karls-Universität Center for Computational Quantum Chemistry

I. History of Computational Chemistry

II. Methods Used in Computational Chemistry
III. Applications of Computational Chemistry
IV. Outlook for Computational Chemistry

GLOSSARY Schrödinger equation A differential equation for the

quantum-mechanical treatment of a system.
ab initio Latin term meaning from the beginning. In Self-consistent field (SCF) method Method used to
the context of computational chemistry, computations solve mathematical equations which depend on their
from first principle without any empirical input except own solution.
fundamental physical constants. Semiempirical Making use of experimental results to de-
Density functional theory (DFT) Theory based on the rive parameters for approximations made in quantum-
electron density as the crucial property rather than the mechanical methods.
wave function in traditional ab initio methods.
Force field A set of equations describing the potential
energy surface of a chemical system. COMPUTATIONAL CHEMISTRY is the scientific dis-
Hamiltonian operator An operator that describes the ki- cipline of applying computers to gain chemical informa-
netic and potential energy of a system treated by wave tion. It is the link between theoretical and experimen-
mechanics. tal chemistry. Theoretical chemistry is mainly concerned
Molecular mechanics Theoretical treatment of mole- with the development of mathematical models which al-
cules by a force field based on classical mechanics and low one to derive chemical properties from calculations
electrostatics. and to interpret experimental observations. The mathe-
Molecular modeling Branch of computational chemistry matical models developed in theoretical chemistry are usu-
concerned with computer-aided molecular design. ally validated by comparison with experiment. Theoretical
Orbital Function to describe a single electron. Molecular chemistry existed before the arrival of electronic comput-
orbitals (MOs) build the total wave function of a sys- ers. Computational chemistry, however, relies heavily on
tem and are expanded in terms of atomic orbitals, AOs powerful microelectronics to cope with huge computa-
(basis functions). Orbitals can be occupied or virtual. tional tasks. It focuses on the application of theoretical
Quantum mechanics Mathematical treatment based on methods which require calculational treatments which are
the wavelike nature of small particles. by far too large to be done without fast computers.

487
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488 Computational Chemistry

Of course, the strict separation of theoretical, compu- phisticated enough to be useful for applications in chem-
tational, and experimental chemistry is of an academic istry. Molecular mechanics emerged in the mid-1960s
nature. In practice, theoreticians often not only develop a and has become more sophisticated and more useful with
new method but also need to design more efficient algo- time.
rithms to make the method applicable. Before computa- Due to the number of various approximations, early
tional results can be interpreted, computational chemists computations performed to try to reproduce experimen-
need to undertake benchmark studies to determine the lim- tal findings yielded varying degrees of success. Compu-
itations of a method. Without the knowledge about the tational chemistry could become a recognized scientific
accuracy of the applied mathematical model, any compu- discipline only after a real predictive power was estab-
tational study is without scientific significance. Likewise, lished. Perhaps the first case in which theory proved to be
many experimentalists use computer programs to support accurate enough to challenge experiment was the structure
or complement their experimental studies. determination of methylene (CH2 ). From a spectroscopic
investigation the ground state of this molecule was first
concluded to be linear. However, this interpretation had to
I. HISTORY OF COMPUTATIONAL be revised after reliable computations predicted a signifi-
CHEMISTRY cantly bent structure in 1970.
The development of different methods and their effi-
As early as 1929, only 3 years after Schrödinger’s formu- cient implementation is only one reason for the success
lation of the fundamental equation that bears his name, of computational chemistry. Another factor is the dra-
Dirac stated correctly, matic development of computer technology (i.e., com-
putational speed as well as the amount of core memory
The underlying physical laws necessary for the mathematical and of disk storage). Today’s personal desktop computers
theory of a large part of physics and the whole of chemistry are provide many times the computer power of early “super-
thus completely known, and the difficulty is only that the exact computers” at a fraction of the price. The combined de-
application of these laws leads to equations much too compli- velopment of both software and hardware allowed com-
cated to be soluble. putational chemistry to become for chemical research an
indispensable tool which allows one to plan experiments
Hence, the further development of quantum chemistry more carefully and hence to optimize the use of labora-
was aiming at approximate solutions of the Schrödinger tory resources. The importance of computational chem-
equation by simplifying the required mathematical istry was honored when the 1998 Nobel Prize in Chem-
treatment. istry was awarded to two pioneers of the field, J. A. Pople
In the 1930s the basics for a wide range of computa- and W. Kohn.
tional methods based on quantum mechanics were laid
by the development of the Hartree-Fock method. In 1951
Roothaan, for the first time, considered molecular or-
bitals as a linear combination of analytic atomic one- II. METHODS USED IN
electron functions, shifting the mathematical task from COMPUTATIONAL CHEMISTRY
the numerical solution of coupled differential equations
to the evaluation of integrals over basis functions. Intro- The methods used in computational chemistry can be clas-
duction of approximations for the most difficult integrals sified according to the sophistication of the underlying
through the use of suitable parameters led to the develop- model (Fig. 1). Molecular mechanics methods are based
ment of semiempirical methods beginning in the 1950s. on classical mechanics and are computationally the fastest.
The more rigorous ab initio methods benefited from the Semiempirical methods are based on a wave function de-
use of Gaussian- instead of Slater-type basis functions, scription, in which some integrals are approximated by
as pointed out by Boys in 1950 but generally accepted means of parameters and many others are neglected to re-
only two decades later. Configuration interaction (CI) was duce the computational cost. Ab initio methods use only
the first theoretical level used to include electron corre- fundamental physical constants but no further experimen-
lation and was widely applied during the 1970s. In the tal results; Hartree-Fock (H F) theory is the starting level,
late 1970s many-body perturbation theory (Møller-Plesset which can be improved upon by accounting for electron
methods), and during the 1980s coupled cluster meth- correlation in various ways. Density functional methods
ods, became more popular because they are more eco- are also quantum mechanical but are based on the electron
nomical and more rapidly convergent, respectively, than density to describe chemical systems. They are often con-
CI. The 1990s can be considered the decade of density sidered “ab initio” although some empirical parameters
functional theory, which by that time had become so- enter the energy functionals.
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Computational Chemistry 489

FIGURE 1 Classification of computational chemistry methods. AMBER, assisted model building with energy refine-
ment; CHARMM, chemistry at Harvard molecular mechanics; GROMOS, Groningen molecular simulation; CNDO,
complete neglect of differential overlap; INDO, intermediate neglect of differential overlap; NDDO, neglect of diatomic
differential overlap; MNDO, modified neglect of differential overlap; AM1, Austin model 1; PM3, parametric method
number 3; HF, Hartree-Fock; MP2, Møller-Plesset, second order; MP3, Møller-Plesset, third order; MP4, Møller-
Plesset, fourth order; CISD, configuration interaction singly and doubly excited; CISD(T), configuration interaction
singly, doubly, and triply (estimated) excited; CCSD, coupled cluster singly and doubly excited; CCSD(T), coupled
cluster singly, doubly, and triply (estimated) excited; LDA, local density approximation; GGA, generalized gradient
approximation; BLYP, Becke/Lee, Yang, and Parr; B3LYP, Becke three-parameter/Lee, Yang, and Parr.

A. Force Field Methods frared (IR) spectroscopy associated with a certain bond
stretch or angle deformation also fall in narrow ranges,
A force field (FF) is a set of equations describing the po-
which demonstrates that the variation of force constants
tential energy surface of a chemical system. A molecular
is also relatively small. The existence of an increment
mechanics (MM) method uses a force field based on a
system for heats of formation, for example, shows that
classical mechanical representation of molecular forces
the energy behaves additively as well. Hence, in MM the
to calculate static properties of a molecule (e.g., structure
energy is expressed classically as a function of geometric
and energy of an energy minimum structure). Molecular
parameters.
dynamics (MD) also implements a force field but gener-
ates dynamic properties (e.g., evolution of an structure
1. Energy Terms
in time) by calculating forces and velocities of atoms.
In MM methods atoms are treated as “balls” of different Advanced force fields distinguish several atom types for
masses and sizes, and bonds are “springs” connecting the each element (depending on hybridization and neighbor-
balls without an explicit treatment of electrons. The main ing atoms) and introduce various energy contributions to
advantage of this simple classical approach is the small the total force field energy, E FF :
computational cost, which allows one to treat very large
E FF = E str + E bend + E tors + E vdW + E elst + · · · ,
molecules. FFs are typically constructed to yield experi-
mentally accurate structures and relative energies. Some where E str and E bend are energy terms due to bond stretch-
FFs are generated to accurately compute other properties ing and angle bending, respectively; E tors depends on tor-
such as vibrational spectra. sional angles describing rotation about bonds; and E vdW
The observation that properties of chemical functional and E elst describe (nonbonded) van der Waals and elec-
groups are normally transferable from one compound to trostatic interactions, respectively (Fig. 2). In addition to
another validates the MM approach. The most basic com- these basic terms common to all empirical force fields
ponent in a FF is the atom type and one element usually there may be extra terms to improve the performance
contributes several atom types. Each bond is character- for specific tasks. Each term is a function of the nuclear
ized by the atom types involved and has a “natural” bond coordinates and a number of parameters. Once the pa-
length since the variation with the chemical environment rameters have been defined, the total energy, E FF , can be
is relatively small. Similarly, bond angles between atom computed and subsequently minimized with respect to the
types have typical values. The energy absorptions in in- coordinates.
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490 Computational Chemistry

FIGURE 3 (Curve a) Harmonic potential, E(R) = k(R0 − R)2 ;

(curve b) third-order polynomial anharmonic potential, E(R) =
k(R0 − R) 
√ + k (R0 − R) ; (curve c) Morse potential, E(R) =
2 3

D(1 − e k/2D(R 0 −R ) 2
) .

with
θ = θ0ABC − θ ABC .
If higher accuracy is desired (e.g., for computing IR fre-
quencies), a third-order term can be included with an an-
harmonicity constant set to be a fraction of k ABC .
FIGURE 2 Most basic energy terms included in empirical force
field (FF) methods. c. Torsion energy. The torsional potential, due to the
rotation of bonds A–B and C–D about bond B–C, is peri-
a. Stretch energy. The harmonic approximation odic in the torsional angle ω, which is defined as the angle
gives the stretch energy of a bond between atom types between the projections of A–B and C–D onto a plane
AB perpendicular to B–C. The torsional energy therefore is
A and B, E str , as
expressed as a Fourier series:
AB
E str (R) = k AB R 2 , 
ABCD
E tors (ω) = Vn cos(nω),
where k AB is the force constant and R = R0AB − R AB is n
the bond length deviation from the natural value, R0AB , for
AB
which E str is defined to be zero. Further improvement can which allows the representation of potentials with various
be achieved by including higher anharmonic terms to the minima and maxima (Fig. 4). Three terms are enough to
equation. While these expressions describe the potential model the most common torsional potentials.
well for R close to R0 , the energy goes to infinity for large
distances (Fig. 3). In contrast, a morse potential allows
the energy to approach the dissociation energy, D, as R
increases:
√
E Morse (R) = D(1 − e k/2DR 2
) ,
but it is much more expensive in terms of computational
cost.

b. Bending energy. The harmonic approximation

ABC
for the bending energy, E bend , due to the deformation of
the angle between the A–B and B–C bonds, is sufficient
for most purposes:
FIGURE 4 A three-minimum potential
 (bold line) represented as
ABC
E bend (θ ) = k ABC θ 2 a three-term Fourier series: E(ω) = 3n=1Vn cos(n ω).
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Computational Chemistry 491

d. van der Waals energy. The van der Waals term, needs to be considered out to very long distances. Fast
E vdW , covers nonelectrostatic interactions between non- multipole methods (FMMs) can be applied to reduce the
bonded atoms. The van der Waals energy is positive (re- computational cost of evaluating E elst .
pulsive) and very large at short distances, zero at large
distances, but slightly negative (attractive) at moderate f. Other energy contributions. So that the perfor-
distances due to temporarily induced multipole attraction mance can be improved, force fields include further pa-
(dispersion force), the most important attractive contribu- rameters to take care of special cases. For example, cross
tion of which (dipole–dipole interaction) has an R −6 de- terms account for the interplay between different contri-
pendence. The Lennard-Jones potential for E vdW includes butions (e.g., longer bonds for small angles). Correction
a repulsive term, which is set proportional to (R −6 )2 to terms may be introduced to describe substituent effects
grow faster than R −6 : (e.g., anomeric effect). Additional terms may be intro-
 12  6  duced to adequately treat special cases like pyramidaliza-
AB
AB R0 R0AB  tion of sp2 hybridized atoms. Hydrogen bonding may be
E LJ (R) = ε −2 .
R R treated explicitly (in addition to the electrostatic interac-
tion) with a special set of van der Waals interaction pa-
εAB determines the energy depth of the minimum. Alter- rameters. Pseudo atoms maybe introduced to model lone
natively, a Buckingham or Hill potential can be used that pairs. In addition, atoms in unusual bonding situations
employs an exponential function for the repulsive term. (three-membered rings, molecules with linearly conju-
For each atom type a van der Waals radius, R0 , and the gated π -systems, aromatic compounds, etc.), which are
atom softness, ε, have to be determined, from which the not described adequately by the normal parameters, can
diatomic parameters are calculated according to be defined as new atom types.
√ The force field energy, E FF , corresponds to the en-
R0AB = R0A + R0B and ε AB = ε A ε B .
ergy relative to a molecule with noninteracting fragments.
e. Electrostatic energy. The electrostatic energy, Therefore, only energies for molecular structures built
E elst , is due to the electrostatic interactions arising from from the same fragments (conformers) can be compared
polarized electron distributions based on electronegativity directly. So that energy between different molecules (iso-
differences. It can be modeled by Coulomb interactions of mers) can be compared, the energy scale is converted to
point charges associated with individual atoms: heats of formation by adding bond increments (estimated
from bond dissociation energies minus the heat of forma-
QA QB tions of the atoms involved) and possibly group increments
E elst (R AB ) = ,
εR AB (e.g., methyl group):
ε being a dielectric constant, which can be used to model 
bonds 
groups
the effect of the same or other molecules present (e.g., Hf = E FF + H AB + H G .
solvent). The atomic charges, Q, are commonly obtained
by fitting to the electrostatic potential as calculated by an
2. Parametrization
electronic structure method. An E elst description based on
dipole–dipole interactions between polarized bonds can Determining the parameters for a force field is a substan-
alternatively be employed. tial task. In general, not all necessary data are available
Hydrogen bonds are nonbonded interactions between from (accurate) experiments. Modern electronic structure
a positively charged hydrogen atom and an electronega- computations can provide unknown data relatively easily
tive atom with lone electron pairs (mostly oxygen or ni- and with sufficient accuracy. Another problem is the large
trogen) and can be adequately modeled by appropriately number of parameters: for a force field with N atom types,
chosen atomic charges. Although a single hydrogen bond the number of different types of bonds, bond angles, and
is a very weak interaction, the large number occurring in dihedral angles scales as N 2 , N 3 , and N 4 , respectively,
biomolecules (e.g., proteins) makes hydrogen bonding a each requiring several parameters. So that the number of
very important factor. parameters can be reduced, the atom dependency can be
In the large size limit, the bonded interactions increase reduced (e.g., the torsional parameters may be treated as
linearly with the system size, but the nonbonded interac- dependent on the B–C central bond only and not on the
tions show a quadratic dependence and determine the com- atom types A and D). The parametrization effort can be re-
putational cost. The van der Waals interactions quickly duced further by defining “generic” parameters to be used
fall off with the distance (R −6 dependence) and may be for less common bond types or when no reference data are
neglected for large separations. The electrostatic interac- available. This, of course, reduces the quality of a calcula-
tion (proportional to R −1 ) is much more far reaching and tion. By deriving the di-, tri-, and tetra-atomic parameters
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492 Computational Chemistry

from atomic data (atom radii, electronegativities, etc.), to reproduce experimental results and are specific to the
universal force fields (UFFs) allow one to include basi- chosen combination of QM and MM methods.
cally all elements. The performance, however, is relatively Alternatively, the total energy, Etot , may be extrapolated
poor. from QM and MM calculations on a small part and on
The kind of energy terms, their functional form, and the whole of a suitably partitioned system (IMOMM-
how carefully (number, quality, and kind of reference integrated molecular orbital, molecular mechanics
data) the parameters were derived determine the quality method)
of a force field. Accurate force fields exist for organic
Etot = EQM (small) + EMM (whole) − EMM (small)
molecules (e.g., MM2, MM3), but more approximate
force fields (e.g., with fixed bond distances) optimized
for computational speed rather than accuracy [e.g., B. Wave Function
AMBER (assisted model building with energy refine- Quantum-Mechanical Methods
ment), CHARMM (chemistry at Harvard molecular me-
The explicit treatment of electrons in atoms and molecules
chanics), GROMOS (Groningen molecular simulation)]
requires quantum mechanics, which invokes a wave func-
are the only practical choice for the treatment of large
tion, , to describe the system of electrons and nuclei. The
biomolecules. The type of molecular system to be studied
square of the wave function represents the probability of
determines the choice of the force field.
a particle’s being at a given position. The central goal be-
One limitation of force field methods is that they can
comes the solution of the (time-independent) Schrödinger
describe only well-known effects that have been observed
equation,
for a large number of molecules (this is necessary for
the parametrization). The predictive power of these meth- H =E ,
ods is limited to extrapolation or interpolation of known which relates the wave function, , to the energy, E, of
effects. the system. The Hamiltonian operator, H, consists of the
kinetic (T) and the potential energy (V) operators:
3. Quantum-Mechanical and H = T + V.
Molecular-Mechanical (QM/MM) Method
The fact that electrons instantly adjust to changes in nu-
Another limitation of MM is the inability to investigate clear positions due to the much greater masses of the nu-
reactions. While force field methods are capable of de- clei allows the motions of electrons and nuclei to be sepa-
scribing conformational changes, for which all bonds re- rated (Born-Oppenheimer approximation). The electronic
main intact along the reaction coordinate, they are by con- wave function depends on only the nuclear position, not
struction not capable of treating reactions in which bonds on the nuclear momenta. The electronic Hamiltonian, He ,
are broken and/or formed. The classical model is not de- in atomic units is given by
signed to describe the electronic rearrangement associ-

1 Elec.
ated with bond breaking and bond formation. Such prob- He = Te + Vne + Vee + Vnn = − ∇i2
lems are better treated by electronic structure methods 2 i
discussed below. For large systems, a combined quantum-
 Elec.
Nucl.  Za  Elec.
Elec.  1
mechanical and molecular-mechanical (QM/MM) method + +
can be applied. In this approach the reactive part of a i
|Ra − ri | i j>i
|ri − r j |
the molecule to be studied is described by a quantum-
mechanical (semiempirical, ab initio, or DFT) method  Nucl.
Nucl.  Za Zb
+ ,
while the rest of the system is treated by a force a b>a
|Ra − Rb |
field. The problem with this approach is the “communica-
tion” between classical and quantum-mechanical poten- where r and R represent the electronic and nuclear coor-
tial (i.e., how the atoms close to the QM/MM border are dinates, respectively, and the Laplacian is defined as
 
treated). ∂2 ∂2 ∂2
The total energy, Etot , may be computed as follows: ∇i =
2
+ 2+ 2 .
∂ xi2 ∂ yi ∂z i
Etot = EQM + EMM + EQM/MM ,
The nucleus–nucleus repulsion, Vnn , is constant for a given
where the quantum-mechanical contribution, EQM , and the geometry, and the kinetic energy, Te , and the electron–
molecular-mechanical contribution, EMM , are defined by nucleus attraction, Vne , are easy to evaluate. The electron–
a QM method and a MM method, respectively. The cou- electron repulsion, Vee , however, depends on the distances
pling term, EQM/MM , includes parameters that can be fitted between electrons and is the reason why the Schrödinger
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Computational Chemistry 493

equation cannot be solved exactly for systems with more For example, a Slater determinant for the ground state
than one electron. of the hydrogen molecule can be written as follow:
The energy can be computed as the expectation value
1 φg (1) φg (1)
of the Hamiltonian operator: (1, 2) = √
∗
2 φg (2) φg (2)
H dτ |H|
E= = , 1
∗ dτ | = √ [φg (1)φg (2) − φg (2)φg (1)] = −(2, 1),
2
where the common bra-ket notation is used. The varia-
where φg represents the bonding molecular orbital (MO),
tional principle states that any trial wave function will
the 1σg orbital.
give an energy equal to or higher than the exact value be-
The electronic Hamiltonian can be written as sums of
cause the real system will adopt the best possible wave
one-electron (hi ) and two-electron (gi j ) operator plus the
function (which corresponds to the exact energy). Thus,
constant nuclear–nuclear repulsion:
a trial wave function constructed in terms of a number  
of parameters can be improved by minimizing the energy H= hi + gi j + Vnn
with respect to the parameters (MO coefficients). i i j>1
A meaningful trial wave function should approach zero with
as r goes to infinity; it should be normalized, that is, 1 
Nucl.
Za
hi = − ∇i2 −
| =1 2 a |Ra − ri |
and
(meaning the probability that the system is located some-
where in space is one); and it should comply with the 1
gi j = .
Pauli principle. The latter states that two electrons must |ri − r j |
differ in at least one quantum number. Furthermore, the The Hartree-Fock energy expression becomes
wave function should be antisymmetric (i.e., it should

N
1 N  N
change sign when two electrons are interchanged). This is E= φi |hi |φi + ( φi φ j |gi j |φi φ j
a characteristic property of electrons. Antisymmetry can i
2 i=1 j=1
be ensured by using Slater determinants with one-electron

N
functions (orbitals) φi in columns and electrons (1, 2, . . .) − φi φ j |gi j |φ j φi ) + Vnn = hi
in rows. i

1 N  N
+ (Ji j − K i j ) + Vnn ,
1. Hartree-Fock Method 2 i=1 j=1
Hartree-Fock theory employs a single Slater determinant. or
In the restricted Hartree-Fock (RHF) method, one spatial 
N
1 N  N
function φi is multiplied by an α (representing spin up, E= φi |hi |φi + ( φ j |Ji |φ j
2 i=1 j=1
spin quantum number m s = + 12 ) or β (representing spin i

down, m s = − 12 ) spin function with the properties − φ j |Ki |φ j ) + Vnn .

α | α = β | β = 1; α|β = β |α = 0 Ji j is called a Coulomb integral because it corresponds to
the electronstatic repulsion of the charge distributions due
to give spin orbitals φα and φβ (or φ and φ̄ for short). to φi2 and φ 2j ; the exchange integral, K i j , has no classical
This is appropriate for closed-shell species with paired equivalent. Ji and Ki are Coulomb and exchange opera-
electrons, but open-shell species with unpaired electrons tors, respectively.
cannot be expected to have identical α and β orbitals. The To find a minimum energy, one can vary the orbitals
unrestricted Hartree-Fock (UHF) method allows a differ- under the condition that they remain orthogonal by us-
ent spatial function for each electron. However, UHF wave ing the method of Lagrange multipliers. This leads to the
functions can suffer from spin contamination (i.e., the spu- definition of the Fock operator, Fi , which describes the
rious mixing of higher spin states into the desired one kinetic energy, the nuclear attraction energy, and the elec-
[more formally, the expectation value of the S2 operator tron repulsion energy of one electron in the field of the
is larger than the correct value of S(S + 1), S being the other electrons:
total spin]). Restricted open-shell Hartree-Fock (ROHF)–
N
based methods avoid the problem of spin contamination Fi = hi + (J j − K j ).
but do not allow spin polarization. j
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494 Computational Chemistry

A set of Hartree-Fock equations is obtained, χα χγ |g|χβ χδ ≡ χα χγ | χβ χδ ≡ αγ | βδ


N
1
Fi φi = λi j φ j , ≡ χα (1)χγ (2) χβ (1)χδ (2) dr1 dr2 .
j |r1 − r2 |
which can be simplified by a unitary transformation, which The Roothaan-Hall equations give the orbital coeffi-
does not change the total wave function, to make the cients as eigenvectors of the Fock matrix. So that the Fock
Lagrange multipliers diagonal: matrix can be constructed, however, the density matrix, D
(i.e., the orbital coefficients), has to be known. To start the
Fi φi = εi φi .
iterative procedure, one must make an initial guess (e.g.,
These special MOs φi are called canonical MOs and the εi from another calculation, or D is just set to zero), from
are the corresponding MO energies, the expectation values which a Fock matrix can be derived. Diagonalization of
of the Fock operator in the MO basis: the Fock matrix gives new (improved) orbital coefficients
εi = φi |Fi |φi . which allow one to build a new density matrix and a new
Fock matrix. The procedure must be continued until the
According to Koopman’s theorem the orbital energy cor- change is less than a given threshold and a self-consistent
responds to the ionization energy for a particular electron field (SCF) is generated (Fig. 5).
(neglecting orbital relaxation). The Hartree-Fock equa- In the large basis set limit the Hartree-Fock method for-
tions can be solved only iteratively because the Fock op- mally scales with the fourth power of the number of basis
erator depends on all the occupied MOs by means of the functions due to the two-electron integrals. In practice,
Coulomb and exchange operators. computations have a more favorable scaling. Modern al-
The molecular orbitals, φi , are constructed as a linear gorithms are close to linear scaling because the Coulomb
combination of atomic orbitals (LCAO), χα , which form part of the electron–electron interaction which contributes
the basis set (see below), the most to the computational effort (the distances where

M exchange becomes negligible is relatively short) can be re-
φi = cαi χα . placed by a multipole interaction for large distances (fast
α
multipole method, FMM). In a conventional HF imple-
This leads to the Roothaan-Hall equations, which corre- mentation the two-electron integrals are computed and
spond to the Fock equations in the AO basis: stored on disk. In contrast, in the direct SCF method,
FC = SCε. the integrals are recomputed whenever they are needed

The elements of the overlap matrix, S, are defined as Sαβ =

χα |χβ , and the Fock matrix elements are given by

occ.MO
Fαβ = χα |h|χβ + χα |J j − K j |χβ .
j

The energy in terms of integrals over basis functions is

given by

M 
M
E= Dαβ χα |h|χβ
α β

1M 
M 
M 
M
+ Dαβ Dγ δ ( χα χγ |g|χβ χδ
2 α β γ δ

− χα χγ |g|χδ χβ ) + Vnn ,
which introduces the density matrix elements, Dγ δ , as

occ.MO
Dγ δ = c γ j cδ j .
j

The two-electron integrals are often written without the

g operator, and for further simplification only the indices FIGURE 5 Schematic representation of the self-consistent field
are given: (SCF) procedure. MO, molecular orbital.
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Computational Chemistry 495

to avoid the storage bottleneck and the slow input–output a. Complete neglect of differential overlap. The
operations. It is also possible to effectively screen for in- complete neglect of differential overlap (CNDO) approx-
tegrals which contribute only negligibly and thus can be imation is the most rigorous: only the one- and two-center
discarded. The use of symmetry, if present, also reduces Coulomb terms among the two-electron integrals survive:
the computational cost considerably.
µA νB | λC σD = δAC δBD δµλ δνσ µA νB | µA νB .
2. Semiempirical Methods µA νB | µA νB are independent of the orbital type (to guar-
The HF method represents a point of departure in elec- antee rotational invariance) and there are only two param-
tronic structure theory. One direction involves improve- eters, µA νA | µA νA = γAA and µA νB | µA νB = γAB ,
ment of the accuracy by including electron correlation for the two-electron integrals. The γAB depends only on
(see Section II.B.3.). Semiempirical methods, however, the nature of the atoms A and B and the distance between
try to provide moderate accuracy, but at much lower cost them and can be interpreted as the average electrostatic
than that of ab initio methods. Therefore, only valence repulsion of one electron at center A and one electron at
electrons are treated explicitly and core electrons are re- center B. The integral γAA is the average repulsion of two
placed by an effective core (covering nucleus plus core electrons at one atom.
electrons) and a minimal basis of orthogonal Slater-type The one-electron integrals are
orbitals (usually only s and p types) is chosen to describe

Nucl.
the valence electrons. µA |h|νA = −δµν µA |Va |µA .
The two-electron integrals require the main compu- a
tational effort in a HF calculation and their number is
The Pariser-Pople-Parr (PPP) method is a special case
significantly reduced in semiempirical methods by the
of CNDO, restricted to the treatment of π electrons.
zero differential overlap (ZDO) approximation. This basic
semiempirical assumption sets products of functions for
b. Intermediate neglect of differential overlap. In
one electron but located at different atoms equal to zero
the intermediate neglect of differential overlap (INDO)
(i.e. µA (1)νB (1) = 0, where µA and νB are two differ-
approximation the two-electron integrals are limited to
ent orbitals located on centers A and B, respectively). The
the Coulomb integrals. One-electron integrals involving
overlap matrix, S, is set equal to the unit matrix, Sµν = δµν ,
different orbitals of one center and Va operator from an-
and the two-electron integrals µν | λσ are zero, unless
other have to disappear to guarantee rotational invari-
µ = ν and λ = σ , that is,
ance. The one-electron integrals are the same as in the
µν | λσ = δµν δλσ µµ | λλ , CNDO approximation and the two-electron integrals are
given by
where δi j = 0 for i = j and δi j = 1 for i = j.
All three-and four-center two-electron integrals vanish µA νB | λC σD = δµA λC δνB σD µA νB | µA νB
automatically. One-electron integrals involving three cen- and parametrized as γAB and γAA .
ters are also set to zero. The remaining integrals are han- INDO is comparable to CNDO in computational cost
dled as parameters which partly compensate the errors but has the advantage that electronic states of different
introduced by the ZDO approximation. The parameters multiplicities can be distinguished.
are derived from experimental data on atoms or are fitted MINDO/3 (modified intermediate neglect of differen-
to reproduce experimental results for molecules. The var- tial overlap) was the first successful semiempirical method
ious semiempirical methods introduce different approxi- to give reasonable predictions of molecular properties. The
mations for the one- and two-electron parts of the Fock main improvement over earlier methods was the use of
matrix elements, molecular data rather than atomic data for the parametriza-

AO 
AO tion. However, the number of parameters to be determined
Fµν = µ|h|ν + Dλσ ( µν | λσ − µλ | νσ ), in MINDO/3 increases with the square of the number of
λ σ atoms included because one parameter depends on the
type of bonded atoms.
with the one-electron operator
1  Z 1  c. Neglect of diatomic differential overlap. Many
h = − ∇2 − a
= − ∇2 − Va ,
a |Ra − r|
2 2 of the shortcomings of MINDO/3 are corrected in the ne-
a
glect of diatomic differential overlap (NDDO) approxi-
where Z a denotes the charge resulting from the nucleus mation, which includes no further approximations beyond
plus the core electrons. ZDO. Thus, all integrals involving any two orbitals on one
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496 Computational Chemistry

center with any two orbitals on another center are kept, 3. Electron-Correlated Methods
which increases the number of integrals dramatically.
In the Hartree-Fock approach the real electron–electron
The one-electron integrals are
 interaction is replaced by an interaction with an averaged
µA |h|νB = µA − 12 ∇ 2 − VA − VB νB field. This means HF suffers from an exaggeration of
electron–electron repulsion. The difference between the
and
  energy obtained at the HF level and the exact (nonrela-
µA |h|νA = δµν µA − 12 ∇ 2 − VA µA − µA |Va |νA . tivistic) energy (for a given basis set) is defined as the cor-
a=A relation energy. The name reflects that this energy differ-
The two-electron integrals are given by ence is connected to the correlated movement of electrons
which is not considered in the HF method and which re-
µA νB | λC σD = δAC δBD µA νB | λA σB . duces the electron–electron repulsion. The HF description
typically allows electrons to be unrealistically resident in
d. Modified NDDO. The more successful semiem- the internuclear region. This leads to an underestimated
pirical methods, MNDO (modified neglect of differential nuclear–nuclear repulsion and to bond lengths that are too
overlap), AM1 (Austin model 1), and PM3 (parametric short. As a consequence, stretching force constants and
method number 3), are all based on NDDO but differ harmonic stretching frequencies computed at the HF level
in the treatment of core–core repulsion and how the pa- are too large. Likewise, the polarity of bonds is overesti-
rameters are assigned. There are only atomic parameters, mated (the more electronegative atom tolerates a higher
no diatomic parameters as in MINDO/3. The “modified” electron density in the HF picture) and computed dipole
NDDO methods calculate the overlap matrix, S, explicitly moments are often too large.
rather than using the unit matrix. Dynamic electron correlation, which is connected to the
The MNDO method tends to overestimate the repulsion correlated movement of electrons, can be distinguished
between atoms separated by approximately the sum of from static (near-degeneracy) electron correlation, which
their van der Waals radii. To correct for this deficiency, deals with the insufficiency of the one-determinant ap-
AM1 modifies the core–core term by Gaussian functions. proach. HF usually provides a suitable description of
PM3 is essentially equivalent to AM1 but uses (automated) closed-shell molecules in their electronic ground state.
full optimization of the parameter set against a much larger However, the homolytic dissociation of such a molecule
collection of experimental data while the AM1 parameters generates two electronic states which are very close in en-
are tuned by hand. PM3 therefore on average gives results ergy. This situation requires a description by more than
in somewhat better agreement with experiment. one Slater determinant (i.e., at least a two-configuration
Extending the basis set to include d functions as in method). The energy difference between the HF method
MNDO/d and PM3(tm) raises the number of integrals and a multiconfigurational method is the static correlation
(i.e., the number of parameters) tremendously but allows energy. Accounting for electron correlation is essential
a larger variety of applications, for example, those includ- for quantitative answers from electronic structure calcula-
ing transition metal compounds (albeit with variable ac- tions. Different post-HF methods which attempt to recover
curacy) or hypervalent molecules. all or part of the correlation energy are discussed in the
Semiempirical programs usually report heats of forma- following text.
tion calculated from the electronic energies less the cal- Within the closed-shell HF picture, molecular orbitals
culated energies for the atoms plus the experimental heat are occupied by either exactly two or exactly zero electrons
of formations for the atoms: represented by the variationally best one-determinant

atoms
wave function. Correlated levels give a different electron
Hf = E calc. (molecule) − E calc. (atom) density which cannot be represented by a single Slater

atoms determinant. A logical starting point to account for elec-
+ Hf (atom). tron correlation is to expand a multideterminantal wave
function with the HF wave function as a starting point:
The semi ab initio model 1 (SAM1) is another modified
NDDO method, but it does not replace integrals by param- 
= a0 HF + ai i ,
eters. The one- and two-center electron repulsion integrals i=1
are explicitly calculated from the basis functions [em-
ploying a standard STO-3G (Slater-type orbital from three where a0 usually is close to 1. Because this is analogous
Gaussian functions) Gaussian basis set] and scaled by a to expanding one MO in terms of AOs, one speaks of
function which has to be parametrized. SAM1 calculations the basis set as the one-electron basis (responsible for
take about twice as long as AM1 or PM3 calculations do. the one-electron functions, the MOs) while the number
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Computational Chemistry 497

sity matrix) may be used, which promise faster conver-

gence of the CI expansion. In general, several Slater de-
terminants are contracted linearly to form eigenfunctions
of the spin operators SZ and S2 and which are called spin
adapted configurations, or configuration state functions
(CSFs):

CI = ai i .
i=0

The expansion coefficients, ai , are then determined varia-

tionally to give the minimum energy.
For a full CI (FCI) the number of determinants grows
factorially with the size of the system. A full CI recovers all
of the electron correlation energy (for a given basis set) but
can be applied only to obtain benchmark results for very
small molecules to assess the performance of more eco-
nomical methods. For applications to larger molecules, the
FIGURE 6 Examples of singly, doubly, triply, and quadruply ex- CI expansion has to be truncated to make the computation
cited determinants derived from a Hartree-Fock (HF) reference. feasible. CIS, CISD, CISDT, and CISDTQ correspond to
expansions through singly, doubly, triply, and quadruply
of determinants included in a correlated wave function excited CSFs, respectively. According to Brilluoin’s the-
builds the many-electron basis. orem, the CI matrix elements of a closed-shell restricted
In closed-shell HF theory there is only one determi- HF wave function with singly excited CSFs vanish. Hence,
nant which has the lowest MOs occupied (occupation CIS does not improve the description of the ground state.
number = 2). The remaining orbitals are empty or “vir- Doubles are found to contribute most to the correlation en-
tual” (occupation number = 0). Additional determinants ergy and consequently CISD (including only singly and
are generated by exciting one or more electrons from an doubly excited determinants) is the most widely applied
occupied MO into an unoccupied (virtual) MO. According CI method because inclusion of triples and quadruples is
to the number of excited electrons, one speaks of singles, typically computationally too demanding.
doubles, triples, quadruples, and so forth (S, D, T, Q, re- FCI is size consistent, but truncated CI methods are
spectively; Fig. 6). not. This means the energy computed for two noninteract-
The larger the basis set the more virtual MOs and the ing molecules is not identical to the sum of the energies
more excited Slater determinants can be generated. The computed for the individual molecules. This unphysical
quality of a calculation is determined by both the size of behavior is a major drawback of any truncated CI. So
the basis set and the number of excited determinants that that CISD can be made approximately size consistent, the
are considered. If all possible determinants together with Davidson correction can be applied in which the contribu-
an infinite basis set could be used, one would get the ex- tion of quadruples, E Q , is estimated from the correlation
act solution of the nonrelativistic Schrödinger equation energy given at the CISD level, E CISD , and the coeffi-
within the Born-Oppenheimer approximation. Because cient of the reference configuration, a0 :
a different chemical environment mostly affects the va-
E Q = (1 − a0 )E CISD .
lence electrons, but does not influence the core electrons,
the frozen core approximation includes only determinants CISD was also extended to quadratic CISD (QCISD) by
with excited valence electrons. Also the highest virtual or- the inclusion of some higher-order terms to yield a size-
bitals may be left unoccupied in all determinants (frozen extensive method.
virtuals).
b. Multiconfiguration self-consistent field. The HF
a. Configuration interaction. In the configuration method does not give a good first-order description when
interaction (CI) procedure the trial function is constructed more than one nonequivalent resonance structure is im-
as a linear combination of the ground (reference configura- portant for the electronic structure of a molecule. A mul-
tion) and excited Slater determinants. The MO coefficients ticonfiguration self-consistent field (MCSCF) calculation
remain fixed throughout the calculation and are usually may be used instead. Not only the coefficients for the de-
taken from the HF orbitals. Alternatively, natural orbitals terminants are optimized in MCSCF, but also the MO co-
(which are defined as diagonalizing the one-electron den- efficients simultaneously. The selection of configurations
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498 Computational Chemistry

is not trivial. One easy way to construct an MCSCF is the Because this equation has to be true for all values of λ, the
complete active space self-consistent field, or CASSCF terms connected to the same power of λ can be separated:
(also called full optimized reaction space, or FORS). In-
λ 0 : H0 0 = E0 0,
stead of choosing configurations, one must select a set
of “active” (occupied and unoccupied) orbitals and all λ1: H0 1 + H1 0 = E0 1 + E1 0,
possible (symmetry-adapted) configurations within this
“active space” are automatically included in the MCSCF. λ2: H0 2 + H1 1 + H2 0 = E0 2 + E1 1 + E2 0,
The method is called restricted active space self-consistent
and so forth, which gives the zeroth-, first-, second-, etc.,
field, or RASSCF, when subsets of the active orbitals are
order perturbation equations. If one chooses the interme-
restricted to have a certain (minimum or maximum) num-
diate normalization condition,
ber of electrons to reduce the computational cost.
0| = 1; 0| = 0, i > 0,
The MCSCF provides a good first-order description 0 i
covering the static electron correlation due to degener-
acy problems. Dynamic electron correlation should be simple energy expressions are obtained:
addressed with the MCSCF wave function as a reference.
E0 = 0 |H0 | 0 ,
The multireference configuration interaction, or MRCI,

generates excited determinants from all (or selected) de- E1 = 0 |H | 0 ,
terminants included in the MCSCF. The complete active

space perturbation theory, second order (CASPT2) is a E2 = 0 |H | 1 ,
more economical approach. Both methods can be applied and so forth. Knowledge of wave function corrections
to compute excited states. up to order i allows calculation of the energy up to or-
der (2i + 1). This relationship is known as the Wigner
c. Many-body perturbation theory. Perturbation theorem.
theory assumes that somehow an approximate solution In Møller-Plesset (MP) perturbation theory the unper-
to a problem can be found. The missing correction, which turbed Hamiltonian, H0 , is taken as the sum over n Fock
should be small, is then considered as a perturbation of operators (n = number of electrons) giving a total of twice
the system. When the perturbation is to correct for the ap- the average electron–electron repulsion energy and the
proximation of independent particles the method is called perturbation operator becomes the difference between
many-body perturbation theory, or MBPT. In electronic the exact electron–electron repulsion and twice the av-
structure theory the Hamiltonian operator, H, is written as erage electron–electron repulsion. With this choice of H0
a combination of a reference Hamiltonian, H0 , which can the zeroth-order energy is just the sum of MO energies and
be solved for, and a perturbation H : the first-order energy equals the Hartree-Fock energy. The
H = H0 + λH , second-order correction, E(MP2), is the first to contribute
to the electron correlation energy and can be calculated
λ being the perturbation parameter (0 ≤ λ ≤ 1) which de- from the two-electron integrals over MOs:
termines the strength of the perturbation. The energy, E,
and wave function, , are expanded as Taylor series in λ: 
occ virt
[ φi φ j | φa φb − φi φ j | φb φa ]2
E(MP2) = .
E = E 0 + λE 1 + λ2 E 2 + λ3 E 3 + · · · i< j a<b
εi + ε j − εa − εb

and MP2 is a very economical method but often overcorrects

for electron correlation effects. The MP2 energy calcula-
= 0 +λ 1 +λ 2
2 +λ 3
3 + ···.
tion scales only with N 4 , but the transformation of AO
The Schrödinger equation, to MO integrals is an N 5 step (Table I). The next step
H =E , in the series, MP3, also includes only contributions from
doubly excited determinants but scales with N 6 . Full MP4
gives 0 and E 0 as the solution in the absence of any involves singly, doubly, triply, and quadruply excited de-
perturbation (λ = 0). E 1 , E 2 , etc., and 1 , 2 , etc., are terminants and is an N 7 method. In applications, triples
the first-, second-, etc., order corrections to the energy are sometimes left out (MP4SDQ is N 6 ) to make the cal-
and wave function, respectively. For λ > 0 the Schrödinger culation affordable. MPn methods with n > 4 are not used
equation becomes routinely because they are both very complex and expen-
  sive in terms of resources.
(H + λH ) 0 + λ 1 + λ2 2 + · · ·
   MP theory is size extensive but not variational (i.e.,
= E 0 + λE 1 + λ2 E 2 + · · · 0+λ 1+λ
2
2 + ··· . there is no guarantee that the correct energy is lower than
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Computational Chemistry 499

TABLE I Formal Scaling of Various Methods The expansion coefficients, t, are called amplitudes. Sub-
with the Size of the Molecular System, N, and stituting the exponential function by a series,
Size-Extensive and Variational Properties
Size
∞
1 k
eT = 1 + T + 12 T2 + 16 T3 + 1 4
T + ··· = T
Methoda Scaling extensive? Variational? 24
k!
k=0
N4
   
HF Yes Yes = 1 + T1 + T2 + 12 T21 + T3 + T2 T1 + 16 T31
MP2 N5 Yes No  
MP3 N6 Yes No + T4 + T3 T1 + 12 T22 + 12 T21 T2 + 24 T1 + · · ·
1 4

MP4SDQ N6 Yes No
MP4SDTQ N7 Yes No
shows that due to the exponential ansatz in CC,
MP5 N8 Yes No
i.) a given excitation level in general is not due to just
MP6 N9 Yes No
one excitation operator (there are “disconnected” terms in
CCSD N6 Yes No
addition to the “connected” term; for example, for doubles,
CCSD(T) N7 Yes No
T21 and T2 , respectively).
CCSDT N8 Yes No
ii.) restricting T generates not only excitations up to
CISD N6 No Yes
a given level, but also higher ones (quartets, etc.) up to
CISDT N8 No Yes
infinity. For example, for T = T2 ,
CISDTQ N 10 No Yes eT2 = 1 + T2 + 12 T22 + 16 T32 + · · · .
a HF, Hartree-Fock; MP, Møller-Plesset (numbers 2–

6 refer to second through sixth order; S, singly excited;

This is in contrast with both perturbation and CI methods
D, doubly excited; T, triply excited; and Q, quadruply ex- and therefore CC theory should provide a better descrip-
cited; CC, coupled cluster (S, D, and T as for MP except T tion of electron correlation effects at a given truncation
in parentheses is estimated); CI, configuration interaction level.
(S, D, T, and Q as for MP). The Schrödinger equation becomes

an MPn energy). This is no problem because usually only H eT 0 = E CC eT 0 ,

relative energies are of interest. However, the MPn series
does not necessarily converge. When the HF reference and the CC energy is given by
provides a poor description of the electronic structure, the 
E CC = 0 H eT 0 .
MPn series may become divergent and produce even worse
results than those of HF. Because the Hamiltonian operator contains only one- and
two-electron operators, only the first few terms of the ex-
d. Coupled cluster methods. Coupled cluster (CC) ponential series give nonzero values:
theory was originally formulated for nuclear physics and   
only later was applied to the electron correlation problem E CC = 0 |H| 1 + T1 + T2 + 12 T21 0 .
in quantum chemistry. Today it is the method of choice
Further simplification leads to a CC energy expression
for highly accurate computations. CC theory uses an ex-
from the two-electron integrals over MOs:
ponential expansion of a reference function 0 , usually
the Hartree-Fock determinant (in contrast with the linear 
occ 
virt
 
expansion of CI): E CC = E 0 + j + ti t j − ti t j
tiab a b b a

i< j a<b
CC = eT 0 ,
× ( φi φ j | φa φb − φi φ j | φb φa ).
where the cluster operator T is defined as
CCSD is the only pure CC method that can be used in rou-
T = T1 + T2 + T3 + · · · T N . tine applications. Explicit treatment of triples (CCSDT)
The excitation operators, Ti , generate all ith excited Slater is usually too expensive. However, the contribution of
determinants from the reference: triples can be estimated perturbatively in the CCSD(T)

occ 
virt method. Brueckner (B) theory is a variation of CC the-
T1 0 = tia ia ; ory which uses orbitals that make the singles contribu-
i a tion vanish. The accuracy and computational cost of BD
is comparable to that of CCSD. Excited electronic states

occ 
virt
T2 0 = j i j ;
tiab ab
··· may be treated within the CC formalism by the equation-
i< j a<b of-motion (EOM-CC) approach.
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500 Computational Chemistry

e. R12 methods. HF is not exact because of the ap-

proximate treatment of electron–electron repulsion. Post-
HF methods try to recover the electron correlation en-
ergy by expanding the N -electron wave function in terms
of Slater determinants built from one-electron functions
(orbitals). But the convergence toward the exact solution of
the Schrödinger equation is typically slow due to the poor
description of the cusp region (r1 − r2 = 0) of the wave
function. Faster convergence may be achieved by adding
terms that describe electron correlation effects more di-
rectly than the product of one-electron orbitals (e.g., by
including a function that explicitly depends on the coor-
dinates of two electrons rather than just one electron: the
interelectronic coordinate r12 ).
The r12 -dependent wave function may then be used with
CI, MBPT, or CC, giving R12 methods. The formula for FIGURE 7 Adding flexibility to basis sets: (a) Split valence basis
computing the energy includes integrals over three- and sets provide more and less diffuse orbitals to adjust to different
four-electron coordinates, which are difficult to evaluate bonding situations (e.g., σ - and π -bonding). (b) Higher angular
and which increase with N 6 and N 8 . However, insertion of momentum basis functions allow for polarization to gain better
a resolution of the identity allows three- and four-electron overlap.
integrals to be written as sums over products of integrals
involving only two-electron coordinates. The substitution be evaluated analytically for STOs). GTOs do not have
is exact only for a complete basis set, but it is a very good the proper behavior near the nucleus (in contrast with the
approximation for fairly big basis sets, which have to be “cusp” of the STOs) and fall off too rapidly far away from
used for very accurate results anyway. R12 methods con- the nucleus. A better description is provided by contrac-
verge to the same basis set limit as conventional electron tions of several Gaussian functions. GTOs are generally
correlation methods do but faster. used because of the computational efficiency.
The number of basis functions employed for each atom
determines the quality of the basis set. A minimum basis
4. Basis Sets
provides only as many shells as necessary to accommo-
A basis set is used to express the unknown MOs in terms of date all electrons (i.e., 1s for H and He; 1s, 2s, and 2p
a set of known functions. The more basis functions used, for first-row elements, etc.) A double zeta basis set adds
the more accurate the description of the MOs. Any type of more flexibility for the description of different bonding
function can be used, but most efficient are basis functions situations (Fig. 7) by using two functions varying in the
with a physical behavior (e.g., approach zero for large dis- exponent ζ (a measure of the diffuseness) for each orbital
tances between electrons and nuclei) and which make the of an occupied shell (i.e., 1s, 1s for H, He; 1s, 1s , 2s, 2s ,
integral evaluation easy. Slater-type orbitals (STOs) are 2p, 2p for first-row elements). Because bonding involves
related to the exact solutions for the hydrogen atom, but valence electrons only, core electrons are described by a
Gaussian-type orbitals (GTOs) are preferable for compu- single basis function and only the valence region is split
tational ease: in split valence or valence double zeta basis sets (1s, 1s
for H, He; 1s, 2s, 2s , 2p, 2p for first-row elements). Basis
χς,n,l,m
STO
(r, θ, ϕ) = NYl,m (θ, ϕ)r n−1 e−ςr sets can be improved by adding more functions: triple zeta
and (TZ), quadruple zeta (QZ), quintuple zeta (5Z), etc., have
three, four, five, etc., times the number of basis functions
(r, θ, ϕ) = NYl,m (θ, ϕ)r 2n−2−l e−ςr ;
2
χς,n,l,m
GTO
of a minimum basis set, respectively. The exponents are
usually determined variationally for the atoms. Each basis
(x, y, z) = N x lx y l y z lz e−ςr .
2
χς,l
GTO
x ,l y ,l z
function may consist of several “primitive” GTOs. Con-
N is a normalization constant and Yl,m are the spherical traction of several GTOs to one basis function (contracted
harmonic functions. STOs lack radial nodes, which are GTO) is especially useful for the inner orbital to mimic the
introduced by making linear combinations of STOs. They cusp at the nucleus. Additional higher angular momentum
are primarily used for high-accuracy atomic and diatomic functions are usually added as polarization functions to al-
calculations and with semiempirical methods, which ne- low for a polarized charge distribution (e.g., one additional
glect all three- and four-center integrals (which cannot p set for H and He; one d set for first-row elements). For
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Computational Chemistry 501

correlated wave functions even more than one set is essen- enthalpies of formation, bond energies, ionization po-
tial if high accuracy is desired (e.g., one d and one p set for tentials, electron affinities, and proton affinities. Starting
H, He; one f set and two d sets for first-row elements). An- from the MP4/6-311G(d,p)//MP2(fu)/6-31G∗ + 0.8929
ionic species or molecules with many lone pairs have very ZPE(HF/6-31G∗ ) level, corrections for diffuse functions,
diffuse electron distributions and require an additional set higher polarization functions, and a more complete elec-
of diffuse functions (often denoted by a “+”). The basis tron correlation treatment, as well as a “higher level cor-
sets by Pople and coworkers are very popular: STO-3G rection” depending on the number of α and β valence elec-
is a minimum basis with three GTOs contracted to rep- trons and an empirical factor, are included to extrapolate
resent one atomic orbital. 3-21G is a split valence basis to the QCISD(T)/6-311 + G(3df,2p) level. This procedure
with core orbitals contracted from three GTOs and the va- gives a mean absolute deviation from experimental data
lence region described by one basis function contracted of 1.21 kcal mol−1 for the “G2 test set,” a large number of
by two primitives and another uncontracted function. 6– various types of relative energies accurately known from
31G∗ is constructed analogously but includes one set of experiment. Variations to the G2 method including the
polarization d functions on heavy atoms (other than hy- use of DFT methods have been proposed either to further
drogen). Dunning’s correlation consistent basis sets (cc-p increase the accuracy (e.g., G3) or to reduce the compu-
VXZ; X = D, T, Q, 5, 6, . . .) represent a series of basis tational expense.
sets converging to the basis set limit. This allows extrap-
olation to the infinite basis set limit. The cc-pVDZ (cor-
relation consistent polarized valence double zeta) basis C. Density Functional Theory
set has [3s, 2p, 1d/2s, 1p] contracted from (9s, 4p, 1d/4s, The Hohenberg-Kohn theorem provides the inspiration for
1p) for first-row and hydrogen atoms, respectively. The density functional theory (DFT): all ground-state proper-
next-better basis set, cc-p VTZ, has one basis function ties of a system are functionals of the charge density. In
more of each type and adds one next-higher angular mo- particular the correct energy can be derived from the cor-
mentum function: [4s, 3p, 2d, 1f/3s, 2p, 1d]. Augmenta- rect charge density. Conversely, an incorrect density will
tion of one extra diffuse function for each type of angular give an energy above the correct energy. In a DFT calcu-
momentum (1s, 1p, 1d for cc-pVDZ) is denoted by the lation the energy is optimized with respect to the density.
prefix aug-. It should be much simpler to handle the total electron den-
sity (which depends on three coordinates) than to treat all
5. Optimizing the Performance/Cost Ratio electrons explicitly (involving one spin plus three spatial
coordinates per electron). Although Hohenberg and Kohn
In any application a compromise between computational proved that the electron density determines the electronic
cost and accuracy has to be made. Accurate geometries ground-state energy, the functional to convert the electron
are relatively easy to compute; MP2 with a polarized density function into an energy value is unknown.
double zeta basis set usually gives satisfactory results. Each contribution to the total energy—the kinetic
Accurate energetics require a better theoretical treatment energy, E T [ρ]; the nucleus–electron attraction, E ne [ρ];
and therefore are generally determined from a “single en- and the electron–electron repulsion, E ee [ρ]—can be ex-
ergy point calculation” at a higher level [e.g., CCSD(T) pressed as a functional of the total electron density:
with a TZP basis set]. Whereas a single slash (/) is
used to separate method and basis set specification, a E[ρ] = E T [ρ] + E ne [ρ] + E ee [ρ].
double slash (//) means “at the geometry optimized at”
In analogy to HF theory, E ee [ρ] can be divided into a
(e.g., CCSD(T)/TZP//MP2/DZP). Zero-point vibrational
Coulomb (E J [ρ]) part and an exchange part. The formula
energy (ZPE) corrections to relative energy are usually
for E ne is exact:
applied but need not be derived from a frequency calcula-
tion at the highest level of optimization. ZPEs are usually 
Nucl.
ρ(r)
scaled by an empirical correction factor (depending on the E ne [ρ] = − Za dr,
a |r − Ra |
theory level) to account for the overestimation of vibra-
tional frequencies. and
To achieve chemical accuracy (i.e., ±1 kcal mol−1 ) for 1 ρ(r1 )ρ(r2 )
relative energies, for molecules of chemical interest, in- E J [ρ] = dr1 dr2
2 |r1 − r2 |
vestigators devised interpolation schemes based on an ad-
ditivity assumption. Most popular is the G2 method, a holds true for electrons moving independently in the field
general procedure based on ab initio theory for the ac- caused by all electrons—approximations which are hoped
curate prediction of energies of molecular systems, like to be corrected by a combined exchange and correlation
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502 Computational Chemistry

term, E XC . The major task of DFT is to develop approxi- assessed by comparison with experimental data and there
mate but accurate functionals for E T and E XC . is no consistent way to improve the quality of a given func-
For the noninteracting uniform electron gas, the kinetic tional. This is in contrast with wave function methods, in
and exchange energies can be derived: which a more complete treatment of electron correlation
E TTF [ρ] = 3
(3π 2 )2/3 ρ(r)5/3 dr (and a more flexible basis set) means a closer approach to
10
the exact solution.
and
 
3 3 1/3
E KD [ρ] = 4 π
ρ(r)4/3 dr. 1. Local Density Approximation
In Thomas-Fermi theory the total energy is expressed as The local density approximation (LDA) assumes varia-
E TF [ρ] = E ne [ρ] + E J [ρ] + E TTF [ρ], tions of the density to be slow and treats the local density
while the Thomas-Fermi-Dirac expression adds the ex- as a uniform electron gas:
 1/3
change expression E kD [ρ]. The uniform electron gas is a E XLDA [ρ] = − 34 π3 ρ 4/3 (r) dr.
model too crude to describe molecules: neither TF nor
TFD gives bonding between atoms. The X α method is an example of LDA in which the cor-
As a way to improve on the expression for the kinetic relation energy is neglected and the exchange energy ex-
energy, Kohn-Sham theory calculates the kinetic energy pression is multiplied by a parameter α. A fairly accurate
for noninteracting electrons and corrects for the error rel- expression for the correlation energy of the uniform elec-
ative to the real kinetic energy by means of the exchange tron gas, the VWN (Vosko, Wilk, Nusair) functional, was
correlation term E XC [ρ]: derived by fitting it to Monte Carlo results.
E DFT [ρ] = E TS [ρ] + E ne [ρ] + E J [ρ] + E XC [ρ],
2. Generalized Gradient Approximation
where E TS [ρ] can be computed from a Slater determinant:
As a way to better treat the nonuniform electron dis-

N

E TS [ρ] = φi − 12 ∇ 2 φi , tribution of molecules, the exchange and correlation
i functionals were modified to include derivatives of the
and E XC [ρ] is usually separated into an exchange contri- density in the gradient-corrected approximation, or gener-
bution (E X [ρ]) and a correlation contribution (E C [ρ]). alized gradient approximation (GGA). Gradient-corrected
In the Kohn-Sham implementation of DFT, the den- exchange functionals were developed [e.g., by Perdew and
sity, ρ, is derived from a single Slater determinant with Wang (PW86) and Becke (B)]. Popular correlation func-
orthonormal orbitals, φi : tionals are those of Lee, Yang, and Parr (LYP), Perdew
(P86), Perdew and Wang (PW91), and Becke (B91). Hy-

occ
ρ(r) = |φi (r)|2 . brid methods (such as the popular Becke three-parameter
i functional, B3) use part of the exchange as computed by
The energy is then optimized by solving a set of one- the HF method. The three parameters in B3 determine
electron equations, the Kohn-Sham equations, but with the mixing of LDA and exact exchange, as well as the
electron correlation included: gradient-corrected contributions to the exchange and cor-
relation terms. The parameters are fitted to experimental
hKS φi = εi φi , thermodynamical data. Exchange and correlation func-
where tionals can freely be combined to give an arsenal of DFT
1 
Nucl.
Za ρ(r ) methods (e.g., BLYP, BP86, B3LYP, etc.), but B3LYP
hKS = − ∇ 2 + + dr + VXC (r). is the most popular because of its consistently good
2 a |Ra − r| |r − r |
performance.
The (Kohn-Sham) orbitals, φi , which are used to represent Recently, the DFT formalism has been extended to treat
the electron density, ρ, can be determined numerically or excited electronic states through the implementation of
variationally as an expansion of basis functions. time-dependent DFT (TD-DFT).
The Kohn-Sham equations have to be solved iteratively
because the Coulomb term depends on the density (i.e.,
the orbitals to be determined). The main advantage of DFT III. APPLICATIONS OF
methods is that they include some treatment of electron COMPUTATIONAL CHEMISTRY
correlation at a computational cost equivalent to that of
the HF method. The main disadvantage of DFT, however, When a chemical problem is to be studied computation-
is that there is no hierarchy of increasingly better func- ally, an appropriate level of theory must first be chosen.
tionals. The performance of a given functional must be Simple qualitative concepts such as the frontier molecular
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Computational Chemistry 503

orbital (FMO) theory or orbital symmetry (Woodward- tive eigenvalue describes the transition mode. Following
Hoffman) rules, which were developed on the basis of the minimum energy path in mass-weighted coordinates
primitive computations, can often successfully predict rel- (intrinsic reaction coordinate, IRC) allows one to confirm
ative reactivities and selectivities. Qualitative concepts which minima are connected by a transition state. Har-
are very useful as they can provide chemical insight and monic vibrational frequencies can be derived from the
understanding. For quantitative answers more sophisti- force constants and allow one to compute entropy and en-
cated computational methods have to be employed and a thalpy values.
compromise between desired accuracy and computational The molecular geometry input can be provided in the
cost has to be made. In any case, it is essential to know form of a Z-matrix [i.e., be defined through internal coor-
about the possibilities and limitations of the method to be dinates (bond length, bond angles, and dihedral angles)].
applied. Due to improved optimization algorithms (handling re-
dundant internal coordinates) and the size of molecules
that can now be computed routinely, the input is mostly
A. The Potential Energy Surface provided as Cartesian coordinates, often generated with
The methods described in Section II provide expressions the help of a graphical user interface to the computational
for the energy as a function of the atomic coordinates [i.e., chemistry program package.
they describe the potential energy surface (PES) for a given The computational speed of the more approximate
molecular formula] (Fig. 8). This allows one to search for methods allows one not only to treat larger molecular
an atomic arrangement which makes the energy a mini- systems, but also to address new problems. The func-
mum (geometry optimization). More efficient optimiza- tion of a protein is determined by its three-dimensional
tion algorithms can be employed when the forces and the structure. Hence, there is considerable interest in solv-
Hessian [first and second derivatives, respectively, of the ing the protein folding problem by predicting the three-
energy with respect to (w.r.t.) the nuclear coordinates] are dimensional (secondary and tertiary) structure of a protein
also known. One global and usually many additional local based on the amino acid sequence (primary structure).
minima exist for a given formula and relative energies for The binding of a substrate (or inhibitor) is crucial for the
isomeric structures can be obtained. The transition struc- catalytic activity of an enzyme. Possible binding modes
ture, which is the highest point on a minimum energy path are investigated by molecular docking, in which various
connecting two minima, can also be localized. This reveals structures of intermolecular complexes are generated and
information about chemical reactions, such as mechanistic evaluated.
details, activation barriers, and so forth, which is difficult
or impossible to deduce from experimental investigations.
Minima and transition states are stationary points (i.e., the B. Analyzing the Wave Function
forces are zero). All eigenvalues of the Hessian are posi- The wave function, , which describes the electron dis-
tive for minima while transition states have one negative tribution around a given nuclear arrangement, not only
eigenvalue. The eigenvector corresponding to the nega- can be used to compute the energy of the system, but also
offers useful interpretation opportunities.

1. Wave Function Analysis in Terms

of Basis Functions
Each MO φi (used to build ) is constructed from ba-
sis functions χi located on the nuclei and is occupied by
n i electrons (0, 1, or 2 for HF, but any number between
0 and 2 is possible for correlated wave functions). It is
therefore possible to distribute the electrons to individual
atoms. However, there is no unique prescription. Mulliken
population analysis, for example, employs

AO 
AO
ρA = Dαβ Sαβ
α∈A β
FIGURE 8 A model potential energy surface showing a transition   
structure, TS, connecting two minima, MIN1 and MIN2; the acti- 
AO 
AO 
MO
vation barrier, E = , for the transformation of MIN1 to MIN2; and = n i cαi cβi χα χβ
the relative energy, Erel , of MIN1 versus MIN2. α∈A β i
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504 Computational Chemistry

to determine the number of electrons ρA associated with orbital (NBO) analysis has some advantages (e.g., has no
atom A. The atomic charge, Q A , is given as the difference strong basis set dependence, is computationally inexpen-
between the nuclear charge Z A and ρA : sive, and can also be applied to electron correlated meth-
ods). In a first step, natural atomic orbitals (NAOs) are
Q A = Z A − ρA .
generated by a diagonalization of the atomic blocks of
Bond orders bAB can be defined on the basis of the sum of the density matrix giving pre-NAOs which are orthog-
electrons shared between atoms A and B: onalized in several steps applying occupancy-weighted
 and normal orthogonalization procedures. Diagonal val-
bAB = (DS)αβ (DS)βα . ues of the density matrix in the resulting NAO basis cor-
α∈A β∈B
respond to orbital populations which can be summed up
It is arbitrary how the electron density arising from ba- to give atomic charges. Off-diagonal blocks define bonds
sis functions located on different atoms is divided. The between atoms. The resulting localized MOs give a de-
Mulliken procedure can give unphysical charges and scription in agreement with chemical intuition (core or-
shows a strong basis set dependence. Because of these bitals, lone pairs, and bonds) and can be analyzed in terms
shortcomings an atom definition which does not depend of bond polarity, bond bending, hybridization, and so
on the basis set is desirable. forth. Effects such as hyperconjugation can be investigated
by analyzing the interactions between formally occupied
2. Wave Function Analysis Based and formally empty orbitals within a localized orbital
on the Electron Density picture.

Bader’s theory of atoms in molecules (AIM) is based on

the electron density ρ(r) (which can be computed by in- C. Computing Properties
tegrating the square of the wave function over the coor-
dinates of all but one electron) and the gradient of the One-electron properties such as the electric dipole mo-
density, ∇ρ(r). Regions in space, so-called atomic basins, ment, the quadrupole moment, and the magnetic suscep-
are defined as all points from which following the gradi- tibility can be evaluated from the wavefunction as the ex-
ent of the density leads to a common attractor = nucleus. pectation value of an operator O which is a sum of n
Integration of the electron density for each basin gives one-electron operators o:
the number of electrons associated with the nucleus in  
|O| = φi |o|φi = Dµν χµ |o|χν .
that basin. However, AIM charges are counterintuitive in µ ν
i
some cases. Neither AIM charges nor Mulliken charges
reproduce the dipole or higher multipoles of a molecule. Most properties represent the response of the system to
For points on the surface separating atomic basins, the a perturbation. The effect can be calculated by derivative
derivative of the electron density along the normal vector methods, perturbation theory, or propagator methods. For
equals zero. Points where the derivative perpendicular to example the wave function, , is changed by an electric
the normal vector is zero as well are called bond critical field which enters the Hamiltonian as part of the potential
points. They are the points of minimum electron density energy term. The energy in the presence of an electric field
along the bond path, the path of maximum electron density F, E(F), can be written as a Taylor expansion:
connecting two nuclei. The electron density at the bond
critical point correlates with the bond strength. E(F) = E 0 − µ0 F − 12 αF2 − 16 βF3 − · · · ,

where the permanent dipole moment, µ0 , the polarizabil-

3. Localized MOs ity, α, and the (first) hyperpolarizability, β, are the first,
The canonical MOs obtained as eigenfunctions of the second, and third derivatives, respectively, of the energy
Fock operator have contributions from all basis functions with respect to the field F. The analogous expression for
and thus are delocalized over all centers. They do not re- the presence of a magnetic field, B, is
flect the common picture of localized bonds between two 1
atoms. However, the orbitals may be freely transformed E(B) = E 0 − m0 B − ζ B2 − · · · ,
2µ0
by making linear combinations without changing the to-
tal wave function. Hence, an orbital rotation matrix can where the magnetic moment, m0 , and the magnetizability,
be applied to transform the canonical into localized or- ζ , are the first and second derivatives of the energy
bitals which reflect bonds between two atoms. Several with respect to the magnetic field (µ0 is the vacuum
localization schemes were proposed, but the natural bond permeability).
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Computational Chemistry 505

D. Dynamics and Modeling Solvation E. Spectroscopic Data

Standard computations treat isolated molecules (i.e., Vertical and adiabatic ionization energies are given as the
model the low-pressure gas phase situation). Chemistry energy difference between the neutral molecule and the
in the condensed phase, however, can be significantly dif- corresponding cation in the neutral geometry and in the re-
ferent because ionic and polar species are specifically sta- laxed geometry, respectively. Analogous comparison with
bilized. Computations can consider solvation explicitly the anion gives electron affinities. The various ionization
by including the solvent molecules or as a continuous energies measured in PE (photoelectron) spectroscopy can
medium effect (reaction field methods). be computed as differences between the neutral ground
When the solute is embedded in a bulk of solvent state and different electronic states of the cation. The en-
molecules, an “ensemble” (i.e., a large number of con- ergy difference between the electronic ground state and
figurations of the molecular aggregation) has to be gener- electronically excited states without the loss of an elec-
ated and properly averaged to derive macroscopic prop- tron corresponds to the transitions observed in UV-VIS
erties. Molecular dynamics (MD) creates a “trajectory”: (ultraviolet-visible) spectroscopy.
the configurations are obtained by following the evolution Many other properties measured by spectroscopic
of the system in time by applying the classical equations methods can be computed as derivatives of the energy.
of motion. The alternative, Monte Carlo (MC) method The force constants (second-derivative w.r.t. the nuclear
produces the configurations randomly: a starting configu- coordinates, r) allow one to calculate harmonic vibrational
ration is perturbed and the new configuration is accepted frequencies and the corresponding normal modes. The
if the new energy is lower (E < 0) than the old one. If derivatives of the dipole moment and of the polarizability
E > 0 the new configuration is accepted with a proba- w.r.t. the normal modes are proportional to the intensity
bility proportional to the Boltzman factor, exp(−E/kT ) of infrared absorptions and of Raman bands, respectively.
(Metropolis method). The forces are needed for MD, but First and second derivatives of the energy w.r.t. nuclear
energies are sufficient for MC simulations. Meaningful magnetic spin, I, give the hyperfine coupling constant g
averaging requires a huge number of conformations to be (measured by electron spin resonance, ESR, spectroscopy)
calculated, which leaves parametrized force fields as basi- and the nuclear coupling constants J of nuclear magnetic
cally the only practible methods to be used in MD and MC resonance (NMR) spectroscopy, respectively. The nuclear
simulations. magnetic shielding constants, σ , are given as the mixed
Reaction field methods model solutions by placing the derivatives of the energy w.r.t. an external magnetic field
solute in a cavity of a polarizable medium. The electro- B and the magnetic moments I of the nuclei. The NMR
static potential due to the solute molecule polarizes the chemical shifts correspond to differences in σ for a nu-
surrounding medium which in turn changes the charge cleus in a given molecule and in a reference compound.
distribution of the solute. Hence, the electrostatic interac- Magnetic properties suffer from the “gauge origin” prob-
tion has to be evaluated self-consistently (self-consistent lem because the magnetic field is a vector potential, which
reaction field, SCRF). A term for creating the cavity (cal- is not uniquely defined. For finite basis sets, results depend
culated from the surface of the cavity) has a be added to the on the choice for the origin. This problem can be largely
solvation energy. Explicit treatment of solvent molecules overcome by using either the gauge-invariant atomic or-
can be combined with a reaction field method. bital (GIAO) method or the individual gauge for local-
Dynamics can also be used to model the mechanics and ized orbital (IGLO) method. Comparison of calculated
rates of reactions at a fundamental level. While a com- and measured spectroscopic data can help to identify new
plete potential energy surface is the ideal starting point of molecules and to determine their structure.
any type of accurate dynamical computation, it can be ob- The wealth of properties (Fig. 9) that can be computed
tained for only very simple systems. Ab initio MD can be as derivatives of the energy stresses the importance of the
performed by repeated calculation of forces, generation of derivative methods. The ability to derive expressions for
a new geometry, and convergence of the MO coefficients at least first and second derivatives is always desirable for
for the new geometry. This iterative scheme, however, is a new theoretical level.
very time consuming because accurate MO coefficients
are required at each point of the simulation. The Car-
Parrinello method does not optimize the electronic (i.e., IV. OUTLOOK FOR
MO coefficients) and nuclear coordinates separately, but COMPUTATIONAL CHEMISTRY
simultaneously, because it could be shown that the errors
in the nuclear forces and in the electronic forces cancel During the last decades computational chemistry has
out. evolved into an indispensable tool for understanding and
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506 Computational Chemistry

FIGURE 9 Some chemical information that can be gained from a computational investigation. NMR, nuclear magnetic
resonance; IR, infrared.

predicting molecular properties and chemical behavior. Kryspin, K. N. Kirschner, P. v. R. Schleyer, and A. Y. Timoshkin. M.H.
The era foreseen by R. S. Mulliken in his acceptance is grateful to Professor R. Krämer for support.
speech for the 1966 Nobel Prize has arrived:

I would like to emphasize strongly my belief that the era of SEE ALSO THE FOLLOWING ARTICLES
computing chemists, when hundreds if not thousands of chemists
will go to the computing machine instead of the laboratory for MECHANICS, CLASSICAL • MOLECULAR ELECTRONICS •
increasingly many facets of chemical information, is already at PHOTOELECTRON SPECTROSCOPY • PROTEIN STRUCTURE
hand. • QUANTUM CHEMISTRY • QUANTUM MECHANICS

Future goals of computational chemistry will be to de-

termine structural, spectroscopic, and dynamic properties BIBLIOGRAPHY
of even larger molecular system, also in the condensed
phase, with even better accuracy and speed. This will al- Dirac, P. A. M., (1929). Proc. R. Soc. Lond. Ser. A, 123, 719.
low computational chemistry to also play an important role Jensen, F. (1999). “Introduction to Computational Chemistry,” Wiley,
in fields related to chemistry such as biology and material Chichester, UK.
science. Leach, A. R. (1996). “Molecular Modelling Principles and Applica-
tions,” Longman, Essex, England.
Lipkowitz, K. B., and Boyd, D. B., eds. (1990–). “Reviews in Compu-
tational Chemistry,” Vol. 1–, VCH, New York.
Mulliken, R. S. (1967). Science, 137, 13–24.
ACKNOWLEDGMENTS Schleyer, P. V. R. et al., eds. (1998). “Encyclopedia of Computational
Chemistry,” Wiley, Chichester, UK.
The authors are grateful to the following persons for comments and Young, D. (2001). “Computational Chemistry,” Wiley, Interscience, New
valuable suggestions: H. F. Bettinger, M. Bühl, B. Goldfuss, I. Hyla- York.
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Dynamics of Elementary
Chemical Reactions
H. Floyd Davis
Hans U. Stauffer
Cornell University

I.Kinetics and Collision Theory

II.Activated Complex Theory
III.Unimolecular versus Bimolecular Reactions
IV. Statistical Theories of Unimolecular
Decomposition
V. Reactions in Solution
VI. Experimental Techniques

GLOSSARY stable molecules (e.g., NO, O2 , or NO2 ), or highly re-

active transitory chemical intermediates (e.g., H, Cl,
Complex-mediated reaction An elementary bimolecu- CH3 ) that react on essentially every collision with sta-
lar reaction proceeding via a long-lived collision com- ble molecules.
plex having lifetimes ranging from several vibrational Ionization The process by which one or more valence
periods (100 fs) to many rotational periods (>10 ps). electrons are removed from an atom or molecule. Most
If complex lifetimes exceed several rotational peri- often achieved by electron impact or absorption of one
ods, product angular distributions from crossed beam or more ultraviolet photons.
reactions exhibit forward-backward symmetry in the Laser-induced fluorescence (LIF) A spectroscopic
center-of-mass frame of reference. technique usually employing visible or UV laser light,
Direct reaction An elementary bimolecular reaction pro- in which the fluorescence emission from a gaseous,
ceeding via direct passage through the transition state liquid, or solid sample is monitored. A fluorescence
region. The absence of long-lived intermediates in such excitation spectrum is a plot of the total emitted fluo-
reactions leads to anisotropic center-of-mass product rescence vs. excitation wavelength and provides infor-
angular distributions that often provide insight into the mation similar to an absorption spectrum.
most favorable geometries for reaction. Molecular beam Collimated stream of gaseous mole-
Free radical An atom or molecule possessing one or cules produced by expansion of a gas through an ori-
more unpaired electrons. Free radicals may either be fice into an evacuated chamber. A supersonic molecular

697
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698 Dynamics of Elementary Chemical Reactions

beam is characterized by a velocity distribution much presence of a third body (M), which may be a molecule
narrower than a Boltzmann distribution. or the wall of the container. Note that the two elementary
Potential energy surface Schematic two- or three- propagating reactions may be added like mathematical
dimensional representation of the total potential en- equations, yielding the overall chemical reaction (1).
ergy of a chemical system as a function of internuclear For an overall reaction such as that in Eq. (1) involving
coordinates. a sequence of elementary steps, the overall rate of forma-
Transition state Region of the PES corresponding to the tion of products may be a complex function of reactant
critical geometry through which a reacting system must concentrations, because products are formed by several
pass for reactants to become products. different elementary processes. In the previous example,
the HCl products are formed by reactions (3) and (4), each
of which has its own rate law and rate constant. Thus, for
AN ELEMENTARY CHEMICAL reaction is any process a complex multistep process such as reaction (1), the rate
involving bond fission and/or bond formation following a law can only be determined through experiment.
single collision between two reactants. Chemical reactions For an elementary bimolecular reaction A + B → C +
occur in all three phases of matter (gas, liquid, and solid), D, the reaction rate is proportional to the concentrations
and at their interfaces. Under the experimental conditions (denoted by [A], [B], etc.) of the reactants:
most commonly used to carry out reactions, the overall d[C] d[D] d[A] d[B]
reaction usually consists of a sequence of two or more el- = =− =− = k[A][B]. (5)
dt dt dt dt
ementary reactions. For example, the reaction of gaseous
hydrogen with chlorine forming hydrogen chloride is rep- The proportionality constant, k, is called the reaction rate
resented by the following balanced chemical equation: constant. Since an elementary reaction involves a single
bimolecular collision between A and B, the maximum
H2 + Cl2 → 2HCl. (1) possible rate constant is usually the frequency of collisions
between reactants. A few simple atom-transfer reactions
This reaction proceeds by a chain mechanism involving
(e.g., F + H2 → HF + H) actually do occur on nearly every
a repetitive sequence of elementary reactions involving
collision, and are said to proceed at or near the “gas kinetic
the three stable molecules listed in Eq. (1), as well as
limit.”
two short-lived free radical intermediates, i.e., chlorine
atoms (Cl) and hydrogen atoms (H). The most important
elementary steps in the overall reaction mechanism are:
I. KINETICS AND COLLISION THEORY
Initiation : Cl2 → 2Cl. (2)
In order to estimate the frequency of collisions between
gaseous A and B molecules, consider a beam of molecules
Propagation : Cl + H2 → HCl + H (3a) of incident flux I A (molecules/cm2 · s) impinging on a
static cell containing molecules at a concentration [B]
H + Cl2 → HCl + Cl. (3b) (molecules/cm3 ). The particles interact in a volume el-
ement V . The collision rate per unit time, Z , is given by

Termination : H + Cl + M → HCl + M (4a) Z = σI A [B]V. (6)

Cl + Cl + M → Cl2 + M (4b) Here, σ is the collision cross section, which may be es-
timated using a simple hard sphere model for colliding
H + H + M → H2 + M. (4c) particles (Fig. 1). Two particles collide with a relative ve-
The chain reaction is initiated by dissociation of Cl2 , a sta- locity vector, g, the magnitude of which is denoted by
ble molecule, to form two highly reactive chlorine atoms g, and impact parameter b, also known as the “aiming
(Cl). Since chemical bond fission requires the input of error” of the collision. A hard sphere collision will occur
energy, initiation may be achieved by heating the sample provided 0 ≤ b ≤ (r A + r B ). The collision cross section is
(see Lindemann mechanism) or by ultraviolet irradiation therefore the area of a circle of radius d AB = r A + r B , i.e.,
(photodissociation). Following initiation, the two elemen- σh.s. = πd AB
2
. The incident flux, I A = [A]g A , may then be
tary bimolecular propagating reactions will continue until substituted into Eq. (6). If the rate of reaction between A
either or both of the reactants (H2 and Cl2 ) are consumed, and B is simply the collision rate, then
at which time the termination steps end the chain reac-
tion. Termination typically involves termolecular recom- d[A]
− = Z = σh.s. g A [A][B]. (7)
bination of two radicals to form a stable molecule in the dt
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Dynamics of Elementary Chemical Reactions 699

Whereas the hard sphere cross section depends only

on the sum of the radii of colliding particles, a reaction
cross section may depend strongly on the energy of the
collision and therefore on the relative velocity of the col-
liding particles, the magnitude of which is given by g. As
illustrated in Fig. 2, the relative velocity vector, g, may
be decomposed into two perpendicular components. The
first is a radial component, gr = ṙ , i.e., the time derivative
of r , the distance between the particle centers. Perpendic-
ular to the radial axis is a tangential component, g⊥ = r θ̇ ,
where θ̇ is the time derivative of θ , the angle between g
and the radial axis. As a result, the total kinetic energy of
collision, E kin = 1/2 µg 2 , can be thought of as a sum of a
radial kinetic energy,
Er = 1/2 µgr2 (11)
and an energy associated with the perpendicular velocity
component,
L2
E ⊥ = 1/2 µg⊥
2
= 1/2 µr 2 θ̇ 2 = , (12)
2µr 2
where L = µr 2 θ̇ = µgb is the magnitude of the angular
FIGURE 1 Depiction of hard sphere collision cross section. Note momentum associated with the colliding pair. Thus, for
that collisions only occur for impact parameters b < dAB . interaction potentials that depend solely on the distance
between the colliding pair, V (r ), only gr is effective in
Comparison of Eqs. (5) and (7) indicates that the collision surmounting potential energy barriers such as those asso-
rate constant, k, is related to the collision cross section and ciated with the energy required to break and form bonds
relative velocity of colliding particles by during reaction; g⊥ is associated purely with rotational
k(g) = σ g . (8) motion of the two particles.
One way to model the energy dependence of σ is to
In deriving Eq. (8), it is assumed that molecules A and B assume that reaction can only occur if the component
collide with a single relative velocity g. In a real gaseous
sample containing both A and B molecules at thermal
equilibrium, the distribution of relative velocities is de-
scribed by the Maxwell–Boltzmann Distribution Law:
 3/2
µ − µg
2

f (g) = 4πg 2 e 2k B T , (9)

2πk B T
where µ = m A m B /(m A + m B ) is the reduced mass of the
colliding particles, k B is Boltzmann’s constant, and T is
the temperature in Kelvin. The hard sphere collision rate
constant, kh .s. , is thus temperature dependent, and may be
evaluated explicitly by integrating over all possible rela-
tive velocities, g:
 ∞  
8k B T 1/2
kh .s. (T ) = σh .s. g f (g) dg = πd AB
2
.
g=0 πµ
(10)
Using typical molecular values of d AB ≈ 0.35 nm and
µ = 14 amu for room temperature collisions between
FIGURE 2 Decomposition of relative velocity vector, g, into radial
N2 molecules, one observes the magnitude of a hard (gr ) and perpendicular (g⊥ ) components, with θ defined as the
sphere collision rate constant to be on the order of angle between g and the internuclear axis. At the moment of a
2.6 × 10−10 cm3 /molecule · s. hard sphere collision, sin θ = b/dAB .
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700 Dynamics of Elementary Chemical Reactions

of kinetic energy along the axis of the collision (i.e.,

Er ), exceeds a critical energy, Vc . Note that during the
course of a collision, θ varies from 0 to 180◦ as r changes
from −∞ to +∞. However, if the particles are treated as
hard spheres, the internuclear potential, V(r ), is zero for
r > d AB , and there is no interaction between them until
collision, at which time (sin θ) = b/d AB . Using the fact
that gr = g cos θ , the radial kinetic energy at the moment
of contact is
 
b2
Er = /2 µg cos θ = E kin (1 − sin θ ) = E kin 1 − 2 .
1 2 2 2
d AB
(13)
In order for the reaction to be successful, Er ≥ Vc . For a
given collision energy, E kin , this implies that the impact
parameter must be smaller than a critical impact parame-
ter, bc , defined such that
 
bc2
E kin 1 − 2 = Vc . (14)
d AB
Thus, the cross section for a reaction involving a critical
energy, Vc , given by
 
Vc
σ = π bc2 = πd AB
2
1− (15) FIGURE 4 Schematic internuclear potentials for different mod-
E kin els of atomic and molecular interactions. The hard sphere model
exhibits only a repulsive component at small r ; more realistic po-
is expected to increase with energy, as illustrated in Fig. 3. tentials exhibit attractive and repulsive components.
Note that this model predicts that the threshold for reaction
occurs at E kin = Vc , and that the cross section reaches
half the hard sphere value at E kin = 2Vc , asymptotically induced dipole interactions (van der Waals’ interactions)
approaching the hard sphere value as E kin → ∞. result in an attractive region of the potential surface at
In many cases, reaction cross sections for real systems longer bond distances even in cases when formal bonds
differ considerably from that shown in Fig. 3. For between the interacting pair cannot be formed. When
example, some processes, such as charge exchange (e.g., strong bonds can be formed between colliding particles,
A+ + B− → A + B), proceed with reaction cross sections as in the case of two halogen atoms like Cl, a strongly at-
far exceeding the hard sphere limit. Here, the long-range tractive component of the potential is present over a wide
Coulomb potential causes reactants to be attracted to one range of internuclear separations. In such cases, the hard
another at large distances, considerably increasing the re- sphere potential would only be useful in modeling the
action cross section. Even for neutral–neutral interactions, interaction potential at small distances where electron–
the interaction potential, V (r ), often differs substantially electron repulsion becomes dominant, as demonstrated
from that of hard spheres. Long-range induced dipole- in Fig. 4. However, the magnitudes of most reaction
cross sections are controlled predominantly by the form
of the attractive component of the potential at longer
internuclear separations.
We now discuss a relatively simple model for reactions
involving gaseous particles interacting through a potential
V (r ) operating at long range. Recall from Eq. (11) and (12)
that E kin can be written as a sum of radial energy, Er , and
energy associated with rotational motion of the interacting
particles. Thus, the total energy, E = E kin + V (r ), of the
colliding partners is
(µgb)2
FIGURE 3 Cross section (σ ) dependence on kinetic energy, Ekin , E = Er + + V (r ), (16)
for the hard sphere model requiring an energetic threshold, Vc . 2µr 2
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Dynamics of Elementary Chemical Reactions 701

making it convenient to conceptualize an effective poten- to the empirical Arrhenius expression found to satisfacto-
tial, rily model a large number of chemical reactions:
(µgb)2 k = Ae−Ea /k B T , (23)
Veff (r ) = + V (r ), (17)
2µr 2
where A is the Arrhenius preexponential factor, and E a is
that governs the radial motion of the particles. At large the Arrhenius activation energy. These quantities are most
internuclear distances, the total energy of the system, readily determined by plotting ln k vs. 1/T , which should
E = 1/2 µg 2 , is simply the radial kinetic energy, since be linear with a slope −E a /k B and intercept ln A. Note that
lim
V (r ) = 0. However, at smaller values of r , where
r →∞ eff this purely empirical relationship often holds for elemen-
Veff (r ) > 0, some of the initial kinetic energy is converted tary as well as multistep reactions. The obvious similarity
into energy associated with the effective potential. The dis- between Eqs. (21) and (23) suggests that E a is at least
tance of closest approach, or turning point, rt. p. , is reached loosely related to the height of the potential energy bar-
when the magnitude of the effective potential is equal to rier for the rate-limiting step in the reaction. However, the
the initial radial kinetic energy, and the radial velocity Arrhenius parameters are only phenomenological quanti-
becomes zero: ties derived from the temperature dependence of reaction
(µgb)2 rate constants. In fact, Arrhenius plots are in many cases
E = 1/2 µg 2 = + V (rt. p. ). (18) found to be markedly nonlinear, suggesting the occurrence
2µrt.2 p.
of a multistep reaction mechanism or a mechanism that
This may be rearranged to solve for b = bmax , the max- changes at different temperatures.
imum impact parameter for a given relative velocity, g, The critical distance model can be used to derive an
that allows the collision partners to reach a fixed critical explicit formula for the temperature dependence of the re-
distance for reaction, rc : action rate constant for charge transfer reactions of the
  form A+ + B− → A + B. Such interactions are subject
2V (rc ) 1/2 to long-range Coulomb attractions of the form V (r ) =
bmax (g) = rc 1 − , (19)
µg 2 −q 2 /4π ε0r , where q is the charge of an electron. Tak-
ing the critical distance, rc , to be the ionic–covalent curve
which holds for g ≥ gmin , where, in order to be physically
crossing radius (R), which corresponds to the distance
meaningful,
at which the Coulomb attraction between ions balances
gmin = [2V (rc )/µ] /2
1
if V (rc ) > 0 the energy required for electron transfer, one obtains by
substitution into Eq. (22) the following expression for the
=0 if V (rc ) ≤ 0. (20) charge exchange rate constant:
   
The reaction rate constant may in both of these cases be 8k B T 1/2 q2
determined analytically by integration over all relative ve- k(T ) = πR 2 1+ . (24)
πµ 4πεo Rk B T
locities exceeding gmin :
This reaction rate constant expression bears some similar-
 ∞ ity to a hard-sphere rate constant; however, an additional
k(T ) = π {bmax (g)}2 g f (g) dg term (q 2 /4π εo Rk B T ) results from the long range attrac-
gmin
tive interaction, and is in general the dominant contribution
 1/2 to the reaction rate constant for reactions of this type.
8k B T − Vk (rcT)
= πrc2 e B if V (rc ) > 0 For attractive potentials of the form V (r ) = −a/r s , Veff
πµ
is given by
(21)
 1/2   L2 a (µgb)2 a
8k B T V (rc ) Veff (r ) = − = − s. (25)
= πrc2 1− if V (rc ) ≤ 0. 2µr 2 r s 2µr 2 r
πµ kB T
Provided s ≥ 3, Veff has a local maximum for a given im-
(22) pact parameter, b, at a radial distance, rmax , determined
In cases where V (rc ) is positive, the critical distance rate by
constant expression [Eq. (21)], is similar to the hard sphere  2−s
sa
collision rate constant [Eq. (10)]; however, an additional rmax = . (26)
µg 2 b2
exponential term is present. This term represents the frac-
tion of molecules at temperature T having sufficient en- For close approach required for reaction, the two parti-
ergy to react. This temperature dependence is thus similar cles must overcome this maximum, Vmax = Veff (rmax ), as
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702 Dynamics of Elementary Chemical Reactions

FIGURE 5 Relationship between Veff (r ) and V(r ) for a given impact parameter, b. Close approach necessary for
reaction requires E >Vmax , where Vmax is the maximum in Veff (r ).

illustrated in Fig. 5. Classically, if the energy of the col- van der Waals interactions (i.e., s = 6) are expected to
liding reactants is exactly equal to Vmax , all of the initial show a small positive temperature dependence (k ∝ T 1/6 ).
kinetic energy is converted into Veff when r = rmax , and The profound effect of the exact form of the internu-
“orbiting” will occur; i.e., the interacting pair will rotate clear potential on the interaction between particles can be
together for an infinite amount of time since both the radial observed in elastic scattering experiments. These studies
kinetic energy and the centrifugal force acting on the parti- allow determination of the angle of deflection of a parti-
cles (−d Veff /dr ) are zero. The orbiting impact parameter, cle from its original direction upon interaction with the
bor b , defined as the impact parameter for a given initial col- second particle. Conceptually, the scattering process can
lision energy, E = 1/2 µg 2 , at which orbiting occurs, can be be understood by considering the effect of a particle of
determined by setting Vmax = E and rearranging to arrive mass µ colliding with an infinitely massive particle fixed
at in space. The deflection angle, χ , defined as the angle be-
    tween the initial and final relative velocity vectors of the
a(s − 2) 2/s s colliding pair, will depend on the form of potential, V (r ),
bor b =
2
. (27)
µg 2 s −2 and, based on the impact parameter at which a given col-
lision occurs, the region of V (r ) that is sampled by the
Since smaller impact parameter collisions will result in a colliding pair.
smaller value of Vmax , only collisions occurring with im- Recall from Eq. (17) that the effective potential, Veff ,
pact parameters less than bor b will lead to a close collision governs the radial motion of the colliding particles, and
and reaction. Thus, the reaction cross section, σ = π bor 2
b, therefore determines the radial turning point, rt. p. , for a
which depends on the relative velocity g, may be inte- given magnitude of initial collision energy, E. Figure 6
grated over all relative velocities to derive the rate constant shows three effective potentials (for impact parameters
temperature dependence: b = 0, b1 , b2 , and b3 , where 0 < b1 < b2 < b3 ) for an in-
 ∞ ternuclear potential, V (r ), with both long-range attractive
k(T ) = π bor
2
b g f (g) dg and short-range repulsive components. If the two particles
0 collide with a fixed collision energy (e.g., that denoted by
 1/2  
3s−4 π s−4 s −2 E 1 ), the radial turning point, and therefore the regions of
=2 2s (s − 2) a (k B T ) 2s
2/s 2/s
, V (r ) accessed during the collision, will depend strongly
µ s
on the magnitude of b. For very large values of b, (b ∼ b3 ),
(28) the turning point lies at very large r , and the particle
where the gamma function, , is available in mathemat- experiences little deflection upon approach (χ ∼ 0). For
ical tables. This equation predicts that reactions involv- smaller values of b (b ∼ b2 ), the turning point moves to
ing quenching of an electronically excited state, which smaller values of r , and the interacting particles therefore
can be modeled using s = 3, will show weak inverse tem- sample more of the long-range attractive part of V (r ), re-
perature dependence, k(T ) ∝ T 1/6 . Ion–molecule reac- sulting in a deflection toward more negative angles. As
tions, having s = 4, are predicted to have rate constants b becomes even smaller, however, the effects of the re-
independent of temperature. Reactions dominated by pulsive part of the potential begin to play a role, and χ
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Dynamics of Elementary Chemical Reactions 703

FIGURE 6 Dependence of Veff on impact parameter, b, where 0 < b 1 < b 2 < b 3 . Larger magnitudes of b result in
larger values of the radial turning point for a given collision energy.

reaches a minimum value, called the “rainbow” angle, χr , imum of χ = π for direct head-on collisions (b = 0). A
by analogy to the optical rainbow resulting from scattering pictorial depiction of the dependence of χ on the impact
in small water droplets. The impact parameter that results parameter, known as the deflection function, is shown in
in this most negative degree of deflection is referred to Fig. 7, where particle trajectories during the course of a
as the rainbow impact parameter, br . For impact parame- collision are shown for a wide range of impact parameters.
ters less than br (b ∼ b1 ), short-range repulsion begins to Note that this figure depicts the dependence of the deflec-
dominate, and the deflection angle becomes less negative, tion angle, χ , on b∗ = b/re , where re is the internuclear
reaching zero at the impact parameter at which the attrac- separation where V (r ) reaches a minimum.
tive and repulsive forces during the collision exactly off- Although collision theory has provided considerable in-
set, the so-called “glory” impact parameter, bg . For impact sight beyond simple hard spheres, it cannot properly ad-
parameters smaller than bg , repulsion dominates, and the dress questions such as what fraction of collision geome-
particle is scattered to positive angles, reaching a max- tries are likely to lead to reaction. Such issues cannot be

FIGURE 7 Deflection angle, χ , dependence on impact parameter. Trajectories depict the degree of deflection of
impinging particle resulting from attractive and repulsive components of the interaction potential. (From Levine, R. D.,
and Bernstein, R. B. (1987). “Molecular Reaction Dynamics and Chemical Reactivity,” Oxford University Press, New
York.)
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704 Dynamics of Elementary Chemical Reactions

properly accounted for unless the details of the molecu- According to transition state theory, a fast equilibrium
lar structure of reactants are considered. Often, the rate exists between reactants and molecules at the transition
constant calculated from collision theory must be reduced state, denoted by AHB‡ :
by inclusion of an ad hoc “steric factor” which represents k1 ω
the fraction of collisions that have proper geometry for A + HB
AHB‡ → AH + B. (31)
k−1
reaction. This additional factor is an empirical factor used
The equilibrium concentration of molecules at the transi-
to bring experimental observation into line with collision
tion state is given by
theory, and accounts for those important factors not ad-
dressed by collision theory. [AHB‡ ] = K ‡ [A][HB], (32)
where K = k1 /k−1 . The overall rate of product formation
‡

depends on the rate constant, ω, with which the activated

II. ACTIVATED COMPLEX THEORY complexes cross over to products:
d[AH]
Many models of chemical reactions are based on the con- = ω[AHB‡ ] = ωK ‡ [A][B]. (33)
cept of an “activated complex,” or “transition state,” which dt
corresponds to the nuclear configuration with the highest A comparison of Eqs. (30) and (33) indicates that the rate
potential energy of the system traversed during the course constant k = ωK ‡ . The equilibrium constant for produc-
of the reaction. The transition state corresponds to a criti- tion of activated complexes K ‡ is related to molecular
cal geometry of the reacting system marking the boundary partition functions (Q), calculated using statistical me-
between reactants and products. Consider the elementary chanics:
reaction: [AHB‡ ] Q AHB‡ −E/k B T
K‡ = = e . (34)
A + HB → AH + B. (29) [A][HB] Q A Q HB
The overall rate for this elementary reaction is given by In the above equation, E = E AHB‡ − E A − E HB is the en-
ergy difference between the reactants and activated com-
d[AH]
= k[A][HB]. (30) plex. Assuming that the reaction involves translational mo-
dt tion of the hydrogen atom from B to A, the rate of passage
The reaction coordinate for this H-atom transfer reaction through the transition state is given by
may be considered to be translational motion of the H atom  
from B to A. A potential energy diagram for this process v k B T 1/2 1
ω= = , (35)
may be represented in 2D or in 3D, as shown in Fig. 8. δ 2πµ δ

FIGURE 8 Schematic potential energy surface of A + HB → AH + B reaction, shown as a two-dimensional contour

plot (left) and a three-dimensional surface plot (right). Trajectory on contour plot corresponds to lowest energy pathway
from reactants to products and traverses the region corresponding to the reaction transition state, AHB.‡
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Dynamics of Elementary Chemical Reactions 705

where v is the velocity through the transition state region The overall rate of product formation is
and δ is the “width” of transition state along the reaction d[P1 ] d[P2 ] d[A] k1 k2 [A][M]
coordinate. = =− = k2 [A∗ ] = .
dt dt dt k−1 [M] + k2
The contribution to the partition function of the acti-
vated complex corresponding to motion along the reaction (41)
coordinate, in this case translational motion, is factored out At high pressure, k−1 [M]  k2 , and d[P1 ]/dt = (k1 k2 /
of the transition state partition function, Q AHB‡ , to yield: k−1 )[A], yielding first-order kinetics. Under low-pressure
(2πµk B T ) /2 δ 
1 conditions, k−1 [M]  k2 and d[P1 ]/dt = k1 [A][M] result-
Q AHB‡ = qtrans,AHB‡ Q AHB‡ = Q AHB‡ . ing in second-order behavior. The important result is that
h
(36) reactions that appear to be unimolecular, exhibiting first-
order kinetics at high pressures, actually involve bimolec-
Note that the width parameter δ appears again in Eq. (36). ular processes.
This parameter ultimately factors out in the transition state An important class of elementary bimolecular reactions
theory rate constant, k TST , which is given by: are those that involve formation of persistent collision
 complexes, denoted AB∗ , that may ultimately form prod-
k B T Q AHB‡ −E/k B T
k TST = ωK ‡ = e . (37) ucts C + D, or decay back to reactants:
h Q A Q HB
k1 k2
A + B
AB∗ → P1 + P2 . (42)
Although we have derived this equation assuming that k−1
the reaction coordinate for atom transfer corresponds Following formation of the AB∗ intermediate by bimolec-
to translational motion, the same expression is obtained ular collision, the reaction dynamics are somewhat analo-
if the reaction coordinate is assumed to be vibrational gous to those in the Lindemann mechanism: an internally
motion. According to Eq. (37), the reaction rate constant excited molecule may decay to products or reform reac-
may be calculated using the relevant molecular partition tants. In the absence of collisions, the dynamics are solely
functions, known from statistical mechanics, remember- determined by the unimolecular dynamics of the complex.
ing that Q AHB‡ does not include the translational motion However, at high pressures, particularly if the lifetime of
contribution to the transition state partition function. the AB complex is long, it may undergo collision with
another body, possibly carrying away excess energy re-
sulting in formation of stable AB:
k3
III. UNIMOLECULAR VERSUS AB∗ + M → AB + M. (43)
BIMOLECULAR REACTIONS

Many early experiments showed that thermal decompo- IV. STATISTICAL THEORIES OF
sition of a molecule A, forming products P1 and P2 , UNIMOLECULAR DECOMPOSITION
often exhibits first order kinetics at high pressure, and
second–order kinetics at low pressure. As first proposed The Lindemann mechanism as well as reactions occurring
by Lindemann, the mechanism involves collisional exci- via formation of long-lived complexes involve participa-
tation of the reactant A: tion of highly internally excited intermediate species that
may ultimately dissociate by one or more chemical chan-
k1 k2 nels. For example, the intermediate complex AB∗ in reac-
A + M
A∗ + M, A ∗ → P 1 + P2 . (38)
k−1 tion (42) may form new products P1 + P2 , or decay back
to reactants, A + B. The total rate constant for decay of
Under steady-state conditions, the concentration of the AB∗ is the sum of the two rate constants, k−1 + k2 , and
collisionally activated molecule, A∗ is constant, i.e., the the relative importance of these competing processes is
rate of its formation is exactly balanced by the rate of its defined as the product branching ratio k2 /k−1 . Of key im-
destruction: portance in understanding these reactions are the reaction
d[A∗ ] rate constants k−1 and k2 . A number of theories have been
= k1 [A][M] − k−1 [A∗ ][M] − k2 [A∗ ] = 0. (39) developed to quantitatively predict rate constants for uni-
dt
molecular reactions.
Rearranging: Rice, Ramsperger, and Kassel developed a simple the-
ory, now known as RRK theory, which contains many
k1 [A][M] fundamental elements underlying most modern theories
[A∗ ] = . (40)
k−1 [M] + k2 of unimolecular reaction. According to RRK theory, the
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706 Dynamics of Elementary Chemical Reactions

energized molecule produced by bimolecular collision With the development of computers, accurate calcula-
may be considered to consist of a group of s identical har- tions using theoretical models better able to represent the
monic oscillators, each of frequency ν. If any oscillator behavior of real molecules has become widespread. A very
accumulates sufficient energy E o = mhν, where m is an important extension of the original theory, due to Marcus,
integer and h is Planck’s constant, the energized molecule is known as RRKM theory. Here, the real vibrational fre-
will dissociate. An underlying assumption of RRK (as well quencies are used to calculate the density of vibrational
as other related theories) is that energy may flow freely be- states of the activated molecule, N (E). The number of
tween the oscillators in the molecule. The total energy of ways that the total energy can be distributed in the acti-
all of the oscillators is denoted by E = nhν. The number of vated complex at the transition state is denoted W (E  ).
ways that n quanta can be placed in a molecule consisting Note that the geometry of the transition state need not be
of s oscillators is: known, but the vibrational frequencies must be estimated
(n + s − 1)! in order to calculate W (E  ). In calculating the total number
wn = . (44) of available levels of the transition state, explicit consid-
n!(s − 1)!
eration of the role of angular momentum is included. The
The number of ways that n quanta can be placed in a RRKM reaction rate constant is given by:
molecule such that at least m quanta are in one oscillator
W (E  )
is given by kRRKM = , (49)
h N (E)
(n − m + s − 1)!
wm = . (45) where h is Planck’s constant.
(n − m)!(s − 1)!
The probability, P, of dissociation is the ratio of these
V. REACTIONS IN SOLUTION
quantities:
wm (n − m + s − 1)!n! The density of molecules is substantially higher in liquids
P= = . (46)
wn (n − m)!(n + s − 1)! than in the gas phase. However, for reactions carried out in
solution under relatively dilute conditions, the concentra-
If n and m are large, then Sterling’s approximation tions of reactants are not appreciably different from in the
(x! ≈ x x /e x ) may be applied, and, if s is small relative gas phase. Since reactant molecules A and B must undergo
to (n − m), then (n − m + s − 1) ≈ n − m. The probability collision in solution in order to react, many of the same
of decomposition then reduces to principles developed for gas-phase reactions also apply
  in solution. However, the presence of solvent molecules
n − m s−1
P= . (47) leads to important differences between reactions in solu-
n
tion and in the gas phase. In solution, the rate of diffusion
The rate constant for unimolecular decomposition is the often limits the rate of approach of molecule A to within
probability P multiplied by a frequency factor ν: a sufficient distance to B for reaction to occur. Once an
    encounter pair AB is formed, however, the solvent may act
n − m s−1 E − E o s−1 as a “cage,” effectively holding them in close proximity,
kRRK = ν =ν . (48)
n E thereby increasing the probability of reaction.
In solution, the overall reaction may again be broken
For a given value of s, the reaction rate constant increases
down into a sequence of elementary steps:
with increasing energy E above threshold, E o . If E  E o ,
the reaction rate constant approaches the frequency factor kd kr
A + M
AB, AB → P, (50)
ν. On the other hand, for reactions involving two simi- k−d
lar but different-sized molecules having the same E and where, AB is an encounter pair, kd and k−d are rate
E o , since the larger molecule has a greater number of os- constants for approach and separation of the reactant
cillators, s, the reaction rate constant k is smaller (since molecules by diffusion, and kr is the rate of conversion
(E − E o )/E < 1). In practice, to obtain agreement with of encounter pairs to products. Applying the steady-state
experiment, it is necessary to use values of s in Eq. (48) approximation to the concentration of encounter pairs, we
which are approximately one half of the actual number obtain
of vibrational modes in the molecule. Of course, because
d[P] k d kr
RRK theory treats all oscillators as having the same vi- = [A][B] = k[A][B]. (51)
brational frequency, the theory employs very simple equa- dt k−d + kr
tions that represent qualitatively but not quantitatively the If the activation energy for the reaction is large, kr  kd
behavior of real molecules. and the reaction rate constant k ≈ kd kr /k−d . Alternatively,
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Dynamics of Elementary Chemical Reactions 707

if kr  kd , then k ≈ kd , and the reaction rate constant is the A. Cross Section Measurements
rate of diffusion of reactants to sufficiently close proximity
The reaction cross section may be determined experimen-
to facilitate reaction. The rate of a diffusion controlled
tally as a function of collision energy using a variety of
reaction is determined by the magnitude of the diffusion
methods. For the reaction H + D2 → HD + D, the reaction
coefficients, D, for the reactants A and B:
has been carried out in a flow cell containing mixtures of
k = 4π(DA + DB )R. (52) D2 and a stable H atom precursor such as HBr. The H
atoms are produced by photolysis of HBr at various UV
The diffusion coefficients are related to the viscosity of the wavelengths. Reaction cross sections are determined by
solvent, η, and hydrodynamic radius, r , of the diffusing measuring the concentration of products relative to reac-
species by the Stokes–Einstein Law: tants directly. In the present case, this involves monitoring
the relative concentrations of H and D atoms (i.e., reactants
kB T and products) as a function of time following photodisso-
D= , (53)
πβηr ciation of reactant precursor. Both H and D atoms may
be detected by laser induced fluorescence (LIF) excita-
where β is a constant typically ranging from 4 to 6. Note tion spectroscopy near 121 nm (Lyman-α). By choosing
that this derivation assumes that diffusing particles are different photolysis wavelengths and H atom precursor
equally likely to move in any direction. However, if the molecules, reaction rate constants may be determined for
reactants are oppositely charged ions, Coulomb attraction different collision energies. In this case, reaction cross sec-
substantially increases reaction rates relative to the rate of tions are determined directly from Eq. (8), since the rela-
diffusion. tive velocity is well defined using photolytic reactants. In
Fig. 9, experimental data from several different laborato-
ries are shown as solid points surrounded by rectangles,
and theoretical values are connected by a solid line. The
VI. EXPERIMENTAL TECHNIQUES
reaction cross section is zero below 0.4 eV due to the
presence of a potential energy barrier for reaction, as dis-
It is well known from the empirical Arrhenius expression
cussed in detail in Section VI.B. The reaction cross section
that reaction rate constants often increase with reactant
increases with increasing energy above threshold, with be-
temperature. One goal of molecular reaction dynamics is
havior qualitatively similar to that predicted by Eq. (15).
to understand the roles that different forms of reactant en-
ergy (translational, electronic, vibrational, and rotational)
play in chemical reaction. Also, if a reaction is successful,
how is the total available energy channeled into the various
available degrees of freedom of the product molecules?
Many of the microscopic details of a chemical reac-
tion are related to the nature of the transition state. Most
insight into the transition state region has been obtained
through experiments focusing on the asymptotic limits
of the reaction; i.e., reactants and products. Four gen-
eral categories of experiments will be discussed here, all
focusing on elementary gas-phase reactions. In the first
type of experiment, the total cross sections for various
chemical reaction channels are measured, usually as a
function of collision energy. In the second type, the an-
gular and velocity distributions of products from single
reactive encounters are measured. In the third type of ex-
periment, the quantum state distributions (vibrational and
rotational) of products are measured using spectroscopic
techniques. In this latter approach, velocity distributions
may also be obtained using Doppler or velocity imag-
FIGURE 9 Cross section for H + D2 → HD + D reaction vs. colli-
ing methods. Finally, a relatively recent development is
sion energy. Solid points surrounded by rectangles are experimen-
“transition state spectroscopy,” which focuses directly on tal data and open points connected by solid line is theoretical cal-
the transition state itself, usually through spectroscopic culation. (From Gerlach-Meyer, U., Kleinermanns, K., Linnebach,
measurements. E., and Wolfrum, J. (1987). J. Chem. Phys. 86, 3047–3048.)
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708 Dynamics of Elementary Chemical Reactions

In some cases, reaction may lead to more than one

type of chemical product. For example, the reaction of
chromium cations, Cr+ , with methane, CH4 , may lead
to production of CrCH+ +
2 + H2 or CrH + CH3 . In order
to study ion-neutral reactions such as these, a beam of
mass-selected reactant ions, e.g., Cr+ , is accelerated to
a well-defined laboratory kinetic energy. The ion beam
encounters target molecules held in a gas cell, where
bimolecular reaction occurs. The product ions are then
extracted from the reaction volume, mass selected, and
counted. A wide variety of reactions have been studied
using such techniques. In Fig. 10, the cross sections for
reactions of ground state Cr+ are shown using solid sym-
bols. Due to the endoergicity of reaction, the formation of
CrCH+ 2 only occurs at energies above ∼2.3 eV, and CrH
+
FIGURE 11 Schematic diagram of crossed molecular beam ap-
formation has a threshold just under 3.0 eV. Reactions of paratus. Beams cross at right angles; products are detected by a
an electronically excited state of Cr+ with CH4 , on the detector that may be rotated with respect to the reactant beams.
other hand, have a large cross section for production of
CrCH+ 2 even down to zero collision energy, as indicated
by open symbols. Experiments such as this provide insight (<10−6 Torr) chamber (Fig. 11). The beams, denoted A
into the role of electronic state on chemical reactivity. Fur- and BC here, are usually generated by a supersonic expan-
thermore, by measuring energetic thresholds for reaction, sion, in which a gas at a pressure near an atmosphere or
thermodynamic quantities such as bond dissociation en- greater passes through a pinhole into an evacuated cham-
ergies may be determined directly. ber. Due to adiabatic cooling of the molecules during ex-
pansion, rotational temperatures are reduced to less than
100 K. Vibrational excitation is also cooled, although less
B. Angular and Velocity Resolved Studies
efficiently. Velocity distributions of molecules in a super-
Crossed molecular beam reactive scattering facilitates ex- sonic beam are typically less than 10% full width at half
perimental determination of the angular and velocity dis- maximum (FWHM); much narrower than in a Boltzmann
tributions of chemical products from elementary bimolec- distribution. One or more collimating devices (skimmers)
ular reactions. The technique involves production of two are used to define the beams to angular divergences of
molecular beams containing the reactants, initially mov- several degrees. Since molecules within the beam move
ing at right angles relative to one another, in an evacuated together at nearly the same velocity in the evacuated cham-
ber, the probability of collisions within a beam or with a
background gas molecule is negligible. A small fraction
of reactants in one beam undergo a single collision with
molecules in the other, forming chemical products, e.g.,
A + BC → AB + C. In a typical experiment, the beams
are several millimeters in diameter and the detector is a
mass spectrometer with electron impact ionizer that may
be rotated in the plane of the beams. By measuring the
arrival times of products at the detector at different an-
gles, the laboratory angular and velocity distributions of
the products are determined.
Reactive and nonreactive scattering data are analyzed
with the aid of a Newton diagram, illustrated in Fig. 12 for
the hypothetical reaction A + BC → AB + C. This vector
diagram in velocity space facilitates the transformation be-
tween the laboratory and center-of-mass (CM) reference
frames. Laboratory angles are denoted by , with  = 0
FIGURE 10 Experimental cross sections for Cr+ + CH4 reaction.
Solid points denote reaction of ground electronic state Cr+ and and 90◦ defined by the directions of the A and BC beams,
open points denote reactions of electronically excited Cr+ . (From respectively. All laboratory velocities are denoted by the
Armentrout, P. B. (1991). Science 251, 175–179.) variable v, and have their origins in the lower left corner of
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Dynamics of Elementary Chemical Reactions 709

locities of A and BC reactants, respectively, in the CM ref-

erence frame. However, depending upon the dynamics of
the reaction, θ can range from 0 to 360◦ . For randomly ori-
ented reactant molecules, CM angular distributions must
be symmetric about the relative velocity vector, i.e., about
θ = 0 and 180◦ .
Among the earliest reactions to be studied using crossed
molecular beams were those producing alkali atoms and
alkali–halide molecules, due to their ease of detection us-
ing surface ionization methods. The reaction of potassium
atoms (K) with molecular bromine (Br2 ) leads to forma-
tion of KBr + Br via the so-called “harpoon mechanism.”
Cuts of the two relevant potential energy surfaces are illus-
trated in Fig. 13. In this reaction, the neutral K + Br2 re-
actants approach on the covalent potential energy surface.
At a distance rc , termed the ionic–covalent curve cross-
ing distance, the energy required to transfer an electron
from K to Br2 , given by IPK − EABr2 , is exactly compen-
sated by the Coulomb energy gained by formation of the
K+ Br− 2 ion pair. Reaction is initiated by electron transfer,
which in the present case occurs at long range (∼7.5 Å),
and is analogous to the throwing of a harpoon during a
FIGURE 12 Newton diagram for A + BC reaction. Note that ve- whale hunt. Because the electron is transferred into an an-
locity scale is indicated on right side of diagram. See text for tibonding orbital, the equilibrium bond length of Br− 2 is
details.
much greater than for Br2 and rapid Br–Br− stretching in
the presence of K+ leads to immediate formation of the
the Newton diagram. The relative velocity vector is given K+ Br− + Br products.
by vrel = vA − vBC = uA − uBC , with velocities in the CM This reaction has been termed a “spectator stripping”
reference frame denoted by u and angles in the CM frame reaction, by analogy with some nuclear reactions. Here,
denoted by θ. the spectator is the bromine atom not involved in forma-
The laboratory velocity of the center-of-mass of the col- tion of the KBr product. Because of the rapid dissoci-
liding partners, vcm , which in this case is oriented along ation of Br–Br− while the K+ is still at relatively long
 = 50◦ , may be calculated from the masses and initial ve- range, the motion of the spectator Br atom remains essen-
locities of the A + BC reactants. Note that AB products tially unperturbed throughout the course of the collision.
scattered from the collision volume will be traveling with
a velocity in the laboratory reference frame that is simply
vcm + uAB . Thus, a circle is shown in Fig. 12, centered
at the tip of vcm . The radius of this circle corresponds to
the maximum possible velocity of AB products in the CM
reference frame, u AB , for all possible orientations of the
vector uAB . From energy conservation, this maximum ve-
locity corresponds to production of internally cold AB + C
products. Thus, if the thermodynamics of the reaction are
known or can be estimated, u AB may be calculated using
energy and momentum conservation laws. According to
Fig. 12, product AB molecules may be observed at labo-
ratory angles  ranging from 30 to 70◦ ; no products can
be observed outside of this range. Products formed with
progressively greater internal energies, and hence smaller
translational energies, are constrained to smaller Newton
circles, which are always centered on the tip of vcm . A sin-
gle CM recoil velocity vector uAB is shown in this figure, FIGURE 13 Ionic and covalent potential energy curves for
at θ = 45◦ , with θ = 0 and 180◦ corresponding to the ve- K + Br2 reaction.
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710 Dynamics of Elementary Chemical Reactions

FIGURE 15 Schematic of one OH + CO collision event showing

FIGURE 14 Energy level diagram for OH + CO reaction. reactant velocities in CM frame. CO2 product velocities are con-
strained by angular momentum conservation to lie in plane near
that of reactants.

Consequently, this spectator atom is produced with a CM

velocity vector that is essentially the same as that of The experimentally measured CO2 angular distribution,
the initial Br2 molecule reactant. This leads to a highly shown in Fig. 16, is broad with products scattered to both
anisotropic spatial distribution of products, with the Br sides of the center-of-mass of the system. Such angular
fragment scattered at CM angles near θ = 180◦ relative distributions are said to exhibit “forward–backward sym-
to the direction of the K atom reactant, whereas the KBr metry” in the center-of-mass frame of reference. From
counterfragment is scattered preferentially near θ = 0◦ . analysis of product translational energy distributions (not
The KBr product is thus “forward scattered” with respect shown), the degree of CO2 vibrational excitation has been
to the incoming K atom in the CM reference frame. Note inferred for this reaction.
that rc ≈ 7.5 Å for the K + Br2 system (Fig. 13). Since a Perhaps the most extensively studied elementary bi-
large fraction of those collisions involving electron trans- molecular reaction is the simplest: the hydrogen exchange
fer lead to reaction, the reaction cross section is essential- reaction and its isotopic variants. For example, studies of
2
ly the electron transfer cross section, σ = πrc2 ≈ 177 Å , reactions such as H + D2 → HD + D provide direct in-
which is much larger than typical hard sphere cross sight into reactive collisions. This reaction is slightly en-
sections. dothermic and exhibits a large (∼0.4 eV) potential energy
The elementary reaction OH + CO → CO2 + H is the barrier to product formation (Fig. 17). The reaction is di-
primary mechanism for formation of CO2 in combustion. rect, and proceeds via a near-collinear H–D–D transition
This reaction, as well as its reverse, have been studied ex- state on a timescale short relative to rotation, leading to
tensively using a variety of methods, including the crossed anisotropic D atom angular distributions.
molecular beams method. The reaction is thought to in- The experimental apparatus used in a recent H + D2
volve the participation of long-lived HOCO intermediates, study is shown in Fig. 18. Two molecular beams con-
as illustrated in Fig. 14. Note that although OH + CO may taining HI and D2 are generated in separately pumped
form the intermediate complex with at most only a small
potential energy barrier, a substantial barrier exists for
H-atom loss forming CO2 .
In a crossed molecular beams experiment using super-
sonic beams in which the OH and CO are in their lowest
few rotational levels, the total angular momentum of the
HOCO intermediate is primarily orbital angular momen-
tum, L = µvr el b, with the vector L lying perpendicular
to the plane containing the colliding species (Fig. 15).
In many reactions, including this one, a relatively small
fraction of total angular momentum appears as product
rotational angular momentum. Consequently, the final or-
bital angular momentum, L  , for the H + CO2 products
is approximately the total angular momentum, L, and the
product CM velocities uAB and uC , must lie in a plane
nearly identical to that of the incident reactants. Because
FIGURE 16 CO2 laboratory angular distribution from crossed
the intermediate HOCO lifetime is long compared to its beams OH + CO reaction. (From Alagia, M., Balucani, N.,
rotational period, uAB may lie in any direction in the plane Casavecchia, P., Stranges, D., and Volpi, G. G. (1993). J. Chem.
of the collision. Phys. 98, 8341–8344.)
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Dynamics of Elementary Chemical Reactions 711

FIGURE 17 Energy level diagram for H + D2 reaction.

regions and allowed to propagate parallel to one another,

30 mm apart. The HI molecules are photodissociated by a
pulsed 266-nm laser, producing ground state H atoms with
a very narrow translational energy distribution. Some of
these H atoms collide with the D2 molecules in the second
beam, leading to chemical reaction forming HD + D. The FIGURE 19 Lower figure: Newton diagram for H + D2 reaction.
D atom products from the reaction are “tagged” before Circles show maximum CM velocities for differerent rotational lev-
they leave the interaction region by excitation to high-n els of HD (v  = 0) products. Upper figure: D atom laboratory an-
Rydberg states using two tunable “probe” lasers. The first gular distribution; solid line shows theoretical simulation. (From
laser, operating at 121.6 nm, is tuned to the n = 1 → 2 Casavecchia, P., Balucani, N., and Volpi, G. G. (1999). Annu. Rev.
Phys. Chem. 50, 347–376.)
transition, and the second laser, at 365 nm, excites from
n = 2 → ∼40. The lifetimes of these highly excited D
atoms are in excess of 100 µs. Since the velocities of the At a collision energy, E coll , of 0.53 eV, the HD product
atoms are essentially unchanged during the tagging step, may be produced in either the ground or first excited vi-
they evolve spatially with their nascent velocities to a de- brational states (Fig. 17). A Newton diagram for H-atom
tector located approximately 30 cm away from the reaction products recoiling from HD in various rotational levels of
zone, where they are field ionized and collected. The de- the ground vibrational state (v  = 0) is shown in Fig. 19.
tector may be rotated with respect to the fixed beams in The largest circle corresponds to the velocity of D atoms
order to map out the angular distribution of the products. recoiling from internally cold HD (i.e., v  = 0, j  = 0).
By measuring the time of arrival at the detector following lSmaller circles correspond to recoil from HD molecules
time zero for reaction, the velocity and hence translational born with progressively greater internal energies. A mea-
energy distribution is obtained. surement of the D atom velocity distribution at different

FIGURE 18 Experimental apparatus for studies of H + D2 reaction in crossed molecular beams. (From Schnieder, L.,
Seekamp-Rahn, K., Wrede, E., and Welge, K. H. (1997). J. Chem. Phys. 107, 6175–6195.)
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712 Dynamics of Elementary Chemical Reactions

tion is based on exact trajectory calculations on high level

ab initio potential energy surfaces. This close agreement
between state-of-the-art theory and experiment is a par-
ticularly impressive achievement, demonstrating that the
hydrogen exchange reaction is presently very well under-
stood from a theoretical standpoint. Other related three
atom systems that have been extensively studied include
halogen atom reactions X + H2 → HX + H; X = F, Cl, and
their reverse. Like the hydrogen exchange reaction, these
reactions proceed via direct mechanisms over substantial
potential energy barriers.

C. Product Detection Using

FIGURE 20 D-atom laboratory kinetic energy distribution from Spectroscopic Methods
H + D2 reaction at 0.53 eV. (From Casavecchia, P., Balucani, N.,
and Volpi, G. G. (1999). Annu. Rev. Phys. Chem. 50, 347–376.)
Many different spectroscopic techniques have been ap-
plied to studies of elementary bimolecular reactions. Mea-
surements of the infrared chemiluminescence emitted
angles thus provides a direct measure of the internal state from reaction provides a direct measure of the product
distribution of the HD product. state (rotational and vibrational) distributions. Studies of
The D atom angular distribution is highly anisotropic, many different types of reactions have led to the devel-
peaking at laboratory angles near zero degrees (Fig. 19). opment of fundamental principles that facilitate an under-
In Fig. 20, the translational energy distribution for the D standing of how various forms of energy are partitioned
product, obtained by time of flight measurements for the D between reactants and products. Recall that the transition
atoms, is shown at a laboratory angle, , of 0◦ . Structure state is a region of the potential energy surface that must be
corresponding to varying degrees of HD (v  = 0) rotational traversed in order for reaction to occur. The location of the
excitation (denoted by j  ) is observed in the D atom kinetic transition state relative to reactants and products has a sig-
energy distribution. Note that in addition to the experimen- nificant effect on the dynamics of the reaction. As shown
tal distributions, a calculated kinetic energy distribution, in Fig. 21, an analogy may be drawn between the motion of
also shown, is found to almost exactly reproduce the de- atoms during a chemical reaction and the motion of a ball
gree of HD rotational excitation. This calculated distribu- rolling on a three-dimensional potential energy surface. If

FIGURE 21 Two-dimensional contour map for AB + C reaction. Figure on left denotes reaction involving “early”
transition state, in which translation is more effective in promoting reaction than is vibration; figure on right denotes
reaction having “late” transition state, where vibrational energy promotes reaction.
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Dynamics of Elementary Chemical Reactions 713

the transition state geometry more closely resembles the

reactants (AB + C), than the products (A + BC), the tran-
sition state is termed “early.” A “late” transition state, on
the other hand, corresponds to the case where the transition
state more closely resembles the products. For reactions
involving an early barrier, reactant translational energy
is more effective than vibrational energy in surmounting
the barrier, and much of the available energy is deposited
into product vibration. Note that the opposite is true for
reactions involving late barriers. In this case, vibrational
energy of the reactants is more effective than translational
energy, and the products from the reaction tend to be vi-
brationally cold, with a large fraction of available energy
appearing in translational energy.
To illustrate these ideas, consider the reaction H + Cl2
→ HCl + Cl. Studies of the infrared chemiluminescence
emitted from the diatomic product HCl indicate that al-
though the reaction is highly exothermic, only a small
fraction of the total available energy is channeled into
HCl vibrational and rotational energy. Since electroni-
cally excited Cl and HCl products are not energetically
accessible, a large fraction of the available energy must be FIGURE 22 OH (v = 0 and 1) rotational distributions from
partitioned into relative translational energy. This reaction H + CO2 reaction. Upper panel indicates distribution obtained
is therefore an example of one involving a late transition from gas phase reaction. Lower panel indicates distribution ob-
state. tained from reaction photoinitiated in CO2 · · · HBr van der Waals
Measurement of product state distributions using vari- complexes. (From Wittig, C., Engel, Y. M., and Levine, R. D. (1988).
Chem. Phys. Lett. 153, 411–416.)
ous spectroscopic techniques has been applied to a wide
variety of reactions, including H + CO2 . The H + CO2
→ OH + CO reaction, the reverse of the reaction shown near the reacting H + CO2 pair in the complex-initiated
in Fig. 14, is substantially endoergic. However, UV pho- reaction.
todissociation of a diatomic molecule such as HI or HBr Spectroscopic methods can also be used to determine
can produce H atoms with more than enough kinetic en- rates of elementary reactions. As noted earlier, the exis-
ergy to react. The OH products may be readily detected tence of HOCO intermediates persisting longer than their
using fluorescence excitation spectroscopy in which the picosecond rotational timescales during the OH + CO re-
total OH fluorescence intensity is monitored as a func- action has been inferred from CO2 product angular dis-
tion of OH excitation wavelength. This provides a direct tributions in crossed molecular beam experiments. More
measure of the OH quantum state distribution from the direct determinations of bimolecular reaction timescales
bimolecular reaction. In the upper panel of Fig. 22, the are often very difficult because molecules must first col-
rotational distribution of OH (v  = 0, 1) from photodisso- lide before they can react. Due to the “random” nature of
ciation of HBr in the presence of CO2 molecules is shown. bimolecular collisions, both in time and in space, it is not
For both OH vibrational levels, the most probable rota- usually possible to define the “time zero” for a bimolecu-
tional level is near j  = 8. In the lower panel, a similar lar reaction to sufficient precision to permit a direct study
experiment is carried out, but in this case the reaction is of reaction timescales. These difficulties, however, have
initiated within weakly bound HBr · · · CO2 van der Waals been surmounted by initiating the bimolecular reaction
complexes, produced by coexpanding HBr and CO2 in a via photodissociation of van der Waals complexes such
dilute He mixture in a supersonic molecular beam. In this as HI · · · CO2 . Since the H + CO2 reactants are already
case, the HBr moiety of the complex is photodissociated, in close proximity, and because the time zero for reac-
producing H atoms that react with CO2 to form OH + CO. tion can be accurately defined using an ultrashort laser
As indicated in the lower panel, the OH rotational distribu- pulse (<1 ps), it is possible to measure the reaction rate
tions are substantially “colder” for products from reactions in real time by measuring the buildup of OH products
initiated within complexes, with the most probable rota- following photodissociation of HI within a binary com-
tional level near j  = 4. The different behavior is believed plex. Rate constants for H + CO2 → OH + CO obtained
to result from the presence of the halogen counterfragment at different HI photodissociation wavelengths, and hence
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714 Dynamics of Elementary Chemical Reactions

ics. For example, the reactivity of H2 O |04, having four

quanta in one OH bond, was compared to that for H2 O
|13, which has three quanta in one OH bond and one in
the other. It was found that Cl + H2 O |04 produced pri-
marily HCl + OH (v = 0), whereas reaction of Cl + H2 O
|13 yielded primarily HCl + OH (v = 1). This illustrates
that the OH bond not involved in the reaction acts much
like a spectator, retaining its initial level of vibrational
excitation in the chemical products.

D. Spectroscopy of the Transition State

In the experiments described previously, much of the in-
formation about the reaction pathway is obtained through
measurements of the velocity, angular, or internal state
FIGURE 23 Experimentally determined bimolecular reaction rate distributions of products, or through measurements of
constants for H + CO2 reaction photoinitiated in HI · · · CO2 van der their cross sections or timescales for formation. In some
Waals complexes. Solid line denotes calculated RRKM decom- cases, the effect of different forms of reactant energy in
position rate for HOCO reaction intermediates. (From Ionov, S. I.,
Brucker, G. A., Jaques, C., Valachovic, L., and Wittig, C. (1992).
promoting chemical reactivity also provided insight into
J. Chem. Phys. 97, 9486–9489.) the thermodynamics of the reaction or on the nature of the
transition state. A conceptually different and more recent
development involves direct measurement of the transition
collision energies, are shown in Fig. 23. Note that the rate state itself. Since, in most reactions, the transition state
constant, k, for this elementary reaction, which is the in- corresponds to an energy maximum along the reaction co-
verse of the HOCO lifetime (τ ), increases monotonically ordinate, this region is only accessed for a very short time,
with increasing energy, E † , in excess of the potential en- typically on timescales comparable to a vibrational period
ergy barrier for H + CO2 production. This behavior is in (<10−13 s). Consequently, the fraction of molecules in a
close agreement with that predicted by statistical theories reacting sample near the transition state at any given time
such as RRKM theory, illustrated by a solid curve.
Through the use of direct optical excitation of reactants,
it has been possible in several cases to direct the course of
reaction to favor certain product channels or product state
distributions. Using an intense pulsed near-infrared laser,
the very weakly absorbing OH vibrational overtones in
small molecules like water may be excited relatively ef-
ficiently, depositing a substantial amount of vibrational
energy into well-defined vibrational modes of reactants.
Using this approach, the role of reactant vibrational exci-
tation in bimolecular reactivity has been studied. Because
of the local mode character of OH bonds in water, the vi-
brational excitation initially deposited into the molecule
remains localized in a well-defined oscillator. For exam-
ple, the reaction of Cl + HOD (4νOH ) (having four quanta
in the OH stretch with zero in the OD stretch), leads to
relatively efficient production of HCl + OD, but essen-
tially no DCl + OH, as determined by LIF detection of
OH and OD products (Fig. 24). In this example of bond
specific chemistry, the vibrationally excited OH bond is
highly reactive, whereas the unexcited OD bond is rela-
tively inert. In other related studies of reactions of H2 O,
FIGURE 24 Fluorescence excitation spectrum for OD and
mode specific chemistry has been observed, in which dif- OH products from HOD(4νOH ) + Cl reaction. (From Sinha, A.,
ferent excited H2 O vibrational states at nearly the same Thoemke, J. D., and Crim, F. F. (1991). J. Chem. Phys. 96, 372–
energy displayed somewhat different reaction dynam- 376.)
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Dynamics of Elementary Chemical Reactions 715

tra, recorded at different experimental resolutions, show

structure corresponding to antisymmetric stretching vibra-
tional levels of the neutral IHI molecule. This approach
has also been applied to studies of a wide variety of other
reactive systems involving transfer of a light atom, such
as F + CH3 OH → HF + CH3 O, and F + H2 → HF + H.

SEE ALSO THE FOLLOWING ARTICLES

ATOMIC AND MOLECULAR COLLISIONS • COHERENT

CONTROL OF CHEMICAL REACTIONS • ENERGY TRANS-
FER, INTRAMOLECULAR • ION KINETICS AND ENERGETICS
• KINETICS, CHEMICAL • MOLECULAR BEAM EPITAXY,
FIGURE 25 Photoelectron spectra at two different resolutions SEMICONDUCTORS
from IHI− photodetachment. Peaks correspond to asymmetric
stretching levels of neutral IHI product. (From Metz, R. B., and
Neumark, D. M. (1992). J. Chem. Phys. 97, 962–977.) BIBLIOGRAPHY

Baer, T., and Hase, W. L. (1996). “Unimolecular Reaction Dynamics,

is vanishingly small, making it difficult to study such Theory and Experiments,” Oxford Univ. Press, New York.
species directly. Much of the recent progress in the area Crim, F. F. (1999). “Vibrational state control of bimolecular reactions:
of transition state spectroscopy has therefore utilized pho- Discovering and directing the chemistry,” Acc. of Chem. Res. 32, 877–
toinitiation qualitatively similar to that described above 884.
Johnston, H. S. (1966). “Gas Phase Reaction Rate Theory,” Ronald Press.
for HI · · · CO2 to produce molecules near the transition
Lee, Y. T. (1987). “Molecular beam studies of elementary chemical pro-
state. cesses,” Science 236, 793–798.
For example, the transition state regions for a num- Levine, R. D., and Bernstein, R. B. (1987). “Molecular Reaction Dy-
ber of hydrogen exchange reactions have been studied by namics and Chemical Reactivity,” Oxford Univ. Press, New York.
first producing molecular beams containing stable nega- Neumark, D. M. (1992). “Transition State Spectroscopy of Bimolecular
tive ions, such as IHI− . The geometries of these stable Chemical Reactions” In Annual Review of Physical Chemistry (H. L.
Strauss, G. T. Babcock, and S. R. Leone, eds.), Vol. 43, pp. 153–176,
negative ions often resemble that of the transition state Annual Reviews Inc., Palo Alto, CA.
for the neutral reaction, e.g., I + HI → HI + I . Photode- Pilling, M. J., and Seakins, P. W. (1995). “Reaction Kinetics,” Oxford
tachment of the electron produces the neutral IHI species. Science Publications, New York.
As in conventional photoelectron spectroscopy, by mea- Polanyi, J. C. (1987). “Some concepts in reaction dynamics,” Science
236, 680–690.
suring the kinetic energy distribution of the ejected elec-
Polanyi, J. C., and Zewail, A. H. (1995). “Direct observation of the
tron, the vibrational energy levels of the molecular coun- transition state,” Acc. Chem. Res. 28, 119–132.
terfragment, in this case IHI at nuclear geometries near Scoles, G. (1988). “Atomic and Molecular Beam Methods, Vol. 1,”
the transition state, are obtained. In Fig. 25, two spelc- Oxford Univ. Press, New York.
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Electrolyte Solutions,
Thermodynamics
J. Barthel
W. Kunz
R. Neueder
University of Regensburg

I. Electrolytes and Solvents

II. Thermodynamics of Electrolyte Solutions
III. Statistical Approaches
IV. Thermodynamic Properties of Electrolyte
Solutions

GLOSSARY trodes of a galvanic cell when no electric current passes

through the cell.
Activity coefficient Ratio of the activity to the concen- Excess property Difference between the actual property
tration of a component Yi in a mixture or solution; the and its hypothetical value calculated for an ideal mix-
activity coefficient represents a measure of the depar- ture or solution at the same temperature, pressure, and
ture from ideal behavior. mole fraction composition.
Aprotic solvent Solvent incapable of acting as a proton Hamiltonian Energy function of a system expressing the
donor; an aprotic solvent may act as an electron donor total energy of the system as a function of the coordi-
or acceptor (Lewis acid or base). nates and momenta of its particles, molecules, and/or
Born process Hypothetical process for calculating the ions.
energy of transfer of an electrolyte compound from Hamiltonian model Statistical mechanical model based
a vacuum into a solvent where the electrolyte exhibits on a Hamiltonian.
complete dissociation into ions. Ideal mixture or solution Mixture or solution that shows
Chemical potential Content in Gibbs energy of a com- no change in volume, enthalpy, and heat capacity when
ponent Yi of a mixture or solution, that is, the change the mixture or solution is being made up from its ini-
in total Gibbs energy of the system at constant tem- tially separated components.
perature and pressure when 1 mol of component Yi is Ionogene Electrolyte compound that in its pure phase ex-
added to an infinite amount of the system. ists as a neutral molecule and forms ions in solution by
Electromotive force Difference in potential at the elec- a chemical reaction with solvent molecules.

219
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220 Electrolyte Solutions, Thermodynamics

Ionophore Electrolyte compound that in its pure phase (e.g., NaHSO4 ) or still more complex
 electrolyte com-
exists as an ionic crystal and forms ions in solution by pounds. Electroneutrality requires νi z i = 0.
decomposition to the preformed ions.
1. Ionophores
Medium activity coefficient Measure for the change in
Gibbs energy when an electrolyte is transferred from Ionophores are substances that already exist as ionic crys-
one solvent to another solvent at infinite dilution. tals in their pure state, such as alkali metal halides. When
Osmotic pressure Additional pressure applied to a solu- dissolved in a solvent, ionophores are initially completely
tion to maintain equilibrium with a pure solvent that is dissociated in the solution and their ions are solvated.
in contact with the solution through a membrane per- However, association to ion pairs and higher ion aggre-
meable only to solvent molecules. gates with and without inclusion of solvent molecules may
Partial molar quantity Increase in any extensive ther- occur in many solvents depending on electrolyte concen-
modynamic property of a system at constant pressure tration and solvent permittivity. Equation (1) shows the
and temperature when 1 mol of component Yi is added ionic species in an aqueous CdSO4 solution—solvated
to an infinite amount of the system; the chemical po- ions and ion pairs—which can be detected by appropriate
tential of component Yi is also the partial molar Gibbs methods and which determine the physical properties of
energy of compound Yi . this solution:
Protic (amphiprotic) solvent Solvent apt to react as a CdSO4 (s) −−−−→ Cd2+ (aq) + SO2− →
4 (aq)←
proton donor or acceptor (Brönsted acid or base). H2 O
Solvation Process leading from the ions of an electrolyte, → [Cd(OH2 )SO4 ]0 ←
→ [CdSO4 ]0 .
[Cd(OH2 )2 SO4 ]0 ←
after complete dissociation in a vacuum, to the ions in
solution surrounded by oriented solvent molecules. (1)
Structure-making (-breaking) ion Ion that by a solva-
Aqueous solutions of alkali metal salts exhibit almost no
tion process increases (decreases) the structure of a
association, in contrast to solutions of 2,2 electrolytes,
pure solvent.
such as CdSO4 . Solutions of low permittivity contain ion
pairs (equilibrium constant K A ), triple ions (equilibrium
constant K T ), and higher associates, such as
ELECTROLYTE SOLUTIONS are solutions of elec-
trolyte compounds in pure or mixed solvents such that 1,2-dimethoxyethane
the solutions become electric conductors in which current LiBF4 (s) −−−−−−−−−−→ Li+ + BF−4
is carried by the movement of ions. They exhibit specific KA  
←→ Li+ BF− 4 ,
0
(2a)
properties due to the more or less complete dissociation
of their solutes into ions. Aqueous electrolyte solutions  + − 0 KT  
− −
Li BF4 + BF− → − +
4 ← BF4 Li BF4 , (2b)
are involved in numerous biological, biochemical, geo-
logical, and technical processes. Nonaqueous electrolyte and
 0 KT  
+ +
solutions are intensively studied owing to unique proper- Li+ BF−
4
→ Li+ BF−
+ Li+ ← 4 Li . (2c)
ties for their application in various new technologies such
as high-energy batteries, electrodeposition, nonemissive
displays, solar cells, phase-transfer catalysis, or electroor- 2. lonogenes
ganic synthesis. Ionogenes, such as mineral or carboxylic acids, form ions
only by a chemical reaction with solvent molecules, for
I. ELECTROLYTES AND SOLVENTS example,
KI  
HClO4 + CH3 COOH ← → CH3 COOH+ 2 ClO4
− 0
A. Classification of Electrolytes
KD
→ CH3 COOH+
←
−
2 + ClO4 . (3)
Electrolytes can be classified into two categories,
ionophores and ionogenes, independent of their stoi- The solution of perchloric acid in glacial acetic acid
chiometry. Stoichiometry entails formal arrangement in [Eq. (3)] shows the typical two-step mechanism of ion for-
classes according to the valency of their cations and an- mation of ionogenes. An ionization (equilibrium constant
z+ z−
ions. An electrolyte of type Cν+ Aν− composed of a z + - K I ) process is followed by a dissociation (equilibrium con-
valent cation C and a z − -valent anion Az− is referred
z+
stant K D ) process. The overall constant K is given by the
to as a binary z + , z − electrolyte, for example, HCl (1,1), relationship
CdCl2 (2,1), and CdSO4 (2,2). Binary electrolytes contain
only one type of cation and anion, in contrast to ternary K = K I K D /(1 + K I ). (4)
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Electrolyte Solutions, Thermodynamics 221

Solvents of type LH (amphiprotic solvents) such as wa- capacity to interact with other species. Four main groups of
ter, alcohols, and carboxylic acids themselves behave as solvents with typical donor–acceptor properties generally
ionogenes in producing their cations LH+2 (lyonium ions) are distinguished:
and anions L− (lyate ions) by autoprotolysis reactions:
→ LH+ − 1. Protic solvents (e.g., water, alcohols, amides, car-
LH + LH ← 2 +L (5)
boxylic acids)
→ H3 O+ + OH− ). The solution of acids and
(e.g., 2H2 O ← 2. Aprotic solvents (e.g., aprotic amides, nitriles, ke-
bases in amphiprotic solvents in generally followed by tones)
a protolysis reaction as a consequence of the following 3. Low-permittivity electron donor solvents (e.g.,
equilibria: ethers)
4. Inert solvents (e.g., hydrocarbons, chlorinated
→ A− + LH+
AH + LH ← (6)
2 hydrocarbons)
and
Despite such limitations as the overlapping of solvent
→ BH+ + L− ,
B + LH ← (7) classes or possible interactions evading the unambiguous
where LH represents the amphiprotic solvent, AH the acid, classification of a solvent, such classifications are useful
and B the base. When these equilibria are shifted markedly for understanding the properties of electrolyte solutions
toward ionization (e.g., HCl + H2 O ←→ H3 O+ + Cl− ), the and for rationalizing the choice of appropriate solvents
acids or bases are almost completely replaced by the lyate and solvent mixtures for particular investigations.
or lyonium ions of the solvent (leveling effect).

II. THERMODYNAMICS OF ELECTROLYTE

B. Classification of Solvents
SOLUTIONS

Two aspects determine the role of the solvent: its bulk A. Fundamentals
properties and its proton or electron donor or acceptor ca-
Electrolyte solutions commonly are one-phase systems of
pabilities. A solvent S may act by a basic center β (accep-
k components. The internal energy U of such systems
tor: βS), an acidic center α (donor: Sα), or both (βSα).
expressed as a function of its extensive variables S (en-
Solvation of an electrolyte, Y = C+ A− , then occurs ac-
tropy), V (volume), and n i (amount of substance of com-
cording to the scheme
ponent Yi , i = 1, 2, . . . , k) yields the fundamental equa-
→ C+ (βS)m + A− ,
Y + m(βS) ← (8a) tion of thermodynamics,
→ C + (Sα)n A ,
Y + n(Sα) ← + − (8b) 
k
dU = T dS − p d V + µi dn i , (9a)
or i=1

→ C+ (βSα)m + (βSα)n A− .
Y + (m + n)(βSα) ← (8c) and its Legendre transforms,

Stabilization of cations and/or anions by the solvent 

k
dH = T dS + V dp + µi dn i , (9b)
molecules (solvation) is essential for the comprehension of i=1
the properties of electrolyte solutions. The mean number
of solvating particles, n or m in Eqs. (8), depends on the 
k
dA = −S dT − p dV + µi dn i , (9c)
nature of the solvent and solute and is specific for every i=1
solution.
Theoretical and semiphenomenological approaches use 
k
dG = −S dT + V dp + µi dn i , (9d)
the bulk properties or molecular quantities, dipole and
i=1
quadrupole moments, polarizability, and so on, or mean
force potentials in order to take these effects into account. and
Empirical methods take account of them with the help of 
k

empirical scales such as donor numbers, acceptor num- 0 = −S dT + V dp − n i dµi , (9e)

bers, or correlation parameters. i=1

Various attempts have been made in the literature to where T (temperature), p (pressure), and µi (chemical po-
classify solvents according to their acid–base properties, tentials, i = 1, 2, . . . , k) are the intensive variables of the
which can be used as a general chemical measure of their system, which are conjugated to the extensive variables. H
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222 Electrolyte Solutions, Thermodynamics

is the enthalpy, A the Helmholtz energy, and G the Gibbs to rationalize thermodynamic properties for chemical en-
energy. Equation (9e) is the Gibbs-Duhem equation. gineering. Graphs of the Gibbs excess energy and ther-
For use in thermodynamic calculations the chem- modynamic functions derived from it such as the excess
ex ex
ical potential at constant temperature and pressure enthalpy, H = −T 2 (∂( G /T )/∂ T ) p , or excess en-
ex ex
µi = (∂G/∂n i ) p,T,n j =ni , is split into two parts, tropy, S = −(∂ G /∂ T ) p , as a function of mole frac-
  tion x can be used for an easy determination of the partial
µi ( p, T ) = µ− −
i ( p, T ) + RT ln ai /ai ,
 
(10) molar quantities Z i = (∂ Z /∂n i ) p,T,n j=i [Eq. (38)] by the
which relates µi ( p, T ) to the reference potential µ− method of intercepts. The partial molar excess Gibbs en-


i for
which the activity is a−
 ergies are the chemical potentials µiex ( p, T ) of the studied
i .
The commonly chosen reference states for solutions are solution.
the pure solvent µ− ∗
S ( p, T ) = µS and for the solute Y the


−
state of infinite dilution µY ( p, T ) = µ∞


Y ( p, T ). The mole B. Activity Coefficients

fraction xS of the solvent equals unity for both states:
If the solute Y in a binary system is an electrolyte com-
µi ( p, T ) = µ−
i ( p, T ) + RT ln x i f i , posed of a cation Cz+ of valency z + and an anion Az− of


valency z − (i.e., Y = Cν+

z+ z−
Aν− ), the appropriate form of the
i =S or Y, −
 = ∗ or ∞, (11a)
chemical potential of the solute is based on the single-ion
and chemical potentials of its cation and anion and is given by
the relationship
µ−
i ( p, T ) = lim [µi ( p, T ) − RT ln x i ],


xS →1 µY ( p, T ) = ν+ µ+ ( p, T ) + ν− µ− ( p, T ), (15)
lim f i = 1. (11b) where
xS →1

In Eqs. (11) the activites of solvent and solute are defined µ+ ( p, T ) = µ∞

+ ( p, T ) + RT ln x + f + ,
with the help of mole fractions xi and activity coefficients (16a)
x + = ν+ x Y ,
fi :
 and
xi = n i ni (12a)
µ− ( p, T ) = µ∞
− ( p, T ) + RT ln x − f − ,
(16b)
and x − = ν− x Y ,
ai = xi f i . (12b)
are determined in agreement with Eqs. (11). In Eqs. (16)
A solution for which the activity coefficients equal unity the mole fraction xY is not the usual stoichiometric mole
independent of the mole fractions is called an ideal so- fraction [Eq. (12a)] but the mole fraction that takes into
lution; the activity coefficients of a real solution can be account the dissociation of the electrolyte component into
interpreted with the help of the excess chemical potentials ions:
µiex with regard to this ideal solution: nY nS
xY = , xS = ,
n S + νn Y n S + νn Y
µi ( p, T ) − µiid ( p, T ) = µiex ( p, T ) = RT ln f i . (13) (17)
xS + νxY = 1.
The Gibbs-Duhem equation [Eq. (9e)] gives the mutual
Combination of Eqs. (15) and (16) yields the chemical
dependencies of the activity coefficients of a solution at
potential of the electrolyte Y:
constant pressure and temperature. Equation (13) permits
the representation of the mean molar µY ( p, T ) = µ∞
Y ( p, T ) + ν RT ln x ± f ± ,
ex  Gibbs excess energy (18a)
of the solution G = G ex / n i , in the form
ν = ν+ + ν− ,
ex 
k 
k
and
G = xi µiex = RT xi ln f i , (14a)
i=1 i=1 µ∞
Y ( p, T ) = lim [µY ( p, T ) − ν RT ln x ± ],
xS →1
which, in turn, may be combined with the help of com- (18b)
monly used fitting equations, for example, for a binary lim f ± = 1.
xS →1
mixture
The so-called mean mole fraction x± and the mean activity
ex
G = x(1 − x)[A + B(2x − 1) + C(2x − 1)2 + · · ·], coefficient f ± of the electrolyte are defined as follows:
 1/ν  1/ν
(14b) x± = x+ν+ x−ν− , f ± = f +ν+ f −ν− . (18c)
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Electrolyte Solutions, Thermodynamics 223

The choice of concentration scales other than the mole trolyte compounds are components. As a consequence,
fraction scale entails changes in the reference potentials there is no rigorous method for measuring the chemical
and activity coefficients: potential or other thermodynamic properties of a single
ionic species.
Molality scale:
Despite this drawback there is an interest in science
µY ( p, T ) = µ∞(m)
Y ( p, T ) + ν RT ln m ± γ± . (19) and technology in single-ion quantities for rationalizing
the discussion of electrolyte solution properties. Various
Molarity scale:
methods have been developed for their estimation based
µY ( p, T ) = µ∞(c)
Y ( p, T ) + ν RT ln c± γ± . (20) on extrathermodynamic assumptions, such as the follow-
ing: (1) The contributions of cation and anion are set equal
In Eqs. (19) and (20) µ∞(m)
Y and µ∞(c)
Y are the reference for a salt composed of ions of equal charge and approx-
potentials at infinite dilution, m ± and c± are the mean imately equal radii; (2) the results of measurements on a
molality (moles per kilogram of solvent) and the mean series of homologous electrolytes are extrapolated with
molarity (moles per cubic decimeter of solution), and γ± regard to ionic radii or ionic volumes to zero ion size or
and y± are the corresponding activity coefficients in the zero reciprocal radii; (3) the differences in conventional
molality and molarity scales. All quantities are defined ac- ionic properties are used for theoretically rationalized ex-
cording to Eqs. (18c). The transfer from one concentration trapolations; and (4) the properties of ions are compared
scale to another is executed with the help of conversion with those of isoelectronic neutral molecules of similar
formulas: chemical constitution and size.
∞(m)
µ∞
Y ( p, T ) = µY ( p, T ) − ν RT ln MS Besides the chemical potentials of single ions, electro-
∞(c)   chemical potentials are defined in electrochemistry. They
= µY ( p, T ) − ν RT ln 103 MS dS , (21) are useful in electrode kinetics and related topics but are
MS of only limited interest in the discussion of the thermody-
x± = m± namic properties of electrolyte solutions. Electrochemical
1 + MS νm ± /Q
potentials µ̃i ( p, T ) are related to chemical potentials with
103 MS the help of the relationship
= c± , (22)
d + 103 (ν MS − MY )c± /Q
µ̃i ( p, T ) = µi ( p, T ) + F z i , (24)
and
f ± = (1 + MS νm ± /Q)γ± where F is the Faraday number, the Galvani poten-
tial of the liquid phase, and z i the valency of the charged
d + 10 (ν MS − MY )c± /Q
3
= y± , (23) species. They are equal to the corresponding chemical
dS potentials for electrically neutral species, molecules, and
where Q = (ν+ν+ ν−ν− )1/ν ; MS and MY are the molecular neutral electrolyte compounds (z i = 0). Their definition
weights of solvent and solute, respectively; and dS and results from formally
 introducing the electrical charge of
d are the densities of the solvent and the solution, re- the phase, q = n i F z i , as a further extensive variable
spectively. These conversion formulas are valid if SI units into Eq. (9a), which yields an additional term, dq.
are used for all quantities except molar concentration c± ,
which traditionally is given as moles per cubic decimeter.
At a pressure of 1 bar and a temperature of 298.15 K D. Ionic Equilibria
the chemical potentials µ−


i are called chemical standard

potentials. Chemical single-ion potentials are referred to If the electrolyte component is not completely dissociated
the chemical standard potential of the proton in aqueous (α, degree of dissociation), as happens for ionogenic elec-
solutions, which is arbitrarily set to zero, µ∞ trolytes, or if partial association of the ions to ion pairs
H+ (aq)( p =
1 bar, T = 298.15 K) = 0. takes place in the solution, Eq. (15) must be replaced by
the relationship

C. Single-lon Quantities µY ( p, T ) = αν+ µ+ ( p, T ) + αν− µ− ( p, T )

The definition of single-ion chemical potentials [Eqs. (16)] + (1 − α)µx ( p, T ), (25)
and the properties derived from them are nonoperational.
There is no way of adding to the solution ions of only where µ+ , µ− , and µx are, respectively, the chemical po-
one species. That is, the ions in a solution are not com- tentials of “free” cations, “free” anions, and the species X,
ponents according to the Gibbs definition; only the elec- which is the nondissociated ionogene or the ion pair.
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224 Electrolyte Solutions, Thermodynamics

The equilibrium between species X and “free” cations to the related osmotic coeffcients, used as molal osmotic
→ X, yields the equilibrium
and anions, ν+ Cz+ + ν− Az− ← coefficient and the rational osmotic coefficient g:
condition
= −(ln aS )/νm MS (31a)
µx ( p, T ) − ν+ µ+ ( p, T ) − ν− µ− ( p, T ) = 0. (26) and
Combining Eqs. (25) and (26) and taking into account the g = (ln aS )/(ln xS ). (31b)
definitions of c± and µ ∞(c) , c± = αc± and µY∞(c) = µ∞(c)
Y , The Gibbs-Duhem equation [Eqs. (14)], when combined
leads to the chemical potential of the electrolyte Y in the with Eqs. (11a) and (19), yields the relationship
form 1
d(ln aS ) + νm d(ln mγ± ) = 0, (32)
µY ( p, T ) = µ∞(c)
Y ( p, T ) + ν RT ln αc± y± , (27) MS
which can be easily transformed with the help of Eq. (31a)
which is identical to Eq. (20) if we set to yield the basic equation for calculating solute activity
y± = αy± . (28) coefficients from solvent activities and vice versa:
d(m ) = dm + m d(ln γ± ). (33)
The importance of Eq. (28) is that both degree of disso-
ciation and activity coefficient of the “free” ions are parts Either or ln γ± is obtained by integration of Eq. (33) to
of the excess Gibbs energy. yield
m
The equilibrium condition [Eq. (26)] yields the 1
=1+ m d(ln γ± ) (34a)
relationship m 0
or
µ∞(c)
x ( p, T ) − ν+ µ∞(c) ∞(c)
+ ( p, T ) − ν− µ− ( p, T ) m
1−
c y ln γ± = ( − 1) − dm. (34b)
= −RT ln x x ν . (29) 0 m
(c± y± )
The peculiar behavior of electrolyte solutions that follow
The left-hand side of Eq. (29) is the molar Gibbs energy a limiting law of type 1 − ∝ Am 1/2 entailing divergency
G∞A of formation of the species X from the initially of the integrand in Eq. (34b) is taken into account by trans-
infinitely separated ions; the right-hand side shows the forming this equation into the relationship
equilibrium constant as the association (K A(c) ) or dissocia- m
1−
tion (K D(c) ) constant [the superscript (c) indicates the mo- ln γ± = ( − 1) − 2 dm 1/2 . (35)
0 m 1/2
lar concentration scale], which for symmetric electrolytes
(ν+ = ν− = 1) takes the form Equations (34) are valid for both completely and incom-
pletely dissociated electrolytes except that for incom-
 −1 1 − α yx pletely dissociated electrolytes γ± is replaced by αγ± ,
K A(c) = K D(c) = 2 . (30)
α c y±2 the degree of dissociation being related to the association
constant in the molal scale (dilute solution, γx = 1):
The quantity yx is the acitivity coefficient of the species
X; the other symbols are explained in the foregoing text. 1−α 1
K A(m) = = K A(c) dS . (36)
In dilute solutions yx equals unity. α 2 m γ±2
Incomplete dissociation and partial association of sym-
metric electrolytes are given here as simple but important F. Partial and Apparent Molar Quantities
examples of ionic equilibria in solution. Other equilibria,
such as those resulting from the formation of solvent- All extensive thermodynamic properties Z (volume, en-
separated and contact ion pairs, triple-ion formation, mul- thalpy, entropy, Gibbs energy, heat capacity) when defined
tistep equilibria of unsymmetric electrolytes, or simulta- as functions of the set of the variables p, T , and n i ,
neous complex ion formation, in the investigated solution Z = Z ( p, T, n i ), i = 1, . . . , k, (37)
can be treated in a similar way. They require in Eq. (25)
the consideration of all identified species in the solution. yield the partial molar (or molal) quantities
∂Z
Zi = (38)
∂n i p,T,n j=i
E. Solvent Activity and Osmotic Coefficient
and
In dilute solutions (xS ∼ = 1) both the activity and the ac-

k
tivity coefficient of the solvent differ only very little from Z= ni Z i , (39)
unity with varying electrolyte concentration, in contrast i=1
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Electrolyte Solutions, Thermodynamics 225

which are the contributions per mole of each component

Yi to property Z of the multicomponent system at con-
stant temperature and pressure. For a pure phase (one-
component system) the molar quantity Z i is denoted by
the symbol Z i∗ .
The solution process of n Y mol of electrolyte Y in n S
mol of solvent S is accompanied by a change in property Z :
 ∗ ∗

sol Z = (n S Z S + n Y Z Y ) − n S Z S + n Y Z Y
   
= n S Z S − Z S∗ + n Y Z Y − Z Y∗ . (40)
Another useful formulation of the extensive property Z is
based on the definition of apparent molar quantities Z
of the solute, which yields
Z = n S Z S∗ + n Y Z. (41)
According to Eq. (38) the partial derivative of Z [Eq. (41)] FIGURE 1 Operations on electrolyte solutions and their appropri-
ate translation into thermodynamic quantities: Z = Zfin − Zinit .
leads to the partial molar quantities Z S and Z Y of the
Abbreviations: lat, lattice; solv, solvation; sol, solution; dil, dilu-
solvent S and the electrolyte Y, tion; tr, transfer from solvent S to solvent S. Z = V (volume),
∂ Z S (entropy), C p (heat capacity), H (enthalpy), G (Gibbs en-
Z S = Z S∗ + n Y (42a) ergy). [Reprinted with permission from Barthel, J., Gores, H.-J.,
∂n S p,T,n Y Schmeer, G., and Wachter, R. (1983). Non-Aqueous Solutions in
Chemistry. In “Topics in Current Chemistry” (F. L. Boschke, ed.),
and Vol. 111, pp. 33–144, Fig. 1. Springer-Verlag, Berlin. Copyright
∂ Z Springer-Verlag 1983.]
ZY = Z + nY , (42b)
∂n Y p,T,n S

which relate the partial molar quantities Z S and Z Y to

the apparent molar quantity Z . When the molal scale infinite dilution in the solvent S. The term Z − ∞ Z is
is used for determining Z as a function of molality, often called the relative apparent molar quantity rel
Z .
Eqs. (42) are converted to the relationships Figure 1 summarizes the operations and notations used
in solution and dilution processes.
MS m 3/2 ∂ Z
Z S = Z S∗ − (43a) Applying the foregoing formalism to the Gibbs energy
2 ∂m 1/2 leads to the standard Gibbs energy of solution, sol G ∞
p,T Y,
and which is the energy difference between the pure electrolyte
m 1/2 ∂ Z component Y and the reference state at infinite dilution:
ZY = Z + . (43b)
2 ∂m 1/2 ∞
= µ∞ ∗
p,T sol G Y ( p, T ) Y ( p, T ) − µY ( p, T ). (46a)
The advantage of using apparent molar quantities is the According to the rules of thermodynamics, differentiation
direct accessibility of Z from experimental results, of sol G ∞
∗ Y yields the molar solution properties
Z = (Z − n S Z S )/n Y [Eq. (41)].
 
At the limit of infinite dilution, Eqs. (42) and (43) yield ∞ ∂ sol G ∞ Y
sol SY = − , (46b)
Z Y∞ = lim Z Y = lim = ∞ ∂T
Z Z . (44) p,n i
n Y →0 n Y →0
 ∞

Hence, the balance of an extensive property, sol Z , in a ∞ ∂ sol G Y
sol VY = , (46c)
solution process can be expressed by the relationship ∂p
T,n i
sol Z ∞
 ∞
  
= + − ∞
2 ∂
sol Z Y Z Z (45a) sol G Y T
∞
sol HY = −T , (46d)
nY
∂T
where p,n i

∞
= Z Y∞ − Z Y∗ . and
sol Z Y (45b)  
∞
∞ ∞ ∂ sol HY
The molar quantity sol Z Y
corresponds to the transfer sol C pY = . (46e)
of 1 mol of electrolyte compound from its pure state to ∂T
p,n i
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226 Electrolyte Solutions, Thermodynamics

Gibbs energies of solution, sol G ∞

Y , are obtained from are often unreliable. Many problems, however, can be re-
solubility or electromotive force (emf) measurements, duced to the comparison of solvation in different solvents
∞ ∞
sol HY from calorimetric measurements, and sol VY based on the transfer quantities tr Z Y∞ , which are easily
from density determinations. The other quantities are ob- obtained from solution properties sol Z Y∞ (see Fig. 1).
tained through the temperature dependence according to Gibbs energy of transfer tr G Y is the change in Gibbs
Eqs. (46b) and (46e). energy when the electrolyte component Y is transported
from solvent S solvent S. If we choose water as the ref-
G. Temperature and Pressure Dependence erence solvent S , the Gibbs energy of transfer at infinite
of Activity Coefficients dilution defines the so-called medium activity coefficients
Using Eq. (11a), we can write the activity coefficient of a m γY:
component Yi as ∞ ∞ ∞
   tr G Y = sol G Y (S) − = RT ln m γY .
sol G Y (W)
ln f i = µi − µ− RT − ln xi .


i (47) (51)
Since the mole fraction xi is independent of temperature Then the Gibbs energy of transfer can be written at any
and pressure, the derivatives of Eq. (47) yield concentration:
∂(ln f i ) Hi − Hi−
  (S) (W) 
=− (48a) tr G Y = RT ln m γY + RT ln aY aY . (52)
∂T p,n j RT 2
At distribution equilibrium of Y between the two solvents,
and (S) (W)
tr G Y = 0, the distribution coefficient aY /aY yields the
∂(ln f i ) Vi − Vi−

transfer activity coefficient.
= . (48b)
∂p T,n j RT Separation into ionic medium activity coefficients is
executed with the help of the equation
Quantities of type Z i − Z−


i are referred to as relative partial

molar quantities. (m γY )ν = (m γ+ )ν+ (m γ− )ν− . (53)
Conversion of the mole fraction scale to the molality Transfer activity coefficients are used in the field of ex-
scale does not change Eqs. (48), whereas the use of the traction processes, ionic equilibria and emf measurements,
molarity scale requires that the temperature and pressure and analytical application. For example, the pH scale is
dependence of molarity be taken into account: transferred from water to other solvents with the help of
∂(ln c) transfer proton activity coefficients m γH+ :
= −α (49a)
∂T p,n j
pH(S) = pH(W) + log m γH+ . (54)
and
∂(ln c)
= β. (49b) I. Ion Solvation
∂p T,n j
Ion solvation is the transfer of ions from a vacuum to an
Here α and β are the thermal expansivity coeffi- infinitely dilute solution in a solvent S. In order for us
cient and the compressibility coefficient of the solution, to represent solvation by models, the ion–solvent inter-
respectively: actions are split into electrostatic, nonelectrostatic, and
1 ∂V chemical contributions.
α= (50a) Dielectric continuum models such as the Born model
V ∂T p,n j
consider the solvent to be a structureless continuum of
and relative permittivity ε. The Gibbs energy of solvation of
1 ∂V an ion, solv G i∞ , is calculated by the difference of the
β=− . (50b)
V ∂p T,n j
charging process in a vacuum (ε = 1) and in the solvent
(ε):

0
H. Thermodynamic Quantities of Transfer ∞ NA (z i e0 )2 1 1
solv G i = λ dλ + λ dλ
Thermodynamic quantities for the solvation process 4π ε0 ai 1 ε 0
∞
solv Z Y are formally obtained from the solution and lat- NA (z i e0 )2 1
tice quantities according to Fig. 1. However, lattice data =− 1− . (55)
8π ε0 ai ε
are lacking for many compounds. Furthermore, the trans-
fer of electrolyte from the gas phase to solution involves The integration is carried out with regard to a charging pa-
a rather complicated measurement, and the resulting data rameter λ, assuming that the ionic radii ai in the vacuum
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Electrolyte Solutions, Thermodynamics 227

and in the solution are equal and the transfer of the un- for the molecule and the ion. The reference electrolyte
charged ion does not affect the Gibbs energy of solvation. method proposes the partition of the measured electrolyte
For an electrolyte component Y, the overall energy is solvation into equal parts for the ions of the electrolyte;
found by summing over the ionic contributions: that is, the electrostatic and nonelectrostatic contributions
∞ ∞ ∞ of cations and anions are assumed to be equal. Also, un-
solv G Y = ν+ solv G + + ν− solv G − . (56) equal partition of solvation quantities between the Ph4 As+
The Born model is only a rough approximation. Im- cation and the BPh− 4 anion is used in the literature.
provements of the method take into account a local per-
mittivity ε∗ and effective ionic radii ai(eff) = ai + δi , where
δi is the distance between an ion and an adjacent solvent III. STATISTICAL APPROACHES
dipole. More elaborate models include in the calculation
the energy of formation of a spherical cavity in the pure A. Hamiltonian Models
solvent into which an ion and its solvation shells can be
Establishing the relationships between the macroscopic
transferred from the vacuum. Further interactions that can
properties of an electrolyte solution and the properties
be taken into account result from ion–quadrupole, ion-
of its particles, ions, and solvent molecules is the task
induced dipole, dipole–dipole, dispersion, and repulsion
of statistical mechanics. Efficient statistical mechanical
forces. For nonaqueous electrolyte solutions most of the
models are based on the Hamiltonian H , which expresses
molecular and structural data needed for this calculation
the total energy of the N -particle system as a function of
of the solvation energy are unknown, and ab initio calcu-
the momenta pi and coordinates ri of the particles:
lations have not so far been very successful. Actual infor-
mation on ion solvation in nonaqueous solutions is based H (r1 · · · r N , p1 · · · p N )
almost exclusively on semiempirical methods and/or the
N
pi2 N  N
extrathermodynamic assumptions quoted in Section II.C. = + u i j (ri , r j ). (58)
Extrapolation methods are based on the representation i=1
2m i=1 j≥i
of the electrostatic ion–solvent interactions as a series ex-
pansion of type b j (ai )− j , where ai is one of the ionic radii. In Eq. (58) limitation is made to models omitting molec-
For example, in a series of electrolytes with a common ular orientation. The first term on the right-hand side of
cation and differing anions, the relationship the equation represents the kinetic energy, and the second
term the potential energy U N (r1 · · · r N ), approximated by
∞ ∞ ∞
solv Z Y = solv Z + + solv Z − a sum of pairwise direct interaction potentials u i j (ri , r j ).

n Hamiltonian models are classified according to their
∞
= solv Z + + b j (a− )− j level of approximation. The features of Schroedinger (S),
j=1 Born-Oppenheimer (BO), and McMillan-Mayer (MM)
∞ level Hamiltonian models are exemplified in Table I by
+ solv Z − (neutral) (57)
a solution of NaCl in H2 O. The majority of investigations
is used for determining single-cation solvation quanti- on electrolyte solutions are carried out at the MM level.
ties from the measured solv Z Y∞ values. The extrapola- BO-Level calculations are a precious tool for Monte Carlo
tion of a− toward infinite values, a− → ∞, yields the and molecular dynamics simulations as well as for integral
∞ equation approaches. However, their importance is widely
quantity solv Z + because the electrostatic contribution
vanishes for the anion. The nonelectrostatic contribution limited to structural investigations. They, as well as the
∞ S-level models, have not yet obtained importance in elec-
solv Z − (neutral) is usually estimated from neutral ref-
erence molecules that are similar in size and chemical trochemical engineering. S-Level quantum-mechanical
constitution. calculations mainly follow the Car-Parinello ab initio
Other extrathermodynamic assumption methods are molecular dynamics method.
based on reference systems, such as large ion couples
and their corresponding uncharged molecules (e.g., fer-
B. Distribution Functions and
rocinium/ferrocene) or systems of large cations and an-
Mean Force Potential
ions of similar structure [e.g., (Ph4 As)+ /(BPh4 )− or
(iAm3 BuN)+ /(BPh4 )− ]. The reference ion–molecule Statistical mechanics when based on Liouville’s theorem
method assumes that the ion–molecule pair shows equal yields a hierarchy of equations (BBGKY hierarchy) that
solvation in the investigated solvent; that is, the electro- makes use of the s-particle distribution function ρ (s) giving
static contribution of the ionic species is neglected, and the the probability of finding s particles, i = 1 . . . s, out of the
nonelectrostatic contribution is considered to be the same N particles in the system in the positions r1 · · · rs and
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228 Electrolyte Solutions, Thermodynamics

TABLE I Hamiltonian Models of Electrolyte Solutions

Level Variables in the Hamiltonian Mechanics Methoda

Schroedinger (S) Coordinates and momenta of all the nuclei Quantum Approximating the wave function
and electrons of all the H, O, Na, and Cl atoms
Born-Oppenheimer (BO) Coordinates and momenta of the water Classical Simulation: MD, MC; perturbation:
molecules and the Na and Cl ions PY, HNC
McMillan-Mayer (MM) Coordinates of the Na and Cl ions only Classical MD, MC, MSA, PY, HNC, ChM
a Abbreviations: HNC, hypernetted chain equation; MC, Monte Carlo simulation; MD, molecular dynamics simulation; MSA, mean spherical

approximation; PY, Percus-Yevick equation; ChM, chemical model.

with momenta p1 · · · ps , regardless of the position and The one-particle distribution function is independent of
momentum coordinates of the remaining particles: particle position and equals the number of particles per
unit of volume (particle density):
ρ (s) (r1 · · · rs , p1 · · · ps , t)
f (1) (ri ) = ρi = Ni /V. (64)
=σ (s)
ρ(r, p, t) drs+1 · · · dr N dps+1 · · · dp N . (59)
The expression for gi j (r ) is easily obtained from Eqs. (61)
In Eq. (59) the coefficient σ takes into account whether
(s) and (63). The equilibrium distribution around a spherically
identical or different particles are observed. ρ(r, p, t) is symmetric ion depends only on the distance r between
the density function of the N -particle system in a 6N - particles i and j, r = |ri j | = |r j − ri |:
dimensional space, the so-called  space. The symbol r 
stands for r1 · · · r N , and an analogous definition holds 2  exp(−U N /kT ) dr3 · · · dr N
gi j (r ) = V . (65)
for p. The density function ρ(r, p, t) tends toward a time- exp(−U N /kT ) dr1 · · · dr N
independent equilibrium distribution, Values of gi j (r ) greater than 1 indicate attraction, and less
exp[−H (r, p)/kT ] than 1 repulsion, between a pair of particles. The particles,
ρ (eq) (r, p) =   , (60) when represented as hard spheres of mutual minimum
exp[−H (r, p)/kT ] dr dp
distance a = ai j , require the boundary condition
where H (r, p) is the Hamiltonian of Eq. (58), k the
Boltzmann constant, and T the temperature. lim gi j (r ) = 0, lim gi j (r ) = 1. (66)
r →a r →∞
It can be shown with the help of the BBGKY hierarchy
of equations that a knowledge of the ρ (1) and ρ (2) functions, A related function of fundamental interest is the potential
together with the pertinent principle of superimposition, of mean (or average) force, which is defined such that its
is sufficient to produce ρ (3) functions and so on. derivative is the force on the selected particle i averaged
Molecular distribution functions f (s) (r1 · · · rs ) at equi- over the position coordinates of all the remaining particles
librium, indicating the probability of finding s particles in the system except those of particle j:
in positions r1 , r2 , . . . , rs , are obtained by integrating the
∂ Wi j
functions ρ (s) themselves with respect to the momentum = K i j (r )
coordinates p1 , p2 , . . . , ps : ∂r

(∂U N /∂r ) exp(−U N /kT ) dr3 · · · dr N
σ (s) UN =  . (67)
f (s) (r1 · · · rs ) = exp − drs+1 · · · dr N exp(−U N /kT ) dr3 · · · dr N
Q (N ) kT
(61) Comparison of Eqs. (65) and (67) yields the link between
and functions gi j (r ) and Wi j (r ),
UN Wi j (r ) = −kT ln gi j (r ), (68)
Q (N ) = exp − dr. (62)
kT
defining the potential of mean force, which is different
The distribution function of interest is the pair correlation from the interaction potential u i j (r ) [Eq. (58)] as a conse-
function gi j (ri , r j ), which is defined by the relationship quence of the averaging procedure by Eq. (67).
The pair correlation functions gi j (r ) can be experi-
f (2) (ri , r j ) mentally determined. They are obtained by using scat-
gi j (ri , r j ) = . (63)
f (1) (ri ) f (1) (r j ) tering techniques such as X-ray or neutron scattering.
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Electrolyte Solutions, Thermodynamics 229

Wide-angle neutron scattering yields them at the BO-level, the MM system are then (ρ, T, P0 ) and the solution is un-
whereas small-angle neutron scattering usually cannot de- der pressure P =  + P0 . The osmotic coefficient in the
tect the structure of the solvent and therefore may be re- MM system is found to be
garded as the experimental analogue of the theoretical MM
= /ρkT. (71)
approach. The vanishing scattering angle in a so-called
contrast experiment is even directly related to the osmotic Thermodynamic functions, however, are defined with the
coefficient. help of the independent variables (m, T, P1 ), where P1
There are two usual routes for determining the thermo- is generally the standard pressure of 1 atm. Hence it is
dynamic properties of the N -particle system in equilib- necessary to convert experimental data to the MM sys-
rium from its pair correlation function gi j (r ): tem when comparison is needed for model calculations at
this level. For dilute solutions the resulting corrections are
1. The pressure or virial equation: negligible.
P  ∂u i j (r ) At the MM level any plausible model for the ion–ion
=1− ρi ρ j 4πr 3 gi j (r ) dr. (69) interactions can be described by the direct potential u i j ,
ρkT i j
∂r
which can be interpreted as the potential of mean force at
2. The energy equation: infinite dilution:
E 3 1  u i j (r ) = u i∗j (r ) + z i z j e02 4π ε0 εr. (72)
= ρkT + ρi ρ j 4πr 2
V 2 2 i j In Eq. (72) the second term on the right-hand side is a
  coulombic potential, ε0 is the permittivity of vacuum, z i e0
∂u i j (r )
× u i j (r ) − gi j (r ) dr, (70) and z j e0 are the charges on ions i and j, and ε is the rela-
∂(ln T ) tive permittivity of pure solvent. The first term, u i∗j (r ), is

where ρ = ρi , P is the pressure, E the internal energy, the short-range noncoulombic part of the direct potential,
V the volume, and the sum is over all particles of interest including repulsion, dispersion, or induction forces.
in the system. In analogy to Eq. (72) the mean force potential, related
to the pair correlation function at finite concentration by
Another, less frequently used relationship, the so-called Eq. (68), can be split into two parts,
compressibility equation, is an alternative to the pressure
Wi j (r ) = Wi∗j (r ) + Wielj (r ), (73)
equation, but the virial equation is more convenient to use.
where Wielj (r ) and Wi∗j (r ) are again the contributions due to
coulombic and noncoulombic interactions, respectively.
C. McMillan-Mayer Solution Theory
The evaluation of the pair correlation functions of both
the solvent molecules and the solutes is feasible but trou- D. The Chemical Model
blesome. For electrolyte solutions, however, averaging 1. Fundamentals
over the solvent effects yields reliable approximations, as
shown by McMillan and Mayer, who considered the solu- The chemical model is an MM-level Hamiltonian model
tion in osmotic equilibrium with the pure solvent (Fig. 2). taking into account both long- and short-range forces. It
They stressed that solutes can be treated as an imperfect has been used for investigating and calculating the prop-
gas, provided that one uses the potential of mean force erties of dilute electrolyte solutions of numerous salts in
at infinite dilution. The calculation yields the osmotic a great variety of solvents and has proved to be successful
pressure  = P − P0 (see Fig. 2) from the virial equa- insomuch as all of the properties of an electrolyte solu-
tion [Eq. (69)] in terms of the forces among the particles tion investigated can be understood from the same set of
for the solution state (ρ, T ). The independent variables of interaction parameters.
The chemical model subdivides the space around an ion
into three main regions (Fig. 3):

1. r ≤ a, where a is the minimum distance of two op-

positely charged ions, which is assumed to be the sum of
effective cation and anion radii, a = a+ + a− .
2. a ≤ r ≤ R, the region of short-range interactions. For
FIGURE 2 Osmotic equilibrium of a solution and its pure solvent; dilute solutions this region is occupied almost exclusively
the separation M is permeable only to the solvent molecules. by paired states of oppositely charged ions.
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230 Electrolyte Solutions, Thermodynamics

pair correlation functions by means of structure factors—

is an integral of the type
∞
r 2 [gi j (r ) − 1] dr
0
R
= r 2 [gi j (r ) − 1] dr
a
∞
+ r 2 [gi j (r ) − 1] dr. (75)
R

2. Ion-Pair Concept
Solution chemists usually think of short-range interactions
in terms of ion-pair formation. Models of the electrolyte
solution allow the introduction of the ion-pair concept if
a critical distance around the central ion can be defined
within which the paired states of oppositely charged ions
are considered ion pairs.
The ion-pair concept for symmetric electrolytes can be
FIGURE 3 Chemical model of electrolyte solutions. O, Observer:
i , ion Xi ; j , ion X j in an arbitrary position r21 with regard to the ion easily introduced into the chemical model, assuming that
Xi ; special positions (contact, separation by one or two oriented the cutoff distance parameter R of the short-range forces
solvent molecules) are sketched with dashed lines; r, a, R, dis- equals the upper limit of ion association. The relationship
tance parameters; Wi j , mean force potentials; v j i and vi j relative (see Table II)
velocities of ions Xi and X j .
(I) 2κqκ T 2κqκ T ∗
W+− (r ) = − + + W+− ;
r 1 + κR
3. r ≥ R, the region of long-range interactions.
e02 |z + z − |
Region 1 is controlled by a hard-sphere potential. The po- q= (76)
8π ε0 εκ T
tentials of mean force of regions 2 and 3, Wi(I) (II)
j and Wi j ,
yields the integral (a . . . R) of Eq. (75) in the form
are split into two parts according to Eq. (73). The elec- 
trostatic parts Wielj are obtained as solutions of Poisson- R (I)  
W i j 2κq
Boltzmann differential equations and appropriate bound- r exp −
2
dr = exp −
a kT 1 + κR
ary conditions; the nonelectrostatic parts can be chosen
as step potentials, that is, Wi∗(I) ∗(II) 
j = const, Wi j = 0. The R
W ∗
2q +−
total mean force potentials are compiled in Table II. The × r 2 exp − dr. (77)
parameter κ is the reciprocal Debye length as defined by a r κT
the relationship At low electrolyte concentrations the activity coefficient of
e02  2 ion pairs may be set equal to unity and Eq. (77) is linked to
κ2 = ρi z i . (74)
ε0 εkT the ion-pair association constant K A and the mean activity
coefficient y± of the free ions by the relationships
The link between the pair correlation function gi j and the
experimentally determined property of the solution—with 1−α 1
= K A = 4000π NA
the exception of scattering experiments, which yield the α 2 c y±2

R ∗
2q W+−
TABLE II Mean Force Potential for the Chemical × 2
r exp − dr (78a)
Model a r kT
Region Mean force potential and
r ≤a ∞ κq
y± = exp − . (78b)
e02 z i z j e02 z i z jκ 1 + κR
a≤r ≤ R − + Wi∗j
4π ε0 εr 4π ε0 ε 1 + κ R
The distance parameter R can either be determined by
e02 z i z j 1 exp[κ(R − r )] experiment or set by chemical evidence; α is the degree
r≥R
4π ε0 ε r 1 + κR
of dissociation.
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Electrolyte Solutions, Thermodynamics 231

The chemical association concept is based on the equi- association constant and its appropriate activity coefficient
∗
librium between “free” ions and ion pairs in the solution are obtained by setting R = q and W+− = 0 in Eq. (78a).
(see Section II.D).
Equation (78a) can also be derived as an equilibrium
3. Debye-Hückel Theory and Extensions
constant in the framework of the statistical mechanical
equilibrium theory based on the molecular partition func- A multitude of MM-level models can be found in the lit-
tions Q + , Q − , and Q P of cations, anions, and ion pairs, erature differing from one another by the underlying as-
QP − E0 sumptions of short-range interactions. The oldest one is
K A = NA V exp (79a) the Debye-Hückel theory, which does not recognize short-
Q+ Q− κT range interactions and association. The Debye-Hückel the-
and ory yields the limiting laws of thermodynamic and trans-
(2π m i kT )3/2 port properties based on the potential of mean force,
Q i = Q itrans Q iint ; Q itrans = V, (79b)
h3
e02 z i z j exp(−κr )
when the cations and anions are represented as charged Wi j (r ) = ; 0 < r < ∞, (80)
hard spheres of masses m + and m − without internal 4π ε0 ε r
degrees-of-freedom Q int + = Q − = 1, and the internal
int which can be deduced from the data in Table II by assum-
molecular partition function of the ion pair is made up by ing a = R = 0 and Wi∗j = 0.
integration over all configurations a ≤ r ≤ R of the paired By adding pairwise short-range interactions β+− be-
states of a cation and an anion with variable distance pa- tween cation and anion, Guggenheim obtained an activity
∗
rameter r . E 0 = 2q/r − W+− /kT is the corresponding coefficient which for 1,1 electrolytes is given by the rela-
distance-depending activation energy per molecule of the tionship (dS : solvent density)
reaction of ion-pair formation. The internal partition func- √
Aγ m
tion thereby is based on an internal degree of translation ln γ± = − √ + 2β+− m;
of a particle of reduced mass m̃ = m + m − /(m + + m − ) rep- 1+ m
3/2
resenting the ion pair P(r ). e02
Figure 4 shows the family tree of some theories which Aγ = (2π NA dS ) 1/2
. (81a,b)
4π ε0 εkT
assume association. For example, the often-used Bjerrum

FIGURE 4 Family tree of association constants of the chemical model. For explanations see the text.
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232 Electrolyte Solutions, Thermodynamics

It may be used in aqueous solutions up to molalities of ticle. This feature is reflected by the Ornstein-Zernicke
0.1 mol/kg. equation:
Among a variety of extensions of the Guggenheim equa-
h i j (r ) = gi j (r ) − 1
tion, those of Pitzer are the most successful ones. For a
single electrolyte in solution they read  ∞
= ci j (r ) + ρs cis (r )h s j (r ) drs . (84)
ln γ± = f (γ ) + m B (γ ) + m 2 C (γ ) , (82a) s 0

When used in connection with integral equations, it is

√ considered the definition for the direct correlation function
Aγ I 1 ci j . It can be shown by cluster expansion that the direct
f (γ )
=− √ ; I = m i z i2 , (82b,c)
3 1+b I 2 i correlation function has the following closed analytical
expression:

B (γ ) = 2β (0) + ξ (1) + ξ (2) , (82d) u i j (r )

ci j (r ) = − + gi j (r ) − 1
kT
and
  − ln gi j (r ) + Bi j (r ). (85)
2β (i) √ √ αi2 I
ξ (i) = 1 − exp(−αi I ) 1 + αi I− . In Eq. (85), Bi j (r ) is the sum of the so-called bridge graphs.
αi2 I 2 The diagrammatic representations and the interrelations
of the correlation functions can be found in textbooks on
(82e) liquid-state chemical physics.
The parameters αi , b, β (0) , β (1) , β (2) , and C (γ ) must be fit- The integral equations themselves are obtained by in-
ted to experimental data. It turns out that αi and b are com- serting various approximations to the direct correlation
mon parameters for large classes of electrolyte solutions. function ci j (r ) into the Ornstein-Zernicke equation. It is
The short-range forces are introduced by Guggenheim’s common practice to omit the bridge graphs Bi j in these
concept. The term ξ (2) is relevant only at significant ion approximations.
association. It is possible to correlate its numerical val- Once the integral equation is solved together with the
ues with association constants stemming from calculations Ornstein-Zernicke equation for a given potential u i j (r ),
similar to those of the chemical model. equations of, the type of Eqs. (69) and (70) may be used to
Pitzer’s equations can be used for mixtures of elec- obtain thermodynamic properties from the resulting gi j (r )
trolyes. Thermodynamic functions are obtained in the functions. At the MM-level, Eq. (69) yields the osmotic
usual way as the derivatives of the chemical potential pressure  instead of the total pressure p of the solution.
with respect to temperature or pressure. However, a con-
siderable number of empirically adjusted parameters is 2. Mean Spherical Approximation
needed to obtain satisfactory data description. The Pitzer
approach is used as a self-standing data-reduction method, The lowest level of the integral equation approach treats
but it is also embedded by engineers in the so-called NRTL the ions as charged hard spheres embedded in a dielectric
(nonrandom two liquid) electrolyte models. continuum. It fulfills the conditions
ci j (r ) = −z i z j e02 4π ε0 εkT for r > ai j (86a)
E. Integral Equation Methods and
1. Direct Correlation Function h i j (r ) = 1 for r ≤ ai j . (86b)
A quite different approach to thermodynamics of ionic Equation (86a) means that all short-range potential con-
solutions consists of solving the integral equations that tributions u i∗j are neglected beyond the contact distance of
relate the correlation functions and the pair potentials. ion i and ion j, ai j [u i∗j (r ) = 0 for r > ai j ; c.f. Eq. (72)], and
For this purpose two new correlation functions are in- that in Eq. (85) only the first term on the right-hand side
troduced: the total and the direct correlation functions. The is considered at larger distances. Equation (86b) means
total correlation function h i j (r ) is simply defined by the that the ions are hard spheres with infinitely large repul-
relationship sion potential up to contact distance ai j [u i∗j (r ) = ∞ for
r ≤ ai j ].
h i j (r ) = gi j (r ) − 1. (83)
These conditions together with the Ornstein-Zernicke
It is made up of two contributions: the direct correlation equation allow the calculation of ci j (r ) at short distances
ci j (r ) and the correlations transmitted through a third par- and gi j (r ) at long distances. This approximation is called
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Electrolyte Solutions, Thermodynamics 233

mean spherical approximation (MSA). Because of its sim-

plicity, obtaining analytical expressions for osmotic and
activity coefficients is possible. For the restricted primi-
tive model, which simply considers cations and anions as
charged hard spheres of equal diameter a, these expres-
sions are
1 + η + η2 − η3 3
= − (87)
(1 − η)3 3πρ
and
(1 + 2η)2 2q
ln γ± = ln − . (88)
(1 − η)4 1 + a
In each of these equations the first term on the right-hand
side is the Carnahan-Starling expression for the interaction
of the uncharged hard spheres, where
π
η = ρa 3 . (89)
6
It is superimposed to the electrostatic MSA contribution
given by the second term, where q is given by Eq. (76). The
key function  is the electrostatic screening parameter
1 √
2 = [ 1 + 2κa − 1], (90)
a
FIGURE 5 Comparison of experimental (points) and calculated
where κ is the reciprocal Debye length [Eq. (74)]. MSA (lines) osmotic ( ) and activity (y± ) coefficients of NaI in (a)
can be considered as an extension of the Debye-Hückel methanol and (b) acetonitrile at 25◦ C. The experimental data stem
theory that correctly takes into account ion sizes. It yields from vapor pressure measurements. MSA calculations are exe-
cuted with one-parameter fits.
satisfactory results for solutions of small to moderate ion
densities and low coupling strength commonly expressed
with the Bjerrum parameter, b = 2q/a, which is the ratio
can be obtained. Because it considers only charged hard
of the coulombic potential to the thermal energy of two
spheres at the MM level, the temperature dependence of
charged hard spheres at contact distance a. The coupling
u i j (r ) at short distances is not correctly taken into ac-
strength is low at low ion charges or high ion concentra-
count, so that the internal excess energy is only poorly
tions, high temperature, or high solvent permittivity. In a
reproduced.
more developed form for unequal ionic diameters and ar-
bitrary charges, MSA yields analytical expressions even
for mixtures. 3. Hypernetted Chain and Percus-Yevick
Figure 5 shows the efficiency of MSA for describing Approximations
experimental data up to molar concentrations even in sol-
From a theoretical point of view the hypernetted chain
vents of moderate permittivity by the use of only one ad-
(HNC) and Percus-Yevick (PY) equations are better ap-
justed parameter.
proximations. Although both can be solved only by numer-
A combination of the hard-sphere MSA concept and the
ical methods, they offer the opportunity to study any model
chemical model (Section III.D) concept permits correct
potential if appropriate computer facilities are available.
data reproduction over large concentration ranges, which
The HNC approximation consists of setting Bi j (r ) equal
makes this type of MSA a good candidate for the data re-
to 0 in Eq. (85):
duction in practical problems treated by engineers. It may
be expected that in the near future MSA can replace more u i j (r )
ciHNC
j (r ) = − + gi j (r ) − 1 − ln gi j (r ). (91)
and more the semiempirical methods commonly installed kT
in process simulators. The PY equation can be obtained from Eq. (85) by drop-
Despite its progress, MSA has some deficiencies. It ping Bi j (r ) and linearizing the logarithmic function:
sometimes yields unrealistic correlation functions for  
equally charged particles, and it seems doubtful whether, u i j (r )
ciPY
j (r ) = gij (r ) 1− exp . (92)
beyond its practical importance, structural information kT
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234 Electrolyte Solutions, Thermodynamics

When applied to the primitive model of electrolyte solu-

tions (i.e., charged hard spheres of arbitrary diameters in a
dielectric continuum), the HNC equation is superior to the
PY equation because it preserves the correct long-range
behavior. On the other hand, in fluids with only short-
range forces the PY equation can be successfully applied
because some of the omitted terms cancel one another.
A widely used, more refined potential was introduced
by Friedman, who split the short-range part into three con-
tributions:
u i∗j (r ) = CORi j (r ) + CAVi j (r ) + GURi j (r ). (93)
FIGURE 6 Ion-pair correlation functions gi j (r ) obtained from
1. The repulsive term CORi j (r ) is deduced from crystal HNC calculations based on experimental small-angle neutron
scattering spectra of a 0.3-M solution of n-tetrabutylammonium
data of the electrolyte and is either of the type
bromide in D2 O at 25◦ C.
FM e02 (ai j /r )9
CORi j (r ) = , (94a)
36πε0 ai j
on the base of one or two solvent molecules. It can be
where FM is the ratio of Madelung’s constant to the coor-
obtained by geometric considerations. The absolute value
dination number, or of type
of the GURi j term may be of the same order of magnitude
 
CORi j (r ) = kB ∗ exp (ai j − r ) R ∗ , (94b) as that of the coulombic interaction term.
Friedman’s model fits the thermodynamic excess func-
where B ∗ and R ∗ are characteristic parameters for each tions (osmotic coefficient, excess volume, and excess en-
salt. The COR term reflects the dominant effect at short ergy) of aqueous solutions of alkali and earth alkaline
distances. halides up to 1-M ionic strength and of tetraalkylammo-
2. The term CAVi j (r ) takes into account the effect of nium halides up to 0.4 M. The variation of the Ai j param-
the local permittivity εc in the ionic cavities, usually set to eters with the ionic parameters is chemically meaningful
the square of the refractive index of the pure solvent. This and permits the estimation of thermodynamic properties
contribution, which is less important than the other terms, of unknown systems by the combination of the parameters
is defined as known from appropriate other systems.
 
[(ε − εc )/(2ε + εc )] ei2 a 3j + e2j ai3 Figure 6 shows pair correlation functions from HNC
CAVi j (r ) = . (95) calculations of an aqueous tetraalkyl-ammonium salt so-
8πε0 εr 4
lution. In contrast to the MSA calculations, the HNC cal-
3. The contribution GURi j (r ) results from the overlap culations yield gi j (r ) functions that give a realistic picture
of the solvation spheres (Gurney spheres) if two ions have of the solution structure. It can be inferred that no notice-
approached each other to distances less than the radii of able cation–anion association takes place, in agreement
their solvation spheres: with chemical model calculations at lower concentra-
tions. Also, no cation–cation association exists, which in-
GURi j (r ) = Ai j Vmu (ai + w, a j + w, r )/Vw (96)
dicates that no hydrophobic interaction occurs between
and the large organic ions. Interpenetration of the cations is
 found, which can be reproduced because of the soft-sphere
a 2 − b2 2(a 3 + b3 )
Vmu (a, b, r ) = π − + COR++ (r ) potential in Eq. (93).
4r 3

r (a 2 + b2 ) r3
− + . (97) F. Semiempirical Equations
2 12
In the field of chemical engineering there is a need for
In Eq. (96) Ai j is the molar free energy change if cosphere equations allowing the description of thermodynamic data
solvent is transferred from the solvate state to the bulk of electrolyte solutions or their prediction over large tem-
solvent, and Vw is the molar volume of the pure solvent perature and concentration ranges. In contrast to the situ-
in the same units as the overlap volume Vmu . The overlap ation for nonelectrolyte solutions, the rigorous theoretical
volume is a function of the distance r , the ionic radii ai , approaches cannot yet yield such equations with a reason-
and the cosphere radius w, which is usually calculated able amount of computing effort. A few pragmatic MSA
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Electrolyte Solutions, Thermodynamics 235

modifications show promising aspects in the description of IV. THERMODYNAMIC PROPERTIES

vapor pressures up to very high concentrations. Also, the OF ELECTROLYTE SOLUTIONS
combination of a pragmatic BO- and MM-level descrip-
tion was successfully applied (e.g., for the description of A. Generalities
multicomponent mixtures based on the parameters of its
constituting binary mixtures without any additional ad- Experimental investigations of thermodynamic properties
justed parameter). It is common to these pragmatic meth- are of importance for both examining theories and provid-
ods to use the permittivity of the solution as an empirical ing data for technology. The limiting values of the proper-
function of the salt concentration, or to vary the size of the ties at zero concentration are of crucial interest; they yield
solvated ions with salt concentration. the standard values of the solution. However, ideality of
Modified integral equation approaches have yet to en- electrolyte solutions, y± = 1, appropriate for such extrap-
ter into industrial process simulations and data descrip- olations, would require experiments at such low concen-
tions, in contrast to the empirical extensions of the Debye- trations that their execution would be either useless as
Hückel theory (see Section III.D.3). a consequence of low precision or even impossible. Re-
liable investigations in the low-concentration region use
computer-assisted data analysis of the experimental re-
G. Other Approximation Methods sults based on appropriate statistical thermodynamic mod-
Two computer simulation methods are widely used for els. The chemical model (Section III.D) provides property
ionic solutions: the Monte Carlo (MC) method and molec- equations of type
ular dynamics (MD). E(c; p, T ) = E ∞ ( p, T ) + E (αc; R; p, T ), (98)
The MC method consists of generating a set of molec-
1−α
ular configurations by random displacements of the N = KA, (99)
particles in the model and is basically a multidimensional α 2 cy±2
integration procedure that evaluates the integrals for the and
calculation of the pair correlation function [Eq. (65)] di- κq
rectly. It can be used to calculate the equilibrium properties − ln y± = , (100)
1 + κR
of a system.
In the MD method the classical Newtonian equations of where E(c; p, T ) is the property investigated and E ∞ its
motion of an assembly of particles are solved numerically limiting value at zero concentration. The basic model pa-
and integrated to yield the evolution of the configurational rameters R (cutoff distance of the short-range interactions
and velocity distributions of the system. It is used to cal- or upper limit of association) and K A (association con-
culate both equilibrium and transport properties. stant) are found independent of the special thermodynamic
Although the progress in computer science is continu- or transport property being investigated. This is a feature
ously increasing the possibilities of computer simulations, of reliable Hamiltonian models at the MM level.
it is currently not possible to use either method to deal with Thermodynamic properties yield a set of values
systems containing more than a few particles in a simu- R, K A , and E ∞ , generally obtained by three-parameter
lation box of reasonable dimensions. The simulation box least-squares fits based on statistical methods known to
is still much smaller than the range of the far-reaching produce reliable data. Transport properties of dilute so-
coulombic interactions. Therefore care must be taken to lutions yield consistent data for K A when R is set to the
avoid size and wall effects by the use of periodic boundary value determined by thermodynamic property equations.
conditions and lattice methods such as the Ewald sum and For example, conductance data yield sets of ∞ and K A ,
so forth. at every temperature and pressure. Limiting values of ion-
Both MC and MD simulation, can be applied to MM and pair formation, HA∞ and VA∞ , can be determined with
BO Hamiltonian models of electrolyte solutions. MD at the help of the relationships
the MM level is known as Brownian dynamics simulation. ∂(ln K A )
It has gained some importance for the study of large ions HA∞ = RT 2 (101)
∂T p
in solution. At the BO level only concentrated solutions
can be considered due to the restricted number of solvent and
molecules per number of ions in the simulation box. ∂(ln K A )
Although thermodynamic properties can be inferred VA∞ = −RT (102)
∂p T
from computer simulations, these methods mainly aim at
a realistic picture of the structure and, in the case of MD, when temperature- and pressure-dependent conductance
of the dynamics of the solutions. data are available.
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236 Electrolyte Solutions, Thermodynamics

TABLE III Thermodynamic Data of Ion-Pair Formation if the solute is a nonvolatile compound such as a salt. The
in Aqueous Solutions symbols are explained in Section II.A. The integration of
KA ∆H ∞
A Rexp Rcalc Eq. (103) gives the solvent activity aS as a function of the
Electrolyte (dm3 mol−1 ) (J mol−1 ) (nm) (nm) vapor pressure p of the solution at temperature T :

MgSOa4 161 5780 0.93 0.88
p VS∗(l) − BS
CaSOa4 192 5570 0.95 0.92 ln aS = ln ∗ + ( p ∗ − p)
p RT
CdSOa4 239 8390 0.96 0.91
CdSOb4 245 7900 — 0.91 ∼ p
= ln ∗ . (104)
a From heats of dilution.
p
b From temperature dependence of conductance.
In Eq. (104) p ∗ is the vapor pressure of the pure solvent.
The nonideality of the gas phase is taken into account
A comprehensive investigation of solution properties with the help of the second virial coefficient of the solvent
in various solvents and with a multitude of electrolytes vapor; VS∗(l) is the molar volume of the pure solvent in
has yielded an important result. Distance parameters can the liquid phase. Neglect of the nonideality and of the
be obtained for all property equations from chemical ev- pressure dependence of the activity yields the well-known
idence: R = a + ns, where a is the center-to-center dis- approximation aS = p/ p ∗ .
tance of closest approach of cation and anion in the so- Vapor pressure measurements can be carried out by
lution, s the dimension of an oriented solvent molecule, static, dynamic, or isopiestic methods. Static methods are
and n = 0, 1, or 2. An example is given in Table III, where based on direct measurements with the help of manome-
Rexp is the distance parameter from heat of dilution mea- ters. They require thorough outgassing of the solution,
surements and Rcalc the quantity calculated from a config- prevention of vapor condensation in any part of the mea-
uration M 2+ (H2 O)2 SO2−
4 .
suring device, and highly precise temperature constancy.
Differential measurements on solution and pure solvent
B. Electrolyte Solution Data Collections are advantageous.
and Databases The dynamic boiling point method (ebulliometry) stud-
ies the solution in a steady-state equilibrium of boiling and
Critically revised data of various electrolyte solution
condensing under a constant pressure of an inert gas. The
properties help scientists and engineers to overcome
difference in boiling points of the solution and the pure
the time-consuming procedure of searching for reliable
solvent, T − T ∗ , at pressure p,
data for technical applications. Special knowledge-based
databases undertake the interpolation, estimation, or sim- vap H
ln aS = (T − T ∗ ), (105)
ulation of data by theory-founded procedures differing RT T ∗
fundamentally from those for nonelectrolytes. The rea-
where vap H is the enthalpy of vaporization, is con-
son for the difference is the essentially different reference
verted to a change in pressure with the help of the
states of electrolyte solutions which are the infinitely di-
Clausius-Clapeyron equation. The boiling point method
lute solutions with at least three interacting components,
at constant pressure and the static vapor pressure method
namely solvent molecules, cations, and anions. In con-
at constant temperature are equivalent methods.
trast, databases for nonelectrolytes always use the pure
The dynamic gas saturation method is based on the de-
substances as the references.
termination by weight of the amount of solvent transported
by a current of an initially dry inert gas after passage
C. Vapor Pressure Measurements
through the solution where the gas is saturated. The con-
Vapor pressure measurements yield the activity and/or tent of solvent per unit volume of gas is proportional to
osmotic coefficients of electrolyte solutions. The equi- the partial pressure of the solvent.
(g)
librium condition µ(l)
S ( p, T ) = µS ( p, T ) for the solvent The isopiestic method is a highly accurate but time-
in the liquid (l) phase and gaseous (g) phase yields the consuming relative method. In a constant-temperature en-
relationship closure the solvent distills isothermally from a reference
 ∗(g) ∗(l) 
 solution of known activity to a solution of unknown activ-
1 ∂ µS − µS ity or vice versa, which entails a change in concentration.
d ln aS = dp
RT ∂p At equilibrium the solvent activities of both samples are
T
equal and (R denotes reference solution)
∗(g)
VS − VS∗(l)
= dp (103) = (νR m R /νm) R. (106)
RT
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Electrolyte Solutions, Thermodynamics 237

   
The accuracy of the method depends on the long-time tem-  MY  m   d
=  − 
V + − 1 −  (111)
perature stability and the accuracy of the reference data, V
d m  md ∗ V
d
usually those of aqueous KCl, NaCl, or H2 SO4 solutions.
The method for obtaining osmotic coefficients of elec- exhibits a contribution that is inversely proportional to mo-
trolytes from solvent activities is shown in Section II.E. lality, thus tending toward infinity if molality decreases
to zero. Assuming precise measurements of 0.001% rel-
ative error, both in density and in molality for aqueous
D. Osmotic Pressure Measurements NaCl solutions, the rapidly increasing error at low con-
Solvent activities can also be obtained from measure- centrations in V is caused entirely by the second term
V = 0.5 cm
3
ments of osmotic pressures. The osmotic equilibrium on the right-hand side of Eq. (111);
−1 −1 −1
µS ( p + , T ) = µ∗ ( p, T ) across a solvent-permeable mol at m = 0.01 mol kg and V = 5 cm mol
3

membrane separating solvent and solution is maintained at m = 0.001 mol kg−1 . Extrapolation with the help of in-
by the osmotic pressure . The osmotic equilibrium appropriate methods would yield seriously erroneous val-
condition, where ues of ∞ V . This example illustrates the necessity of using
theoretically well founded extrapolation methods.
p+
µS ( p + , T ) = µS ( p, T ) + VS d p Thermodynamics yields the relationship
p
∞ ν RT m
∂(ln γ± )
= µS ( p, T ) + VS , (107) V = + dm, (112)
V
m 0 ∂p T
yields the desired relationship
from which the limiting law of apparent molar volumes
ln aS = −VS /RT. (108) ∞
V = V + SV c1/2 , (113a)
Equation (108) is an approximation assuming a pressure- 1/2

independent molar volume of the solvent. In practice, this NA2 e03 |z i z j | 1000 νi z i2
method is limited to large solute particles such as polymers SV =
4π ε03 ε 3 RT
or biocolloids since it is difficult to find an impermeable
 
membrane for small ions. ∂(ln ε) β
× − , (113b)
∂p T 3
E. Molar Volumes is obtained by introducing the activity coefficient of the
Molar volumes of solute and solvent, VY and VS , are de- infinitely dilute solution (κ R  1) of statistical thermo-
termined from apparent molar volumes V (Section II.F) dynamics. Equations (113) are valid for a completely dis-
by density measurements. In terms of the measured den- sociated electrolyte.
sities of the solution and the pure solvent, d and d ∗ , the The treatment of partially associated electrolytes subdi-
apparent molar volume is given by (molarity and molality vides the space around every ion into a region populated by
scale, respectively) ion pairs (a ≤ r ≤ R) and a region of free ions (r ≤ R) (see
Section III.D); the volume V of the electrolyte solution is
d∗ − d MY d∗ − d MY then given by the relationship
V = + = + . (109)
1000cd ∗ d∗ mdd ∗ d
V = n S VS∗ + n Y [α V + (1 − α)VA ], (114)
Then the molar volumes VY and VS are obtained with the
help of the relationship (molality scale; see Section II.F) where VA is the concentration-independent molar volume
MS m 3/2
∂ V of the ion pair. Equation (114) can be transformed to yield
VS = VS∗ − (110a) the density equation for associated electrolytes:
2 ∂m 1/2 p,T
 
and d = d ∗ + MY − ∞ ∗ ∗
V d αc − SV d (αc)
3/2

 
m 1/2 ∂ V + MY − VA d ∗ K A y±2 (αc)2 . (115)
VY = V + . (110b)
2 ∂m 1/2 p,T
Equation (115) is a property equation of the type given
The main problem in calculating molar volumes from den- by Eq. (98) and is consequently combined with Eqs. (99)
sity measurements is the difficulty of measuring reliable and (100) for data analysis. Even measurements of the
densities at low electrolyte molalities. An estimation of highest obtainable precision (σd < 10−7 g cm−3 ) are not
the error of apparent molar volumes sufficiently precise for the simultaneous evaluation of
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238 Electrolyte Solutions, Thermodynamics

Partial molar volumes of ions are discussed in terms of

ion solvent interactions, that is,
∞ ∞ ∞ ∞
Vion = Vcryst + Velect + Vdisorder + Vcaged . (116)

It is assumed that the “nonsolvated” part Vcryst , the crys-

tal volume, is calculated from ionic crystallographic radii,
∞
Velect , the electrostrictive contribution, is due to solvent
molecules adjacent to the ion, which are more closely
packed than those in the bulk solvent. Highly structured
solvents such as water exhibit a region of disordered sol-
vent between the electrostricted region and the bulk sol-
∞
vent which gives rise to the Vdisorder term in the molar
volume equation for an ion. Ions with large hydrophobic
surfaces such as tertaalkylammonium ions in effect in-
FIGURE 7 Apparent molar volume of aqueous CdSO4
solutions at 25◦ C in the conventional c1/2 plot. The full crease hydrogen bonding in the adjacent water structure,
∞
line (1) is calculated from the experimental data [10−2 < which entails a further contribution, Vcaged . If this effect
c (mol dm−3 ) < 5 × 10−2 ) by the help of the chemical model; (2) is prevails, the ion is a structure-making ion, in contrast to
the limiting law; the dashed lines (3) indicate the limits of error on ∞
the structure-breaking ions with a large Vdisorder term.
resulting from a precision of σd = 4 × 10−6 g cm−3 in density
measurements. [Reprinted with permission from Schwitzgebel,
G., Lührs, C., and Barthel, J. (1980). Ber Bunsen-Ges. Phys.
Chem. 84, 1220–1224.] F. Heats of Solution and Dilution
Heats of solution and dilution, sol HY and dil HY , re-
∞
V , A, K A , and R; K A and R must be known from in- spectively, are determined with the help of calorimetric
dependent measurements (e.g., conductance or heat of di- measurements. According to Fig. 1 and Eqs. (45) the fol-
lution measurements). Figure 7 shows the apparent mo- lowing relationships can be written:
lar volume of CdSO4 in water and the extrapolation
to zero concentration based on Eq. (115). The quantity sol H ∞ ∞
= sol HY − dil HY ,
VA = VA − ∞ V is the molar reaction volume of ion- nY
pair formation; it is related to the pressure derivative of ∞ ∞
dil HY =− rel
H = H − H. (117)
the association constant of Eq. (102) and can also be ob-
tained from the pressure dependence of the association Thermodynamics yields the relationship
constant of conductance measurements at various pres-
sures, for example, VA (CdSO4 ) = 9.4 cm3 mol−1 from 1 m
∂(ln γ± )
rel
= −ν RT 2 dm, (118)
density measurements and 11.7 cm3 mol−1 from conduc- H
m 0 ∂T p
tance measurements, which is fairly good agreement when
the mutual limits of error are taken into account. from which the limiting law of the heat of dilution of
The molar volumes of electrolytes Y = [Cν+ z+ z−
Aν− ] at completely dissociated electrolytes
∞ ∞
infinite dilution, VY or V , do not depend on ion–
ion, but only on ion–solvent interactions and therefore
rel
H = S H c1/2 , (119a)
should be additively composed of the ionic quantities (i.e.,  1/2
NA2 e03 |z i z j |T 1000 νi z i2
VY∞ = ν+ V+∞ + ν− V−∞ ). The partition of the VY∞ values SH = −
into their ionic parts can be executed with the help of 4π ε03 ε 3 RT
extrathermodynamic assumptions (see Section II.C). The  
∂(ln ε) α 1
assumption that the ratio of the molar ionic volumes in × p+ + , (119b)
∂T 3 T
aqueous solutions, V+∞ /V−∞ , of Ph4 AsBPh4 equals the ra-
3
tio a+ /a−3
(a+ , a− : ionic radii) yields VH∞+ (aq) = −4.1 cm3 is obtained with the help of the activity coefficient of the
mol−1 ; equating the ratio to that of the ionic vander Waals infinitely dilute solution (κ R  1).
volumes yields a value of −5.5 cm3 mol−1 ; and the use of Associated electrolytes are treated in the usual way by
a series of ions of various sizes yields VH∞+ (aq) = −4.5 cm3 superimposition of the contributions of the free ions and
mol−1 . Ionic vibration potential measurements, the only ion pairs, rel H (FI) and
rel
H (IP); the quantity
rel
H (IP) is
∞
method for a direct determination of ionic molar volumes, the molar enthalpy of ion-pair formation, HA , from the
yields VH∞+ (aq) = −5.4 cm3 mol−1 . initially infinitely separated cation and anion:
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Electrolyte Solutions, Thermodynamics 239

rel
H =α rel
H (FI) + (1 − α) rel
H (IP),
G. Electromotive Force
(120)
rel
H (IP) = HA∞ . For a galvanic cell,

Heats of dilution dil HY∞ are determined by the measure- M(Hg) | MX(c in S) | AgX(s) | Ag(s), (122)
ments of intermediate heats of dilution (see Fig. 1), which involves the chemical reaction
rel
H (m 2 ) − rel
H (m 1 ) = α2 rel
H (FI, m 2 ) − α1 rel
H (FI, m 1 ) → MX(solv) + Ag(s),
M(Hg) + AgX(s) ← (123)
+ (α1 − α2 ) HA∞ , (121) emf is given by the relationship
an appropriate extrapolation to infinite dilution. Heats of 
ν 
k
(β) (β)
dilution yield precise information on association constants −n FE = ωi µi . (124)
K A , heats of ion-pair formation HA∞ , and cutoff dis- β=1 i=1
tances of the chemical model R. Entropies of ion-pair
formation SA∞ can be calculated from K A and HA∞ by In Eqs. (122) and (123), M(Hg) is an alkali metal amalgam
the usual thermodynamic relationships. Table III shows electrode, MX the solvated halide of the alkali metal M at
the agreement of HA∞ values from heat of dilution concentration c in a solvent S, and AgX(s)/Ag(s) a silver
and temperature-dependent conductance measurements; halide–silver electrode. Equation (124) is the general ex-
Fig. 8 shows the dependence of heat of dilution on the pression for the electromotive force E of a galvanic cell
concentration of a partially associated electrolyte. without liquid junction in which an arbitrary cell reaction
Heats of solution, sol HY = HY − HY∗ , are obtained by ω1 Y1 + ω2 Y2 + · · · ←→ ωi Yi + · · ·, takes place between
direct measurements and can be combined with the ap- k components in ν phases. In Eq. (124) n is the number
propriate heats of dilution to yield the quantities sol HY∞ of moles of electrons transported during this process from
(Fig. 1), which in turn yield the enthalpies of solvation the anode to the cathode through the outer circuit, F the
(β)
∞
solv HY when combined with lattice energies lat HY .
Faraday number, and µi the chemical potential of com-
Single-ion enthalpies of solvation are obtained with the ponent Yi in phase β. Cells with liquid junctions require
help of extrathermodynamic assumptions. the electromotive force E in Eq. (124) to be replaced by
the quantity E − E D , where E D is the diffusion potential
due to the liquid junction. The standard potential E ◦ for the
cell investigated by Eq. (122) is given by the relationship
 
FE ◦ = − µ∗Ag + µ∞ ∗
MX − µAgX − µM(Hg) .
sat
(125)

That is, E ◦ would be the emf measured if all components

were in their standard states. Hence, for the example given,
Eq. (124) can be written as
RT aMX
E = E◦ − ln
F aM(Hg)
2RT
= E◦− ln (αcy± ) (126)
F
if the metal concentration of the amalgam is kept constant
for a series of measurements.
Equation (126) again is of the type given by Eq. (98).
Data analysis on dilute solutions together with equations
(99) and (100) yield E ◦ and K A as the desired informa-
FIGURE 8 Relative apparent molar enthalpy rel H of potassium tion. The association constant K A obtained in this man-
iodide–propanol solutions at 25◦ C in the convetional c1/2 plot.
The full line curve (1) is calculated from the experimental data
ner is in agreement with those from heats of dilution or
[10−3 < c (mol dm−3 ) < 10−2 ] with the help of the chemical model; conductance measurements.
the dashed curve (2) depicts the limiting law. [Reprinted with per- According to Eq. (126) the reference potential E ◦ at
mission from Barthel, J., Gores, H.-J., Schmeer, G., and Wachter, activity aM(Hg) is given by the relationship
R. (1983). Non-Aqueous Solutions in Chemistry. In “Topics in Cur-
rent Chemistry” (F. L. Boschke, ed.), Vol. 111, pp. 33–44, Fig. 4. RT
Springer-Verlag, Berlin. Copyright 1983 Springer-Verlag.] E ◦ = E◦ + ln aM(Hg) (127)
F
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240 Electrolyte Solutions, Thermodynamics

and yields the standard potential E ◦ when the activity for biopolymers. The effectiveness of anions for salting-
aM(Hg) is known. Hence the Gibbs energy of transfer of in and salting-out follows the so-called Hofmeister series.
the electrolyte MX from the pure to the infinitely dilute Despite numerous efforts a satisfactory explanation of this
state in the solvent S is available: series by proper models is still unavailable.

µ∞ ∗
MX −µMX =
∞
sol G MX = −FE ◦ +µ∗AgX −µ∗MX . (128)
I. Phase Separation by Electrolytes
Measurements of emf as a function of temperature yield Specific electrolyte solutions have been discovered and in-
∞ tensively studied which can produce a phase with a higher,
sol HMX in agreement with calorimetric data.
Measurements of emf are also widely used for cal- and a phase with a lower salt concentration. The reasons
culating activity coefficients at concentrations higher for phase separation may be different. For aqueous solu-
than the limit of validity of the model calculations. For tions of large organic ions (e.g., tetra-n-pentylammonium
this purpose Eq. (126) is used for the determination of bromide), the phenomenon is ascribed to hydrophobic in-
y± , y± = αy± , after previous determination of E ◦ from teraction; for large ions in low permittivity solvents (e.g.,
dilute-solution data. tetra-n-pentylammonium picrate in 1-chloropentane), it is
due to the long-range electrostatic interactions (coulombic
phase separation).
H. Solubility
Making solubility measurements is another method for J. Nernst’s Distribution Law
the determination of Gibbs energies. A precipitated elec-
trolyte when studied in equilibrium with its saturated An important technical application of liquid–liquid equi-
solution libria uses Nernst’s law of phase distribution of a solute
Y between two nonmiscible solvents to make up the two
µ∗Y (S) = µY (sat sol) = µ∞
Y + ν RT ln a±
sat
(129) phases in contact, α and β. The equilibrium condition,
(β)
µ(α)
Y ( p, T ) = µY ( p, T ) yields the relationship
sat ∞(β)
yields the mean activity at saturation a± and hence of- aY(α) KY
∞ = = N, (132)
fers the possibility of calculating sol G Y with the help of
Eq. (129).
(β)
aY K Y∞(α)
Solubility measurements may advantageously replace where aY means the activity of the solute and N is Nernst’s
emf methods for the determination of sol G ∞ Y values and
distribution coefficient which is the ratio of the Henry
∞(β)
related quantities of sparingly soluble electrolytes, such constants, K Y∞(α) and K Y , for the solution of Y in the
as the Gibbs energy of transfer from a solvent S to a two separate solvents. Distribution coefficients of water–
solvent S: octanol are widely used in toxicological and ecological
studies.
∞
tr G Y (S → S) = µ∞ ∞
Y (S) − µY (S )
sat
a± (S ) SEE ALSO THE FOLLOWING ARTICLES
= ν RT ln sat . (130)
a± (S)
CHEMICAL THERMODYNAMICS • ELECTROCHEMISTRY •
Frequent use of the solubility method is made for inves-
ELECTROLYTE SOLUTIONS, TRANSPORT PROPERTIES •
tigating activity coefficients of ternary systems where the
LIQUIDS, STRUCTURE AND DYNAMIC • PERMITTIVITY OF
variation of the activity coefficient γY of the electrolyte
LIQUIDS • SOLVENT EXTRACTION
is studied as a function of the concentration of a second
solute Z. Thermodynamics provides the relationship
BIBLIOGRAPHY
∂(ln γY ) ∂(ln γZ )
= . (131)
∂m Z mY ∂m Y mZ Barthel, J., Krienke, H., and Kunz, W. (1998). “Physical Chem-
istry of Electrolyte Solutions—Modern Aspects,” Steinkopf,
If the solute Z is a nonelectrolyte, the sign of the par- Darmstadt/Springer-Verlag, New York.
tial derivative (∂(ln γZ )/∂m Y )m determines whether Z is Blum, L. (1980). Primitive electrolytes in the mean spherical approxi-
mation. In “Theoretical Chemistry: Advances and Perspectives,” pp.
salted-in (−) or salted-out (+) by the electrolyte. 1–66, Academic Press, New York.
Salting-in and salting-out of electrolytes is an important Bockris, J. O., Reddy, A. K. N. (1998). “Modern Electrochemistry”
effect with regard to charged polymers and particularly (Vol. 1, Ionics), 2nd ed., Plenum, New York.
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Electrolyte Solutions, Thermodynamics 241

DECHEMA Datenbank DETHERM (1989). Elektrolytdatenbank Barthel, J. et al., Electrolyte Data Collection (12 partial volumes),
ELDAR, DECHEMA, Frankfurt a.M. DECHEMA, Frankfurt, to be continued.
Friedman, H. L., and Dale, W. D. T. (1977). Electrolyte solutions in equi- Pitzer, K. S. (1991). “Activity Coefficients in Electrolyte Solutions,” 2nd
librium. In “Statistical Mechanics,” Part A, Equilibrium Techniques ed., CRC Press, Boca Raton, FL.
(B. J. Berne, ed.), pp. 85–135, Plenum, New York. Robinson, R. A., and Stokes, R. H. (1970). “Electrolyte Solutions,” 2nd
Kreysa, G., ed. (1992 ff). DECHEMA Chemistry Data Series, Vol. XII, rev. ed., Butterworth, London.
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Electrolyte Solutions,
Transport Properties
J. Barthel P. Turq
W. Kunz O. Bernard
University of Regensburg University Pierre et Marie Curie

I. Thermodynamics of Irreversible Processes

II. Statistical Mechanical Theory of Electrolyte
Transport Properties
III. Electrolyte Conductivity and Transference
Numbers of Dilute Solutions
IV. Viscosity
V. Transport Equations for Concentrated
Electrolyte Solutions

GLOSSARY Glass transition temperature Temperature at which

transition of the undercooled solution to an amorphous
Chemical diffusion Transport of matter caused by a gra- solid state takes place.
dient in concentration. Hamiltonian Energy function of a system expressing the
Electrolyte conductivity Transport of electric charges by total energy of the system as a function of the position
ions in the gradient of an electric potential. Also known and momentum coordinates of its particles.
as electrolyte conductance. Hamiltonian model Statistical mechanical model based
Electroneutrality Compensation to zero of positive and on a Hamiltonian.
negative charges in a finite volume of the solution. Intensive property Property of the system that is inde-
Electrophoretic effect Hindrance of the undisturbed pendent of the mass of the system (e.g., density, vis-
movement of the ions in the solution, produced by hy- cosity, molar conductance).
drodynamic interactions of ions and solvent molecules. Migration Movement of particles under the action of
Equilibrium state State of the system in which, during driving forces.
the observation time, no measurable flows of matter Mode Motion characterized by a time constant, due to
and/or energy and no measurable changes of the inten- specific effects.
sive properties of the system take place. Phase space 6N -dimensional space defined by an

243
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244 Electrolyte Solutions, Transport Properties

orthogonal coordinate system of the 3N momentum conductance according to Ohm’s law. Temperature gra-
and 3N position coordinates of the N particles of the dients yield thermal conductance according to Fourier’s
system. law. Inhomogeneities of drift velocity entail Newton’s
Relaxation effect Hindrance of the undisturbed move- law. Gradients of electric potential, temperature, and drift
ment of the ions in the solution, produced in an exter- velocity are observed in both pure phases and mixtures.
nal electric field by the nonspherical symmetry of the Coupled transport phenomena obey Onsager’s laws of ir-
charge distributions around the ions. reversible processes, yielding the appropriate cross co-
Self-diffusion Transport of matter caused by Brownian efficients. However, only diffusion, viscosity, migration,
motion. electric conductance, and related topics will be considered
s-Particle distribution function Probability of finding in this article; little or no information on the other trans-
s particles out of the total number of particles of a port processes in electrolyte solutions can be found in the
system at time t with given momenta at given positions. literature.
Steady state State of a system in which, during the obser- The formulation of transport processes requires the
vation time, measurable flows of matter and/or energy use of time and space variables t and ri , in contrast
may take place without changing the intensive proper- with equilibrium thermodynamics which does not recog-
ties of the system. nize time as a variable. The object of investigation is a
phase with local inhomogeneities, composed of particles
X 1 , X 2 , . . . , X i , . . . , molecules or ions, at particle num-
AN ELECTROLYTE SOLUTION that is not in ther-
ber densities ρi (ri ; t) and particle velocities vi (ri ; t), the
modynamic equilibrium is subject to generalized forces
generalized forces being also functions of time and space.
that control the irreversible processes taking place in such
If particle X i is an ion of valency z i , the charge density at
systems. Processes of this type are chemical reactions,
point ri would be e0 NA z i ci ; e0 is the proton charge, NA
including relaxation processes, and transport properties.
Avogadro’s number (e0 NA = F, Faraday constant), and ci
Homogeneous chemical reactions do not presuppose spa-
the concentration of particle X i (ci = ρi /NA ).
tial inhomogeneities, in contrast with transport phenom-
The amount of particles X i passing per interval of time
ena requiring a gradient of concentration, electric poten-
dt in a perpendicular direction through an elementary sur-
tial, temperature, or drift velocity. Transport phenomena in
face dS of a volume V is given by the quantity ci vi dSdt
electrolyte solutions can involve both types of irreversible
if the solution does not move with regard to the chosen
processes, taking place simultaneously, since ion-pair for-
reference system, the “laboratory frame.” If the solution
mation in electrolyte solutions and formation of higher
moves at velocity s v with regard to its reference system,
aggregates are related to chemical reactions.
this quantity is charged to ci (vi − s v) dSdt.
The models of electrolyte solutions and the fundamen-
In solutions the reference velocity s v is given by the
tals of thermodynamics and statistical thermodynamics
relationship
are given in Electrolyte Solutions, Thermodynamics.  
Just as in the case of equilibrium thermodynamics, ther- s
v= gi vi ; gi = 1, (1)
modynamics of irreversible processes yields phenomeno- i i
logical equations which in principle are independent of the where gi is the weight factor for particle X i . Various refer-
molecular nature of the system. In contrast, statistical me- ence systems are used in the literature. The most important
chanics derives transport properties from the microscopic examples are the Hittorf reference system, in which the
picture of the solution. Considerable progress has been velocity of solvent particles v0 is chosen as the reference,
made in this latter type of approach during recent years. and the Fick reference system, in which the mean volume
velocity of the system is chosen.
I. THERMODYNAMICS OF IRREVERSIBLE Investigations on transport properties commonly are
PROCESSES based on diffusion current densities Ji (also, flux or
flow):
A. Definitions  
Ji = ci vi − s v . (2)
Gradients of properties produce flows that at low concen-
trations are proportional to these gradients. Concentration Then the total diffusion current φi of particles X i through
inhomogeneities entail chemical diffusion as the trans- an observed surface S enclosing volume V is given by the
port process. Concentration presupposes a system of at relationship
 
least two components for its definition. The law linking ∂ci
diffusion and flow is Fick’s law. Electric potential gradi- − dV = φi = Ji dS. (3)
∂t
ents produce ion migration and are manifest by electric (V ) (S)
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Electrolyte Solutions, Transport Properties 245

Equation (3) presupposes that there is no source of parti- K c , as usual in chemical kinetics. The determination of
cles X i within volume V . Transformation of the surface quantities σi is straightforward:
integral to a volume integral by the help of Gauss’s theo-
σ+ = σ− = −k1 c+ c− + k2 cp (8a)
rem yields the relationship
and
∂ci
−
= div Ji . (4) σp = +k1 c+ c− − k2 cp . (8b)
∂t
In the theory of electrolyte conductance, reference is made The quantities c+ , c− , and cp are the molarities of the
to the density of charges e0 NA ci z i (C m−3 ) rather than to “free” cations, anions, and ion pairs in the solution which
the density of particles. Then Eqs. (2) and (3) are trans- are related to electrolyte concentration cE by the degree of
formed to dissociation α of the ion pair:
 
ji = e0 NA z i Ji = e0 NA z i ci vi − sv , (5a) c+ = c− = αcE , (9a)

cp = (1 − α)cE , (9b)
Ii = ji dS, (5b)
  and
 
j= ji = e0 NA z i ci vi − sv , (5c) (1 − α)
Kc = . (9c)
i i
α 2 cE
and This simple case of a nonconserved system is chosen for

I = j dS. (5d) exemplifying the fundamental concept. Electrolyte solu-
tions exhibiting more complex equilibria can be treated in
In Eqs. (5), ji is the partial electric current density of ions the same way, the quantities σi always being functions of
X i , j the total current density, and Ii and I the partial and rate constants and concentrations of free particles in the
total electric currents (A). Electroneutrality within each solution.
elementary volume, With the sources taken into account, Eqs. (3) and (4)
 must be transformed to
ci z i = 0, (6)    
∂ci
i − − σi d V = Ji dS (10)
∂t
entails that the electric current density j is independent of (V ) (S)
the reference system, in contrast with the partial current and
densities ji .
∂ci
+ div Ji − σi = 0. (11)
∂t
B. Electrolyte Solutions in Irreversible Equations (10) and (11) apply to a system removed from
Thermodynamic Processes equilibrium as well as to a system in equilibrium under-
The application of Eq. (3) or Eq. (4) to electrolyte so- going spontaneous fluctuations. For this purpose, super-
lutions would require a solution made up of completely position is assumed of the average values ci , Ji , and
dissociated electrolytes. This restriction can be overcome σi and the fluctuations δci , δJi , and δσi :
by the introduction of sources that do not produce spatial ci (ri ; t) = ci + δci (ri ; t), (12a)
inhomogeneities in the solution. A simple but important
example of such sources is the chemical reactions of ion- Ji (ri ; t) = Ji + δJi (ri ; t), (12b)
pair formation and decomposition, which produce particle and
densities per unit of time σi at rate constants k1 and k2 :
σi (ri ; t) = σi + δσi (ri ; t). (12c)
k1
C z+ −→ [Cz+ Az− ]0
+ A ←− z−
(7a) Introduction of expressions (12) into Eq. (11) permits the
k2
discussion of
and
the relaxation to equilibrium if macroscopic hetero-
k1
= Kc. (7b) geneities are imposed on the initially equilibrated system;
k2 systems in equilibrium undergoing fluctuations:
In Eqs. (7), Cz+ , Az− , and [Cz+ Az− ]0 are the z + -valent Ji = 0, σi = 0; and
cation, the z − -valent anion, and the electrically neutral ion systems in steady states: ci (ri ; t) is constant in time
pair (z + = |z − |). The ratio of the rate constants k1 and k2 but not in space, ci (ri ; t) = ci (ri ); Ji and σi are also
yields the concentration-dependent equilibrium constant constant in time but may have nonzero values.
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246 Electrolyte Solutions, Transport Properties

The electroneutrality condition, Di = ωi kT. (15)


ci z i = 0, (13) The total force Fi applied on particle X i is given as the
reduces the number of independent species. In dilute so- gradient of the electrochemical (i = +, −) or chemical
lutions the solvent transport generally can be neglected. (i = p) potential:
The problem of how to fulfill the average condition (13) 1 
both locally and instantaneously cannot be solved com- Fi = − grad µi∞ + RT ln ci yi + e0 NA z i ψ ,
NA
pletely in a description of the electrolyte solution based
(16a)
on Eqs. (11). These equations, however, give the impor-
tant information on the time that is needed by the system i = +, −, (16b)
to return to the local electrostatic equilibrium (Debye re-
and
laxation time) after perturbation. The ionic representation
1 
of electrolyte solutions is not generally necessary since Fi = − grad µi∞ + RT ln ci yi . (16c)
most of the transport processes in electrolyte solutions NA
take place with a characteristic time larger than the Debye In Eqs. (16), µi∞ is the chemical reference potential at
relaxation time. infinite dilution, yi the corresponding activity coefficient
For moderately concentrated solutions of 1,1 elec- in the molarity scale, and ψ the electric potential acting
trolytes this time is in the nanosecond range. At longer on the ions. The “thermodynamic” forces grad(ln yi ) will
times cations and anions diffuse with a common diffu- be neglected in the following discussion for the sake of
sion coefficient and the ionic equations can be replaced simplicity. The electric potential ψ is related to the electric
by component equations. field E by the relationship
The general method for solving Eqs. (11) consists of
transforming the partial differential equations with the E = −grad ψ, (17a)
help of Fourier-Laplace transformations into a set of linear N A e0 
algebraic equations that can be solved by the standard tech- div E = ci z i , (17b)
ε0 ε
niques of matrix algebra. The roots of the secular equation
are the normal modes. They yield the laws for the decays in where ε0 is the permittivity of the vacuum and ε the relative
time of all perturbations and fluctuations which conserve permittivity of the solvent. The sources σi in Eqs. (11) are
the stability of the system. The power-series expansion in given by Eqs. (8).
the reciprocal space variables of the normal modes permits As a result, the diffusional transport of a symmet-
identification of relaxation, migration, and diffusion con- ric electrolyte in a solvent in which ion-pair formation
tributions. The basic information provided by the normal takes place is given by the following set of differential
modes is that the system escapes the perturbation by any equations:
means at its disposal, regardless of the particular physical ∂c+ z + e0
or chemical reason for the decay. = D+ div grad c+ − c+ E
∂t kT
− k 1 c+ c− + k 2 cp , (18a)
C. Chemical Diffusion
∂c− z − e0
Diffusional transport of symmetric electrolytes superim- = D− div grad c− − c− E
∂t kT
posed by ion-pair formation kinetics, Eqs. (7), is chosen as
an example for exemplifying the methods of irreversible − k 1 c+ c− + k 2 cp , (18b)
thermodynamics. and
Time and space evolution of the observed system,
∂cp
symmetric electrolyte Cz+ Az− in a solvent, are given by = Dp div grad cp + k1 c+ c− − k2 cp . (18c)
Eqs. (11), one equation for each species i (i = +, − , p). ∂t
The flows Ji are given by Eq. (2): This set of partial derivative equations can describe ei-
ther a macroscopic diffusion phenomenon taking place in
Ji = ci vi = ci ωi Fi (14a) a measuring cell with a small concentration gradient or
and a fluctuation process [see Eqs. (12)], for example, as ob-
served in dynamic light-scattering experiments. In the first
vi = ωi Fi , (14b)
case, the boundary conditions (fixed concentration gra-
where vi is the velocity of particle i (s v = 0, dilute solu- dients) are determined by the experiment; in the second
tion), and ωi is the generalized mobility coefficient related case, small perturbations on the initial equilibrium are pro-
to the diffusion coefficient Di by the Einstein relationship duced from thermal fluctuations. For a fluctuating system,
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Electrolyte Solutions, Transport Properties 247

 
the mass-action law applied only to the equilibrium con- D+ D− q+2 + q−2 2D+ D−
centrations [ σi = 0], DNH = = . (24)
q+2 D+ + q−2 D− D+ + D−
k1 c+ c− − k2 cp = 0, (19) The chemical diffusion coefficient is a phase property
where the reference velocity is chosen in the Fick refer-
and the electroneutrality of the equilibrium distribution of ence system. Various methods are known for the experi-
the ions entails [ Ji = 0] mental determination of chemical diffusion coefficients,
e0 N A  such as open and closed capillary methods, dynamic light
div E = z i δci . (20) scattering, or the Taylor dispersion method.
ε0 ε i
In contrast with chemical diffusion, the self- (or intra-
The investigation of relaxation times and diffusion coeffi- or tracer-) diffusion of ions simply is the manifestation
cients requires the determination of the eigenvalues of the of Brownian motion. It can be visualized by labeling a
matrix corresponding to the system of algebraic equations small amount of ions and observing their displacement in
obtained from Eqs. (18) after Fourier-Laplace transforma- an environment of nonlabeled ions of the same type. Nu-
tion (s, Laplace transform of time; q, Fourier transform clear magnetic resonance (NMR) spin-echo experiments
of the space coordinate). The roots of the secular equation use spin labeling; radioactive tracers are used in closed
are capillary methods. At infinite dilution the self-diffusion
Di∞ of an ion Xi is linked to its limiting ion conductivity
s1 = 0, (21a)
  λi∞ , Eq. (43), and its generalized mobility ωi , Eq. (15),
s2 = − q+2 D+ + q−2 D− , (21b) (F = e0 NA , Faraday constant):
kT
and Di∞ = λ∞ = ωi kT. (25)
e0 |z i |F i
s3 = −(k1 c+ + k1 c− + k3 ), (21c)
where qi2 is the partial contribution of the ionic species Xi D. Reaction–Diffusion Coupling
to the Debye parameter κ: In this section interest is focused on the influence of the
e2 z 2 NA rate constants of chemical processes on observable trans-
qi2 = 0 i ci (22a) port coefficients, in contrast with the common point of
ε0 εkT
view following the limitations of kinetics by the trans-
and port of matter, for example, the arrival of reactants or the
departure of products. An example is given in Fig. 1 for
κ 2 = q+2 + q−2 . (22b)
the electrophoresis of ligand-exchanging transition-metal
The root s1 simply indicates that infinite distances are cor- complexes.
related with infinite time, s2 is the reciprocal of the Debye Again, time and space evolution of the observed system
relaxation time, and s3 is the kinetic relaxation frequency are given by a set of equations of the type of Eqs. (11),
of the system. Depending on the kinetic parameters of the where the flows are
chemical process, the kinetic relaxation frequency can be
Ji = ci vi = ci (ωi Fi + vi ). (26)
faster or slower than the Debye frequency of the system.
If the kinetic relaxation frequency is much smaller than In Eq. (26), vi is the velocity of the solvent at the position
the Debye mode, it can be determined experimentally by of particle i due to the average effect of the hydrodynamic
conductance fluctuation analysis. interactions of solute and solvent (electrophoretic effect);
The diffusional modes are the roots of the secular the other symbols were explained in the preceding section.
equation which are proportional to q 2 . The correspond- Exchange reactions of the type
ing diffusion coefficient is given by the relationship k12
( c+ = c− ) −→ X z2
X 1z1 + L z1 ←− (27)
2
k21
DNH Dp
D= + , (23) between the complexes X 1 of charge e0 z 1 and X 2 of charge
1 + 2K A c+ 1 + 1/(2K A c+ ) e0 z 2 in a solution, containing an excess of the ligand L of
where DNH is the chemical diffusion coefficient of the charge e0 z 1 , are independent of the ligand concentration.
dissociated part of the electrolyte (free ions), which is This simple kinetic situation is exemplified in Fig. 1 by
related to the individual ionic diffusion coefficients by the the reaction
 − 2+  
Nernst-Hartley equation, and Dp that of the associated RuNO NO3 −→ RuNO NO− +
←− (28)
− 3 2
ions (ion pairs): NO3
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248 Electrolyte Solutions, Transport Properties

Again the term −q 2 D shows the diffusional broaden-

ing of the peaks; −k21 and −k12 indicate the diminu-
tion of the peaks by the relaxation factors exp[−k12 t] and
exp[−k21 t], respectively; t is the observation time; and the
terms iωe0 Eqz i characterize the migrational separation of
the two peaks according to the effective values z 1 and z 2
and velocity vi (which is included in the effective values
of z 1 and z 2 by the underlying theory).
The high-field approximation does not exhibit the con-
tribution due to the production of compounds by the ex-
change reactions to the electrophoretic pattern. This ef-
fect can be illustrated by the fast-exchange approximation
which yields the roots
z 2 k12 + z 1 k21
s1 = −q 2 D + iωe0 Eq (30a)
k12 + k21
and
z 1 k12 + z 2 k21
s2 = −q 2 D +iωe0 Eq −(k12 +k21 ). (30b)
k12 + k21
FIGURE 1 Paper electrophoresis of a mixture of RuNO(NO− 3)
2+

and RuNO(NO− )
3 2
+
in 2-M HNO 3 at various temperatures. Low Equation (30a) shows that the relevant peak undergoes a
temperature: two peaks, separation of the two complexes. High simultaneous migration and diffusion process but is free
temperature: one peak, no separation of the two complexes.
from kinetic attenuation. Equation (30b) shows a kineti-
x Axis: broadness of the Ru zone after migration (relative dis-
tance scale); y axis: Ru distribution after migration (relative con- cally fast-attenuated mode which yields a negligible con-
centration scale). [Orcil, L., Fatouros, N., Truq, P., Chemla, M., tribution to the electrophoretic pattern.
and Barthel, J. (1983). Zeitschrift Phys. Chem. N. F., Oldenberg
Verlag, München, 138, 129–136.]

II. STATISTICAL MECHANICAL THEORY

OF ELECTROLYTE TRANSPORT
PROPERTIES
in aqueous solutions of HNO3 . The figure shows the pat-
terns at various temperatures for the paper electrophoresis
A. Hamiltonian Models of Transport Processes
of a mixture of RuNO(NO− 3)
2+
and RuNO(NO− +
3 )2 after
migration under the following experimental conditions: Another type of approach to transport properties, also fre-
initial concentration of ruthenium in the active drop about quently used in the theory of electrolyte solutions, is based
10−3 mol dm−3 and initial concentration of NO− 3 in the on statistical mechanics and starts with Liouville’s theo-
supporting electrolyte (aqueous solution of HNO3 ) about rem. Electrolyte conductance is chosen to exemplify the
2 mol dm−3 . The separation into two peaks occurs only features of this theory.
for slow-exchange reactions, that is, at low temperatures. In terms of statistical mechanics the electrolyte solu-
Fast-exchange reactions do not permit the separation, ex- tion is made up of N solute particles (ions) at positions
cept at much higher electrical fields which, however, can- r1 , . . . , r N and N0 solvent particles r N +1 , . . . , r N +N0
not be applied to the highly conducting solutions used in with momenta p1 , . . . , p N and p N +1 , . . . , p N +N0 yield-
this experiment. ing the density function ρ of the configurational points in
The experiment illustrates well the existence of the the 6(N + N0 )-dimensional  space:
modes deduced from the secular equation of this prob-
lem. The separation of peaks takes place at high fields. ρ = ρ N +N0 (r1 , . . . , r N , r N +1 , . . . , r N +N0 ;
Under this condition the roots of the secular equation are p1 , . . . , p N , p N +1 , . . . , p N +N0 ; t). (31)
(D1 ≈ D2 = D)
Hamiltonian models are based on the Hamiltonian H ,
s1 = −q D + iωe0 Eqz 2 − k21
2
(29a) which expresses the total energy of the system as a function
of the momenta pi and coordinates ri of all particles:
and
 p2 1 
H= i
+ Ui j (ri , r j ; t). (32)
s2 = −q 2 D + iωe0 Eqz 1 − k12 . (29b) i
2m i 2 i j
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Electrolyte Solutions, Transport Properties 249

The first term on the right-hand side of Eq. (32) represents ions i and t, and χ ti is the hydrodynamic coupling tensor
the kinetic energy; the second term is the potential en- of ions t and i. The forces F(N )
k (k = i or t) are given by
ergy U N +N0 (r1 , . . . , r N +N0 ; t) approximated by a sum of the relationship
pairwise direct interaction potentials Ui j (ri , r j ; t); both
momenta pi and coordinates ri are functions of time. F(N
k
)
= e0 z k E − kT gradk (ln D N )
The Liouville equation [cf. Eq. (4)],

N

∂ρ  ∂ H ∂ρ ∂ H ∂ρ − gradk Ukm (rk , rm ), (38)

= −div(ρv) = − , (33) m=1
∂t i
∂r i ∂ pi ∂ pi ∂ri
where Ukm is the direct interaction potential of ions k and
entirely determines the distribution function ρ N +N0 at m [Eq. (32)], the term kT gradk (ln D N ) takes into account
time t = 0 once the initial state ρ N +N0 (r1 , . . . , r N +N0 ; Brownian motion, and e0 z k E is the electric force acting
p1 , . . . , p N +N0 ; 0) is given. In Eq. (33), the operator “div” on the charge e0 z k (ion k) in the external field E.
is a 6(N + N0 )-dimensional operator, and vector v has the Stepwise reduction of the N -particle distribution func-
components (r1 , . . . , r N +N0 ; p1 , . . . , p N +N0 ). tion by integration [cf. Eq. (34)] yields the s-particle cor-
Averaging over all position and momentum variables of relation functions g (s) (s < N ),
the solvent molecules and all momentum variables of the 
ions yields the N -particle distribution function D N of the g (r1 , . . . , rs ; t) = V
(s) s
D N drs+1 · · · dr N , (39)
ions:
D N (r1 , . . . , r N ; t) and the velocity vi(s) of ion i,

= ρ N +N0 dr N +1 · · · dr N +N0 dp1 · · · dp N +N0 . vi(N ) D N drs+1 · · · dr N
vi(s) (r1 , . . . , rs ; t) = , (40)
(34) D N drs+1 · · · dr N
The N -particle distribution function D N gives the prob- at arbitrary positions of the ions (s + 1) to N ; V is the
ability of finding at time t the N ions in the positions volume of the solution.
r1 , . . . , r N regardless of the momenta and positions of The use of s-particle correlation functions g (s) and ve-
the solvent molecules and the momenta of these ions. locities vi(s) permits the integration of Eq. (37) with regard
Hamiltonian models based on Hamiltonians averaged with to all coordinates except ri to yield the velocity of ion i
regard to the coordinates of the solvent molecules are regardless of the position of all other ions:
referred to as Hamiltonian models at McMillan-Mayer
vi(1) (ri ; t) = v0 (ri ) + ωi e0 z i E
(MM) level.
The velocity vi(N ) of ion i out of N ions is then given by  N 
the relationship − ωi n k gradi Uik gik drk
k=1
vi(N ) (r1 , . . . , r N ; t) 
 
N

−1
+ ωk n k χ ik gik Fk drk . (41)
= DN vi (r1 , . . . , r N +N0 ; p1 , . . . , p N +N0 ; t) k=1

ρ N +N0 dr N +1 · · · dr N +N0 dp1 · · · dp N +N0 , (35) In Eq. (41), gik is the two-particle correlation function g (2)
of ions i and k (see Fig. 2); the force Fk , depending on both
and the Liouville equation yields the continuity equation the action of the external field E and the ion–ion interaction
∂ DN    forces in the solution, is given by the relationship
=− divi D N vi(N ) . (36)
∂t i Fk = e0 z k E − kT gradk gik − gradk Uik
The ion velocity vi(N )depends on the applied external elec-  N 
gikm
tric field E (which is independent of the position vari- − nm gradk Ukm drm , (42)
gik
ables), the ionic interactions, and the hydrodynamic cou- m=1
pling effects of ion i with the remaining ions: where gikm is the three-particle correlation function g (3)

N of ions k, i, and m; and n k and n m are the one-particle
vi(N ) = v0 (ri ) + ωi Fi(N ) + ωt χ ti F(N
t .
)
(37) distribution functions of ions k and m, which are the par-
t=1
ticle densities of Section I in the molecular scale, ρi (Sec-
In Eq. (37), v0 (ri ) is the velocity of solvent at position ri , tion I) = n i /NA . The velocities vi(1) and v0 of Eq. (41) are
and ωi and ωt are the generalized ion mobilities of ions i the particle velocity vi and the Hittorf reference velocity
and t [see Eq. (15)]. Fi(N ) and F(N
t
)
are the forces acting on v0 as defined in Section I.
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250 Electrolyte Solutions, Transport Properties

of drift velocities. The approximation used for the pair

potentials Ui j depends on the model underlying a con-
ductivity equation. The most elaborated models use the
superposition of long-range Coulomb Uicj and short-range
potentials Ui∗j :

e02 z i z j
Ui j = Uicj + Ui∗j = + Ui∗j . (47)
FIGURE 2 Explanation of the two-particle distribution and cor- 4π ε0 εri j
relation functions, f i j and gi j . The probability of simultaneously
finding an ion i in dV1 and an ion j in dV2 is given by the relation- Less elaborated theories neglect the short-range potentials.
ship. The theory of electrolyte conductivity is based on the
f i j (r1 , r21 ) = ni (r1 )n j (r2 )gi j (r1 , r21 ) two-particle continuity equation
= n j (r2 )ni (r1 )g j i (r2 , r12 ) = f j i (r2 , r12 ).
The elementary volumes dV1 and dV2 , with ion- and solvent- divi ( f i j vi j ) + div j ( f ji v ji ) = 0. (48)
permeable walls, are immovably fixed in relation to the observer
O at positions r1 and r2 in the solution. The quantities ni and n j where vi j and v ji are the relative velocity of ion X j in
are the concentrations of ions i and j in the solution (number of the vicinity of ion X i and vice versa. Equation (48), often
ions per unit of volume). called the Onsager continuity equation, is obtained from
the general continuity equation (36) by the usual averaging
processes, that is, integration over all momenta and N − 2
B. Single-Ion and Electrolyte Conductivity
space coordinates of the ions. The resulting two-particle
In a homogeneous and isotropic medium (solvent), the ion continuity equation yields Eq. (48) for the stationary case,
velocity vi is independent of position and yields the molar ∂ f i j /∂t = 0.
single-ion conductivity The boundary conditions for the continuity equation
|vi (t) − v0 | are
λi = e0 |z i |NA . (43)
|E| lim gi j = 0 (49a)
|r12 |→∞
Equation (43) is the basic relationship of electrolyte con-
ductivity. An electrolyte C z+ A z− shows the molar elec- and
trolyte conductivity  
ri j
(vi j − v ji ) = 0, (49b)
m = λ+ + λ− . (44) ri j ri j=R

Both single-ion and electrolyte conductivity depend on requiring attenuation to zero of the perturbation function
three effects: at infinite ion distance, Eq. (49a), and zero normal compo-
unperturbed ion migration [second term in Eq. (41)], nent of the relative ion velocity at a distance R, Eq. (49b);
relaxation effect [third term in Eq. (41)], and only the tangential component is different from zero at R.
electrophoretic effect [fourth term in Eq. (41)]. For the chemical model, distance R is the cutoff distance of
the short-range forces, which is also assumed to be the up-
Relaxation and electrophoretic effects are calculable with per limit of ion-pair association. Paired states of unequally
the help of Kirkwood’s superposition approximation for charged ions of symmetric electrolytes (z + = |z − |) at dis-
the three-particle correlation function gikm : tances lower than R are considered to be nonconducting
gikm = gik · gmk . (45) ion pairs.
The integration of the continuity equation is a laborious
The two-particle correlation functions gi j do not show the and time-consuming task, even for simple models of vi j
spherical symmetry of equilibrium functions as a conse- and gi j .
quence of the applied external field. The calculation of gi j Onsager’s limiting law is based on the correlation func-
functions requires a further approximation: the superpo- tion gi j of the Debye-Hückel theory which is the first cor-
sition of the unperturbed equilibrium function gi0j and a rect chemical model. It neglects the noncoulombic interac-
perturbation function gi j of axial symmetry, tion potentials. Since it was developed many attempts have
been made to put the concentration limit to higher values.
gi j (r1 , r12 ; t) = gi0j (r ) + gi j (r1 , r12 ; t). (46)
During the last 20 years, a quantitative description of
The perturbation term equals zero for correlation functions conductance and self-diffusion up to 1-M solutions has
of equal ions, gii = g j j = 0. been achieved by the use of modern gi j functions coming
The hydrodynamic coupling tensor χ ik is given by the from integral equation techniques such as the hypernetted
Oseen or the Navier-Stokes equations for Newton’s law chain (HNC) equation or mean spherical approximation
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Electrolyte Solutions, Transport Properties 251

(MSA). Some of these approaches will be discussed in

detail in the following sections.
The progress in equilibrium correlation functions has
also been used to extend the validity range of relations of
irreversible thermodynamics to higher concentrations. An
example is the Nernst-Hartley equation, Eq. (24), for com-
pletely dissociated electrolytes to yield the relationship
Q 1 D2∗ + Q 2 D1∗
D= , (50)
Q1 + Q2 FIGURE 3 Fundamentals of the moving boundary (mb) method.
where
ci 
Q i = z i e02 z i Dio + k B T z k ik (51a) t+ (C+ + − + −
k B T εεo k 1 ) is to be determined, or of C A1 and C A2 for the
−
anionic transference number t− (A1 ).
and The passage of a quantity of electricity I × t through
∞ a fixed reference plane perpendicular to the direction of
2NA
ik = ck h ik (r )r dr. (51b) migration is accompanied by a boundary movement, ob-
3η servable by spectroscopic or electrical methods, which
0
defines a volume V between the boundary positions b at
The term ik gives the hydrodynamic corrections on the time t = 0 and t. The transference number is given by the
moving ion X i due to all ions X k , h ik = gik − 1 is the relationship
total correlation function, and η is the solvent viscosity.
(1)
There are two routes to derive the chemical (or mutual) c+ VF
diffusion coefficient. One has been taken for HNC calcu- t+ = t+ (C+
1)= , (53)
It
lations and the other for an MSA treatment. It should be (1)
noted that while the HNC calculation is generally regarded where c+ is the equivalent concentration of the cation
+
as more accurate, it does not lead to explicit analytical ex- C1 and F the Faraday constant. The precision of transfer-
pressions, in contrast with the MSA which is simpler, but ence numbers obtained from mb experiments approaches
perhaps not as accurate, and leads to explicit formulas 0.02% for some systems.
that are reasonably accurate when the energy route for the Conductivity measurements on electrolyte solutions are
thermodynamic quantities is used. generally carried out with the help of bridge methods, a
conductance cell filled with the electrolyte solution being
one of the resistances in the arms of an ac Wheatstone
III. ELECTROLYTE CONDUCTIVITY bridge. Bridge and cell design is highly developed, and a
AND TRANSFERENCE NUMBERS precision of 0.01% is not unusual.
OF DILUTE SOLUTIONS Specific conductivities at temperature T, κ(T ), are ob-
tained from the measured resistances of the electrolyte
A. Transference Number and solutions R, after correction for the resistance of the pure
Conductivity Measurements solvent Rs by using the temperature-dependent cell con-
stant A(T ):
The transference number ti of an ion X i is equal to the
net number of faradays carried by this ion, free ion, or κ(T ) = A(T )[1/R − 1/Rs ]. (54)
constituent of an ionic species, across a reference plane The cell constant is obtained from measurements on aque-
that is fixed with respect to the solvent, when one faraday ous KCl solutions.
collectively passes (total electric current I ; partial electric z
Equivalent conductivities  of electrolytes Cν++ Aν−− ,
z
currents I+ and I− [see Eqs. (5)]:  = m /n e , are related to specific conductivities κ by the
I+ I− relationship (n e , electrochemical valency)
t+ = ; t− = ; t+ + t− = 1. (52)
I I κ
= ; n e = ν+ z + = ν− |z − |. (55)
Transference numbers ti are available by measurements, 1000n e c
the most reliable method at low electrolyte concentrations
being the moving boundary (mb) method (see Fig. 3).
B. Dispersion of Conductance
This method requires the formation of a sharp boundary
b between the solutions of two salts C+ − + −
1 A and C2 A in The time dependence of pair correlation functions
the same solvent when the cationic transference number gi j (r1 , r2 ; t) entails dispersion of conductivity when the
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252 Electrolyte Solutions, Transport Properties

applied external field is a high-frequency field. Finite re- C. Conductivity Equations of Dilute
laxation times of the ions surrounding the moving central Electrolyte Solutions
ion as a cloud of axial symmetry more or less prevent the
Onsagar’s limiting law is obtained from Eq. (57) when in
ion cloud from taking on the configuration that it would
Eq. (56) the passage to zero frequency is made, ν → 0.
have in a static external field, which thus diminishes the
Improved approximations in the calculation of pair cor-
conductance-hindering relaxation effect.
relation functions gi j and the introduction of short-range
According to the discussion in the preceding section,
potentials have led to improved conductivity equations of
molar conductivity can be expressed by an equation of
the type given by Eq. (56) or its truncated series develop-
type
ments of type
 m = ∞
m +  m + m ,
rel el
(56)  = ∞ − Sc1/2 + Ec ln c + J1 c − J2 c3/2 . (61)
showing the three contributions to conductivity: In Eq. (61) every coefficient, S, E, J1 , and J2 , contains
unperturbed ion movement in the external field at infi- the contributions of the electrophoretic and relaxation ef-
nite dilution of the electrolyte compound, ∞ fects, el and rel . The coefficients of the series-developed
m;
relaxation effect, rel ; and Fuoss-Hsia equation, including the so-called Chen effect
m
electrophoretic effect, el (see Section III.D), are given in Table I. Onsager’s limit-
m.
ing law in terms of Eq. (61) would be given by the series
At the lowest meaningful level of theory (limiting law at development
very low electrolyte concentrations), the relaxation term at
frequency ν of the external field is given by the relationship  = ∞ − Sc1/2 . (62)

e02 z + z − It should be stressed that the coefficients S and E are in-

rel
m = κ∞
m f (ν) (57) dependent of short-range contributions, that is, indepen-
12πε0 εkT dent of the model parameters a and R, in contrast with J1
where f (ν) is a frequency-dependent function which gives and J2 .
rise to the relaxation time of the ion cloud, The literature shows contributions by Justice and
Ebeling to the so-called echo or feedback effect dealing
(z + z − )2 e02 NA with the action of the electrophoretic and relaxation ef-
τ=  2 ∞ 2 ∞
, (58)
kT pκ 2 z + λ− + z − λ− fects on the underlying pair correlation functions gi j . This
and at zero frequency has the value
p |z + z − | λ∞
+ + λ−
∞ TABLE I Coefficients of the Conductivity Equation of
f (0) = √ ; p= ∞.
Symmetric Electrolytes
1+ p |z + | + |z − | |z + |λ∞
− + |z − |λ+
Λ = Λ∞ −Sc1/2 + Ec log c + J 1 (R)c − J 2 (R)c3/2
(59a,b) [z + = |z − | = z; SI units except c/(mol dm−3 )]

Quantity κ is the reciprocal radius of the unperturbed S = S1 ∞ + S2 ; S1 = 0.82043 × 106 z 3 (εT )−3/2
Debye ion cloud; it is given by the relationships (22). S2 = 82.484 × 10−5 z 2 (εT )−1/2 η−1
The electrophoretic term is given at this level by the E = E1 ∞ − 2E 2 ; E 1 = 6.7749 × 1012 z 6 (εT )−3
relationship E 2 = 0.99750 × 103 z 5 (εT )−2 η−1

2 2b2 + 2b − 1 κR
2 NA e0 J1 = σ1 ∞ + σ2 ; σ1 = 2E 1 + 0.9074 + ln 1/2
el
m = −(ν+ z + + ν− z − )
2
κ. (60a) b3 c
6πη 
35 2 κR
For symmetric 1,1 electrolytes (ν+ z + = ν− |z − | = 1) in the σ2 = E 2
3b
+ 2 − 2.0689 − 4 ln 1/2
b c
concentration range of the chemical model, Eq. (60a) is 
changed to κR  4.4748 3.8284
J2 = σ3 ∞ + σ4 ; σ3 = 1/2 E 1 0.6094 + +
c b b2
NA e02 κ 
el
m = . (60b) κR 34 2
3πη 1 + κR σ4 = 1/2 E 2 −1.3693 + − 2
c 3b b
The frequency dependence of conductivity was postulated κR
where = 0.50290 × 1012 z(εT )−1/2 ;
in 1928 by Debye and Falkenhagen from theoretical con- c1/2
siderations; a satisfactory experimental proof of this effect b = 16.709 × 10−6 z 2 (εT )−1 R −1 ; E 1 = 0.43429E 1 ;
E 2 = 0.43429E 2
is still lacking.
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Electrolyte Solutions, Transport Properties 253

effect is small and does not change the coefficients of the c+ = c− = αc are conducting species leads to an expres-
conductivity equation to a significant extent. Conductivity sion of the equivalent conductance:
equations for unsymmetric electrolytes, such as MgCl2 or
Na2 SO4 , are also given in the literature. /α = ∞ − S(αc)1/2 + Eαc ln(αc)
The chemical model of electrolyte solutions introduces + J1 (R)αc − J2 (R)(αc)3/2 , (65a)
short-range interactions by means of potentials of mean
1−α 1
force Wi∗j , which can be considered as contributions to KA = ; y±2 = y+ y− , (65b)
ion-pair formation. α 2 c y±2
For electrolyte conductivity, ion pairs of symmet- and
ric electrolytes are considered to be nonconducting,
κq
electrically neutral species. The appropriate expression − ln y± = . (65c)
of the thermodynamic equilibrium constant of ion-pair 1 + κR
formation, The coefficients J1 (R) and J2 (R) depend on the cutoff dis-
−→ [Cz+ Az− ]0 , tance R and thus include the influence of the short-range
C z+
+ A ←−
z−
(63)
forces on the transport phenomenon; for the activity coeffi-
introduced ad hoc into conductance theory, is given by the cient y± of the chemical model, see Electrolyte Solutions,
relationship Thermodynamics.
 R   Figure 4 shows the typical concentration and tempera-
2q Wi∗j
K A = 4000π NA 2
r exp − dr, (64a) ture dependence of the conductivity of a moderately asso-
a r kT ciated electrolyte in a nonaqueous solvent. The calculated
e02 |z + z − | conductivity curve [Eqs. (65)] reproduces the measured
q= . (64b) conductivities (open circles) with a precision of better
8πε0 εkT
than 0.02%. The broken line of 25◦ C is the limiting law,
The upper limit of ion-pair association and the cutoff dis- Eq. (62). There is no doubt that the Onsager limiting law
tance of short-range interactions in electrolyte solutions can be confirmed by highly precise measurements, but its
are considered identical in the framework of the chemi- validity range is limited at very low concentrations.
cal model. Association constants are independent of the Data analysis of conductivity measurements yields the
electrolyte property, thermodynamic property, or trans- limiting conductivities ∞ and the association constants
port property for which they are determined. Table II KA.
proves this statement by comparison of association con-
stants obtained from conductance measurements and mea-
surements of the heat of dilution.
The inclusion of the ion-pair concept in the statistical
thermodynamic theory is made by setting the distance R
of the boundary condition, Eqs. (49), equal to the upper
limit R of the association integral. Taking into account
that only the “free” cations and anions at concentrations

TABLE II Comparison of Association Constants from

Calorimetric KA (∆H ) and Conductivity KA (Λ) Measurements
at 25◦ C
K A (∆ H) K A (Λ)

Solvent Electrolyte mol−1 dm3 mol−1 dm3

Water MgSO4 161 162

CaSO4 192 189
NiSO4 210 209
2-Propanol Pr4 NI 513 516
Bu4 NI 534 515
i-AM4 NI 581 573 FIGURE 4 Temperature dependence and concentration de-
pendence of a moderately associated electrolyte, Bu4 NCIO4
Acetone LiBr 4593 mean value: 4530
[116 (−40◦ C) < K A /mol−1 dm3 < 904 (25◦ C)], in propanol [31.2
KI 164 177
(−40◦ C) > ε > 20.5 (25◦ C)] solutions at various temperatures.
Bu4 NI 242 232
Broken line: limiting law at 25◦ C.
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254 Electrolyte Solutions, Transport Properties

D. Theory of Transference Numbers The first is the contribution to the electrophoretic part of
of Dilute Solutions conductance, and the second results from the negligibly
small space-dependent part of the interionic two-particle
The definition of transference numbers, Eqs. (52), entails
force, λel(2) ∼
= 0 (Chen effect).
for 1, 1 electrolytes the relationships
Combining Eqs. (66)–(68) yields the transference-
Ii λi number equation in the form
ti = = , (66a)
I  ti − 0.5 ∞
λi∞ = . (69)
ti∞ = ∞, (66b) ti∞ − 0.5 ∞ + el

Equation (69) indicates that the relaxation effect does not
and influence transference numbers of symmetric electrolytes.
 = λ+ + λ− , (66c) Using Eq. (60b) for el yields the relationships
√
where λi and  are the single-ion and the electrolyte ti − 0.5 ∞ ∞ S2 αc −1
=   − + Bαc, (70a)
conductivities and λi∞ and ∞ the corresponding lim- ti∞ − 0.5 1 + κR
iting values. Single-ion conductivities contain relaxation 1−α 1
(λirel = λi∞ × E/E) and electrophoretic (λiel ) contribu- KA = , (70b)
α 2 c y±2
tions, just as electrolyte conductivity does; E is the
change in the electric field caused by the ion charges in and
κq
the solution: − ln y± = . (70c)
1 + κR
E
λi = λel + λi∞ 1 + . (67) In Eq. (70a) the coefficient B is not completely calculable;
E
B results from the terms of improved theories that are
The electrophoretic effects on anions and cations are neglected in Eq. (70a) and might include the consequence
equal. The electrophoretic contribution consists of two of unknown corrections needed in the experiments; S2 and
parts: κ R are given in Table I.
E Figure 5 shows the features of transference numbers.
λel = λel(1) 1 + The symmetry of Eq. (70a) is obvious. If t+∞ > 0.5, the
E
transference numbers increase with increasing concen-
E 2λel tration and decreasing temperature, and vice versa if
+ λel(2) 1 + + ∞ . (68) t+∞ < 0.5. Transference-number measurement yield the
E 

FIGURE 5 Temperature dependence and concentration dependence of cationic transference numbers of methanol
solutions of Me4 NSCN ( ❤) and KSCN (♦) at various temperatures. The full lines are the computer plots according to
Eqs. (70). [From Barthel, J., Ströder, U., Iberl, L., and Hammer, H. (1982). Ber. Bunsenges. Phys. Chem. 86, 636–645.]
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Electrolyte Solutions, Transport Properties 255

quantities ti∞ by extrapolation as the only character- where commonly the two formation constants K T+ and K T−
istic quantities of the electrolyte solution; the small are supposed to be equal. The maximum results from the
concentration dependence of the transference num- competition of ion aggregates of various types.
bers for symmetric electrolytes does not permit the The conductivity equation of Fuoss and Kraus,
determination of association constants, in contrast with
conductance measurements. The most important applica- y± c1/2
tion of transference-number measurements for symmetric 1 − S(∞ )−3/2 [c(1 − /∞ )]1/2
electrolytes is the determination of precise single-ion con- ∞ KT
ductances. Transference numbers were also successfully = 1/2
+ λ∞
T 1/2
(1 − /∞ )c, (72)
KA KA
applied in investigations of ion aggregates, which con-
tribute to ion mobility by their charges, such as ion pairs is the appropriate equation for reproducing the conductiv-
of nonsymmetric electrolytes and triple ions of symmetric ity curve up to concentrations near the conductivity min-
electrolytes. imum (cmin = 2.14 × 10−2 mol dm−3 at 25◦ C in Fig. 6).
In Eq. (72), y± is the mean activity coefficient of the free
ions; S the limiting slope (see Table I); λ∞ T the limiting
E. Triple-Ion and Higher-Ion
value of the triple ions C+ A− C+ and A− C+ A− ; and K A
Aggregate Formation
and K T = K T+ = K T− are the equilibrium constants of ion-
For low-permittivity solutions, the highest concentration pair, Eq. (63), and triple-ion, Eqs. (71), formation.
for which pairwise additivity of the potential functions is At concentrations far below the conductivity minimum
reasonable in MM-level Hamiltonian models is found at (c  10−3 mol dm−3 in Fig. 6), triple-ion formation can
very low concentrations, for example, 10−4 M in Fig. 6. be neglected. Data analysis is possible with the help of
Figure 6 shows the dependence on concentration Eqs. (65), in agreement with pairwise additive potential
and temperature of the molar conductivity of 1,2- functions, and yields the values of ∞ in Table III. The
dimethoxyethane solutions of LiBF4 from infinite dilution ion-pair association constants K A(1) of these plots agree
to saturation. The plots of  versus c1/2 show a minimum well with the K A(2) determined independently at higher
at moderate concentrations and a maximum at high con- concentrations with the help of Eq. (72), which takes into
centrations. Although the minimum is only weakly de- account both ion-pair and triple-ion formation. No method
pendent on temperature, the maximum exhibits a strong is known for the determination of the values of λ∞ T ; data
displacement. The minimum is a general feature of bilat- analysis yields only the product λ∞ T K T , in which the quan-
eral triple-ion formation: tity λ∞
T is commonly estimated to be 2 ∞
/3. Both ion-pair
−→ [C+ A− C+ ]+ ; K +
[C+ A− ]0 + C+ ←− (71a) and triple-ion formation decrease with decreasing temper-
T
ature in accordance with increasing solvent permittivity.
and The conductivity equation for electrolytes undergoing
−→ [A− C+ A− ]+ ;
A− + [C+ A− ]0 ←− K T− , (71b) unilateral triple-ion formation, Eq. (71a) or Eq. (71b), is
given by the relationship

2 (y±2 )2 c(1 − /∞ )

1 − S(∞ )2 [c (1 − /∞ )]1/2
(∞ )2 KT c  ∞ ∞
= + 2λT  − (∞ )2 (1 − /∞ ).
KA KA
(73)

TABLE III Limiting Conductivities and Ion-Pair and Triple-

Ion Formation Constants of LiBF4 Solutions in 1,2-
Dimethoxyethane at Various Temperatures from Conductivity
Measurements
Temperatures [◦ C] −45 −25 −5 15 25
FIGURE 6 Ion-pair, triple-ion, and higher-ion aggregate forma- ∞ /(S cm2 mol−1 ) 46.5 68.8 94.1 123 139
10−6 K A /(mol−1 dm3 )
(1)
tion exemplified by measurements of the equivalent conductivity 0.57 1.7 5.1 14.4 24
of LiBF4 in 1,2-dimethoxyethane solutions at 25◦ C and −45◦ C. 10−6 K A /(mol−1 dm3 )
(2)
0.53 1.7 5.0 13.9 23
[From Barthel, J., Gerber, R., and Gores, H.-J. (1984). Ber. Bun-
K T /(mol−1 dm3 ) 15 19 23 28 30
senges. Phys. Chem. 88, 616–622.]
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256 Electrolyte Solutions, Transport Properties

Triple-ion formation is commonly restricted to low- are rigorous statistical mechanical approaches. Only a few
permittivity solvents (ε < 15), but it is also known in high- of those that have attracted the interest of applied research
permittivity solvents as a consequence of noncoulombic and engineering science are treated here.
interactions. Three classes of transport equations can be found in the
literature: molten salt approaches, empirical extensions of
the equations for dilute solutions, and empirical equations
IV. VISCOSITY just for fitting measured data.
Molten salt approaches such as the Vogel-Fulcher-
The concentration dependence of the viscosity η of elec- Tamman (VFT) equation have been used repeatedly for
trolyte solutions up to moderate electrolyte concentrations analyzing the temperature dependence of transport prop-
is commonly represented by the equation erties W (T ) such as diffusion, conductance, and fluidity,
η(c) √ or of relaxation processes:
− 1 : A c + Bc. (74)  
ηs B
W (T ) = A exp − . (78)
In Eq. (74), ηs is the viscosity of the solvent, η(c) is the R(T − T 0 )
viscosity of electrolyte concentration c, and A and B are Equation (78) can be deduced from the equilibrium dis-
constants. Coefficient A is available from the theoretical tribution of an isothermal, isobaric ensemble of coop-
z+ z−
limiting law for Cν+ Aν− electrolytes: eratively rearranging domains in the liquid, which can
  √  undergo a transition to a new configuration without con-
1 e02 NA p̄ 2 1 − p ∗
η(c) − η = κ p̄ + 4 √ , figurational change at and outside its boundary.
480π ν+ z +2
ν− z −
2 p̄ 1 + p ∗ At the glass transition temperature T 0 of the system
(75) the configurational part of entropy vanishes. It is assumed
that the transition of the supercooled melt to the glass is a
where type of second-order transition to obtain Eq. (78), where
2 2 B is a temperature-independent energy term of transport,
3 3 2 2
z+ z− z+ z−
p̄ = ν+ ∞ − ν− ∞ ; p̄ = ν+
2
∞ + ν− ∞
R is the gas constant, and A is a temperature-independent
λ+ λ− λ+ λ− quantity, depending on the composition of the solution.
(76a,b) Equations based on empirical extensions of the equa-
and tions for dilute solutions use the fact that the viscosity
1 ν+ z + λ∞ ∞
+ − ν − z − λ−
of the system is the most important effect on the transport
p∗ =    . (76c) properties and introduce appropriate viscosity corrections.
ν+ z +
2
+ ν− z −
2
λ∞ ∞
+ /z + − λ− /z −

κ is given by Eqs. (22).

A rough estimation based on the approximation A. Empirical Equations
z + λ∞ ∞
+ = |z − |λ− shows that the relative viscosity increases The representation of physical properties of electrolyte
proportionally to the ratio of the radii of ion and ion solutions by the use of fitting equations is commonly ex-
cloud. ecuted with polynomials of concentration, temperature,
Coefficient B is an empirical quantity which reflects pressure, and so forth, or with mathematical functions
the effects of ionic size, solvent structure, and ion–solvent known for the appropriate representation of the shape of
interactions. Commonly it is split into ionic contributions the experimentally determined curves.
B = ν+ B+ + ν− B− , (77) One of the most useful expressions of this type is given
by Amis and Casteel for the specific conductivity of con-
which are related to crystallographic radii and structure centrated solutions:
parameters of ion–solvent interactions known from molar  
κ m m−µ
volumes. = b(m − µ) − a
2
. (79)
κmax µ µ
It makes use of four parameters (κmax , µ, a, b) for the rep-
V. TRANSPORT EQUATIONS FOR resentation of the measured data over wide concentration
CONCENTRATED ELECTROLYTE ranges and reproduces well the maximum of specific con-
SOLUTIONS ductivity κmax and its position µ (see Figs. 7 and 9); a and
b have no physical meaning.
Today, empirical transport equations of concentrated elec- The specific conductivity of concentrated electrolyte
trolyte solutions are available, as well as equations which solutions and its temperature dependence are of crucial
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Electrolyte Solutions, Transport Properties 257

For data analysis of specific conductivities based on the

VFT equation, Eq. (78), the glass transition temperature of
the electrolyte solution at molality m, T 0 (m), is assumed
to be
T 0 (m) = T 0 (0) + am + bm 2 ,

T 0 (0) = lim T 0 (m). (81)

m→0

In Eq. (81), T 0 (0) is the glass transition temperature of

the pure solvent. The temperature dependence of specific
conductivity at molality m, κm (T ), is then given by the
relationship
 
Bm(κ)
κm (T ) = Am exp −
(κ)
. (82)
R[T − T 0 (m)]
A similar equation is obtained for viscosities and other
transport properties.
The glass transition temperature of the pure solvent
T 0 (0), obtained by extrapolation (m → 0), is found to be
independent of the solutes in a given solvent and equal
FIGURE 7 Specific conductivity of LiBF4 in propylene carbonate to that from viscosity measurements, which shows that
at various temperatures from dilute solutions to saturation. Points:
the glass transition temperature is the appropriate refer-
experimental data; lines; Eq. (79). [From Barthel, J. (1985). Pure
and Appl. Chem. 57, 355–367.] ence temperature for transport processes in the liquid state.
Using this result in Eq. (82) yields the further important

interest in technology. Figure 7 shows the features of spe-

cific conductivity.
The maximum of specific conductivity κmax is a feature
of every electrolyte solution permitting sufficiently high
solubility of the solute. It follows from the competition be-
tween the increase dc of the electrolyte concentration and
the decrease d of the ion mobility when the electrolyte
concentration increases. The variation dκ of the specific
conductivity is given by the relationship
dκ = dc + cd. (80)
Equation (80), following from the definition of molar con-
ductivity  ∝ κ/c [Eq. (55)], shows that maximum spe-
cific conductivity κmax is attained at a concentration µ, at
which dκ equals zero.
The maximum of specific conductivity κmax and the con-
centration µ at which it is attained are correlated. Figure 8
indicates linear correlations as observed for propylene car-
bonate solutions at various temperatures.
This correlation is due to the existence of an energy
barrier depending on the temperature and on the solvent
parameters, particularly viscosity. At concentration µ, the
electrolyte shows an activation energy for the transport
process equivalent to that of the barrier. FIGURE 8 Linear correlation of maximum specific conductivity
κmax and corresponding values of µ exemplified by propylene
The concentration µ at maximum specific conductivity
carbonate solutions of various 1,1 electrolytes at 25◦ C, −5◦ C,
decreases with decreasing temperature, cf. Fig. 8, which and −35◦ C. (1) LiBF4 , (2) LiClO4 , (3) Bu4 NPF6 , (4) KPF6 , (5)
proves that viscosity is the most important conductance- Pr4 NPF6 , and (6) Et4 NPF6 . [From Barthel, J., and Gores, H.-J.
determining factor. (1985). Pure and Appl. Chem. 57, 1071–1082.]
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258 Electrolyte Solutions, Transport Properties


δµel δE
λi = λi∞ 1 + ∞i 1+ (83)
µi E

after the second-order effects are neglected.

The first-order approximation to the electrophoretic ef-
fect can be inferred from the electrophoretic velocity cor-
rection δµiel . The MSA pair distribution functions permit
an easy extension of Henry’s law of electrophoretic mo-
bility, cf. Eq. (60b),

δµiel kT 
∞ =− ∞ , (84)
µi 3π ηDi 1 + σ
where µi∞ is the electrophoretic velocity, Di∞ is the ionic
diffusion coefficient at infinite dilution [deducible from
λi∞ ; see Eq. (25)], and  is Blum’s screening parameter
of the MSA:
κ
2 = . (85)
FIGURE 9 Specific conductivity κ versus molarity m at 25◦ C
(1 + σ )
for Bu4 NClO4 in mixed solvents propylene carbonate–acetonitrile
In Eq. (84) σ is an average ionic diameter calculated from
(mole fraction of acetonitrile is indicated on the right side of each
curve). Points: measured data; full lines: Eq (79); dashed lines: the ionic diameters σi and the ion concentrations ci :
MSA equation.  2
i z i σi ci
σ =  . (86)
feature that the temperature coefficients of conductivity z i2 ci
for all electrolyte solutions at infinite dilution in a given κ is Debye’s parameter [Eqs. (22)].
solvent, and of viscosity, are equal at every temperature; The first-order relaxation effect is obtained by the solu-
that is, infinitely dilute solutions are corresponding states tion of the continuity equation at this level, which yields
in terms of transport energies. Suffice it to note that the
values extrapolated toward zero concentration of transport δE 1 β 2 e02 |z i z j |
=−
energies from highly concentrated solutions based on the E 4π ε0 ε 6kT σ (1 + σ )2
VFT equation equal those obtained from the conductivity
1 − exp(−2βσ )
equations based on MM-level Hamiltonian models. × , (87)
β2 + 2β + 2 2 [1 − exp(−βσ )]
B. Statistical Mechanical Approaches where
2 ∞ 2 ∞
Extended laws are available for the variation with con- e02 NA ci z i Di + c j z j D j
centration of the transport coefficients of strong and as- β2 = . (88)
ε0 εkT Di∞ + D ∞j
sociated electrolyte solutions at moderate to high concen-
trations. Like the CM calculations, this work is based on Association can be included in the extended theory with
the Fuoss-Onsager transport theory. The use of MSA pair the help of the CM, which yields the association con-
distribution functions leads to analytical expressions. Ion stant given by Eq. (65b). For the calculation of the portion
association can be introduced with the help of the chemical (1 − α) of ion pairs, Eq. (65b) is subjected to an iteration
method. A simplified version of the equations, by taking process beginning with yIP = y± = 1:
average ionic diameters, reduces the complexity of the  1/2
original formulas without really reducing the accuracy of yIP 1 2
yIP 4yIP
the description and is therefore recommendable for prac- 1−α =1+ − + .
2K A cy±2 2 K A2 c2 y±4 4K A cy±2
tical use for up to 1-M solutions.
(89)
C. Conductivity Equations The single-ion and the ion-pair activity coefficients of
MSA are made up by an electrostatic part and a hard-
For a completely dissociated electrolyte, the
 appropriate sphere contribution:
equivalent conductivity expression,  = λi , follows
from the ionic conductivities ln yi = ln yiel + ln yihs ; i = +, − or IP. (90)
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Electrolyte Solutions, Transport Properties 259

The electrostatic part yiel is given by the expression Ebeling and Kraeft developed a statistical theory for
ion–dipole solutions (physical model) with the aim of tak-
1 e02 z i2  ing into account ion–solvent interactions.
ln yiel = − , (91)
4πε0 ε kT 1 + σ Computer simulations such as molecular dynamics
el
that is, yIP = 0 for a symmetric electrolyte. For the hard- (MD) and Brownian dynamics (BD) permit the study of
sphere contribution, only the ratio transport properties. Self-diffusion coefficients can easily
be obtained by differentiation of mean-square displace-
 hs 2
y± 1 − 0.5ξ πσ 3 NA  ments or by integration of the velocity self-correlation
= ; ξ = cj (92) functions of the ion. In contrast, the evaluation of con-
hs
yIP (1 − ξ )3 6
ductivity by means of cross-correlation functions is cum-
is needed for the calculation of the association constant. bersome and computer-time-consuming and can only
The data analysis with the help of Eqs. (83), (84), (87), scarcely be executed.
and (88) where association constants are used with MSA The advantage of computer simulations is the possi-
activity coefficients [Eqs. (90), (91), (92)] yields a good bility of obtaining transport data that cannot or can only
reproduction of experimental data up to molar concen- barely be measured. It is possible in this way to simulate
trations. As an example, Fig. 9 shows the conductivity diffusion coefficients of solvent molecules in the ionic sol-
of Bu4 NClO4 in the mixed solvent system acetonitrile– vation shells and to compare them with those of the bulk
propylene carbonate. Comparison is made of measured solvent molecules and with those of the ions, or to study
data with MSA and the Amis-Casteel equation, which both transport coefficients at different time scales.
exactly reproduce the conductivity maximum at every sol-
vent composition.
SEE ALSO THE FOLLOWING ARTICLES

D. Self-Diffusion CHEMICAL THERMODYNAMICS • ELECTROCHEMISTRY •

ELECTROLYTE SOLUTIONS, THERMODYNAMICS • ELEC-
The self-diffusion coefficient is computed from the inter-
TROPHORESIS • STATISTICAL MECHANICS
diffusion coefficient of two isotropically different species
or from tracer diffusion, where a labeled ion in tracer
amount diffuses in a large excess of another electrolyte of BIBLIOGRAPHY
the same ion. The diffusion coefficient Di of the species
Xi is given by the expression Barthel, J., Krienke, H., and Kunz, W. (1998). “Physical Chemistry
of Electrolyte Solutions—Modern Aspects,” Steinkopf, Darmstadt/
δki
Di = Di∞ 1+ , (93) Springer-Verlag, New York.
ki Bernard, O., et al. (1992). J. Phys. Chem. 96, 398–403, 3833–3840.
Bernard, O., Turq, P., and Blum, L. (1991). J. Phys. Chem. 95, 9508–
where ki is the diffusive force acting on an ion Xi and 9513.
δki is the relaxation force. In the framework of MSA, the Bockris, J. O., and Reddy, A. K. N. (1998). “Modern Electrochemistry,”
first-order contribution to the relaxation effect for the ionic Vol. 1, 2nd ed., Plenum, New York, London.
species Xi reads Covington, A. K., and Dickinson, T., eds. (1973). “Physical Chemistry
of Organic Solvent Systems,” Plenum, New York.
δki 1 z i2 e02 κ 2 − κdif
2 Falkenhagen, H. (1971). “Theorie der Elektrolyte,” 2nd ed., Hirzel,
=−  , Leipzig (Engl. ed., 1952).
ki 4π ε0 ε 3k B T (1 + σ )2 κdif
2
+ 2(1 + σ ) Friedman, H. L. (1985). “A Course in Statistical Mechanics,” Prentice
(94) Hall, Englewood Cliffs, N.J.
Hansen, J. P., and McDonald, I. R. (1976). “Theory of Simple Liquids,”
where
Academic Press, London.
e02 NA  cn z n2 Dn∞ Justice, J. C. (1983). Conductance of electrolyte solutions. In “Compre-
κdif
2
= . hensive Treatise of Electrochemistry,” Vol. 5 (B. E. Conway, J. O.
ε0 εkT n Di∞ + Dn∞
Bockris, and E. Yeager, eds.), pp. 233–337, Plenum, New York.
Resibois, P. M. V. (1968). “Electrolyte Theory: An Elementary Introduc-
 is given by Eq. (85) and κ by Eqs. (22); σ is the average
tion to a Microscopic Approach,” Harper & Row, New York.
diameter, Eq. (86). Robinson, R. A., and Stokes, R. H. (1970). “Electrolyte Solutions,” 2nd
rev. ed., Butterworth, London.
Spiro, M. (1984). Conductance and transference determinations. In
E. Other Approaches “Physical Methods of Chemistry,” 5th ed. (B. W. Rossiter, J. F.
Hamilton, eds.), Wiley (Interscience), New York.
Altenberger and Friedman have given a conductance equa- Turq, P., Barthel, J., and Chemla, M. (1987), “Transport, Relaxation and
tion based on an HNC approach which is also valid up to Kinetic Processes in Electrolyte Solutions,” Lecture Notes in Chem-
concentrations of about 1 mol dm−3 . istry, Springer-Verlag, Heidelberg.
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Energy Transfer, Intramolecular

Paul W. Brumer
University of Toronto

I. Introduction
II. Qualitative Dynamics
III. Dynamics: Theory
IV. Statistical Approximations and Dynamics
V. Experimental Studies
VI. Control of Dynamics
VII. Summary

GLOSSARY Mixing Classical mechanical system that is ergodic

and possesses additional properties associated with
Adiabatic Process during which there is no change in the relaxation.
electronic configuration of the molecule. Pure state State of a system in which all information
Constant of the motion Property of a system, expressible about the state is known and specified.
as a smooth function of the coordinates and momenta, Relaxation Tendency of a system to evolve from a spe-
whose numerical value remains unchanged during the cific time-dependent initial state to a time-invariant
course of the system dynamics. final state.
Ergodic Classical mechanical system in which a trajec- Statistical Qualitative term signifying models or dy-
tory uniformly covers a specific surface in phase space. namics with characteristics of ergodic and mixing
The physics literature utilizes this term to imply uni- behavior.
form coverage of the surface in phase space defined by Unimolecular decay Process in which an energized
fixed total energy. molecule breaks up into smaller molecular consti-
Integrable Also termed regular or quasiperiodic. Classi- tuents. The molecular analog of nuclear fission.
cal mechanical system characterized by the existence
of a set of independent constants of the motion equal in
number to the number of degrees of freedom of the sys- INTRAMOLECULAR dynamics is the time evolution of
tem. Specific attributes of such systems are discussed rotational, vibrational, and electronic degrees of freedom
in the text. of isolated individual molecules, that is, molecules in a
Mixed state State of a system in which there is some collision-free environment. As in any mechanical system,
information missing relative to a complete specification one can consider the time evolution of any of a variety of
of the state. system properties. Intramolecular energy transfer focuses

477
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478 Energy Transfer, Intramolecular

on the dynamical flow of energy among subcomponents dance with quantum mechanics. Third, the time-evolved
of the molecule as the primary property of interest. state of the system is analyzed, that is, measured. Ex-
plicit emphasis in a measurement (and sometimes prepa-
ration) on the flow of energy among subcomponents of
I. INTRODUCTION the molecule (e.g., chemical bonds or rotational degrees
of freedom) constitutes the study of intramolecular energy
Naturally occurring systems in the gaseous or liquid transfer.
phase at typical temperatures are composed of vast It is advantageous to distinguish two qualitatively dif-
numbers of atoms and molecules in constant motion. The ferent types of intramolecular energy flow, which we
well-defined system temperature is a reflection of the shall term reversible and irreversible. In the former, en-
stored energy content, both in the form of intermolecular ergy flows from one part of the molecule to another,
features such as molecule–molecule interactions and but then subsequently returns, reforming the initial state.
translational motion and in the form of motion internal to That is, the system shows no long-term trend toward a fi-
individual molecules. The latter, the motion of isolated nal redistribution of energy among subcomponents of the
molecules, is termed intramolecular dynamics. Included molecule. In the latter, there is a transfer of energy within
within this definition are both dynamics at energies below the molecule, with a general trend toward a stationary final
the dissociation energy of the molecule, in which case state. The latter behavior is that associated with relaxation,
it remains perpetually bound, and dynamics at energies or statistical, dynamics and has historically been assumed
above dissociation, in which case the molecule can break to occur in highly excited molecules. Conditions under
up into different chemical products. which molecular systems appear to display reversible vs
Intramolecular energy transfer is the subset of in- irreversible energy transfer are discussed in detail later.
tramolecular dynamics in which the focus of attention is Intramolecular dynamics and intramolecular energy
on the flow of energy within the isolated molecule. As the transfer have been, and continue to be, areas of intense
simplest of models, one may imagine a linear molecule scientific interest. Such interest falls into two categories,
A B C as being three mass points coupled by springs. loosely termed “practical” and “fundamental.” From the
Initiating an oscillation of the model by stretching the A B practical viewpoint, note that the outcome of a molec-
spring and subsequently observing the time-dependent al- ular process is heavily linked to the flow of energy in
teration of lengths of the A B and B C springs correspond the molecular participants. That is, an understanding of
to a simple model of an experiment on vibrational energy intramolecular energy transfer proves central to the in-
transfer. Indeed, modern experimental techniques allow terpretation of chemical processes and their dependence
for the creation of collision-free environments in which on system conditions. For example, unimolecular decay,
such isolated intramolecular dynamics may be studied and in which an isolated energized molecule dissociates into
possibly externally influenced. chemical products (e.g., ABC → A + BC, where ABC, A
The isolated molecule, comprised of a set of N atoms and BC are arbitrary molecules), occurs via the concen-
bound by interatomic forces, is a complex physical sys- tration of sufficient energy in the A BC bond. Further
tem. It possesses 3N degrees of freedom related to nuclear practical interest arises from important developments in
motion, three being associated with center-of-mass trans- laser technology that permit the introduction of energy
lation, three with rotation (or two if the molecule is linear), into molecules in a variety of controlled ways. This opens
and the vast remainder with vibration. The molecule also the possibility of externally influencing the outcome of
has electronic degrees of freedom associated with the con- a molecular process by varying the initial mechanism of
figuration of its electrons. Additional degrees of freedom, preparation (e.g., producing AB + C, rather than A + BC,
related to internal nuclear composition, are not readily from ABC by judicious preparation of the initial state).
altered at the energies of interest in molecular chemistry Indeed, theoretical developments over the past three years
and physics and can therefore be neglected. Thus, even have led to several proposals for controlling chemical re-
the simplest description of the dynamics of a typical small actions in this manner (see Section VI).
molecule such as benzene (C6 H6 ), which regards it as be- From a fundamental viewpoint, intramolecular energy
ing composed of 12 atoms, involves the complex motion transfer links to three basic scientific issues: (1) rever-
of 33 interacting degrees of freedom. sible vs relaxation phenomena, (2) quantum vs classical
It is convenient to visualize intramolecular dynamics in chaos, and (3) quantum/classical correspondence. These
terms of three steps, not necessarily independent. First, the are briefly introduced in Section II, where it becomes clear
molecule is prepared in a time-dependent state by any of a that intramolecular energy-transfer studies provide a use-
variety of means (e.g., collisions, chemical reaction, laser ful laboratory for the study of fundamental questions in
excitation). Second, the molecule evolves in time in accor- these areas.
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Energy Transfer, Intramolecular 479

Experimental and theoretical studies of intramolecular separate steps. In the first step, the forces between the
energy transfer and intramolecular dynamics have a long atoms in the molecule are determined or modeled, while
history. This article, designed as an introduction rather in the second step one considers the dynamics determined
than as a survey, focuses on recent directions in this field of by these forces. This dynamics is done either quantum
research. Of specific interest are insights gained into gen- mechanically, which is correct but difficult, or via
eral rules for understanding and measuring intramolecular classical mechanics, which is often a good approximation
dynamics. For this reason we cite only a few sample com- to the quantum result. In either case, the forces describing
putations to illustrate relevant general features and provide the dynamics are sufficiently complex to necessitate
only a brief qualitative discussion of experimental meth- numerical computer solutions. As an introduction to
ods. References to more historical interests in the field are the nature of intramolecular dynamics and to issues of
provided at the end of this article. interest in this area, we consider two examples.
The organization of this article is as follows. Section II
is designed to provide qualitative insight into intramolec-
ular energy transfer via two subsections. The first, Sec- A. Two Model Calculations
tion II.A, discusses selected computational results on two As a first example, consider nuclear motion in a four-
molecular models, and the second, Section II.B, quali- atom system, A B C D. Two qualitatively different en-
tatively introduces the fundamental problems alluded to ergy ranges are possible. In the first, the system is pro-
above. The reader who is interested in a qualitative pic- vided with sufficient energy to induce vibrational and ro-
ture is urged to first focus on these sections. Section III tational motion but insufficient energy to break any of
contains a description of isolated molecule dynamics from the bonds. This is bound-state intramolecular dynamics.
both the quantum and the classical viewpoints. Emphasis In the second regime, there is sufficient energy to allow
here is on several general features of classical and quan- molecular dissociation to one or more of the molecular
tum intramolecular dynamics. Finally, two brief sections, products (e.g., A B + C D). Typically, each of the inter-
Sections IV and V, discuss statistical approximations to atomic bonds will have a different dissociation energy, the
intramolecular energy transfer and the nature of modern energy required to break the bond. Thus, several dissoci-
experiments designed to probe molecular motion. ation “channels” are possible, such as
Space limitations, coupled with the author’s intention
to provide a useful introductory treatment, have led to A B C D → A B+C D E1
restrictions on the material that can be covered. Thus, A B C D → A+B C D E2
we focus throughout this article on adiabatic processes,
that is, dynamics that take place without change in the A B C D → A+B+C+D E3
electronic configuration of the molecule. When this is where the lowest energy required for each of the particular
not the case, a remark to this effect is made. In addi- processes is arbitrarily labeled E 1 , E 2 , etc.
tion, we assume throughout that the radiation field, be Consider the specific case of NaBrKCl for which the-
it associated with radiative absorption or emission, is suf- oretical, classical dynamics studies are available at en-
ficiently weak to be treatable as a perturbation. Further, ergies where two dissociative channels are energetically
the field of intramolecular dynamics is replete with model accessible. (Questions as to the validity of the classical
approaches that, albeit reasonable, have not been justi- picture are relegated to later sections.) This system pos-
fied either theoretically or experimentally—the latter due sesses attractive forces between the atoms such that the
principally to technological limitations. The modern focus bound NaBrKCl species lies at an energy of approxi-
on accurate dynamics is emphasized in this article, with mately 40 kcal/mol below NaBr + KCl or NaCl + KBr.
the consequence that such simple models are necessarily Specifically, consider the case where energized NaBrKCl
slighted. is formed by the collision
NaBr + KCl → NaBrKCl
II. QUALITATIVE DYNAMICS with sufficient energy to dissociate as
Information regarding intramolecular dynamics is avail- NaBrKCl → NaCl + KBr
able from three sources: experimental studies on specific
NaBrKCl → NaBr + KCl.
molecular systems, theoretical computations on spe-
cific systems or models, and formal studies of typical The initial collision between NaBr and KCl is here
(“generic”) systems. At present, the latter two provide regarded as the preparatory step to the subsequent in-
considerably greater detail than the first and involve two tramolecular dynamics and decay of the intermediate
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480 Energy Transfer, Intramolecular

Here, the system forms a bound four-body molecule at ap-

proximately 38,000 atu that persists until t = 240,000 atu.
During this time the various bond distances go through
a variety of values between 4 and 11 Bohr radii, a sort
of vibrant dance of four bound particles. Decay follows
thereafter to the product diatomics.
In a classical picture, knowledge of the distances and
momenta of the atoms as a function of time permits com-
plete knowledge of all properties. Figure 3 shows, for ex-
ample, the calculated energies in each of the alkali–halide
bonds during the course of the dynamics for the same col-
lision as seen in Fig. 2. Figure 4 contains an analogous pic-
ture of the rotational energy of the four-atom system. The
dynamics is clearly marked by extensive energy exchange
between the bonds and among rotation and vibration.
These examples provide a picture of the complexity of
individual trajectories in bound intramolecular dynamics.
Such a trajectory emerges from a precise specification of
initial particle momenta and coordinates. A comparison
FIGURE 1 Time dependence of each of the six interatomic dis- with real phenomena requires, however, averaging over
tances during a trajectory describing the collision of NaBr with all initial conditions not precisely specified in the given
KCl. System energy is E = 0.0912 a.u. [From Brumer, P. (1972). experiment. For example, the experiment may only have
Ph.D. dissertation, Harvard University.] initially fixed the translational and internal energies of
the colliding partners. Figure 5 provides a typical exam-
ple of the result of averaging over a set of trajectories
NaBrKCl species. An analogy to the collision, bound where the trajectory in Fig. 2 is one participant. Here, we
molecule dynamics, and subsequent decay is a system of show a typical measurable in the decay of NaClKBr, that
two balls, attached by a spring, colliding with two other is, the probability of independently finding the products
such balls on a billiard table containing a deep hole in the NaCl and KBr with particular vibrational energies. Note
center. The springs are breakable and endowed with the that the results are simpler than the complex underlying
ability to exchange between pairs of particles. trajectories. This is a result of both the comparatively sim-
The basic dynamics in classical mechanics is embod- pler question being asked and the averaging implicit in the
ied in trajectories, that is, the dynamics following precise computation.
specification of the system initial conditions. Comparison The details of the dynamics ongoing during the course
with experiment then involves averaging results over a set of the collision also often simplify as a result of averaging
of trajectories consistent with the specific experimental over a set of trajectories. Consider, for example, Fig. 6,
conditions. Two such trajectories are considered in Figs. 1 which shows the average vibrational energy in each of the
and 2, where we show the time dependence of the dis- four alkali–halide bonds during the collision; in this case
tances between all the atoms during the collision. In one the calculation only shows trajectories prior to dissocia-
case the initial conditions lead to a long-lived intermedi- tion. The results are to be compared to Fig. 3, although
ate, and in the other case they lead to a short-lived species. the overall energies in the two figures are somewhat dif-
Consider the shorter trajectory (Fig. 1) first. A careful ex- ferent. One sees that each of the bond energies changes
amination of the figure indicates the initial oscillations of rapidly over the initial time period but then tends to level
the bound NaBr and KCl, with the other atomic distances out. This is an example of apparent intramolecular energy
shrinking in time as the two diatomics approach one an- relaxation during the course of the dynamics. That is, the
other. The collision between them occurs at approximately system seems to reach, at least with respect to these vari-
12,000 atomic time units (denoted atu, where an atomic ables, a relatively invariant state reminiscent of the behav-
time unit is 2.4 × 10−17 sec) and is promptly followed ior of macroscopic systems relaxing to equilibrium. The
by decay to NaCl + KBr. Thus, for these particular ini- observation of relaxation behavior is, of course, not ubiq-
tial conditions, the intermediate species NaClKBr is only uitous and is dependent on gross system conditions (e.g.,
a fleeting phase in the collision. Results in Fig. 2 are in total energy, total angular momentum, etc.). Understand-
sharp contrast, showing a long-lived intermediate that dis- ing conditions under which intramolecular dynamics may
plays complex dynamics in a bound energized molecule. be approximated by a statistical model is indeed one of the
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Energy Transfer, Intramolecular 481

FIGURE 2 Similar to Fig. 1 but at a lower energy, E = 0.0227 a.u. [From Brumer, P. (1972). Ph.D. dissertation,
Harvard University.]

main themes in intramolecular energy transfer. Such sta- role of the relative rates of intramolecular energy trans-
tistical models have both advantages and disadvantages. fer and other competitive processes. That is, the degree of
They are advantageous in that they considerably simplify intramolecular energy flow within the molecule depends
the description of the dynamics. They are disadvantageous on the length of time the system exists as a bound en-
in that they imply that the final state of the system is rela- tity, as well as on some (as yet undefined) “rate of in-
tively insensitive to the initial state. That is, the outcome tramolecular energy flow.” In cases where competitive
of a chemical event is not readily influenced by altering processes such as dissociation (or the ever-present radia-
initial conditions. tive emission) are possible, effective intramolecular en-
The example discussed here displays a number of rele- ergy flow requires a larger rate of energy transfer than of
vant features. Clearly noticeable is the complexity of indi- competitive processes. (Note, however, that in the case
vidual trajectories modeling long-lived dynamics, as well of competitive dissociative or other nuclear rearrange-
as the possibility of simplifications that result if a statistical ment processes, both the energy transfer and the compet-
description that includes relaxation applies. The partici- itive process are governed by the same set of underlying
pation of rotations as well as vibrations in the dynamics dynamical equations for the nuclear motion. This leads to
is also evident. In addition, it makes clear the important a natural difficulty associated with attempting to partition
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482 Energy Transfer, Intramolecular

FIGURE 3 Vibrational energy in each of the four alkali–halide bonds, as a function of time, for the trajectory shown
in Fig. 2. [From Brumer, P. (1972). Ph.D. dissertation, Harvard University.]

the dynamics into distinct parts labeled intramolecular dy- mechanics, where the initial state is a mixed state (see
namics and dissociation.) Section III.C). One useful measure of system dynamics is
The computation described above is completely classi- the probability of the system returning to the state from
cal: the nuclear motion is assumed to be well described which it started. Figure 7 shows the time dependence of
by Newton’s equations. The extent to which classical me- this probability for one case, where the quantum and clas-
chanics provides a useful description of intramolecular en- sical results are seen to be in excellent agreement. In sharp
ergy flow is another focus of current research in this area. contrast is the comparison shown in Fig. 8, which cor-
As one example of the validity of classical mechanics, responds to the probability of return to another, higher
consider the bound-state dynamics of a three-atom sys- energy initial mixed state where classical–quantum dis-
tem confined to a line, that is, A B C. Computations on agreement is substantial. The effect has also been seen
the case where the A B and B C bonds are anharmonic for the higher energy decay of A B C to AB + C as
have been performed using both classical and quantum shown in Figs. 9 and 10. Specifically, the probability of the

FIGURE 4 Total rotational energy associated with the NaClKBr system during the trajectory shown in Fig. 2. [From
Brumer, P. (1972). Ph.D. dissertation, Harvard University.]
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Energy Transfer, Intramolecular 483

disagreement in the other, with the classical being more

statistical. The origin of this difference lies, in this case, in
the existence of so-called quantum trapping states, which
lead to classical results that behave more statistically than
the quantum. Such states occur when there is a very asym-
metric distribution of energy among the bonds in the
molecule. Although here classical mechanics is more sta-
tistical than quantum mechanics, this is not always the
case.
The computations described above are useful in that
they provide some qualitative insight into the nature of
intramolecular dynamics and energy flow in particular
systems. They are, in essence, theoretical experiments on
given systems in that they provide only hints of the general
rules that govern rates, nature, and degree of intramolec-
ular energy interchange. In the sections that follow, we
describe the current state of understanding on the general
principles that underlie these processes. Prior to doing so,
FIGURE 5 Probability of producing a specific vibrational state of we emphasize, in the next section, some of the fundamen-
NaCl or of KBr from collisions of NaBr with KCl at E = 0.0411
a.u. [From Wardlaw, D. (1982). Ph.D. dissertation, University of
tal issues related to intramolecular energy transfer that
Toronto.] have been alluded to above.

system remaining in its initial state is shown in Figs. 9

B. Fundamental Issues: Qualitative Overview
and 10 for dynamics initiated in two different mixed states.
Once again, agreement is achieved between classical and The goal of science is to provide a qualitative and quantita-
quantum mechanics in one case, but there is substantial tive description of natural phenomena. Such a description

FIGURE 6 Average energy in each of the four alkali–halide bonds as a function of time. Here, the average values
are obtained from a set of NaBr + KCI trajectories. “Error bars” show the range of values associated with the set of
trajectories incorporated in the calculation. [From Brumer, P. (1972). Ph.D. dissertation, Harvard University.]
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484 Energy Transfer, Intramolecular

the former we mean a description based on Newton’s equa-

tions in classical mechanics or Schrodinger’s equation in
quantum mechanics. By the latter we mean descriptions
characteristic of nonequilibrium statistical mechanics,
such as the Boltzmann or Fokker–Planck equation. Dy-
namics (either quantum or classical) is based on a set of ba-
sic equations that are time-reversal invariant. This property
means that the final state of a process may be time reversed
to recover the initial state. It implies that the final state of
dynamical evolution contains all the information associ-
ated with the initial state. As a consequence, relaxation to
a final equilibrium state, independent of the fine details of
the initial state, does not occur, and hence, the final state
may be a sensitive function of the initial state. Relaxation
to equilibrium is, however, a familiar feature in macro-
FIGURE 7 Classical (dashed) and quantum (solid) probability, as
a function of time, of a coupled Morse oscillator system remaining scopic systems, and the equations of statistical mechanics
in its original state. [From Kay, K. (1980). J. Chem. Phys. 72, 5955.] are designed to provide a nonmicroscopic description that
encompasses the relaxation process. The link between the
underlying time-reversible equations of motion and the
is most useful if it is as simple as possible. For example, macroscopic irreversible equations is not well established
there is little reason to invoke relativistic quantum mechan- and has been the subject of extensive, long-standing dis-
ics to describe planetary motion; classical mechanics will cussions on the basic equations of nature. Typical ques-
normally suffice. Furthermore, such a scientific descrip- tions include the following. Are time-reversible equations
tion is most useful if it is computationally tractable. Thus, more fundamental than statistical relaxation equations, or
for example, thermodynamics often provides a more use- do they have equal, but independent, roles as models of
ful route to disallowing certain processes in a bulk system nature? Is observed relaxation a consequence of coarse
than does a full dynamics calculation involving the under- graining associated with macroscopic measurements on
lying Avogadro number of molecules. It is in this spirit that intrinsically time-reversible systems?
the utility of two approximate descriptions—classical me- Isolated-molecule dynamics is expected to be a suf-
chanics in lieu of quantum mechanics, and statistical ap- ficiently elementary process to permit observation of
proaches in lieu of full dynamics calculations—is a central microscopic reversibility in the dynamics and, hence, to
theme in contemporary intramolecular dynamics. Indeed, display a dependence of the outcome of dynamics on ini-
they intertwine in an interesting fashion. tial conditions. This dependence is desirable since the
Consider first the essential difference between a dynam- ability to retain information about initial conditions is
ics description and a statistical description of a system. By necessary in order to achieve the technologically desir-
able goal of externally influencing chemical reactions.
However, a great many experiments, perhaps with insuffi-
ciently well-characterized preparation and measurement,
have indicated that time-irreversible relaxation is a useful
model for many intramolecular processes. Thus, isolated-
molecule intramolecular dynamics serves as a laboratory
for the study of the inter-relationship between irreversible
relaxation behavior in systems that are fundamentally de-
scribable by time-reversible equations of motion. It also
presents an experimental challenge to prepare sufficiently
well-characterized states to observe time reversibility and
sensitivity to initial conditions.
Two further issues of fundamental importance, that of
quantum–classical correspondence and that of “quantum
chaos,” are intimately linked to studies in intramolecu-
lar dynamics. Extensive theoretical studies, beginning in
FIGURE 8 Same as Fig. 7, but for a different initial state. [From the early 1960s, showed that a great many phenomena
Kay, K. (1980). J. Chem. Phys. 72, 5955.] involving the dynamics of atoms and molecules are well
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Energy Transfer, Intramolecular 485

degrees of freedom) can display highly statistical behav-

ior, termed chaos. One can show formally, however (as
will be described further below), that such chaotic behav-
ior is not possible in bound-state quantum mechanics. Fur-
ther, typical semiclassical schemes that base quantization
on the classical system motion (e.g., Einstein–Brillouin–
Keller quantization) do not hold in this classically chaotic
regime.
Computational studies have indicated that chaotic be-
havior is expected in classical mechanical descriptions of
the motion of highly excited molecules. As a consequence,
intramolecular dynamics relates directly to the fundamen-
tal issues of quantum vs classical chaos and semiclassical
quantization. Practical implications are also clear: if clas-
sical mechanics is a useful description of intramolecular
FIGURE 9 Classical (dashed) and quantum (solid) probability of
dynamics, it suggests that isolated-molecule dynamics is
a coupled Morse–harmonic oscillator system remaining in its initial sufficiently complex to allow a statistical-type descrip-
state. The energy is sufficient to allow dissociation. [From Kay, K. tion in the chaotic regime, with associated relaxation to
(1984). J. Chem. Phys. 80, 4973.] equilibrium, and a concomitant loss of controlled reaction
selectivity.
described by classical mechanics. That is, atomic and
molecular dynamics are at the borderline between clas-
sical and quantum mechanics, in that dynamic phenom- III. DYNAMICS: THEORY
ena in molecules are often well approximated by classical
dynamics. This is not always the case, as shown in the ex- This section provides an introduction to the theory of clas-
ample in Section II.A, and so studies in intramolecular dy- sical and quantum intramolecular dynamics, with empha-
namics provide insight into the utility of classical mechan- sis on general principles.
ics as an approximation to quantum mechanics. Phrased
in this manner, this appears to be a question of relative A. The Hamiltonian
accuracy, with the expectation that the process is qualita-
tively similar in both mechanics. Recently, however, ma- A complete description of the dynamics of any molecular
jor qualitative distinctions between classical and quantum system is contained in the Hamiltonian H , which is the en-
mechanics have been noted. Specifically, it is now known ergy operator in quantum mechanics or the energy function
that even small classical mechanical systems (e.g., two in classical mechanics. In general, the Hamiltonian is a
function of the electronic and nuclear degrees of freedom,
as is the description of the system dynamics. This com-
plex problem simplifies through the adoption of the Born–
Oppenheimer approximation, which is the assumption that
nuclear and electronic motion are independent due to their
substantially different time scales and masses. This as-
sumption allows one to first solve for the dynamics of the
electrons and then obtain the forces experienced by the
nuclei as determined by this fixed-electron configuration.
Within the Born–Oppenheimer approximation, the nu-
clear Hamiltonian may be written in the form
H (q, p) = T (p) + V (q), (1)
where T (p) is the nuclear kinetic energy and V (q) is the
nuclear potential energy. Classically, p is the momentum
of the nuclei, whereas in quantum mechanics it is the mo-
mentum operator. In general, q has 3N components for an
FIGURE 10 As in Fig. 9, but for a different initial state. [From Kay, N -atom system. However, it is always possible to elimi-
K. (1984). J. Chem. Phys. 80, 4973.] nate three coordinates corresponding to the center of mass
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486 Energy Transfer, Intramolecular

of the system, and we shall assume this reduction to the phase space, with (q, p) as coordinates. A trajectory is a
internal molecular coordinate system has been carried out; curve in this space parametrized by the index t.
thus, q denotes 3(N − 1) coordinates. Modeling a realistic system necessitates producing a set
Central to the nature of dynamics is the notion of cou- of trajectories with varying initial conditions and looking
pled vs uncoupled degrees of freedom. Consider, for ex- at averages of system properties over this set. It is this
ample, a system whose Hamiltonian is the sum of two trajectory technique, where V (q) is a model or realistic
terms, such that potential and where Hamilton’s equations are solved nu-
merically on a computer, that has been extensively used
H (q, p) = h 1 + h 2 , (2) to study intramolecular dynamics in small molecules. Re-
where h 1 depends on a different set of coordinates and sults typical of those obtained were shown in Section II.A.
momenta than h 2 . Under these circumstances, the dynam- The flexibility of Hamilton’s approach lies in the ap-
ics of the degrees of freedom in h 1 are independent of pearance of generalized canonical coordinates (p, q). As
those in h 2 . That is, the total system is composed of two a consequence of their generality, one may seek out the set
independent subsystems. Introduction of a coupling term, of coordinates and momenta within which the dynamics
to give is most easily performed and understood. For example,
a conservative Hamiltonian system may have, along any
H = h 1 + h 2 + V (1, 2), (3) trajectory, a constant value of total angular momentum J.
Such a quantity is said to be a constant of the motion and
where V (1, 2) is a term dependent on the coordinates and
can prove useful as a momentum, since the equation of
momenta of both h 1 and h 2 , induces energy exchange
motion for J is particularly simple, dJ/dt = 0. Indeed, the
and interrelated dynamics among the entire system. Major
idea of seeking constants of motion for use as coordinates
qualitative changes in the dynamics can result from small
or momenta is the central goal of the Hamilton–Jacobi
perturbations or couplings.
approach to classical dynamics. The essential approach is
It is important to note that although Eq. (3) is conceptu-
simple. One seeks a set of M constants of the motion A of
ally pleasing, there is no unique division into subsystems
the system via a systematic procedure. Once found, these
and into intersubsystem coupling for a given physical sys-
momenta are known to be constant along any trajectory,
tem. Rather, such a division must be motivated by an ex-
and the time dependence of the conjugate coordinates is
perimental or theoretical interest in a particular property,
generally simple. With the constants of the motion known,
such as the energy flow between subsystems h 1 and h 2 .
along with the procedure for generating them, it is a rel-
Central to the nature of intramolecular energy transfer is
atively straightforward algebraic problem to express the
an understanding of the effect of the coupling V (1, 2) on
desired q(t), p(t) in terms of these constants and their
the energy flow among the subsystems represented by h 1
conjugate coordinates. That is, we have
and h 2 .
p(t) = A = const 1
(5)
B. Classical Mechanics q(t) = q(t, A).
There are a number of formulations of classical mechan- Although we shall not deal with Hamilton–Jacobi theory
ics, each providing different insights into its nature. For here, the concept of a set of constants of the motion is vital
example, Hamilton’s method, used here, describes dynam- to an understanding of the issue of intramolecular energy
ics in terms of trajectories in generalized coordinates and flow and statistical vs nonstatistical behavior. In essence,
momenta. Consider an M degrees of freedom system with the number of global constants of the motion provides a
system Hamiltonian H (q, p), where (q, p) is a complete method for grouping systems into general categories.
set of M conjugate generalized coordinates and momenta. Consider an M-degrees-of-freedom system. How many
The time evolution of the system is given by Hamilton’s constants of the motion can we identify for a given tra-
equations, jectory? The answer is clearly 2M, with the simplest set
dqi /dt = ∂ H/∂ Pi d pi /dt = −∂ H/∂qi (4) consisting of the initial values of the coordinates and mo-
menta that define the trajectory and that surely constitute
with i = 1, . . . , M. Specifying the state of the system at a set of 2M equations for q(t), p(t) in terms of constants.
t = 0 via the initial conditions q(t = 0) = q0 , p(t = 0) = p0 That is,
then leads to a solution, a trajectory p(t), q(t), from which
q(t) = q(q0 , p0 ; t) p(t) = p(q0 , p0 ; t).
the time dependence of all system properties along that
trajectory can be computed. The motion may be best visu- These constants of the motion, however, are of little inter-
alized as taking place in a 2M-dimensional space, termed est. Although knowing them does identify the trajectory
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Energy Transfer, Intramolecular 487

uniquely, it provides no reduction of the complexity of Note then that trajectories in such systems come arbitrarily
solving the full problem for q(t), p(t). Clearly, what we close, during the course of their dynamics, to their orig-
seek is a set of global constraints that define smooth sur- inal starting position. For this reason, such dynamics is
faces in phase space on which the trajectories lie. Members termed “quasiperiodic.” The vast majority of “textbook”
of such a set of functions are called global constants of the problems dealt with in elementary and advanced analyti-
motion. The number of global constants of motion that a cal mechanics treatises are of this type. Examples include
system possesses provides a means of generally classify- the hydrogen atom or the small-vibrations Hamiltonian,
ing the system behavior. although these systems tend to be, in addition, separable,
that is, of the form H = H (K 1 ) + H (K 2 ) + · · · .
1. Integrable Systems Trajectories in integrable systems are stable with
respect to small changes in initial conditions. In
Consider first the case in which an M-degrees-of-freedom particular, consider a trajectory [q(t), p(t)] emanat-
system possesses M independent global constants of the ing from initial conditions q(0) = q0 , p(0) = p0 and an
motion, denoted K. Selecting these as the M generalized initially close trajectory [q (t), p (t)] originating from
momenta K, with conjugate momenta Q, allows us to write q (0) = q0 + δ Q, p (0) = p0 + δ P with δ Q and δ P very
the Hamiltonian as H (K). Hamilton’s equations then be- small. Then define d(t) as the time-dependent “distance
come in phase space” between these two trajectories,
d K i /dt = −∂ H/∂ Q i = 0 d(t) = [ p1 (t) − p1 (t)]2 + [ p2 (t) − p2 (t)]2
(6)
d Q i /dt = ∂ H/∂ K i = ωi (K), + · · · + [q1 (t) − q1 (t)]2 + · · ·]1/2 . (8)
This quantity measures the rate at which two nearby tra-
where the last equation defines the frequencies ωi (K). Sys-
jectories separate as a function of time.
tems allowing this description are termed integrable, or
4. Then, for regular systems, d(t) grows linearly with
regular, and possess a number of important properties:
t, a relatively slow rate of separation characteristic of
stability.
1. Trajectories lie on M-dimensional surfaces in phase
space whose topology is that of a torus. The tori are la-
All these features are, in a qualitative sense, indicative
beled by the values of K. For example, in a two-degrees-
of essentially predictable motion in integrable systems.
of-freedom system, the motion lies on the surface of a
doughnut (see Fig. 11).
behavior is repetitious, or at least describable by a simple
2. The frequencies of motion about the independent
set of frequencies. The linear growth of d(t) suggests that
directions on the torus are given by ω(K).
knowledge of the behavior of a single trajectory allows
3. The time dependence of the coordinates and mo-
prediction, over a fair length of time, of the behavior of its
menta for a given trajectory are given by the Fourier series
initially nearby neighbors.
(where n is a vector of M integers)
 As a simple example of regular dynamics, to be em-
q(t) = qn (K)exp[in · ω(K)t] bellished later, consider a system of two uncoupled
n oscillators,
 (7)
H = H1 ( p1 , q1 ) + H2 ( p2 , q2 ), (9)
p(t) = pn (K)exp[in · ω(K)t].
n where the individual oscillators, with Hamiltonians
Hi (qi , pi ) = T ( pi ) + V (qi ), have potentials terms of the
Morse form,
V (qi ) = Di [exp(−qi /ai ) − 1]2 . (10)
Here, Di is the oscillator dissociation energy and ai is
a system parameter. Equation (10) might, for example,
model three atoms on a line where the coupling poten-
tial between the oscillators has been eliminated. The in-
dividual Hamiltonians H1 and H2 are then the conserved
integrals, and their numerical values remain constant at
FIGURE 11 Sample quasiperiodic trajectory in a two-degrees-
of-freedom system as it moves on the surface of a torus in phase their initial values throughout the dynamics. Since this is
space. The trajectory shown is actually periodic; in general, the a two-degrees-of-freedom system and since two constants
trajectory will fill the entire torus surface. of the motion exist, the system is integrable.
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488 Energy Transfer, Intramolecular

Consider a measurement on the dynamics of this sys- to actual experimental techniques and measurements are,
tem. If an experiment were able to begin with an initial however, not well formulated.
state consisting of a single trajectory, then the time evolu- The regular system constitutes one major category of
tion would be on a torus in phase space and there would observable dynamical behavior. Systems that are inte-
be no energy transfer between the subsystems H1 and H2 . grable are well known and have been experimentally ob-
Sufficiently long-time observations on the system would served, as discussed later. A second major category of
reveal repetitive quasiperiodic motion. Two remarks re- Hamiltonian systems emerges from formal ergodic the-
garding such measurements are, however, important. First, ory, which defines a set of increasingly idealized statistical
if one is interested in the dynamics of a subcomponent systems. Such systems (in terms of increasing statistical
other than H1 and H2—say one interrogates the time de- characteristics) are termed ergodic, mixing, K-systems,
pendence of the harmonic oscillator p12 /2m 1 + q12 —then and Bernoulli systems. Each category imposes additional
the measurement would reveal energy flow into and out conditions, leading to requirements difficult to verify for
of this subsystem. Quasiperiodicity would still be evident, realistic systems. Thus, they are to be regarded as idealized
however, after a suitable time. Second, if the time scale of models of statistical motion.
the experiment is short compared to the relevant system
frequencies, then this quasiperiodicity will not be man- 2. Ergodic
ifest. The essential point then is that the nature of the
Consider first the integrable system where each trajectory
measurement of interest determines whether the regular
lies on the surface of a torus. Two conditions are possible.
system behavior is fundamental to, or observable in, the
In the first, the trajectory wraps about the torus and closes
particular experimental study.
on itself without covering the torus completely. An exam-
There is another feature of integrable systems that is
ple is shown in Fig. 11, where it is clear that this property
important. Specifically, consider the concept of statistical
arises if the frequencies of motion about the torus are re-
behavior in dynamics. The fundamental features of such
lated to one another by the relation n 1 ω1 + n 2 ω2 . Such a set
behavior are that a trajectory at energy E fills the entire
of frequencies is said to be rationally related and results in
volume of phase space associated with that energy E, that
the trajectory returning exactly to its original position. On
a set of trajectories relaxes to a long-time limit that no
the other hand, the frequencies on the torus may not be ra-
longer varies with time, and that the final state is depen-
tionally related, in which case the trajectory fills the entire
dent solely on the energy of the system. It is clear that
surface of the torus. Under such conditions the dynamics
the first of these properties is not satisfied by a regular
is said to be ergodic on the torus. This formal terminol-
system, since a trajectory lies on the surface of a torus
ogy does not correspond to the historical use of the term
of dimensionality M, whereas the constraint to constant
ergodic as found in the physics literature. There, ergodic
energy would confine dynamics to a larger surface of di-
tends to mean ergodic on the energy hypersurface, that is,
mension 2M−1. It would also appear, from the list of pro-
on the (2M−1)-dimensional surface in 2M-dimensional
perties above, that a regular system does not relax. This is,
phase space that results from constraining the system to
in fact, not the case. That is, properties (1)–(4) constitute
constant energy. For clarity, we shall term this E-ergodic.
features of the trajectories of a regular system. As al-
Thus, the characteristic of an E-ergodic system is the
ready remarked, however, typical comparisons with phys-
existence of a single trajectory at each energy E that comes
ical systems require information on the average behavior
arbitrarily close to all points on the energy hypersurface.
of the time development of a collection, or ensemble, of
It is important to note, however, that this property does
trajectories. It is therefore important to note that despite
not ensure that the system displays irreversible relaxation
the quasiperiodic behavior of integrable systems, an en-
during the course of the dynamics. A pictorial analog of
semble of trajectories in a regular system can relax to a
possible motion of an ergodic system is provided by imag-
long-time, stationary distribution. The final relaxed state
ining a speck of carbon in a continuously stirred fluid. The
of the system is, however, intimately related to the initial
carbon speck, representative of the system in phase space,
conditions of the dynamics. This is clear from the simplest
moves throughout the fluid without constraint, but does
of considerations. That is, each of the trajectories in the
not settle down to some long-time stationary state.
set of trajectories retains its original values of the con-
served quantities. Thus, the final state of the system will
3. Mixing
depend on more than just the total overall energy of the
system. A system that is ergodic but has the rudimentary prop-
Each of properties (1)–(4) gives rise to useful computa- erties associated with statistical irreversible behavior is
tional tools for the theoretical identification of integrable the mixing system. Such a system displays the following
behavior in models of molecular motion. Relationships properties.
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Energy Transfer, Intramolecular 489

Consider the system at energy E. Denote the average tween nearby trajectories that grows exponentially, that is,
over the energy surface by the expression f , where f (q, d(t) = d(0)exp(kt), indicative of trajectory instability.
p) is any dynamical property. Then, This set of properties gives rise to useful theoretical
indicators of irregular motion, but connections with actual
1. lim f [q(t), p(t)] = f t → ∞. experimental observables are not well established.
2. The correlation between any two dynamical From the viewpoint of measurement, if one were able
properties, that is, to prepare a single trajectory as the initial state of an ir-
regular system, then the subsequent measurement of any
g[q(t), p(t)], f [q(0), p(0)] property, other than energy, would show continual varia-
− g[q(t), p(t)] f [q(0), p(0)] , tion with time. The trajectory would, in addition, display
no tendency to return to the original state over any fi-
goes to zero as t → ∞. nite time. If one prepared an ensemble of trajectories, it
3. Subdivide the total phase space into regular regions of would approach a long-time stationary distribution depen-
particular volume. Then the probability of going from dent solely on energy.
region i to region j in the long-time limit depends
only on the size of the phase space regions i and j.
4. Typical Molecular Systems
Thus, a mixing system satisfies a number of simple
properties that are in qualitative agreement with statistical Both regular and irregular motions are extremes of behav-
relaxation dynamics. A particle of soluble colored material ior, and their relation to the dynamics of realistic systems
stirred into water provides a pictorial analog of mixing dy- has principally been established through numerical com-
namics. Once again, the fluid models the phase space. The puter studies. These studies indicate that many, but cer-
system evolves over time to reach a final macroscopically tainly not all, molecular systems display behavior charac-
invariant distribution of uniformly colored fluid through- terizable as regular at low energies and irregular at higher
out the container. energies. The example of carbonyl sulfide, OCS, is shown
It is unfortunate that the formal definitions of ergodic, in Fig. 12, where the percentage of phase space not show-
mixing, etc. systems involve the infinite time limit. As a ing exponential divergence is shown. The system is seen
consequence, a system may, for example, still be mixing to display a transition to chaotic motion at an energy of
even if relaxation is not observed in the finite time asso- approximately 14,000 cm−1 . By 20,000 cm−1 , close to
ciated with a realistic measurement. This limitation sig- dissociation, almost all of the phase space is irregular.
nificantly reduces the practical utility of formal concepts To appreciate the origin of the regular behavior at
such as mixing behavior. low energies, we note two common approximations
A host of other formal systems with additional, and
hence stricter, requirements have been defined. Here, we
only mention the C-system, which is ergodic and mixing
and which possesses the important characteristic that the
distance d(t) between any two initially close trajectories in
phase space grows exponentially in time. This trajectory
instability leads to the rapid parting of trajectories from
one another and, hence, the inability to predict the dynam-
ics of trajectories, even for a relatively short time period,
from knowledge of the dynamics of their neighbors.
A system that displays characteristics of mixing as
well as exponential divergence of adjacent trajectories
is termed irregular or chaotic. In contrast with the char-
acteristic properties of a regular system, an irregular
system displays (1) trajectories that lie upon the (2M−1)-
dimensional energy hypersurface in phase space (addi-
tional simple constants of the motion such as angular mo-
mentum may also be incorporated), (2) and (3) trajectory
FIGURE 12 Percent regular trajectories as a function of energy
dynamics that cannot be written in terms of a Fourier se- for model OCS. The symbol D denotes the molecular dissociation
ries involving a simple set of discrete frequencies and their energy. [From Carter, D., and Brumer, P. (1982). J. Chem. Phys.
overtones and combinations, and (4) a distance d(t) be- 77, 4208.]
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490 Energy Transfer, Intramolecular

in low-energy molecular motion. The first, rotation– The relationships in Eqs. (15) and (16) allow us to
vibration decoupling, assumes that the rotational and vi- rewrite V2 (P, Q) as
brational motions are essentially uncoupled at low ener-
gies, that is, that the Hamiltonian is the sum of vibrational V2 = A(I1 I2 /ω1 ω2 )1/2 [cos(θ1 −θ2 )−cos(θ1 +θ2 )], (18)
and rotational parts: where A is a constant.
H = Hvib + Hrot . (11) Hamilton’s equations of motion [Eq. (4)] then provide
expressions for d Ii /dt that are nonzero due to the cou-
Second, we recall the standard normal-mode procedure pling V2 . In the event that the coupling is small, one may
for small-amplitude vibrational motion wherein, at suffi- approximate the solution for the time dependence of the
ciently small energy, the vibrational Hamiltonian is of the angles as that of the time dependence in the absence of
form the perturbation. This approach, a classical perturbation
Hvib = H0 theory, gives the following result for the time dependence
  of Ii (t):
1  2 
= Pi + λi Q i2 + V (P, Q), (12) 1/2
2 i I1 I2
I1 (t) = I1 (0) − A
with V (P, Q) sufficiently small to be negligible. The Q, ω1 ω2
 
P are called normal coordinates and momenta. Thus, low- × cos (ω1 − ω2 )t + θ10 − θ20 (ω1 − ω2 )
energy vibration is well approximated by a sum of M  
harmonic-oscillator Hamiltonians. In some instances an − cos (ω1 + ω2 )t + θ10 + θ20 (ω1 + ω2 ), (19)
alternative separable Hamiltonian, composed of the sum where θ10 , θ20 are the initial values of the angles. The quan-
of bond Hamiltonians, provides a superior separable rep- tity I2 (t) is similar, but out of phase. Thus, the action
resentation. In either case, the low-energy vibrational mo- variables oscillate about their unperturbed values with
tion is regular and separable. frequencies (ω1 − ω2 ) and (ω1 + ω2 ). Since ω1 − ω2 is as-
The situation changes dramatically with increasing en- sumed large, the total variation of I1 and I2 as a function
ergy as V (P, Q) becomes larger and the system begins of time is small.
to exchange energy between the decoupled harmonic os- The result is quite different if the system is resonant,
cillators. The subsequent dynamics, as observed in the that is, ω1 = ω2 . In this case, the effect of the perturbation
measurement of the energy in a normal mode, depends in- is more drastic, and energy can be exchanged completely,
timately on the nature of the coupling, which is typically albeit periodically, between the two harmonic oscillators.
expandable in the form There are several reasons why the example treated

V (P, Q) = Vn (P, Q), (13) above is a gross oversimplification of the situation in
n molecules. First, the unperturbed system is assumed har-
where Vn (P, Q) denotes polynomial terms of the form monic, that is, linear in I. Second, the perturbation has been
Q ik P jm with k + m = n. assumed to be composed of a single term. Third, only one
As a simple example of the effect of coupling, consider type of perturbation has been included. We now qualita-
a two-degrees-of-freedom system with tively examine the important effects associated with the
breakdown of these simplifying assumptions.
V (P, Q) = V2 (P, Q) = AQ 1 Q 2 . (14)
It is convenient to first identify the constants of the motion a. Anharmonicity of H0 . In general, H0 is not har-
in the harmonic Hamiltonian and use them as the new monic, but is rather of the general anharmonic form
momenta. Consider then the momenta H (I). As a result, the zero-order system frequencies
  ωi (I) = ∂ H0 /∂ Ii are no longer independent of the actions
Ii = (4λi )−1/2 Pi2 + λi Q i2 (15)
I; that is, the frequencies depend on the energy content
and conjugate coordinates of the oscillators. As a consequence, anharmonic systems
 1/2  will display regions of the I1 , I2 space where ω1 (I) and
θi = cot−1 −λi Q i Pi . (16)
ω2 (I) are resonant as well as other regions where they are
In these coordinates, H0 assumes the form not. Thus, in the course of the dynamics, the zero-order
system can go into and out of resonance as the energy of
H0 = ω1 I1 + ω2 I2 , (17)
the oscillator varies. Regions of I space where the system
1/2
where ωi = λi . We shall assume ω1 and ω2 to be unequal. is resonant are called resonance zones. Note that despite
These specific types of momenta and coordinates I are the coupling, the dynamics within this resonance region
termed action-angle variables. is regular.
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Energy Transfer, Intramolecular 491

A well-known example provides a picture of the reso-

nance zone and the “trapping effect” associated with a non-
linear resonance. Consider a child’s swing being pushed at
a fixed frequency. The nonlinear swing, well approximated
by a pendulum, will gain energy from the “pusher” until
the system is well out of resonance. At this stage the swing
loses energy until it once again comes into resonance with
the driving frequency. The system is therefore effectively
trapped in a range of swing energies determined by the
resonance zone associated with this driven pendulum. A
similar effect is associated with the single resonance re-
gion associated with ω1 (I) = ω2 (I) in the example above,
the system being essentially trapped in the region about the
resonance center if the dynmics is initiated in that region. FIGURE 13 Resonance structure of a model system A B C
where each atom has a mass equal to that of carbon. The
b. Other coupling contributions. The above discus- A B bond has frequency 1000 cm−1 and dissociation energy
sion emphasizes the ω1 = ω2 resonance, which results Dc , whereas the B C bond has corresponding parameters
1300 cm−1 , 1.5Dc . Black areas denote single-resonance regions,
from the assumed form of the coupling in Eq. (14). In
and cross-hatched areas denote regions of overlapping reso-
general, the coupling is more complicated, but is still ex- nances. [From Oxtoby, D., and Rice, S. A. (1976). J. Chem. Phys.
pected to be expandable in the form 65, 1676.]

V (I, θ) = Vm,n (I1 , I2 ) exp(inθ1 + imθ2 ). (20)
mn
ing indicates regions dominated by a single resonance and
The V2 coupling term in Eq. (14) is an example of the cross-hatched areas are those dominated by overlap-
|n| = 1, |m| = 1 contributions to this expansion and leads ping resonances. In the case shown, there is a general trend
to the ω1 = ω2 condition for resonance. Similarly, the n, toward overlapping resonances as the energy increases,
m term in this series leads to an “n, m resonance” at action consistent with the observation of increasing chaotic be-
variables satisfying nω1 (I) = mω2 (I). Once again, within havior with increasing energy. For the particular param-
the neighborhood of this single resonance, the system dis- eters shown, however, the system, even at energies near
plays regular energy transfer between the zero-order oscil- dissociation (E = 1.5Dc ), displays regions of regular be-
lators. We note that the size of the resonance zones tends havior dominated by a single resonance. Alternate system
to decrease with increasing n, m. parameters can result in larger or smaller contributions
from overlapping resonances.
c. Overlapping resonances. When a few terms in In summary, the picture that emerges with respect to
Eq. (20) contribute to the coupling, there is little reason energy transfer between specified zero-order oscillators is
to expect that specific regions of I space are influenced qualitatively straightforward. The coupling between the
by solely one resonance. Under rather general conditions, specified oscillators induces nonresonant energy transfer
the resonance regions in phase space arising from different between the oscillators if the system is initiated, and re-
terms in the coupling expansion [Eq. (20)] may overlap. mains, within a nonresonant region of I values. Reso-
Numerical studies have shown that energy flow between nant energy transfer results if the system begins within
the zero-order oscillators assumes chaotic characteristics a resonance zone, or enters the resonance zone, during
in regions of overlapping resonances. the dynamics. In both cases, energy transfer has well-
As an example, consider the resonance and resonance- defined pathways: the energy transfer is well described
overlap structure associated with a collinear molecule in terms of the time-dependent energy content of the
A B C where H0 is the sum of two Morse oscillators zero-order oscillators. Finally, chaotic energy transfer be-
[Eq. (10)] corresponding to the bond potentials and the tween the zero-order oscillators is expected in the I-space
coupling term is the form Ap1 p2 . Here, p j is the momen- regime dominated by overlapping resonances. Computa-
tum associated with the jth bond. With E i defined as the tional results on bound molecules indicate that the vol-
energy of the ith bond and E the total energy of the sys- ume of resonance regions increases with increasing system
tem, quantitative application of resonance theory allows energy.
for the explicit determination of E i , E regions dominated One important aspect of this discussion is worthy
by either a single resonance or by overlapping resonances. of emphasis. Specifically, the subdivision of the system
Sample results are shown in Fig. 13, where the solid shad- into zero-order oscillators and coupling terms, and the
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492 Energy Transfer, Intramolecular

subsequent expansion of the coupling term, must be moti-

vated by the experimentally measured quantities. Specif-
ically, one may see apparent chaotic motion between par-
ticular zero-order oscillators even if the system is regular.
This would be the case if the time scale of measurement
is short and the observed oscillators are not those directly
related to the conserved integrals of motion.This feature
also makes clear that overlapping resonances do not nec-
essarily ensure true irregular motion.
Detailed studies on the dynamics of realistic molecular
systems are just becoming available. As a consequence,
it is unclear whether the vast majority of highly excited
molecules are weakly coupled with few overlapping res- FIGURE 15 A schematic of the coupling scheme linking the C H
onances or are strongly chaotic. As a specific example of stretch to the various modes of the benzene ring. Schemes (a)
resonant coupling with weak coupling characteristics, and and (b) represent the same coupling schemes described in two
hence a specific energy-transfer pathway, we discuss be- different zero-order mode languages. [From Sibert, E. L., Hynes,
J. T., and Reinhardt, W. P. (1984). J. Chem. Phys. 81, 1135.]
low the study of overtones in the benzene molecule. As
an example of chaotic energy transfer, we call attention to
the NaBrKCl example discussed in Section II. labeled s1 and s6 , with the C H bond distance being la-
Recent experimental studies on benzene have shown beled s. Also shown is the angle β associated with the
that the absorption spectrum contains local mode features, wag motion of the C H relative to the ring. The picture
that is, evidence of local isolated bond motions. In the ben- that emerges from numerical studies is that with increas-
zene case, the C H bonds, if they contain sufficient energy, ing excitation of the C H bond, the C H bond frequency
appear directly in the spectrum, as if they were decoupled comes into resonance with the wag, where the resonance
from the remainder of the molecular framework. In par- is characterized as n = 2, m = 1. Energy transfer from the
ticular, one sees evidence of excitation to the overtones of C H bond first occurs as resonant energy transfer to the
C H stretch, that is, five, six, seven, etc. quanta of energy wag. Energy is subsequently transferred from the CCH
in the bond. The experimental results further indicate that wag to the remainder of the modes of the molecule. This
if energy is deposited in these bonds, it would transfer to is pictorially shown in Fig. 15. Trajectory calculations of
the remainder of the benzene nuclear framework within the time dependence of the flow of energy out of the ex-
about 10−13 sec. Although apparently rapid, this rate of cited C H mode, for various degrees of excitation, are
energy transfer is substantially slower than that expected shown in Fig. 16. A complementary picture of the growth
from a C H bond democratically linked to all the degrees of energy in the ring modes of the benzene framework and
of freedom in the ring. into the lower lying states of C H on the benzene ring is
Detailed quantum and classical studies of the dynam- shown in Figs. 17 and 18. On the time scale shown, the en-
ics of benzene indicate the following picture. Consider ergy flow out of the C H bond is irreversible. Agreement
first the immediate local environment of a C H bond at- with experiment is good, providing evidence that energy
tached to the ring (Fig. 14). Two C C bond distances are flow in this case occurs through a well-defined pathway
of resonances. The comparative quantum calculations are
discussed later.
Further experimental and theoretical efforts are under-
way to establish the extent to which energy-transfer mech-
anisms in molecules are either chaotic or rather specific
in their nature.

C. Quantum Dynamics
Molecules are, of course, properly described by quantum
mechanics, and classical mechanics is recognized as a par-
ticular approximation. Nonetheless, an introductory de-
FIGURE 14 Coordinates defining the C H bond distance (s).
C C bond distances s6 , s1 ; and wag angle β in benzene. [From scription of intramolecular energy transfer via classical
Sibert, E. L., Hynes, J. T., and Reinhardt, W. P. (1984). J. Chem. mechanics has proven useful since it contains few con-
Phys. 81, 1135.] cepts that are truly unfamiliar to the macroscopic world.
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Energy Transfer, Intramolecular 493

tions prevent a discussion of these quantum phenomena,

and the interested reader is referred to the bibliography for
details. We focus rather on the dynamical consequences
of energy quantization in quantum mechanics. This prop-
erty means that a system can only exist at specific energy
values, a property shared by other observables as well.
Energy is, however, intimately linked to dynamics, since
the Hamiltonian determines system time propagation, as
discussed later.
One important remark is in order. That is, although
quantum phenomena have been observed in molecular
systems, we possess only the very qualitative “traditional”
rules regarding conditions under which quantum effects
predominate. Specifically, if the initial state involves large
classical actions and the initial state is one that is allowed
classically, then quantum effects tend to be small. Con-
siderably more work is necessary, however, before more
quantitative, predictive statements can be made and before
our understanding of classical/quantum correspondence in
bound molecular systems is complete.
Considerations of the quantum dynamics of bound
molecules shows that, in the absence of the emission
of radiation from energized molecules, all dynamics is
quasiperiodic and regular. That is, quantum mechanics
FIGURE 16 Time dependence of the average energy in the C H
oscillator for three cases: excitation in the ninth C H vibrational
does not admit the possibility of long-time relaxation to
level (v = 9), v = 6, and v = 5. [From Sibert, E. L., Hynes, J. T., and a time-independent stationary state, a property that char-
Reinhardt, W. P. (1984). J. Chem. Phys. 81, 1135.] acterizes a classical mixing system. This property creates

Although it is possible to cast both quantum and classical

mechanics in a similar formal language (i.e., distributions
in phase space and a Liouville propagator), standard quan-
tum mechanics is based on a mathematical structure that is
substantially different from that of classical Hamiltonian
mechanics. We first provide a brief qualitative summary
of some results of quantum investigations, and then we
present details that can be best appreciated by the reader
who is well versed in quantum mechanics.
First and foremost, we note that classical mechanics
does not allow a number of phenomena that occur in na-
ture. A familiar example is tunneling, in which a system
has finite probability of being in a region of phase space
where it is not permitted classically. The simplest exam-
ple of tunneling occurs in a system consisting of a particle
moving in a potential that has two minima with a poten-
tial barrier between them. Classically, a particle initiated
in one of the wells with energy below the barrier height is
confined to that well forever. In the quantum case, how-
ever, the system flows between the two wells: it “tunnels”
through the potential barrier. Tunneling effects are most
FIGURE 17 Growth of energy content of ring modes in benzene
certainly important in the intramolecular dynamics of sys-
associated with the v = 6 case in Fig. 16. Note that only a few
tems at energies below such potential barriers. Less well ring modes, labeled by their frequency, are shown. [From Sibert,
known are symmetry effects, resonances, etc. that can play E. L., Hynes, J. T., and Reinhardt, W. P. (1984). J. Chem. Phys.
important roles in intramolecular dynamics. Space limita- 81, 1135.]
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494 Energy Transfer, Intramolecular

Quantum mechanics describes system behavior in terms

of operators that represent measurable quantities, their
eigenfunctions, which describe possible states of the sys-
tem, and their eigenvalues, which correspond to allowable
values of the measurable. If the system is presumed best
described in terms of a specification of the system energy,
then one looks for states |ψ that are eigenfunctions of the
molecular Hamiltonian operator H. That is, one solves the
problem
H|ψ(t) = −i h ∂|ψ(t) /∂t,
✟
(21)
where t is the time. The nature of this equation is such as
to admit the solutions
|ψ j (t) = |ψ j exp(−i E j t/ h ),✟
(22)
where |ψ j is the solution to the eigenvalue problem
H|ψ j = E j |ψ j . (23)
Here, the Hilbert space vector |ψ j has a coordinate space
representation ψ j (q) = q|ψ j , and |ψ j (q)|2 is the prob-
ability of observing a given value of q when the system
is in a state defined by energy E j . In general, the system
may be degenerate, in which case several E j may have the
same numerical value.
This treatment and the one that follows provide an ide-
alized picture in which the molecule is entirely isolated
from external influences. Such an ideal picture cannot, in
fact, apply. Specifically, although one may be able to ex-
perimentally isolate the molecule from interactions with
other molecules (e.g., via high-vacuum techniques), the
molecule will always interact with the background radi-
ation field to radiate energy. In this discussion we regard
FIGURE 18 Probability of finding i quanta in the C H oscillator this emission as a small perturbation that can be introduced
as a function of time for the case of initial v = 6. [From Sibert, E. as part of the measurement process.
L., Hynes, J. T., and Reinhardt, W. P. (1984). J. Chem. Phys. 81, Consider time dependence in quantum mechanics, with
1135.] the experimentally prepared initial state assumed com-
pletely specified as the Hilbert space vector |φ(0) . That
a number of difficulties in understanding the formal rela- is, the system is initially in a pure state and may be ex-
tionship between classical and quantum mechanics, par- panded in a linear combination of energy eigenstates |ψ j
ticularly for energized molecules that display classically as
chaotic behavior. Practically, however, one finds that if 
the system is close to the classical limit, then quantum |φ(t = 0) = c j |ψ j c j = ψ j |φ(0) . (24)
j
and classical dynamics agree over a significant time scale.
This time scale is expected, in the vast majority of typical Then, from Eq. (22), the subsequent time evolution is
chemical experiments, to be in excess of the time of inter- given by
est for the process. Under these circumstances, the formal 
|φ(t) = c j |ψ j exp(−i E j t/ h ). ✟
(25)
discrepancy between classical and quantum mechanics is
irrelevant to the specific chemical problem. Nevertheless, In the alternative case, the so-called mixed state, one
since quantum mechanics does not admit anything other does not have a complete specification of the initial state;
than quasiperiodic behavior, attention has recently been that is, the initial state cannot be described as a single
focused on other quantities that might provide the quali- Hilbert space vector, nor can it be written in terms of a
tative distinction between quantum systems that display, linear combination of |ψ j . It can, however, be written in
more or less, statistical behavior. terms of a density matrix,
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Energy Transfer, Intramolecular 495


ρ(0) = wn |χn χn |, (26)
n

where the states |χn can be written in terms of a linear

combination of |ψ j and where n wn = 1, with wn equal
to or greater than 0. The essential feature of such states is
that ρ(0) is lacking information on the relative phases of
the participating eigenstates |ψ j .
We focus on the pure state, although it is the exception,
rather than the rule, in experimentally prepared systems.
In accordance with quantum mechanics, a measurement
of a particular property during the course of the system
time evolution consists of evaluating the average value of
the corresponding operator. For example, if one measures
the property described by the quantity F, then the average
value of F as a function of time is given by
F(t) = φ(t)|F|φ(t)

= di, j exp(iωi, j ) (27)
i, j

di, j = ψ j |F|ψi c∗j ci ,

where ωi, j = (E i − E j )/ h. Thus, F(t) may be written
as a linear combination of terms involving a discrete set
of frequencies ωi, j . By analogy with the discussion of
classical systems, this sum is seen to be quasiperiodic.
The number of terms contributing to the sum in Eq. (27)
and the relationship between the frequencies ωi, j deter-
mine the kind of qualitative behavior observed. In the case
where only a few terms contribute, the dynamics is almost
periodic. Such behavior is observable as, for example, a
FIGURE 20 Density of states (i.e., number of states per unit en-
periodic modulation of the fluorescence emitted from a ergy interval) as a function of energy for a number of molecules.
molecule prepared in a linear combination of a few states, The abcissa is in number of photons, rather than energy, where
a phenomenon known as quantum beats. An example of the type of laser photon used depends on the particular molecule.
beats in SO2 is shown in Fig. 19, where the fluorescence For example, the state density for CF3 CH2 OH is plotted vs pho-
reflects the interference between two contributing levels. tons, from an HF laser, associated with the P1 (7) line. The energy
of each of these photons is 0.01660 a.u. Other photons used
are the P1 (6) line with a photon energy of 0.01683 a.u. and the
CO2 10P(20) line with energy of 0.00430 a.u. per photon. [From
McAlpine, R. D., Evans, D. K., and McClusky, F. K. (1980). J. Chem.
Phys. 73, 1153.]

Such simple behavior emerges only when the initially cre-

ated state is composed of a few levels. This is seldom the
case, as seen from Fig. 20, which shows the density of
states (i.e., the number of states per unit energy interval)
D(E) for some typical molecules. The quantity D(E) is
seen to be an increasing function of the size of the molecule
and, for even small molecules such as SF6 , can reach very
large values (e.g., 103 cm−1 ). As a result, chemical ex-
periments, whose energy resolution is often not sharp, will
typically involve an initial state composed of many many
FIGURE 19 The intensity of fluorescence, as a function of time,
from SO2 created in a superposition state composed of two levels. levels. The subsequent dynamics emerges through the
[From Ivanco, M., Hager, J., Sharfin, W., and Wallace, S. C. (1983). simultaneous interference of a multitude of terms, and the
J. Chem. Phys. 78, 6531.] resultant behavior is difficult to qualitatively extract from
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496 Energy Transfer, Intramolecular

a formal sum [Eq. (27)] of contributions from individual Hi χ ij = εij χ ij i = 1, 2. (29)

levels.
For example, the system can display short-time behav- The perturbation V couples the zero-order states so that
ior reminiscent of relaxation. Consider the case where the exact-energy eigenstates |ψk are linear combinations of
these zero-order states or vice versa. That is,
coefficients di, j are distributed in a smooth fashion about 
a particular frequency value. Then one can show that for χi1 χ 2j , = bi,k j ψk . (30)
short times compared to the density of frequencies, F(t) k
decays smoothly as a function of time, with a time scale Using this expression and Eq. (22) gives the following
governed by the inverse of the frequency width of the co- form for the time evolution of these zero-order basis-set
efficients di, j . This behavior is termed dephasing, to dis- states;

tinguish it from irreversible relaxation of the initial state. χi1 χ 2j (t) = bi,k j ψk exp(−i E k t/ h ).✟
(31)
That is, despite this decay, the system will eventually re- k
assemble to form the initial state, although this time scale If the initial state consists of a linear combination of the
may be exceedingly long. Thus, an experiment measuring zero-order states, then the populations of the zero-order
F(t) over a time scale short compared to the recurrence states are seen to be time dependent.
time will show apparent relaxation of F(t) . Nonethe- The degree to which the zero-order states enter into the
less, formally, the system is quasiperiodic. The facts that exact eigenstates [i.e., the nature of the sum in Eq. (30)]
quantum bound-state dynamics is quasiperiodic, classi- is a measure of the strength of the coupling and provides
cal mechanics can be mixing, and the latter is expected an insight into the nature of the exact eigenstates from the
to approximate the former, make up the essence of the view-point of this particular zero-order basis. It essen-
important unresolved problem “what is quantum chaos?” tially provides the time-independent picture of the possible
The quantum picture of bound-state dynamics calls at- zero-order states that can be coupled during the dynamical
tention to an important aspect of intramolecular dynamics. evolution of the system. Equation (28), treated quantum
Specifically, the state |φ(t) is composed of a linear com- mechanically, admits the same kind of perturbation treat-
bination of states |ψ j . The probability of observing the ment as in the classical case, with a similar emphasis on
system in an exact eigenstate |ψ j at time t is given by isolated resonances and overlapping resonances emerging.
|c j exp(−E j t/ h )|2 = |c j |2 . Thus, the population of each
✟

As in the classical case, the question of the nature of

exact eigenstate does not change as a function of time. intramolecular energy flow—whether it is statistical or
If, in fact, one were solely interested in the population of whether it displays a specific pathway—is of interest. Un-
these exact levels, then there is no such thing as time de- fortunately, few quantum calculations on realistic molec-
pendence in the dynamics of bound molecules (other than ular systems have been performed. The example of the
radiative emission)! Clearly, the focus of intramolecular dynamics of benzene, initially prepared in an excited state
dynamics and energy transfer is on attributes other than of the C H bond, has, however, been treated quantum me-
exact eigenstates populations. chanically. Here, the relevant zero-order Hamiltonian is of
To appreciate the desired description of energy flow the form
in chemistry, recall the historical origin of the interest in
intramolecular energy flow. The most prominant case is H = HL + HN + HLN , (32)
that of unimolecular decay, in which a molecule, suffi- where HL is the Hamiltonian for the local C H vibrational
ciently energized, breaks into a variety of products (e.g., motion, HN is the Hamiltonian for the remainder of the
ABC → A + BC). In this case the focus of attention, and molecule, and HLN is the coupling between them. Com-
therefore of the measurement, is on the energy content of putations have been carried out, including the coupling
the A B bond. This is typical of chemical descriptions in between the C H vibration and the CCH wag motion,
which the analysis is in terms of subunits of the molecule via terms in HLH . In the adopted model, HN is essen-
that are not, in themselves, naturally distinct subcompo- tially harmonic so that the zero-order states are of the
nents of the molecule. Such a description results when form |vL , kN = |vL |kN , denoting v quanta in the C H
a zero-order basis set is used. Specifically, consider the stretch and k quanta in the ring modes.
Hamiltonian for a two-degrees-of-freedom system writ- As in the classical treatment in Section II, interest is
ten, as in the classical case, in the form in the dynamics of benzene in the energy range where the
C H bond is prepared with considerable energy. Figure 21
H = H0 + V H0 = H1 + H2 , (28)
shows some of the many zero-order energy eigenstates
where H1 and H2 describe two distinct subcomponents of in the energy regime associated with the zero-order state
interest in a particular experiment and the eigenfunctions |6L , 0N . Not shown are states with less than four quanta in
of Hi are denoted by |χ ij , where HL , which, although coupled to the |6L , 0N state, were too
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Energy Transfer, Intramolecular 497

As a starting point, note that chaotic classical systems

possess a number of prominent features. First, the system
relaxes to a long-time stationary distribution. Second, the
long-time limit is sensitive to only a few simple constants
of the motion (e.g., the total energy). Third, as a direct
consequence, the computation of system properties can
be done by replacing the actual dynamics by simplified
statistical models. The first property is clearly not satis-
fied by a quantum bound system, which has been formally
shown to be quasiperiodic. Nonetheless, one possibility is
that the system approach a long-time value about which
fluctuations are small and that this long-time value be sen-
sitive to only a few simple properties. Indeed, if all wave
functions in an energy interval are basically the same (i.e.,
have similar properties), then the system will evolve in a
fashion that is relatively insensitive to the nature of the
preparation. Further, if there are no integrals of motion
other than the total energy, then one might expect the en-
ergy eigenvalues to display rather simple properties re-
flecting this characteristic. These remarks motivate one
FIGURE 21 (a) Some of the zero-order states of benzene in the current view on the nature of quantum chaos. Specifically,
energy neighborhood near that of excitation to the sixth vibrational
in such a system the eigenfunctions are proposed to be
level of C H. States are organized, for clarity, in ladders associ-
ated with the number of quanta in the C H mode. (b) Levels for similar to one another in character as the energy varies,
the analogous monodeuterated benzene case. [From Sibert, E. and the probability of observing a particular level spacing
L., Reinhardt, W. P., and Hynes, J. T. (1984). J. Chem. Phys. 81, is expected to be of a specific form (the Wigner adjacent-
1115.] level distribution). The former requirement, coupled with
the condition that all eigenfunctions be orthogonal, that is,
numerous to be included in the computation. For conve-
ψi |ψ j = 0, (33)
nience, the levels are stacked in ladders, or “tiers,” with the
ladder labeled by the quanta of energy in the C H oscil- hints at the nature of these wave functions; that is, they
lator. Calculations show that the exact system eigenstates display erratic nodal patterns. This is clearly not the case
are a strongly coupled mixture of the zero-order states.
Figure 22 shows the result of a calculation on the quan-
tum dynamics of benzene initially excited to the sixth vi-
brational level of C H. The population of the sixth level
(denoted |cCH (t)|2 ) is seen to decay rapidly in time, with
concomitant growth of population in the various tiers. The
essential features of this quantum calculation are in accord
with the classical results by the same authors and describe
the dynamics of benzene, initially energized in the C H
vibration, as decay via a specific pathway of resonances
between zero-order modes.
Although specific examples of this kind are of consid-
erable importance, general rules regarding quantum in-
tramolecular dynamics would be far more useful. Indeed,
this was the motivation for investigating ergodic, mix-
ing, etc. systems classically. Similarly, it is the reason for
the general interest in the question of “what is quantum FIGURE 22 The time dependence of various quantities associ-
chaos?” We comment briefly (and only qualitatively) on ated with the quantum dynamics of benzene initially excited to the
sixth level of C H bond excitation. Labels are defined in the text,
recent developments in this area, noting first that an ap-
other than Pi (t), which denotes the probability of being in the i th
propriate definition of chaos can only involve properties tier of energy levels. Only three tiers were included in this calcula-
of the central participants in the time evolution, that is, the tion. [From Sibert, E. L., Reinhardt, W. P., and Hynes, J. T. (1984).
energy eigenstates and eigenvalues. J. Chem. Phys. 81, 1115.]
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498 Energy Transfer, Intramolecular

ond, even if such potentials are available, large-molecule

motion treated quantum mechanically involves huge num-
bers of participating energy eigenstates. Techniques for
efficiently computing large numbers of eigenstates in sys-
tems with significant numbers of degrees of freedom are
only now being developed. Alternative techniques, which
rely on the direct, numerical, temporal propagation of ini-
tial states [i.e., via Eq. (21)], do not utilize eigenstates but
suffer inaccuracies in long-time applications. An analo-
gous difficulty exists in attempting numerical studies of
FIGURE 23 Contour plot of ψ(q) associated with a typical state dynamics using classical mechanics; in this case, the expo-
of the particle in a stadium potential. Only positive contours are nential growth of distances in phase space (see Section III)
shown. Note the highly erratic pattern of contour lines proposed to translates into the rapid growth, with time, of numerical
be a characteristic of wave functions associated with chaotic clas-
sical systems. [From Brumer, P., and Taylor, R. D. (1983). Faraday
errors.
Discuss Chem. Soc. 75, 171.] Since the vast majority of interesting molecules have
many degrees of freedom, the need for models that sim-
plify the dynamics is evident. The most popular of such
for the vast majority of typical systems studied in elemen- models relies on a statistical assumption of relaxation dur-
tary quantum mechanics (e.g., the H atom, the particle ing the course of the dynamics. That is, one assumes that
in a box), which are, in fact, integrable and separable in after preparation of the energized molecule, the system
classical mechanics as well. relaxes to a well-defined state that is dependent on only
Note that the condition of erratic nodal patterns makes gross features (e.g., the total energy) of the preparation.
sense with respect to the view resulting from an analysis Assumptions of this kind predate detailed dynamical stud-
in terms of a zero-order basis set. In particular, expand- ies of molecular dynamics.
ing such exact wave functions in any arbitrary basis is To appreciate the simplifications resulting from such
expected to yield populations spread over all zero-order models, consider the paradigm case of unimolecular
wave functions in the energy neighborhood. Thus, there is decomposition (A → B + C, where A, B, and C are
a form of statistical coupling between all zero-order basis molecules), where this assumption leads to statistical
functions. theories of the rate of unimolecular decay. Here, A, suf-
Numerical computations on model systems have, in ficiently energized to dissociate, is prepared by any of a
fact, revealed erratic wave functions for some systems that variety of means (e.g., laser excitation, collisions, or as the
are classically mixing. An example is shown in Fig. 23, product of a chemical reaction). A detailed computation
where the system is a particle confined by infinite poten- of the dynamics of this process for a realistic molecule, an
tial walls to a region that is the shape of a racetrack (the intractable computational feat, would entail the following
so-called stadium system). The nodal patterns are clearly steps. One first specifies the exact nature of the molecular
highly disordered and in marked contrast with the sim- potential, the nature of the process that prepares the
ple nodal lines associated with, for example, the separa- excited molecule, and the state of the molecule prior to
ble particle in a rectangle case. Unfortunately, there is no preparation. Second, the exact dynamics of the evolution
one-to-one correspondence between systems that display of the molecule, from preparation to decay, is computed.
chaotic classical behavior and the observation of erratic Such a computation must be repeated for each and every
wave function nodal patterns. type of initial state of the molecule and each and every
type of state preparation. In contrast, the formulation of a
typical statistical model proceeds as follows. First, define
IV. STATISTICAL APPROXIMATIONS the region of phase space in which the molecule A is to
AND DYNAMICS be regarded as being bound and a complementary region
in which it is characterizable as B + C. Then assume that
Accurate dynamical studies, such as those discussed the rate of dissociation of the excited molecule depends
above, are limited to small molecular systems and rela- primarily on the magnitude of simple known constants of
tively short times (e.g., typically 100 vibrational periods). the motion, that is, energy E and total angular momentum
These restrictions stem from a number of sources. First, J. Assume further that any initially prepared state rapidly
reliable computations of forces between atoms in large relaxes to a uniform distribution over the surface in phase
molecular systems are extremely difficult, and few quan- space characterized by fixed E, J and within the region
titatively accurate models of interatomic forces exist. Sec- where A is regarded as bound. The computation of the
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Energy Transfer, Intramolecular 499

rate of decay of such a system then entails an analysis of ple, as is the case in some of the available techniques, the
the rate at which the relaxed uniform distribution crosses initial state of the molecule is in itself highly randomized
over into the dissociation region. Such a computation is energetically, then a subsequent measurement that shows
straightforward in both classical and quantum mechanics, that the energy is statistically distributed among the sys-
if a number of approximations on the structure of the tem modes is of little consequence. That is, this particular
molecule are made, and leads to statistical theories, such observation would be a consequence of the preparation,
as RRKM theory, discussed in the bibliography. as distinct from the evolution, of the molecule.
The essence of such theories is, then, that the system The dynamics of molecules with low energy content is
undergoes memory erosion during the dynamics so that usually well described by a Hamiltonian that is the sum
information on initial conditions is lost; only knowledge of independent degrees of freedom, and absorption spec-
of E and J remains. Similar theories have been proposed troscopy has provided considerable information on the
for a wide variety of processes that involve the participa- nature of such systems. The situation with respect to ener-
tion of long-lived molecular intermediates. These include gized molecules is far more complex. A number of exper-
chemical reactions that proceed via collision complexes, imental tools have been utilized over the past 30 years to
photodissociation where molecular preparation is through examine the nature of energy transfer in such systems, as
controlled laser excitation, molecules adhering to surfaces discussed next. Many suffer from the inaccurate knowl-
where detachment is induced via a variety of means, etc. edge of the initial system state. In our brief description
Such theories have the advantage of yielding rather gen- of several experimental methods it will become clear that
eral results, which are amenable to both theoretical and experimental tools have been rapidly developing over the
experimental analysis. For example, in the case of uni- past few years and that an explosion of highly informative
molecular decay, the rate constant for dissociation is found experimental data is now underway.
to increase with increasing energy and decrease with the First and foremost, note that interest is in the nature of
number of participating degrees of freedom in the system. intramolecular dynamics of molecules in isolation. That
Experimental studies on the validity of such theories is, observations must be made over a time scale where
have been ongoing for many years, as discussed briefly in the molecule does not collide with others in the reaction
the next section. The theoretical examination of the valid- vessel. Modern techniques allow very low pressures un-
ity of such approaches is more recent and links directly der which such measurements can be made. Most desir-
to the issues discussed in Section III. At present, classi- able among these methods are beam techniques in which
cal mechanical studies have shown the possibility of both molecules are studied in a low-density beam produced,
statistical and nonstatistical decays, depending on the de- for example, by vaporizing molecules in an oven. Exper-
gree and extent of exponential divergence of trajectories iments prior to this “beam age” (circa 1960) often in-
in phase space. The greater the degree and extent of expo- ferred information about intramolecular dynamics from
nential separation, the closer the agreement with statistical bulk data, which contained effects due to collisions, with
approaches. Similarly, quantum-mechanical studies have resultant loss in accuracy.
shown that model systems can display unimolecular rate Measurement techniques in typical experiments can be
constants whose energy dependence is inconsistent with subdivided into two categories. The first and most modern
that predicted by simple statistical theories. It is fair to probes the bound molecular dynamics directly, for exam-
say, however, that a clear understanding of the interrela- ple, by observing radiation emitted or absorbed during
tionship between molecular properties and the validity of the course of the dynamics. The second infers informa-
statistical theories is in its early stages of development. tion about the nature of bound molecular dynamics by
indirect means, typically by analyzing the outcome of a
process that involves the molecule of interest as a long-
V. EXPERIMENTAL STUDIES lived intermediate. These latter types of measurement are
readily clarified by considering the NaCl + KBr example
The ideal experiment on intramolecular energy transfer, discussed in Section II. Specifically, this particular reac-
as yet unachieved, entails a number of simple features. tion proceeds via the bound NaC1KBr intermediate to
Specifically, the molecule is prepared in a well-defined yield two different sets of products, either NaCl + KBr
and well-characterized state and evolves for a known time or NaBr + KCl. The probability of observing these two
interval, after which the state of the system is precisely de- product “channels” depends on the nature of the NaCIKBr
termined via a high-finesse experimental probe. The im- dynamics. That is, the product ratio will provide insight
portance of each of these components to the resolution of into whether intramolecular energy transfer in NaCIKBr
even the most qualitative of questions (e.g., is the energy is rapid or not. More extensive measurements will entail
transfer statistical or not) should be clear. If, for exam- analysis of the internal states of the product molecules
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500 Energy Transfer, Intramolecular

(see Fig. 5), as well as of the relative velocities of the information to the molecule upon which they impinge. As
products. Thus, these kinds of measurements allow one to a consequence, by controlling the phases of these laser
infer information on the characteristics of the dynamics of sources, one can affect the nature of the molecular dy-
the intermediate without directly observing it. Other ex- namics. More careful examination indicates that the ex-
amples of this kind include measurements on the products perimentalist must control the relative phases of two laser
of unimolecular decay, photodissociation, etc. sources, rather than the absolute phase of a single source,
Similarly, most experiments on intramolecular energy a far more feasible prospect.
transfer fall into one of two categories with respect to These proposals for the control molecular dynamics and
preparation of the molecule. In the crudest, the system chemical reactions rely heavily on quantum interference
is prepared by a “coarse” technique where little detail phenomena similar to that seen in the famous “double-
about the initial molecular state is available. Such, experi- slit” experiment. As a consequence they herald a new age
ments include preparation via collision that is, where the in molecular reaction dynamics, one in which quantum
molecule of interest, A, collides with, and absorbs energy aspects of molecular motion are utilized to alter molecular
from, another molecule B and preparation via reaction, dynamics.
where the molecule A is the product of a “precursor” re-
action. Although the bulk of early work on intramolecular
dynamics was carried out with these techniques, far greater VII. SUMMARY
insight emerges from modern experiments in which the
molecule A is prepared by the absorption of radiation. Understanding the nature of intramolecular energy flow
The optimum experiment would therefore proceed by in isolated molecules is of great practical and fundamen-
preparing the molecules in a precise state using beam tal interest. Early developments, both theoretical and ex-
methods and laser excitation, followed by measurement perimental, were hampered by a number of technolog-
of the radiative emission as well as other properties ical problems now being overcome. As a consequence,
of the bound molecule. Such experiments are, in fact, general features that determine the rate and extent of in-
underway on a variety of molecules in several labora- tramolecular energy transfer are slowly emerging. These
tories around the world. In addition, information on the include generic features of classical Hamiltonian systems
bound-state dynamics of molecules has emerged from and the way in which coupling terms influence the na-
pump-probe techniques in which two lasers are utilized, ture of the dynamics, the dependence of observed energy
one to prepare the molecule in the desired state and the transfer on the zero-order system, the interaction between
second to interrogate the dynamics. Along with these state preparation and state measurement on the qualitative
experimental developments, we note a need for reliable interpretation of the dynamics, and the differences and
theories to understand the interrelationship between the similarities between the quantum and classical views of
observed features and the nature of the dynamics. Such dynamics. Nonetheless, general rules regarding the rates
developments are in progress. and extent of intramolecular energy flow have yet to be
established. Similarly, a number of fundamental issues
arising in the study of intramolecular energy flow have
VI. CONTROL OF DYNAMICS yet to be resolved. Rapid technological developments in
computational and experimental tools hold great promise
We noted, in Section I, that the study of intramolecular en- for substantial developments over the next decade.
ergy transfer is linked to the practical goal of controlling
the dynamics of molecules. Since the 1980s theoreticians
have made giant strides which make control over mol- ACKNOWLEDGMENT
lecular dynamics feasible. Space restrictions prevent any-
thing other than a brief comment; the reader is referred to We are grateful to the donors of the Petroleum Research Fund, admin-
the Accounts of Chemical Research reference for further istered by the American Chemical Society, for partial support of the
details. research on which this overview is based.
Equation (27) makes clear that the dynamics of a molec-
ular process is intimately linked to the phases of the system
preparation, contained in the di, j coefficients. It is clear, SEE ALSO THE FOLLOWING ARTICLES
then, that if one were able to control the phases and mag-
nitude of these terms, the subsequent system dynamics ATOMIC AND MOLECULAR COLLISIONS • CHAOS • CHEM-
would also be controlled. Recently, a number of theoreti- ICAL KINETICS, EXPERIMENTATION • CHEMICAL PHYSICS
cians have noted that coherent laser sources transfer phase • COLLISION-INDUCED SPECTROSCOPY • DYNAMICS OF
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Energy Transfer, Intramolecular 501

ELEMENTARY CHEMICAL REACTIONS • MECHANICS, Gruebele, M., and Bigwood, R. (1997). Int. Rev. Phys. Chem. 17, 91.
CLASSICAL • QUANTUM MECHANICS • STATISTICAL ME- Gruebele, M. (2000). Adv. Chem. Phys. 114, 193.
Lehmann, K. K., Scoles, G., and Pate, B. H. (1994). Annu. Rev. Phys.
CHANICS
Chem. 45, 241.
Levine, R. D. (1969). “Quantum Mechanics of Molecular Rate
Processes,” Oxford Univ. Press, London.
BIBLIOGRAPHY Noid, D. W., Koszykowski, M. L., and Marcus, R. A. (1981). Annu. Rev.
Phys. Chem. 32, 267.
Brumer, P. (1981). Adv. Chem. Phys. 47, 201. Rice, S. A. (1975). “Excited States” (E. C. Lim, ed.), Vol. 2, Academic
Brumer, P., and Shapiro, M. (1988). Adv. Chem. Phys. 70, 365. Press, New York.
Brumer, P., and Shapiro, M. (1989). Accts. Chem. Res. 22, 407. Rice, S. A. (1981). Adv. Chem. Phys. 47, 117.
Faraday Discuss. Chem. Soc. (1983). 75. Stechel, E. B., and Heller, E. J. (1984). Annu. Rev. Phys. Chem. 34,
Felker, P. M., and Zewail, A. M. (1988). Adv. Chem. Phys. 70, 265. 563.
Forst, W. (1973). “Theory of Unimolecular Reactions,” Academic Press, Wyatt, R. E., Iung, C., and Leforestier, C. (1995). Accts. Chem. Res. 28,
New York. 423.
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Hydrogen Bond
Krzysztof Szalewicz
University of Delaware, Newark, Delaware

I. Historical Perspective
II. Quantum Mechanical Description of Hydrogen
Bond
III. Analytic Representations of Potential Surfaces
IV. Nature of Hydrogen Bond
V. Properties of Hydrogen Bonds
VI. Types of Hydrogen Bonds
VII. Hydrogen Bonds in Clusters
VIII. Hydrogen Bonds in Solids
IX. Hydrogen Bonds in Liquids
X. Proton Transfer
XI. Hydrogen Bonds in Biological Structures

GLOSSARY Dimer A complex formed by two molecules that do not

react chemically with each other. The two constituent
Basis functions In the context of solutions of the elec- molecules of the dimer, called monomers, are disturbed
tronic Schrödinger’s equation for hydrogen-bonded upon the formation of the dimer but preserve their
system, this term refers to Gaussian functions of the identity.
form exp[−αr2 ], where r is the position vector, mul- Electron density The probability density of finding any
tiplied by powers of the coordinates x, y, and z. The electron of a molecule at a given point in space. Often
basis functions are usually located at the nuclear po- visualized as the “electron cloud.” Electron density can
sitions and near the midpoint of the hydrogen bond be obtained by integrating the square of the modulus
(midbond functions). Linear combinations of such ba- of an electronic wave function over the coordinates of
sis functions form molecular orbitals. all electrons but one.
Coulomb interaction The interaction between two Euler angles A set of three angles that uniquely deter-
charged particles. According to Coulomb’s law of elec- mines the orientation of a solid body in space.
trostatics, the energy of such interaction is q1 q2 /R, Hamiltonian The operator appearing in the Schrödinger
where qi is the charge of the ith particle and R is the equation of quantum mechanics. Operators act on
particles’ separation. wave functions, transforming them into other wave

505
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506 Hydrogen Bond

functions. For an isolated molecule the Hamiltonian H K = E K K ,

contains second partial derivatives with respect to co-
ordinates of all constituent particles—which describe where H is the Hamiltonian,  K is the wave function,
the kinetic energy—and the sum of Coulomb interac- and E K is the energy of the system in its K th state. The
tions between all the particles—which describes the ground state of the system is denoted by K = 0.
potential energy. Supermolecular approach The method of calculating
Hartree-Fock method A method of solving the the interaction energies by subtracting the monomers’
Schrödinger equation that assumes that particles’ mo- total energies from the dimer total energy.
tions are independent of each other and a given particle Symmetry-adapted perturbation theory (SAPT) The
interacts only with the averaged charge distribution of method describing the intermolecular forces including
other particles. The electronic wave function can then the hydrogen bonds.
be approximated by an antisymmetrized product of Wave function A solution of the Schrödinger equation.
one-electron functions (orbitals). The effects neglected The square of the absolute value of a one-particle wave
by the Hartree-Fock method are called correlation function is the probability density of finding the particle
effects. at a given point in space. The wave functions replace
Molecular simulations Computer modeling of the mo- the trajectories of classical mechanics.
tion of an assembly of atoms or molecules. In molecular
simulations only the motions of nuclei are considered,
(i.e., one assumes that the electronic Schrödinger equa- IN SIMPLEST TERMS the hydrogen bond is a type of in-
tion has been solved providing intermolecular interac- termolecular interaction characterized by the equilibrium
tion potentials.) In practice empirical interaction poten- configuration involving a hydrogen atom located close to
tials are utilized in most cases. Two main approaches the line connecting the two nearest nonhydrogen atoms of
are used: the Monte Carlo (MC) method and molec- the interacting molecules. Intermolecular interactions are
ular dynamics (MD). The former relies on statistical interactions between molecules that do not lead to forma-
sampling of the configuration space of the systems, tion of chemical bonds. Such interactions are also called
whereas the latter solves classical mechanics (Newton) noncovalent interactions or intermolecular forces. To dis-
equations to find trajectories of molecules. cuss properties of hydrogen bonds, it will be convenient to
Perturbation expansion A method of solving the denote one of the monomers as R1 -X-H and another one
Schrödinger equation by dividing the Hamiltonian H as Y-R2 . R1 and R2 are arbitrarily large molecular frag-
into an unperturbed part H0 and the perturbation V . H0 ments, X and Y are sufficiently electronegative atoms—
is chosen such that an accurate solution of the “unper- in most cases oxygen, nitrogen, or fluorine—and H is a
turbed” Schrödinger equation H0 0 = E 0 0 is pos- hydrogen atom. Usually there is a lone electron pair on
sible. The wave function  and the energy E which atom Y. The hydrogen-bonded dimer can be then denoted
solve H  = E are expanded as power series in V as R1 -X-H· · ·Y-R2 , where R1 -X-H is called the hydrogen
starting from 0 and E 0 , respectively, which leads to donor and Y-R2 is called the hydrogen acceptor. In a typ-
a hierarchical set of equations for the coefficients in ical hydrogen-bonded complex, the atoms X-H· · ·Y form
these power series called the wave function and en- approximately a straight line. The name hydrogen bond—
ergy corrections, respectively. The simplest implemen- which comes obviously from the central position of the
tation of the perturbation method is called the Rayleigh- hydrogen atom in the dimer—is misleading because this
Schrödinger perturbation theory. atom as such has no particular bonding properties (some-
Quantum mechanics Theory describing behavior of times the term hydrogen bridge is used, which perhaps
matter and radiation on the atomic and subatomic scale. would be more appropriate). Instead, the bond results from
Applied to chemical problems, quantum mechanics ac- a balance of four fundamental physical interactions taking
counts for the properties of atoms and molecules in place between the whole monomers. The definition of the
terms of the interactions between the constituent parti- hydrogen bond will be discussed further in sections VI
cles: electrons and nuclei. The motion of these particles and VII. Examples of hydrogen-bonded systems are pre-
is described in the nonrelativistic quantum mechanics sented in Fig. 1. Two monomers can be connected by more
by the Schrödinger equation. than one hydrogen bond, as in the case of the formic acid
Schrödinger equation Partial differential equation of dimer shown in Fig. 1(b). Sometimes also some interac-
quantum mechanics used to calculate wave functions tions within a single molecule resemble hydrogen bonds,
and energies of atoms and molecules. In chemistry it is as in the case of salicylic acid shown in Fig. 1(d). While
often sufficient to consider only the time-independent hydrogen bonds involving N, O, and F atoms (both as
version of this equation which can be written as donors and acceptors) are most common, also C and P can
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Hydrogen Bond 507

in this case is shown in Fig. 2. The value of R where the

attraction changes to repulsion is sometimes called the σ
point, Rσ , of the potential (it is, of course, dependent on
the mutual orientation of the two molecules). This distance
can also be called “the distance of closest approach” of the
two monomers. Although monomers with enough energy
can get a little closer, the repulsive wall is so steep that the
differences compared to Rσ are minor. The two monomers
interacting via intermolecular forces can be bound or not.
In a dilute gas, most monomers will have a positive energy
of relative motion (i.e., these monomers will be in a scat-
tering state, getting momentarily close to each other and
then separating into remote regions of space.) A smaller
number of monomers will be in bound states, staying at
a finite distance from each other that is close to the equi-
librium distance at the minimum of the potential, Re . The
energetic location of such a bound state and the vibrational
wave function are indicated in Fig. 2.
The intermolecular forces are much weaker than the
chemical forces because the interaction energy at the
point where the attraction is strongest is typically smaller
than 20 kcal/mol. For the weakest intermolecular bonds,
the depth of the interaction potential can be as small as
0.02 kcal/mol, as is the case for the helium dimer. Inter-
molecular forces are the most prevalent forces of nature
around us. The structure of all liquids and of most solid
matter (an exception are metals) is determined by inter-
FIGURE 1 Examples of hydrogen-bonded systems. The hydro- molecular forces. These forces also play a major role in
gen bonds are indicated by broken lines. (a) Ammonia· · ·hydrogen shaping the properties and functions of biological systems.
chloride; (b) formic acid dimer; (c) formamide dimer; (d) intra-
monomer bond in salicylic acid.
The intermolecular forces are often called van der Waals
forces, although some authors reserve this name only for
the interactions not stronger than a couple of kcal/mol.
play the role of donors, and S, Cl, and Br can appear in The boundary between chemical forces and intermolec-
both roles. ular forces is, of course, flexible. Systems exhibiting the
The hydrogen bond is a special case of intermolecular strongest intermolecular interactions may also be classi-
or interatomic interactions. Consider two monomers: each fied as being bound by chemical forces. An additional,
of them can be an atom or molecule, separated by a dis- although still subjective, criterion in borderline cases can
tance R. To be precise, let R denote the distance between be the extent of the deformation of a monomer’s geome-
the centers of masses of each monomer. When R is suf- tries and electron densities upon the formation of the
ficiently large, the monomers will typically attract each complex.
other (exceptions include large-R interactions dominated The physical processes leading to intermolecular forces
by dipole–dipole terms that can be of either sign, depend- are well understood. The total interaction energy is com-
ing on mutual orientation). When R is shortened, up to posed of four components: electrostatic, induction, dis-
some point the attraction will keep increasing. Upon a fur- persion, and exchange energies. The electrostatic compo-
ther shortening of the intermonomer separation there are nent is due to Coulomb interactions of the unperturbed
two possibilities. The monomers may undergo a chemical charge distributions of the monomers. The charge distri-
reaction, forming a new molecule and releasing energy on butions do get perturbed during the interaction: the charge
the order of 100 kcal/mol. This new molecule is bound by distribution on monomer A produces an electric field on
chemical forces. In most cases, however, the monomers monomer B which in turn induces a charge deformation
just begin to repel each other, with the repulsion increas- (i.e., polarizes monomer B and vice versa). This process
ing very quickly with the decrease of R. The forces acting gives rise to the induction energy. The two discussed com-
between two such monomers are called intermolecular ponents are completely defined in the framework of clas-
forces, and a typical shape of the potential energy surface sical electrostatics. The third component, the dispersion
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508 Hydrogen Bond

FIGURE 2 A generic one-dimensional interaction potential. The equilibrium separation Re and the separation Rσ ,
where the potential changes from repulsive to attractive, are marked. De denotes the potential depth at the equilibrium.
The position of the ground vibrational level and the ground vibrational wave function are indicated. D0 is the dissociation
energy.

energy, is of quantum mechanical origin. It results from minimum on the potential energy surface. Thus, the use-
correlations of the fluctuations of the electronic charges fulness of the hydrogen bonding concept may simply re-
on monomers A and B. The exchange energy is also of sult from our ability to predict structures of dimers and
quantum origin. This component is the consequence of the larger clusters. A further reason for recognizing hydro-
electrons tunneling through the potential barrier between gen bonding as a phenomenon worth a separate treatment
the monomers. The name follows from the fact that the are spectroscopic properties of the X-H stretching mo-
electrons are exchanged between monomers during this tion when the hydrogen atom participates in a hydrogen
process. Sometimes the exchange energy is interpreted bond. The fundamental frequency of this vibration is sig-
in terms of the “repulsion of the electron clouds.” This nificantly lowered (red shifted) in the dimer compared to
picture—which derives from the fact that the exchange that in the isolated monomer. The shift is very sensitive to
energy is proportional to the overlap of electronic charge the molecular environment and therefore provides a ma-
distributions—does not reflect the physics of the interac- jor tool to investigate the structure of hydrogen-bonded
tion as well as the tunneling picture. clusters, liquids, and solids.
Hydrogen bonds result from the same physical forces as The hydrogen bond has been the subject of numerous
all other intermolecular interactions. Thus, from this point review papers and monographs. It is always treated in
of view there would be no need to define hydrogen bond- works devoted to intermolecular interactions [see, e.g.,
ing as a distinct process. Therefore, the phenomenon of Hobza and Zahradnik (1988), Stone (1996), Jeziorski and
hydrogen bonding is related to the structural characteris- Szalewicz (1998), Müller-Dethlefs and Hobza (2000), as
tics of hydrogen-bonded dimers rather than to the physical well as a special issue of Chemical Reviews (1994)].
nature of the interaction. As we will discuss below, if two Monographs restricted to the hydrogen bond include
monomers can be brought together to form a hydrogen- Schuster (1984), Jeffrey (1997), Scheiner (1997), and
bonded structure, this structure will likely be close to the Desiraju and Steiner (1999).
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Hydrogen Bond 509

I. HISTORICAL PERSPECTIVE date back to the 1950s). The method of neutron diffrac-
tion has an advantage over the X-ray diffraction—it gives
The subject of hydrogen bond (or bonding) is certainly a information about the positions of hydrogen atoms. In the
popular one. The ISI Science Citation database lists more 1980s high-precision near-infrared spectra of clusters in
than 26,000 papers that use this phrase in the title, ab- molecular beams gave reliable information on the frequen-
stract, or as a keyword. In the year 1999 alone there were cies of intermonomer vibrations in hydrogen-bonded clus-
about 3,000 such papers published. The importance of the ters. In the 1990s it became possible to measure the same
hydrogen bond stems mainly from the fact that for certain frequencies directly using the techniques of far-infrared
types of molecules formation of such bonds determines spectroscopy. Very recently these methods have enabled
the structure of the dimers or of larger molecular clusters. a rather complete spectroscopic characterization of small
Thus, hydrogen bonds are characteristic features of many clusters such as the water dimer.
clusters, biological aggregates, and of condensed phases.
Chemical structures containing what we now call hy-
drogen bonds were considered already in the early 1900s.
II. QUANTUM MECHANICAL DESCRIPTION
The concept itself appeared around 1920 in works of
OF HYDROGEN BOND
Huggins and of Latimer and Rodebush. The term hydro-
gen bond was used for the first time by Pauling in the early
The hydrogen bond can be completely described from
1930s. In the same period it became clear that anomalous
first principles by solving the Schrödinger equation for
properties of bulk water are due to the formation of hydro-
a set of molecules. In practice such solutions involve sev-
gen bonds. An important paper on this issue was published
eral approximations. Despite these approximations, with
in 1933 by Bernal and Fowler (despite their not using the
the current computer capabilities the solutions predict
term hydrogen bond). The idea was then extended to other
properties of small clusters with accuracy approaching,
“associated” fluids. The hydrogen bonding concept was
in some cases, experimental accuracies and provide ex-
popularized by Pauling’s 1939 book Nature of Chemical
tremely useful information on hydrogen-bonded systems,
Bond.
including information on systems and properties that can-
While initially the experimental evidence of hydrogen
not be measured. In addition to numerical information,
bonding was coming from thermodynamic measurements
quantum mechanics provides the framework necessary to
of anomalous properties and from X-ray measurements
understand the hydrogen-bond phenomenon. The theoreti-
of crystal structure, in the 1930s it was realized that the
cal approach most useful for an analysis of hydrogen bond-
formation of a hydrogen bond has a profound effect on
ing is symmetry-adapted perturbation theory (SAPT). For
the frequency of the X-H stretch. This started the in-
a more detailed presentation of SAPT and references to the
frared investigations of hydrogen bonds, which became
original papers, see Jeziorski and Szalewicz (1998). This
the most sensitive and the most widely applied exper-
approach serves four main purposes: (a) it provides the
imental method of studying this phenomenon in clus-
basic conceptual framework within which intermolecular
ters and in the liquid and solid phases. In the condensed
interactions—including hydrogen bonds—are discussed;
phase the vibrational spectra are often determined with
in particular it provides the standard division of the inter-
the Raman techniques, which detect lines corresponding
molecular interaction into four fundamental components:
to vibrational transitions in scattered radiation of visi-
electrostatic, induction, dispersion, and exchange; (b) it
ble frequencies. Since the early 1950s the nuclear mag-
is the source of models used in the construction of em-
netic resonance (NMR) spectroscopy has been applied to
pirical potentials (empirical force fields); (c) it provides
hydrogen-bonded systems. This technique is, however,
asymptotic constraints on any potential energy surface de-
utilized less often than the infrared spectroscopy due to
rived either from experiment or from theory; and, finally,
complexity of the spectra. In the 1960s the microwave
(d) it can accurately predict the complete intermolecular
spectra in gas phase for some fairly strongly bound clus-
potential energy surfaces for hydrogen-bonded molecu-
ters were measured and gave precise information about
lar complexes. The last goal can also be obtained using
structures of the clusters. Starting in the 1970s, molecular
the so-called supermolecular approach [Chalasinski and
beam techniques provided a major tool for investigating
Szczesniak (1994), van Duijneveldt et al. (1994)].
small clusters. Spectroscopic measurements in molecular
beams produced—via the rotational spectra—a wealth of
information on geometries of clusters, including even very
A. Interaction Energy
weakly bound ones. Also in the 1970s, neutron scattering
techniques were applied to the condensed phase contain- To study hydrogen bonding it is sufficient to use the
ing hydrogen bonds (although the earliest such studies time-independent, nonrelativistic Schrödinger equation.
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510 Hydrogen Bond

As usual for most of chemistry, the Born-Oppenheimer dinates. The set of equilibrium coordinates, which will be
approximation is assumed. This approximation relies on denoted by re , describe the geometry of the monomer at its
the observation that the electronic motion is orders of mag- potential energy minimum. Another reasonable choice of
nitude faster than the nuclear motion. Therefore, the mo- intramonomer coordinates is the geometry averaged over
tion of electrons is computed by solving the electronic monomer vibrations, r 0 . The two geometries will be dif-
Schrödinger equation with nuclei clamped in space. The ferent since the monomer vibrations are always to some
solution of this equation provides the potential energy sur- extent anharmonic. However, intuitively one can expect
face governing motion of the nuclei. For investigations of that the best effective potential can be obtained by av-
intermolecular interactions, this surface is conveniently eraging of the complete, monomer geometry-dependent
divided into the energies of monomers and the interaction potential over an appropriate vibrational wave function of
energy E int . In the dimer case the monomer. Computation of such an averaged potential,
E int 0 , although as expensive as the computation of the
E AB (R, ω A , ω B ; Ξ A , Ξ B ) = E A (Ξ A ) + E B (Ξ B ) complete potential energy surface, represents a useful task
+ E int (R, ω A , ω B ; Ξ A , Ξ B ), (1) because its availability simplifies dramatically the spectro-
scopic, scattering, and bulk phase computations. For atom-
where E AB is the total energy of the dimer, E X is the total diatom complexes the E int 0 potentials predict spectral
energy of monomer X, ω X denotes the Euler angles defin- quantities that are only about 0.1% different from those
ing the orientation of monomer X in a dimer-embedded obtained from full three-dimensional nuclear dynamics
coordinate system, and Ξ X is the set of internal coordi- calculations. Recently it has been shown [Jeziorska et al.
nates of each monomer. The energies entering Eq. (1) are (2000)] that the r 0 geometry is the optimal choice if
solutions to the electronic Schrödinger equation. It should only a single monomer geometry can be considered. The
be noted that in definition (1) the energies of the dimer spectra of atom-diatom complexes computed using r 0
and of the monomers correspond to the same values of the potentials exhibit deviations from the spectra computed
internal coordinates Ξ X . with three-dimensional potential, which are about four
In most cases of hydrogen-bonded systems, the mono- times smaller than the analogous deviations produced by
mers are nearly rigid compared to the dimer (i.e., the am- the re potentials.
plitudes of intramonomer motions are much smaller than The rigid-monomer approximation will not work well
those of the intermonomer ones). This is reflected in the if the monomers are too floppy and for complexes involv-
monomer vibrational frequencies being much higher than ing charged monomers. In the latter case the reason is
the intermolecular ones. Thus, one can expect that the de- that the monomers may be fairly significantly distorted
pendence of the interaction energy on the intramonomer upon the formation of the complex. For biopolymers, cer-
coordinates can be neglected and that a large body of spec- tain intramolecular coordinates do vary significantly, and
troscopic, scattering, and bulk phase experiments can be these coordinates have to be included in the description of
interpreted in terms of effective potentials depending on hydrogen bonds in such systems.
intermolecular coordinates only. This approximation leads In the supermolecular method the interaction energy is
to a dramatic simplification in studies of hydrogen-bonded computed by subtraction of the individual energies E AB ,
complexes. For general complexes consisting of N atoms, E A , and E B . These energies are in practice calculated us-
there are 3N nuclear degrees of freedom, (i.e., 3N coor- ing finite basis sets. As a result, the monomer part of the
dinates are needed to describe the position of the system dimer energy is improved by utilizing the basis functions
in space). However, different locations of the center of of the interacting partner. This leads to a spurious lower-
mass of the complex in space as well as rotations of the ing of the interaction energy, referred to as the basis set
whole system do not change interaction potentials. Be- superposition error (BSSE). This error can be removed us-
cause of these translational and rotational invariances, the ing the counterpoise (CP) technique introduced by Boys
energy surface of a system containing N atoms depends and Bernardi. Denoting by E Sσ (G) the electronic energy
on 3N − 6 coordinates (3N − 5, i.e., one coordinate for of system S at geometry G computed with basis set σ , the
a diatomic dimer like Ar2 ). Even for relatively small sys- definition of the CP correction takes the following form
tems like the water dimer 3N − 6 = 12 is a large number β α∪β α∪β
δ E CP = E αA (AB) + E B (AB) − E A (AB) − E B (AB),
of degrees of freedom to treat. The “frozen” monomer ap-
proximation reduces the number of degrees of freedom to (2)
only 6 for any dimer consisting of two general molecules. where α and β stand for the basis sets used for monomers
The simplest and apparently most natural way of ob- A and B, respectively. The use of AB geometry for a
taining rigid-monomer potentials is to perform interaction monomer means that the nuclei of this monomer are at the
energy calculations assuming equilibrium monomer coor- same relative positions as in the dimer AB, and the basis
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Hydrogen Bond 511

functions originating from the interacting partner (often and ρ B (r ) of the monomers, showing clearly its relation
called the “ghost” functions) are located at the same spatial to the Coulomb law
positions as in the dimer. The SAPT approach by definition 
(1) 1
does not include BSSE, since it calculates the interaction E elst = ρ A (r 1 ) ρ B (r 2 ) d 3r 1 d 3r 2 . (6)
energy directly rather than by subtraction of monomer |r 1 − r 2 |
energies from the energy of the dimer. This feature made The total electric charge distribution ρ X (r ) for monomer
it possible to prove the correctness of the CP method by X is the sum of the electronic contribution—which can
comparisons of supermolecular and SAPT calculations be obtained from the wave function 0X —and the nuclear
[van Duijneveldt et al. (1994)]. contribution.
The electrostatic interaction plays a major role in de-
B. Perturbation Theory of Hydrogen Bond termining the structure of dimers consisting of polar
molecules, in particular hydrogen-bonded systems. The
In the SAPT method, the total Hamiltonian H of the dimer evaluation of the electrostatic interaction energy for such
is partitioned as H = H A + H B + V , where H X , X = A or systems is often performed by approximating the elec-
B, is the total Hamiltonian for monomer X , and V is the trostatic potential of a molecule by that resulting from
intermolecular interaction operator. The operator V col- a set of point charges or from a single-center or multi-
lects Coulomb interactions of all the particles of monomer center distribution of multipole moments. However, one
A with those of monomer B. This partition means that the should emphasize that the electrostatic energy contains
unperturbed operator is chosen as H0 = H A + H B and V also important short-range terms due to the mutual pen-
is the perturbation. The interaction energy is then obtained etration (charge overlap) of monomers’ electron clouds.
directly in the form of a perturbation series in V , This short-range part of the electrostatic energy, neglected
(1)
E int = E pol (1)
+ E exch (2)
+ E pol (2)
+ E exch + ···, (3) both in the monocentered and distributed multipole expan-
sions, makes significant contributions to the stabilization
with each term of the sum having a well-defined physical energy of hydrogen-bonded systems. The electrostatic in-
meaning. The polarization components, denoted by the teraction can be either attractive or repulsive. This property
subscript “pol,” are determined by the standard Rayleigh- is best illustrated by large-R interactions of two neutral
(1)
Schrödinger perturbation expansion. The correction E pol molecules possessing dipole moments. The electrostatic
is the classical electrostatic (Coulomb) interaction energy dipole– dipole term dominates then the interaction energy.
of two unperturbed charge distributions and will be written This term can be either attractive or repulsive, depending
(1)
as E elst . The remaining components, denoted by the sub- on the mutual orientation, with the maximum and mini-
script “exch,” are the exchange corrections accounting for mum of equal magnitudes.
the effect of resonance tunneling of electrons between the Often the electrostatic interaction energy alone, or
interacting systems. These contributions originate from rather its asymptotic form, is used to determine the approx-
the antisymmetrization of the polarization corrections to imate equilibrium orientation (but not the equilibrium sep-
the wave function. The second-order corrections can be aration) of hydrogen-bonded clusters. Due to the impor-
further divided into induction and dispersion components: tance of this interaction, such predictions are frequently
(2)
E pol (2)
= E ind (2)
+ E disp , (2)
E exch (2)
= E exch−ind (2)
+ E exch−disp . correct, and a few examples will be given in section V.
The electrostatic predictions are not correct when other
(4) components of the interaction energy have anisotropies
The polarization energies through second order have a significantly different from the anisotropy of the electro-
simple physical interpretation and can be rigorously ex- static component (cf. section V). In fact, those anisotropies
pressed through monomer properties. are always to a smaller or larger extent different so that
the exact minimum structure of a hydrogen-bonded cluster
1. Electrostatic Interaction can be found only by taking into account all of them.
The electrostatic energy, the lowest order polarization
component, is defined as 2. Induction Interaction
  
(1)
E elst = 0A 0B V 0A 0B , (5) (2)
The second-order polarization energy E pol is given by the
where 0X is the expression
 unperturbed wave function of monomer X
and  f | g = f ∗ gdτ with the integration extending over   
  0A 0B V  KA  LB 2
all electron coordinates. The electrostatic energy can be (2)
E pol = , (7)
expressed in terms of the total charge distributions ρ A (r ) KL E 0A + E 0B − E KA − E LB
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512 Hydrogen Bond

where K and L label excited states of the monomer A and ponent any further. In contrast, the difference between the
B, respectively, and the prime over the summation sign in- dimer electron density and the sum of the densities of the
dicates that the term with K = 0 and L = 0 is excluded. two monomers is perfectly well defined and can be com-
Eigenfunctions  M X
and eigenenergies E M X
are solutions puted to interpret experimental observations related to the
of the Schrödinger equation, with the Hamiltonian H X for charge density, like, for example, NMR spectra.
monomer X describing the ground and excited states of
this system. The induction energy is obtained when the
sum over states in Eq. (7) is restricted to functions ex- 3. Dispersion Interaction
(2)
cited on only one monomer (i.e., to the functions of the The second-order dispersion energy E disp is defined as
(2)
form 0A  LB and  KA 0B ). The corresponding part of E pol , the difference between the second-order polarization and
(2) (2) (2) (2)
denoted by E ind , is given by E ind = E ind (A) + E ind (B), (2)
induction energies, E disp (2)
= E pol (2)
− E ind . Therefore it can
where be written as
     
(2)
E ind (A) = 0A  B (1)
ind (A) (8) (2)
   0A 0B V  KA  LB 2
E disp =
(2)
and a similar expression holds for E ind (B). The induction K =0 L =0 0
E A + E 0B − E KA − E LB
(1)
function ind (A) is defined by   
   = 0A 0B V (1)disp , (10)
(1)
  KA  B 0A
ind (A) =  KA . (9) where
E A
− E A
  
K =0   KA  LB V 0A 0B
0 K
(1) =  KA  LB , (11)
The operator B = 0B |V 0B  is the electrostatic poten- disp
K =0 L =0
E 0A + E 0B − E KA − E LB
tial generated by the unperturbed monomer B.
Equation (8) has the form of the second-order en- is the “dispersion function” representing the leading in-
ergy correction arising when monomer A is perturbed termolecular correlation contribution to the dimer wave
by the static electric field generated by the (unperturbed) function. This function is a sum of products of wave func-
monomer B. Notice that Eqs. (8) and (9) include only tions that are describing the electronic excitations on both
the coordinates of electrons belonging to system A, all the monomer A and B; therefore the dispersion inter-
the effects of system B entering via the potential B . The action can be viewed as the stabilizing energetic effect
second-order induction energy results, thus, from the po- of the correlation of instantaneous multipole moments of
larization of the monomers by the static electric fields the monomers. Since the dispersion energy is a correlation
of unperturbed partners (in older literature the induction effect, it cannot be reproduced at the Hartree–Fock level of
contribution is sometimes referred to as the polarization theory. The dispersion force results from the dependence
energy). Asymptotically, at large intermolecular distances of electrons of system B on the position of an electron in
R, this effect is fully determined by the permanent multi- molecule A; therefore it goes beyond the averaged charge
pole moments and static multipole polarizabilities of the distributions characteristic of the Hartree–Fock method.
monomers. At finite R, additional monomer information The dispersion energy is usually the most isotropic com-
is needed to account for the short-range, penetration part ponent of the interaction in hydrogen-bonded clusters.
(2)
of E ind . Although it does not have a large effect on the cluster’s
Because monomers that form hydrogen bonds almost equilibrium orientation, it contributes significantly to the
always are very polar, the induction energy for hydrogen- energy of hydrogen bonds, being of similar size to the in-
bonded clusters makes a very significant contribution to duction energy for medium-size systems but playing an
the total interaction energy. It is also quite anisotropic al- increasingly larger role as the system size grows.
though less than the electrostatic energy. Some authors
proposed to identify within the induction energy a term
4. Exchange Interaction
called the charge transfer energy. This term was assumed
to describe the interactions due to the transfer of a part The sum of low-order polarization corrections, even when
of the electronic charge from monomer A to monomer evaluated exactly without the use of the multipole ex-
B or vice versa. Although such a transfer certainly takes pansion, is not able to predict the existence of the van
place to some extent, a quantitative determination of this der Waals minimum or the repulsive wall at shorter inter-
component proved to be not possible thus far. Methods molecular separations. The repulsive contributions are due
proposed by various authors lead to dramatically differ- to the electron exchange (i.e., to the physical process of
ent estimates of the size of this effect. Therefore, we will the [resonance] tunneling of electrons between interacting
not discuss the hypothetical charge-transfer energy com- systems). The unperturbed function 0 = 0A 0B as well
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Hydrogen Bond 513

as higher-order polarization functions such as (1) ind (X ) and

cases the exchange contribution at the potential minimum
(1) describe the situation when the electrons stay within is the component that is largest in magnitude. It is also
disp
their monomers, but the permanent and instantaneous po- significantly anisotropic.
larization is allowed (therefore the name “polarization ex-
pansion”). The true wave function contains also compo- 5. Multipole Expansion
nents corresponding to tunneling of one, two, or more
electron pairs between interacting units. In the case of two As the distance between monomers grows larger, the im-
hydrogen atoms, both electrons can simultaneously tun- portance of various components of the interaction energy
nel in opposite directions between the two potential energy changes. The exchange effects, dominating at short sep-
wells in the six-dimensional configuration space (one well arations, become negligible due to their fast, exponential
with electron 1 at nucleus A and electron 2 at nucleus B and decay with R. The polarization components decay much
the other with the electrons exchanged). Because the two slower. This is easy to understand for the electrostatic en-
wells are equivalent by symmetry, the tunneling leads to ergy which—in the case of neutral polar monomers—has
the resonance splitting of the unperturbed energy level into to reduce for very large distances to a dipole–dipole inter-
the energies of the singlet and the triplet states. Asymptot- action proportional to 1/R 3 . One can show in general that
ically at large R the exact wave function becomes a linear at large R the interaction energy E int has the following
combination of two equally weighted “resonance struc- asymptotic expansion in powers of 1/R:
tures” 0 = φ1s A B
(r 1 )φ1s (r 2 ) and P12 0 ≡ φ1sA B
(r 2 )φ1s (r 1 ), 
∞
the second of which cannot be recovered by a low-order E int (R, ω A , ω B , Ξ A , Ξ B) ∼ Cn(ω A , ω B , Ξ A , Ξ B)R −n.
X
polarization theory (φ1s is the 1s orbital of hydrogen cen- n=1
tered on atom X). It is clear that A0 ≡ √12 (0 ± P12 0 ) (12)
rather than 0 should be used as the unperturbed wave
function in the perturbation theory of intermolecular inter- Although it is only asymptotically convergent in Eq. (12)
actions. Unfortunately, the use of A0 in the conventional can approximate the exact interaction energy arbitrarily
Rayleigh-Schrödinger perturbation procedure (employing closely when R is sufficiently large. Therefore, the knowl-
the sum of the monomer Hamiltonians as the unperturbed edge of the Cn coefficients is very useful in estimating
operator) is impossible since A0 is not an eigenfunction the interaction energy at large distances, and is necessary
of the zeroth-order operator H0 . Therefore, a modifica- to guarantee the correct large-R asymptotic behavior
tion of the perturbation procedure is required such that the of empirical or theoretically derived potential energy
function A0 can be utilized in the perturbation develop- surfaces. The angular dependence of the coefficients
ment. Such a modification, usually referred to as symmetry Cn (ω A , ω B , Ξ A , Ξ B ) for fixed internal geometries Ξ A ,
adaptation, was first attempted in 1930 by Eisenschitz and Ξ B of the monomers can be expressed in a closed form.
London, and there has been continued activity in this field The coefficients Cn can be computed from properties
since the late 1960s. The currently most popular variant of of monomers such as multipole moments and polarizabili-
symmetry adaptation, called the Symmetrized Rayleigh– ties. The relevant formulas are obtained from the polariza-
Schrödinger method, was proposed in 1978 by Jeziorski, tion series truncated at some finite order by replacing the
Chalasinski, and the present author. potential V by its asymptotic expansion in powers of 1/R.
Since the exchange effects decay exponentially with For the Coulomb potential 1/|r 1 −r 2 |, such expansion has
distance, they are negligible for large R. In the region of the form

1  ∞ 
l<
(−1)l B (l A + l B )!
= √
|r 1 − r 2 | l A ,l B =0 m=−l< (2l A + 1)(2l B + 1)(l A + m)!(l B + m)!(l A − m)!(l B − m)!

× r1l A r2l B YlmA (θ1 , φ1 )Yl−m

B
(θ2 , φ2 )R −l A −l B −1 , (13)

the potential minimum these effects are, however, always where ri , θi , φi are the polar coordinates of ith parti-
very important. In the case of hydrogen-bonded dimers cle and l< denotes the smaller of l A and l B . The coor-
near the potential minimum, the electrostatic, induction, dinates of particle 1 are measured in system A, while
and dispersion effects are all negative (the latter two are those of particle 2 are measured in system B. The two
in fact always smaller than zero). The positive exchange coordinate systems have their z axes along the same line,
energy cancels a large part of the attractive effect. In many and the other axes of one system are parallel to the
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514 Hydrogen Bond

respective axes of the other system. The functions proximation to the interaction energy. The distance where
Ylm (θ, φ) are the standard spherical harmonics. The ex- this starts to happen is significantly larger than the equi-
pansion is valid only when R > r1 + r2 . Combining the librium separation. The quantitative measure of the devi-
equivalents of Eq. (13) for other Coulombic terms in the ation can be obtained by comparing the results of SAPT
intermolecular interaction operator V , one gets the asymp- calculations and of the multipole expansion for a given
totic expansion of V . Individual terms in this expansion configuration. At large enough distances SAPT agrees
are interpreted as arising from the interaction of a 2l A - with the asymptotic expansion arbitrarily well. In addi-
pole moment on monomer A (i.e., an instantaneous dipole, tion, SAPT electrostatic, induction, and dispersion en-
quadrupole, etc., moment formed by an electron) with a ergy components can be directly compared with analo-
2l B -pole moment on monomer B. Therefore the expansion gous components of the asymptotic expansion, and the
in Eq. (13) is often called the multipole expansion of the agreement is reached for each component separately. As
potential. the distance decreases, the exchange effects are becoming
Equation (13) shows that after the multipole expansion important so that the total interaction energies predicted
of the potential is performed, the coordinates of electrons by SAPT and by the asymptotic expansion begin to dif-
of molecule A are separated from those of molecule B. fer. The individual components begin to differ as well,
Therefore, if this expansion is substituted in Eqs. (5), (8), although these differences are smaller than the exchange
(10), and (11), the asymptotic interaction energy is ex- effects. The discrepancies in the components appear be-
pressible in terms of integrals each involving only coor- cause the terms neglected when assuming the multipole
dinates of one monomer. Thus, this energy is expressible expansion of the interaction potential are not negligible
in terms of monomer properties only. This fact makes the anymore. These terms are related to the overlap of electron
calculations in the asymptotic region much easier than for charge distributions and therefore are called the overlap
the finite distances, where this approximation cannot be or penetration effects. When analytic forms of the po-
applied. It is important to realize that the multipole ex- larization components are developed using the multipole
pansion has built-in dependence on the mutual orientation expansion, the penetration effects have to be taken into
of two monomers. Thus, asymptotically the anisotropy of account. Most often this is done by multiplying the 1/R
the polarization part of the interaction energy is precisely terms by the so-called damping functions, decreasing the
predicted by this expansion. Although for finite separa- magnitude of these components for smaller R. In addition
tions this anisotropy is modified by the penetration effects to damped 1/R terms, the polarization energies contain
discussed below, the asymptotic prediction remains useful also purely exponential components that have to be in-
at finite R. cluded for an accurate modeling of these energies. The
The lowest power of 1/R appearing in the asymp- type of analysis of the interaction energy presented here is
totic expansion determines the behavior of the energy very useful for obtaining analytic fits to potential energy
for very large separations. Monomers forming hydrogen surfaces.
bonds almost always have nonzero dipole moments. The
electrostatic dipole–dipole interaction becomes then the
dominating long-range term at very large R, because it de- C. Many-Body Effects
cays as 1/R 3 . The consecutive electrostatic terms, dipole–
quadrupole and quadrupole–quadrupole, decay as 1/R 4 The interaction energy of a system consisting of N
and 1/R 5 , respectively. For neutral monomers with non- molecules can be defined similarly to the dimer energy
vanishing dipole moments, the induction energy decays of Eq. (1) as
as 1/R 6 , whereas the dispersion energy always decays as 
E int (ξ 1 , . . . , ξ N ) = E tot (ξ 1 , . . . , ξ N ) − E i (Ξi ), (14)
1/R 6 (i.e., both components decay faster than the elec-
i
trostatic interaction of polar monomers). Thus, the elec-
trostatics strongly dominate the long-range interaction where E tot is the total energy of the N -mer, E i is the energy
energy for hydrogen-bonded systems. For charged sys- of the ith monomer, and ξi = (Ri , ω i , Ξi ) stands for the
tems the role of electrostatics is even more important: set of all coordinates needed to specify the spatial position
the charge–charge, charge–dipole, and charge-induced Ri , orientation ω i , and the internal geometry Ξi of the ith
dipole terms decay as 1/R, 1/R 2 , and 1/R 4 , respectively. monomer. The N -mer interaction energy can be expressed
Notice that for polar monomers at some angular orien- as a sum over 2, 3, . . . , N -body interactions:
tations the interaction energy will be positive rather than
negative for large enough R due to the positive dipole– E int = E int [2, N ] + E int [3, N ] + · · · + E int [N , N ], (15)
dipole contribution.
When the intermolecular distance gets sufficiently where K -body contributions to the N -mer energy,
short, the multipole expansion fails to provide a good ap- E int [K , N ], can be written as the following sums:
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Hydrogen Bond 515


E int [2, N ] = E int (ξi , ξ j )[2, 2], (16) sion nonadditivity in the third order of perturbation theory.
i< j Only recently, however, have the many-body effects (par-
 ticularly in hydrogen-bonded systems) become the subject
E int [3, N ] = E int (ξi , ξ j , ξ k )[3, 3], (17) of quantitative investigations also for finite intermolecu-
i< j<k lar separations, and most of the available information con-
cerns the three-body nonadditivities. At the minimum con-
and so on. The two-body or pairwise additive interaction figuration of the water trimer, this term contributes about
energies E int [2, 2] are analogous to the dimer interaction 15% to the trimer’s interaction energy. Simulations of liq-
energies defined by Eq. (1). The higher-body terms (i.e., uid water performed with two-body only and two-body
the nonadditive contributions to the N -mer interaction en- plus three-body potentials give internal energies differing
ergy) are defined recursively. For example, the three-body by 22%. Clearly, the nonadditive effects are very important
nonadditive contribution to a trimer interaction energy, for water and most other hydrogen-bonded clusters and
E int [3, 3], is the difference between the total interaction the condensed phase. Very little is known about the four-
energy of a given trimer and the sum of all pair energies. body and higher nonadditivities; however, the available
It should be noted that the many-body expansion of the results indicate that these are smaller than the three-body
interaction energy can be defined only when the quan- ones, contributing only a few percent to the interaction
tum states of all subsystems are unambiguously defined. energy.
For strongly interacting systems such as liquid metals or Figure 3 presents the leading components of the three-
chemically bound molecules this condition is not fulfilled body nonadditivity for hydrogen-bonded systems (or for
and the applicability of the many-body expansion can be any significantly polar systems). The electrostatic en-
questioned. ergy is always purely additive. The dispersion energy
The nonadditive effects play an important role in con- is nonadditive, but this nonadditivity plays a minor role
densed phases of hydrogen-bonded systems. However, it in hydrogen-bonded systems. Thus, the nonadditivity re-
is important to realize that even if a cluster or solid is duces in practice to the exchange and induction compo-
described using only two-body potentials, the properties nents. The S n components of the first-order exchange non-
are not just a superposition of dimer properties. The sim- additivity are proportional to the nth power of overlap
ple reason is that a given monomer may interact via two- integrals between the orbitals of the monomers. The phys-
(1)
body potentials with more than one nearest neighbor and ical mechanism of E exch [3, 3](S 2 ) interaction is as fol-
that it interacts not only with its nearest neighbors but lows. The two-body exchange interaction between a pair
also with all the other molecules in the cluster, liquid, or of monomers, A and B in Fig. 3, leads to a deformation of
solid. Since the other molecules are farther apart, the lat- the electronic charges, which can be described mainly by
ter interaction is almost always attractive and therefore a quadrupole moment on this pair. This quadrupole mo-
stabilizing. An instructive exercise is to consider the min- ment is represented in the figure by a set of charges on AB.
imum structures and binding energies of a linear chain This set of charges can also be replaced by two dipole mo-
of atoms interacting via a Lenard–Jones potential (this ments on monomers A and B, symbolized by the dotted ar-
potential will be discussed in section IV). Assuming for rows. The exchange quadrupole interacts electrostatically
simplicity that all the bonds in an N -mer are of the same with the permanent dipole moment µ of molecule C. The
(1)
length, one can easily find the increased binding ener- next term, E exch [3, 3](S 3 ), is of purely exchange origin, as
gies per monomer and decreased interatomic distances as it results from cyclic permutations involving three elec-
the chain grows larger. Similar summations over a three- trons from three monomers. This is the minimal number
dimensional lattice mimic the lowest order trends in rare of electrons needed to perform exchange between all three
gas crystals. One may use the phrase pairwise-additive monomers. Terms with higher powers of S result from ex-
cooperative effects to describe the properties of N -mers changes involving more electrons. The next term, the non-
(2)
resulting from two-body forces only, while the true nonad- additive induction energy E ind [3, 3], is the most important
ditivity would define pairwise-nonadditive cooperative ef- nonadditive component for hydrogen-bonded systems. It
fects. The three- and higher-body nonadditive forces may is the only term used—in the asymptotic approximation—
introduce both a stabilizing or a destabilizing effect. In in the so-called polarizable intermolecular potentials. The
the case of rare gas crystals, the three-body nonadditive mechanism leading to this term results from the per-
contribution to the interaction energy is positive, whereas manent dipole moment of one of the monomers, A in
for hydrogen-bonded systems the net effect is usually Fig. 3, polarizing another monomer and therefore pro-
stabilizing. ducing on it an induced dipole moment µind , shown as
The long-range asymptotic effects have been investi- the broken arrow on monomer B. This induced moment
gated for more than 50 years, starting from the derivation interacts in turn with the permanent dipole moment of
of the familiar Axilrod-Teller-Muto triple-dipole disper- molecule C.
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516 Hydrogen Bond

FIGURE 3 Major components of three-body nonadditivity for hydrogen-bonded systems.

III. ANALYTIC REPRESENTATIONS large exponent would do—except that it speeds up calcula-
OF POTENTIAL SURFACES tions since (R 6 )2 = R 12 . The potentials of Eq. (18) or (19)
can represent isotropic interactions of apolar systems. For
Knowledge of the interaction potential for a hydrogen- modeling the hydrogen-bonded interactions, the potentials
bonded system on a grid of points would not be convenient have to be supplemented by at least the multipole inter-
for most applications. Therefore, analytic representations actions, dipole–dipole, dipole–quadrupole, etc. Alterna-
of this potential are needed (i.e., reasonably simple math- tively, one may assign to chosen sites on each monomer—
ematical expressions depending on the intermolecular and typically atoms but other choices are possible—charges
possibly intramolecular coordinates). Parameters in such simulating the multipoles of the monomer. Most of the
an analytic potential can be fitted to the computed inter- popular potentials fitted to thermodynamic properties of
action energies. Alternatively, the parameters can be ad- liquids are a combination of an isotropic term of the form
justed by comparing predictions of a trial potential to the of Eq. (18) or (19) and of terms describing the Coulombic
observed quantities. The existing potentials for hydrogen- interactions of a set of distributed charges. Examples in-
bonded systems range from very simple functions con- clude the SPC potentials of Berendsen et al. and the TIP
taining only a few terms to rather elaborate functionals potentials of Jorgensen et al. developed in the 1980s to de-
with dozens of parameters. The simplest forms of the in- scribe liquid water. More accurate representations of the
termolecular potentials are the Lennard–Jones potential interaction potentials, in particular those fitted to ab ini-
A B tio calculations or to spectroscopic data, have to assume
E int (R) =12
− 6 (18) more complicated forms. An example of such a potential
R R
can be the SAPT-5s potential for water [Groenenboom et
and the so-called “exp-6” potential al. (2000)] which is of the form:
C 
E int (R) = A e−α R − , (19)  qa q b
R6 E int = f 1 δ1ab , Rab + Aab g ab (Rab )e−βab Rab
where A, A , B, C, and α are adjustable parameters. The a∈A,b∈B
R ab

1/R 12 and the exponential terms model the repulsive wall,

 Cnab
while the 1/R 6 term models the dispersion energy. There + f n δnab , Rab , (20)
is nothing special in the choice of power 12—any other n=6,8,10
(Rab )n
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Hydrogen Bond 517

where the sum extends over eight sites (five of them sym- better than the effective two-body potentials. Applications
metry distinct) a(b) in molecule A (B). Three of the sites of the former potentials in condensed phase simulations is
are on the atomic nuclei, two are in the region of lone a few times more time consuming than calculations with
pairs, and the three remaining are on the bisector plane the latter ones. Obviously, the many-body effects have also
between the hydrogens. Not all sites are involved in all to be taken into account if ab initio two-body potentials
interactions. The first term represents the Coulombic in- or the potentials fitted to dimer spectra are to be used in
teractions between charged sites. The exponential terms condensed phase simulations.
are multiplied by polynomials

3
g(R) = 1 + am R m IV. NATURE OF HYDROGEN BOND
m=1
To see how the interplay between the four fundamental
for increased flexibility. In addition to the leading induc-
physical forces creates the hydrogen bond, we will con-
tion and dispersion 1/R 6 terms, also the terms with inverse
sider a number of hydrogen-bonded systems: N2 · · ·HF,
powers of 8 and 10 are included (odd powers are nonzero
hydrogen fluoride dimer, HF· · ·ClF, water dimer,
in an exact expansion but are very small). All 1/R terms
dimethylnitramine (DMNA)· · ·methyl alcohol complex,
are damped using the Tang-Toennies function:
and ammonia dimer. The first molecule represents a

n relatively weak hydrogen bond, with the interaction
f n (δ, R) = 1 − e−δ R (δ R)m /m! (21) energy at the potential minimum of only −2.3 kcal/mol.
m=0
The water dimer, certainly the most important hydrogen-
The potential of this form is capable of fitting the computed bonded system, is bound twice as strongly, by
points to within about 0.1 kcal/mol. 5.0 kcal/mol, and the bond in the HF dimer is of similar
The potentials become still more complicated if the strength. The complex of DMNA with methyl alcohol,
rigid monomer approximation is abandoned. Unfortu- bound by about 6 kcal/mol, is discussed to show a
nately, at the present time very little reliable information system for which a very plausible hydrogen-bonded
is available about flexible-monomer potentials. What is configuration is not the global minimum structure.
often done is to assume that the flexible potential can be The components of the interaction energy of N2 · · ·HF
obtained by simply letting the sites centered on atoms to as functions of the orientation of HF denoted by the angle
move with atoms, but this assumption has not been truly θ2 are shown in Fig. 4. For θ2 = 0◦ (180◦ ) the configuration
tested so far. is linear, of the form N-N· · ·F-H (N-N· · ·H-F). The pref-
The potentials discussed above are pairwise or two- erence for the hydrogen-bonded minimum at θ = 180◦ is
body potentials (i.e., potentials describing dimers). Yet, clearly due to the electrostatic interaction. The negative
in many cases such potentials are fitted to thermodynam- dipole–quadrupole term dominates this component (the
ics data for liquids and solids. In such media the pairwise magnitude of this term is maximized at the N-N· · ·H-F
nonadditive effects are usually quite important. Therefore, geometry), but the next term in the multipole expansion,
potentials of this type are called “effective” two-body po- the quadrupole–quadrupole interaction, is not negligible,
tentials since they approximate the many-body effects by contributing close to 50% of the electrostatic energy at
an unphysical distortion of the two-body potential rela- some configurations. At the minimum this term is attrac-
tive to the exact two-body potential. As a consequence, tive and contributes about 28%. A rotation of N2 can only
the effective two-body potentials perform poorly in pre- make both terms less attractive, so that it is clear that we do
dicting pure dimer properties such as dimer spectra or not need to consider other positions of this monomer. As
second virial coefficients. In fact, the effective two-body Fig. 4 shows, the minimum configuration is also preferred
potentials perform poorly also in predicting trimer prop- by the induction energy and (slightly) by dispersion. Even
erties (although the three-body component dominates the the rather small term denoted by δ E intHF
—which contains
nonadditive effects, cf. section III.C). the induction and exchange-induction effects of the order
A partial solution to the problem is offered by the so- higher than second computed at the Hartree–Fock level
called polarizable potentials. As discussed in section III.C, of theory (these effects cannot at present be separated,
the major component of the three-body nonadditivity for therefore δ E int
HF
is not included in the four fundamental
hydrogen-bonded systems are the induction effects. These interaction energy components)—favors the same config-
effects can be modeled by computing the electric field on uration. On the other hand, the N-N· · ·H-F configuration
a given monomer due to other monomers and finding the is strongly disfavored by the exchange effects. This is to be
dipole moments induced by this field. The polarizable wa- expected, since the size of these effects is proportional to
ter potentials are able to predict the dimer properties much the overlap of electronic clouds and when HF rotates from
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518 Hydrogen Bond

FIGURE 4 Components of the interaction energy for N2 · · ·HF shown as functions of the angle θ2 formed by HF with
the intermolecular axis (θ2 = 0◦ for the N–N· · ·F–H geometry) at R = 3.6 Å, close to the minimum separation, and the
N2 molecule lying on the intermolecular axis. SAPT, symmetry-adapted perturbation theory. (Data from Jankowski
et al., 2000.)

0 to 180◦ around its center of mass, close to the F atom, the ical van der Waals radii of atoms. Since hydrogen bonds
overlap strongly increases. The increase of the exchange are shorter than other van der Waals bonds, the radius of
repulsion is in fact larger than the absolute increase of the hydrogen equal to 1.2 Å is conventionally neglected
the magnitude of electrostatic interaction. Only the inclu- when adding van der Waals radii. For example, for water
sion of the induction and dispersion effects leads to the the sum of oxygen’s van der Waals radii is 2.8 Å, reason-
hydrogen-bonded minimum. N2 · · ·HF is a good example ably close to the accurate value of Re = 2.9 Å. A similar
of quite a typical situation in hydrogen-bonded complexes. calculation including also the hydrogen atom gives too
The prediction based on electrostatics alone gives the cor- large a distance of 3.6 Å.
rect minimum angular configuration, which is then con- Some authors describe an even simpler model of the
firmed by a more detailed analysis, despite the fact that the hydrogen bond than the purely electrostatic model. This
other physical components (and their anisotropies) may be model is based on the observation that the X-H bond is
of similar size or larger than in the case of the electrostatic polarized such that there is a net positive charge on the
component. However, there are also cases where predic- hydrogen and negative on the atom X. The positive charge
tions based on electrostatics fail (see below). Of course, on H is attracted to a negative charge on the electroneg-
the electrostatic model cannot predict the radial position ative atom Y. Since both X and Y are negatively charged,
of the minimum since the electrostatic interaction only in- the hydrogen bond has to be linear to attain the minimum
creases in magnitude as the separation decreases (in most repulsion of these charges. This model is too simple to
cases this is true, but for some combinations of dipole and completely predict the minimum geometry in most cases.
quadrupole moments the electrostatic energy may change Let us see how this model works for N2 · · ·HF. Although
sign at short R). Therefore this model assumes a hard due to symmetry there is obviously no charge flow from
sphere repulsion at a distance determined from the empir- one nitrogen atom to another in N2 , there is an excess
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Hydrogen Bond 519

electron density on the molecular axis outside the nuclei, Consider now the water dimer. The minimum structure,
where the lone pairs are located. Thus, the positive charge shown in Fig. 5, can be rationalized in a simplistic way as
on the hydrogen is attracted to this place and the negative follows. The water molecule has two lone electron pairs in
charge on F is repelled, leading to a linear hydrogen bond. a tetrahedral arrangement with the hydrogen atoms. Since
However, this model is not able to determine the angle there is an excess negative charge on the lone pair, the
between the N-N and N· · ·H-F axes. The linear structure O-H· · ·O line should lie along the position of one of the
of the whole dimer cannot be explained by repulsion of pairs. If one uses an additional argument that the accep-
the negative charge on F by the negative charge on the tor’s hydrogens should maximize the distance from the
other side of the N2 molecule, as there are regions of free hydrogen of the donor to minimize the repulsion of
either sign between the nitrogen nuclei. positive charges, an almost correct dimer structure is ob-
Our next example will be the hydrogen fluoride dimer. tained (cf. Fig. 5). Now let us see what structure would
It is a good example to show that the electrostatics re- be predicted taking into account the electrostatic interac-
stricted to the dipole–dipole interaction (or the equivalent tion only. Although for interactions involving diatoms the
charge interaction model) is not sufficient to determine dipole–dipole model predicting a linear dimer may some-
the minimum orientation even for interactions of diatomic times be correct, it is rather clear that it will rarely work for
monomers. Such a model predicts the linear F-H· · ·F-H general monomers. Indeed, for the water dimer the elec-
structure dictated by the optimal orientation of the dipoles, trostatic picture limited to the dipole–dipole interaction
which disagrees with the observed structure in which the would predict a head-to-tail geometry without specifying
hydrogen acceptor is tilted away from the linear geometry the dihedral angle between the planes of the monomers. If
by about 60◦ we use an additional argument taking into account the re-
pulsion of the charges on the hydrogens, a bifurcated struc-
H ture is predicted, far from the true minimum (this structure,
#
F H· · · ·F however, is a saddle point on the potential energy surface,
see section VIII.A). That this approach cannot be suffi-
The electrostatic model gets the right geometry if one in- cient can be seen by recalling the charge distribution of
cludes the dipole–quadrupole and quadrupole-quadrupole the water monomer. The simplest representation of this
interactions. The former interaction is zero for linear ge- distribution is two positive charges on the hydrogens and
ometry, as the dipoleA –quadrupoleB term cancels with a twice larger negative charge on the oxygen—quite a dif-
the quadrupoleA – dipoleB term, but the sum of the two ferent distribution than a dipole along the symmetry axis.
becomes negative for a tilted acceptor. The quadrupole– The description of the water electrostatics limited to the
quadrupole interaction also prefers nonlinear structures. In dipole–dipole term does work at very large intermonomer
fact, a simple electrostatic calculation involving only the separations, as this term decays slower than other electro-
dipole and quadrupole moments predicts the tilting angle static terms. At distances near the minimum, the dipole–
of 68◦ , in reasonable agreement with the observed value. quadrupole and the quadrupole–quadrupole interactions
The overall stabilizing electrostatic effect between the lin- are, however, very substantial. Taking them into account
ear and the tilted configurations is about 2 kcal/mol. As for a fixed R of 3 Å gives a geometry very close the true
in the case of N2 · · ·HF, the exchange interaction acts op- minimum shown in Fig. 5: the hydrogen bond nonlinear-
posite to the electrostatics, but the destabilizing exchange ity angle α is only 8◦ too large and the angle β between
effect when going from the linear F–H· · ·F–H to the non- the O-O axis and the bisector of the hydrogen acceptor is
linear configuration is in this case smaller than electro- 9◦ too large compared to the values computed using the
static stabilization. The induction and dispersion energies SAPT method. The complete, ab initio computed elec-
both favor the nonlinear configuration but only by a frac- trostatic energy (including the charge penetration effects)
tion of kcal/mol. Experiment and ab initio calculations predicts the minimum parameters even more accurately:
also predict that the bonding hydrogen is somewhat tilted both α and β are only 2◦ too small.
away from the F–F axis, by about 10◦ down on the diagram The minimum structures of the DMNA complex with
above. methyl alcohol are shown in Figs. 6 and 7. The first struc-
An example where electrostatics does fail to predict the ture is the global minimum and as one can see it is not
correct minimum structure is the complex formed by HF hydrogen bonded. The local minimum shown in Fig. 7 is
and ClF. This complex is experimentally found to exist hydrogen bonded but it is located 1.1 kcal/mol above the
in the “anti-hydrogen bonded” HF· · ·ClF configuration global minimum of 5.8 kcal/mol. It is also at 1.1 Å larger
rather than in the hydrogen-bonded structure ClF· · ·HF separation than the global minimum. Sure enough, the
predicted by electrostatic arguments analogous to those electrostatic prediction favors the hydrogen-bonded struc-
discussed for the HF dimer. ture. The peculiar shape of the global minimum structure
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520 Hydrogen Bond

FIGURE 5 Water dimer equilibrium geometry. The system has the Cs symmetry. The angles are computed from the
symmmetry-adapted perturbation theory (SAPT)-5s potential (Mas et al., 2000) and the angles measured by Odutola
and Dyke (1980) are given in parentheses. The equilibrium separation is a mixed theoretical/experimental value.

results from competing tendencies to maintain a reason- all the components of the interaction energy at the global
ably favorable electrostatic interaction and to maximize minimum are fairly close to the corresponding compo-
the dispersion attraction while at the same time keeping nents at the local minimum, except for the dispersion en-
the methyl groups of both monomers as far apart as possi- ergy, which is more than 2 kcal/mol larger in magnitude in
ble to reduce the exchange repulsion. It is interesting that the former configuration. Thus, the dispersion component
plays here a decisive role. The dispersion energy is not par-
ticularly anisotropic for this complex, and the increase in

FIGURE 6 The global minimum structure of the dimethyl- FIGURE 7 The secondary (local) minimum structure of the
nitramine complex with methyl alcohol. The carbon atoms are gray, dimethylnitramine complex with methyl alcohol. The carbon atoms
hydrogens—white, nitrogens—blue, and oxygens—red. (From are gray, hydrogens—white, nitrogens—blue, and oxygen—red.
Bukowski et al., 1999.) (From Bukowski et al., 1999.)
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Hydrogen Bond 521

Perhaps the most important observation based on these

data is how important all the components are in determin-
ing the depths at the minima. In all cases the magnitudes
of the electrostatic and exchange energies are similar to or
larger than the magnitude of the total interaction energy.
The magnitudes of the induction and dispersion energies
FIGURE 8 The nonhydrogen bonded (a) and hydrogen-bonded are typically at least half of the magnitude of the interac-
(b) structures of the ammonia dimer.
tion energy. Clearly, the total strength of interaction results
from a subtle balance between these components. One can
its magnitude results mainly from the shortening of R. For observe various trends in the physical components. Since
the electrostatic component the increase in the magnitude all the systems are similarly polar and the equilibrium sep-
due to the decrease in separation is offset by the decrease arations are not much different, the electrostatic energies
due to less favorable orientation at the global minimum. are of similar size except for N2 · · ·HF. In the latter case
The final example is the ammonia dimer. This sys- the electrostatic interaction is about twice smaller than
tem is unusual in this respect that the question whether for the other dimers due to the lack of a dipole moment
it is hydrogen bonded does not have a yes or no answer. on N2 . The dispersion energy is larger in magnitude for
Ammonia forms hydrogen-bonded complexes with many DMNA· · ·HOCH3 than for other systems, which reflects
molecules, for example, the H3 N· · ·HCl complex shown the general increase of the importance of this term with
in Fig. 1. Therefore, one would expect the ammonia dimer the increase in the number of electrons. It is worth men-
to be hydrogen bonded. Indeed, numerous ab initio cal- tioning that in the literature the dispersion energy is often
culations predicted the hydrogen-bonded structure shown considered to be a negligible component of interactions in
in Fig. 8(b). However, spectroscopic measurements by hydrogen-bonded systems. Table I clearly shows that this
Nelson et al. (1987) clearly indicated that the dimer has is not the case. The reason for this misconception could
the nonhydrogen-bonded structure similar to that depicted be that reliable values of dispersion energy for hydrogen-
in Fig. 8(a) (the positions of the hydrogens were deter- bonded systems were not known until 1970s. In fact, the
mined up to a rotation around monomers’ symmetry axes). first ab initio calculation of the dispersion energy for such
This controversy was explained by Olthof et al. (1994) a system was the work of Jeziorski and van Hemert pub-
based on accurate quantum solutions for the dimer rovi- lished in 1976. The exchange energies are larger for the
brational states. They have shown that while the equilib- water dimer and for DMNA· · ·HOCH3 than for the other
rium structure is hydrogen bonded, the large amplitude two systems. This is a consequence of the large magnitude
of intermolecular motions leads to vibrationally averaged of the sum of attractive contributions for the two former
structure similar to that shown in Fig. 8(a). dimers. A stronger attraction results in a shorter inter-
Table I lists physical components of the interaction ener- monomer separation and, consequently, in a larger charge
gies at the minima for the systems discussed in this section. overlap.
A question sometimes discussed in the literature is
whether the hydrogen bond is a purely electrostatic phe-
TABLE I Components of Interaction Energies (in kcal/mol) nomenon or does it have a covalent character. From the
at the Minima of Selected Dimersa,b
examples presented previously, it is prefectly clear that
N2 · · ·HF (HF)2 (H2 O)2 DMNA· · ·HOCH3 the former interpretation is not valid. The electrostatic in-
teraction plays an important role in shaping the hydrogen
Re 3.56 2.73 2.95 3.22
bond, but it is only one of the four fundamental effects, the
E elst −2.74 −5.87 −7.50 −6.2
other three interactions being of comparable importance.
E ind −1.68 −2.00 −2.88 −2.9
However, this statement does not imply that the hydro-
E disp −1.59 −1.87 −2.77 −5.3
gen bond should be called a covalent bond. The name
E exch 4.25 4.79 8.91 9.1
covalent bond is used primarily in the context of chemical
δ E int
HF −0.42 0.10 −0.82 −0.4
bonds (except for those in highly ionic compounds like
E int −2.18 −4.85 −5.05 −5.7
inorganic salts). The covalent bond is formed between
a Data from Jankowski et al. (2000), Rybak et al. (1991), Mas and open-shell systems (i.e., systems with partially occupied
Szalewicz (1996), and Bukowski et al. (1999). electronic shells). The internal coordinates of the interact-
b The equilibrium separations are given in Å. E
elst , E ind , E disp , and ing monomers undergo significant changes upon forma-
E exch are the electrostatic, induction, dispersion, and exchange compo-
nents, respectively, of the interaction energy while δ E int HF contains both tion of a chemical bond. The chemical forces are distinctly
induction and exchange-induction components of the order higher than different from the intermolecular forces, which arise be-
second. tween closed-shell systems. The distinction can be further
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522 Hydrogen Bond

related to the physical picture of hydrogen bonding involv- different. As is shown in Fig. 9, the difference in transition
ing the electrostatic, induction, dispersion, and exchange energies is equal to the difference of the dimer dissociation
forces. Such a picture does not apply to covalently bound energies D0 in the interactions potentials corresponding to
compounds. Only the exchange interactions (related to the ground and excited X-H vibrations
electron tunneling) can be identified in covalently bonded
E monomer − E dimer = D0 (v = 1) − D0 (v = 0).
compounds. However, the contribution of these interac-
tions to the chemical bond energy is stabilizing, in contrast Depending on the sign, this difference is called either
to intermolecular interactions where it is always repulsive. the red or blue shift. For a hydrogen-bonded system the
Therefore, it is better to reserve the descriptor “covalent” excited-state potential is almost always deeper; therefore
to the chemical bonds. In fact, Muller-Dethlefs
¨ and Hobza the frequency shift is to the red. This deepening of the po-
(2000) use the term noncovalent interactions for inter- tential is usually attributed to an increase in magnitude of
molecular interactions (including hydrogen bonds). the electrostatic and induction components, although re-
cent ab initio calculations have shown that the change of
V. PROPERTIES OF HYDROGEN BONDS the dispersion component also plays a major role. The in-
crease of the former two components can be related to the
The hydrogen-bonded complexes are characterized by lengthening of the X-H distance upon vibrational excita-
several structural and spectroscopic properties that pro- tion. The longer distance results in larger magnitudes of
vide means of identifying the presence of such bonds. multipole moments, which increases both the electrostatic
The most typical hydrogen bonds would exhibit all those and induction energies. This fact explains also why the
properties. Some authors require that all the characteris- magnitudes of the red shift are correlated with strengths of
tics listed below should be present to classify dimers as hydrogen bonds. The bond strength is measured by its dis-
hydrogen-bonded ones, but recently the more “relaxed” sociation energy D0 . Generally one may expect that if D0
definition of the hydrogen bond given in section I, which is getting larger, also the difference D0 (v = 1) − D0 (v = 0)
does not include this requirement, has become generally (i.e., the red shift) will get larger. There exist, in fact, em-
accepted. pirical formulas relating the red shift to the strength of hy-
drogen bond. The red shift is accompanied by an increase
(a) The H· · ·Y distances in hydrogen-bonded systems in the intensity of the X-H stretch due to the appearance
are shorter than generally expected of intermolecular of the induced dipole moments, as discussed next. Upon
bonds. This fact is a simple consequence of the strength formation of a hydrogen-bonded dimer, most of the other
of hydrogen bonds and has been historically important for monomer vibrational frequencies are also shifted, either
the formation of the concept of hydrogen bonding. The to red or to blue, but these shifts are typically a few times
distances between atoms in molecular crystals have been smaller in magnitude than the red shift of the hydrogen-
known for a long time. Based on these data, Pauling de- bonded X-H stretch.
fined the van der Waals radii of elements such that the sum (c) The dipole moment of a hydrogen-bonded complex
of such radii gives the interatomic distance. For example, is larger than the vector sum of the monomer’s moments.
the radii for oxygen, nitrogen, and fluorine are 1.4, 1.5, This effect is due to the presence of the induced dipoles.
and 1.35 Å, respectively. Also, somewhat more arbitrar- Although a dipole moment of a cluster is well defined,
ily, a radius of about 1.1–1.3 Å was assigned to hydrogen attempts to determine the dipole moments of the individ-
(other authors use even 1.0 Å). The hydrogen bonds are ual monomers within the cluster encounter difficulties in
much shorter than the sum of van der Waals radii of hydro- the partition of the total quantity. For large water clusters
gen and atom Y. In the case of the water dimer discussed and for ice, the literature values vary from about 2.3 to
above, the H· · ·O distance is about 2.0 Å, whereas the sum 3.1 Debye, depending on the method of partition, com-
of H and O van der Waals radii gives 2.5 Å. pared to the monomer’s value of 1.86 Debye.
(b) The fundamental frequency of the X-H bond stretch (d) The length of the X-H bond is often increased upon
is lowered upon the formation of a complex resulting in the formation of the cluster. This increase is almost negli-
a red shift, which is a very sensitive probe of hydrogen gible for the dimers. In the case of the water dimer, recent
bonds in clusters and in the condensed phase. The origin ab initio calculations have found that the O-H distance
of this effect can be understood as follows. In an iso- increases by only 0.006 Å compared to its equilibrium
lated monomer the fundamental frequency of the X-H vi- value of 0.958 Å [Klopper et al. (2000)]. However, for ice
bration is proportional to the energy difference between some experiments indicated that this bond can be length-
the ground (v = 0) and the first excited (v = 1) vibrational ened to about 1.000 Å, a factor of seven more than for
states of the monomer. When the transition takes place in the dimer. These experimental observations remain con-
a dimer, it involves also the ground van der Waals inter- troversial and can be alternatively explained by disorder-
molecular vibrations and therefore its frequency will be ing of oxygen atoms off the hexagonal axis. Another often
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FIGURE 9 An illustration of the origin of the red shift in vibrational frequencies upon formation of hydrogen bond.

quoted experimental result is 0.973 Å [Kuhs and Lehmann nucleic acids, and typical hydrogen bonds forming within
(1986)], only 0.015 Å more than the monomer equilibrium or between proteins. The strong hydrogen bonds involve
value. An increase of this order is predicted by ab initio ionic species. Examples include Cl− · · ·H2 O, F− · · ·H2 O,
calculations for clusters of size of about six molecules. H3 O+ · · ·H2 O, and F− · · ·HF with interaction energies of
about 15, 30, 35, and 40 kcal/mol, respectively. In the
case of the last complex, the bond is so strong that this
VI. TYPES OF HYDROGEN BONDS complex could also be classified as a chemically bonded
one. Furthermore, the H· · ·F− distance of about 1.3 Å
The hydrogen bonds are classified based mainly on the is closer to distances typical for chemical bonds (about
strength of interaction as measured by the depth of the in- 1 Å) than to H· · ·Y hydrogen bond distances (about 2 Å).
teraction potential De at the minimum of the complex. Strong hydrogen bonds result in a significant distortion of
Usually three classes are distinguished: weak, moder- the monomer’s structure. The H-F bond in F− · · ·HF is of
ate, and strong bonds, with energetic boundaries at about the same length as the F− · · ·H hydrogen bond (i.e., the
2 and 15 kcal/mol. The weak hydrogen bonds involve complex is centrosymmetric). Thus, the F-H distance is
less polar X-H groups in proton donors, like C-H or
P-H groups, or less polar acceptors, like the N2 molecule
in the N2 · · ·HF complex discussed above. Also, the hydro-
gen bonds where X-H attaches to a π bond on the acceptor
belong to this group (examples of such bonds are given
in Fig. 10). The weakest hydrogen bonds considered in
the literature are about 0.5 kcal/mol. Most of hydrogen-
bonded complexes of interest form the group of moderate
hydrogen bonds. Water dimer or hydrogen fluoride dimer FIGURE 10 Examples of hydrogen-bonded compounds where
are typical examples for this group. Other well-known an X-H group attaches to a π bond. (a) Complex of chloroform
dimers in this group involve carboxylic acids, base pairs of with benzene. (b) Complex of hydrogen chloride with ethylene.
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524 Hydrogen Bond

increased from 0.93 Å to 1.30 Å upon the dimer forma- of the two monomers agrees very well with results of mod-
tion. This is, however, an extreme case. For F− · · ·H2 O the ern ab initio calculations. The equilibrium O-O distance
hydrogen-bonded O-H distance increases by about 0.1 Å cannot be directly measured, but spectral data provide the
from its equilibrium-isolated monomer value of 0.96 Å, value of R −2 0 . This value together with the difference
and this size of elongation is typical for ionic systems. The between R −2 0 and Re from dynamical calculations in
hydrogen bonding between ions and water is the principal the SAPT-5s potential (Groenenboom et al. 2000) gave a
mechanism of the hydration processes. mixed experimental/theoretical estimate of 2.91 ± 0.005
Most of hydrogen-bonded molecules exhibit to a larger Å (Mas et al., 2000), which agrees to all digits with the
or lesser extent all of the properties described in section VI. value obtained in large-scale ab initio calculations [Klop-
There exist cases, however, when some of these features per et al., 2000]. The depth of the water dimer potential
are not present or even the trend is opposite. An example has been accurately determined by ab initio calculations
are complexes in which the X-H vibrations are blue shifted to be 5.0 kcal/mol (Klopper et al., 2000). Knowledge of
(see Hobza et al., 1999, and Gu et al., 1999). Some au- the limit value of De allowed scaling of the dissociation
thors questioned if such complexes should be considered energy computed from the SAPT-5s potential (Groenen-
hydrogen bonded. According to the definition adopted in boom et al., 2000) to obtain an estimate of D0 equal to
this article, the hydrogen-bonded classification will be ap- 1165 ± 54 cm−1 , in excellent agreement with the value
propriate if the equilibrium geometry has a nearly linear derived from experiments equal to 1168 ± 245 cm−1 (Cur-
X-H· · ·Y shape, and the bond is reasonably strong (i.e., tiss et al., 1975). The water dimer comparison represents
not much weaker than about 1 kcal/mol). an unprecedented level of agreement between theory and
experiment on the equilibrium parameters for a hydrogen-
bonded system.
VII. HYDROGEN BONDS IN CLUSTERS As an example, Fig. 11 presents the intermonomer
vibrational-rotational-tunneling (VRT) energy levels of
Small clusters offer substantial advantages in investiga-
tions of hydrogen bonds compared to the condensed phase,
where one can observe only statistically averaged proper-
ties. Clusters can be detected in bulk gas phase or in molec-
ular beams, the latter method being presently the method
of choice. Various spectroscopic techniques applied to in-
vestigations of hydrogen bonds have been discussed in
section II. Most information about clusters comes from
infrared techniques, both near and far infrared. The former
method operates in the range of several thousand inverse
centimeters and excites one of the vibrational modes in a
monomer with a simultaneous transition between various
van der Waals vibrations. The van der Waals transitions
have much lower frequencies because the intermonomer
motion is much slower than the intramonomer one. The
far infrared method operates in the range from a few to a
few hundred inverse centimeters and therefore can be used
to observe pure transitions between the intermolecular vi-
brational modes. Another technique used to investigate
hydrogen-bonded clusters are matrix isolation methods,
where clusters are included in solid matrices made mostly
of rare gases. Such spectra, however, give much less pre-
cise information due to relatively strong interactions of
polar molecules with the matrix.

FIGURE 11 Vibrational-rotational-tunneling (VRT) spectra of the

A. Dimers water dimer. AT, acceptor twist (A ); AW, acceptor wag (A ); DT,
donor torsion (A ); GS, ground state (A ). Broken lines A sym-
Rotational spectroscopy measurements predicted the
metry and solid lines, A symmetry with respect to the equilibrium
structure of the water dimer shown in Fig. 5. A similar structure. K = 0, rotational ground state, K = 1, first excited state.
structure had been predicted even earlier by ab initio calcu- The calculated results are from Groenenboom et al. (2000), while
lations. The experimental equilibrium angular orientation the experimental data are from Braly et al. (2000).
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Hydrogen Bond 525

TABLE II Vibrational Frequencies of Water (in cm−1 ) DT, AW, and AT in Fig. 11 denote the ground state (A ),
Monomer a Bend 1595 donor torsion (A ), acceptor wag (A ), and acceptor twist
Symm. stretch 3657 (A ) modes. The solid lines refer to A symmetry and
Asymm. stretch 3756 the dashed lines to A symmetry with respect to the point
Dimer inter b Donor torsion 86 group Cs of the equilibrium structure. Experimental levels
Acceptor wag 112 not shown have not been measured to date. The K = 0 and
Acceptor twist 121 1 columns describe the rotational ground and first excited
Stretch 187 states, respectively. The agreement between the spectra
In-plane bend 370 measured and calculated from the SAPT-5s potential is
Out-of-plane bend 565 very good for most levels. Some of the existing discrep-
Dimer intra Acceptor H-O-H bend 1593c ancies may result from misassignments of the measured
Donor H-O-H bend 1611c lines.
Donor bridge O-H stretch 3530d The intramonomer vibrational frequencies change sig-
Donor free O-H stretch 3730d nificantly upon the formation of a hydrogen-bonded dimer
Acceptor symm. stretch 3600d compared to the isolated monomers’ frequencies. Table II
Acceptor asymm. stretch 3745d presents the fundamental vibrational frequencies for the
Liquid watere Intermonomer stretch 65, 162 water monomer, dimer, and condensed states of water.
Librational 430, 650, 795 The monomer frequencies are related to the characteristic
H-O-H bend 1581, 1641 vibrational types of motion called normal modes. There
O-H stretch 3051, 3233, 3393 are three normal modes in the water monomer: a bending
3511, 3628 mode and the symmetric and asymmetric stretches. In the
Ice I f Intermonomer stretch 50, 164, 229 water dimer there are six intramonomer modes. We expect
Librational 840 that the vibrational modes of the acceptor will be closer to
H-O-H bend 1650 those in the monomer than those of the donor. Since the
O-H stretch 3220 dimer bending modes are available only from measure-
ments in matrices, we should use monomer’s frequency
from matrix measurements, which is equal to 1590 cm−1
aFland et al. (1976).
bGroenenboom et al. (2000). The three lower frequencies are from
in argon matrix. Thus, as Table II shows, the acceptor’s
exact calculations, whereas the three higher ones are harmonic.
c Bentwood et al. (1980), in argon matrix. bend is blue shifted by 3 cm−1 , while the donor’s bend is
d Huang and Miller (1989). blue shifted by 21 cm−1 . We also expect that the stretch of
e Carey and Korenowski (1998), measured at temperature of 24◦ C
the O-H bond containing the bridge hydrogen will be af-
and pressure of 256 bar. fected most. This motion cannot be anymore classified as
f Franks (1972), p. 133–135.
a symmetric or asymmetric stretch, and instead we distin-
guish just the bridge O-H and donor’s free O-H stretches.
Compared to the frequency of the monomer symmetric
the water dimer. The numerical values of the inter- stretch, the bridge O-H stretch is red shifted by as much
monomer vibrational frequencies are also presented in as 127 cm−1 . The free O-H stretch is shifted 26 cm−1 to
Table II. The water dimer potential has eight equivalent the red compared to the monomer’s asymmetric stretch.
minimum structures differing only by a permutation of For the acceptor molecule we still can recognize the sym-
hydrogen atoms. The monomers can tunnel between these metric and antisymmetric stretches, which are red shifted
minima through the separating barriers (this tunneling by 57 and 11 cm−1 , respectively.
should not be confused with the electron tunneling lead-
ing to the exchange forces). The major tunneling processes
are shown in Fig. 12. The tunneling results in a splitting
B. Trimers and Larger Clusters
of the vibrational energy levels. The presence of tunnel-
ing splittings explains the name VRT for these spectra. The structures of hydrogen-bonded clusters have been the
The donor-acceptor interchange splittings are of the or- subject of extensive research in the past 20 years [see, e.g.,
der of 1 cm−1 and would not be visible on the scale of Xantheas and Dunning (1998); Buck et al. (1998); Lee
Fig. 11. The levels shown, denoted as 1 and 2, are av- et al. (2000)]. The hydrogen-bonded N -mers with N = 3,
erages of sets of three levels split by the donor-acceptor 4, and 5 tend to be of cyclic form. The preference for the
interchange tunneling. The distance between the levels 1 cyclic form can be understood from simple arguments.
and 2 is the measure of the acceptor tunneling splitting. Consider water clusters as an example. Various isomers
The bifurcation tunneling does not lead to additional split- of water clusters from trimer to hexamer are displayed in
tings but to small shifts of levels. The abbreviations GS, Fig. 13. A chain of three water molecules can be formed
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526 Hydrogen Bond

FIGURE 12 Water dimer tunneling paths. The numbers below transition states are barrier heights computed from
the symmetry-adapted perturbation theory (SAPT)-5s potential.

such that the two hydrogen bonds are in dimer equilibria resulting in a trimer bound by about 16 kcal/mol. Thus,
configurations. Neglecting the three-body effects this con- the trimer is more strongly bound than the dimer in the
figuration would be bound by about 11 kcal/mol, including sense that the separation of the equilibrium dimer into
about 1 kcal/mol energy from the “second-neighbor” inter- monomers requires about 5 kcal/mol of energy (neglecting
action. If instead a cyclic trimer is formed, three hydrogen zero-point energy) while separation of one monomer from
bonds are present. Of course, the energy of each bond is the trimer’s equilibrium structure requires 11 kcal/mol.
smaller than dimer’s minimum energy of 5 kcal/mol; how- Often the binding energy of a cluster is divided by the
ever, this decrease turns out to be small and the two-body number of monomers, defining the average binding energy
binding effect at the trimer minimum is about 14 kcal/mol. as
Three-body nonadditive energy adds about 2 kcal/mol,  N = −E int /N ,

FIGURE 13 Water clusters from trimer to hexamer. The top row shows the global minima isomers, the structures in
the bottom row are local minima isomers. The global minimum structure of the hexamer is called “cage,” whereas the
noncyclic local minima hexamers in the bottom row are known under names “prism,” “book,” and “bag,” respectively.
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Hydrogen Bond 527

where E int is the interaction energy at the minimum of gen bonds and the interaction energy per molecule, ∞ , is
the cluster (global or local). For the smallest clusters this about 14 kcal/mol). An interesting question is how large a
quantity changes rapidly (it is equal to 2.5 kcal/mol for cluster one has to consider to get close to the ice-binding
the water dimer and 5.3 kcal/mol for the cyclic trimer). energy. Ab initio calculations for water decamers gave 10
This rapid change is mainly due to two-body cooperative of only about 9 kcal/mol [Lee et al. (2000)]. Unfortunately,
effects. Even for the chain-like trimer the number of hy- for clusters with N larger than 10 reliable ab initio results
drogen bonds increases by a factor of two, whereas the are very difficult to obtain. In addition, the potential en-
number of monomers increases by a factor of 1.5 com- ergy surfaces for clusters of this size contain enormous
pared to the dimer, and for the cyclic trimer the number of numbers of local minima and therefore finding the global
hydrogen bonds increases by a factor of three. In the in- minimum is a highly nontrivial task.
crease of  N between the dimer and the cyclic trimer about The infrared spectra of water clusters provide infor-
0.7 kcal/mol is due to nonadditive effects. The number of mation which in conjunction with ab initio calculations
hydrogen bonds per monomer grows further in larger clus- can be used to determine clusters’ structures. As an ex-
ters, reaching the maximum value of four bonds per water ample, spectra of water clusters with N = 8, 9, and 10
molecule in ice. measured by Buck et al. (1998) are shown in Fig. 14.
Similar considerations to those for the trimer explain The octamer and decamer are of particular interest due to
the greater stability of the cyclic tetramer and pentamer their possible importance in liquid water. Let us consider
over the possible chain structures. In these two cases the octamer first. One of possible octamer structures is
the number of hydrogen bonds is four and five, respec- displayed in Fig. 14. One can see that this structure in-
tively. Unlike in the step from the dimer to trimer, there is cludes exactly two types of water molecules: those that
no increase of  N resulting from increase of the number are double-proton donors but accept only a single proton
of hydrogen bonds per monomer. However,  N does in- (and will be denoted as DDA monomers) and those that
crease quite substantially, by nearly 2 kcal/mol, between are single-proton donors and double acceptors (DAA). All
the trimer and the tetramer. This increase is due to the hydrogen bonds are between a DDA and a DAA molecule
“second-neighbor” two-body interactions and to the in- but are of two kinds, depending whether the O-H group
creased number of three-body interactions: there are four is on DDA or on DAA monomer. Therefore, one may
trimers in a cyclic tetramer. However, the increase in  N expect that the spectrum will consist of three groups of
between tetramer and pentamer is less than a half kcal/mol lines: two connected with the two discussed types of hy-
despite the number of three-body interactions growing to drogen bonds and the third one due to the vibrations of
10. One of the reasons is the “frustrated” structure of the free hydrogens. Indeed, Fig. 14 shows that this is the
pentamer with two free hydrogens on the same side of case. Based on calculations using an empirical model,
the ring, which leads to an increased repulsive contribu- the lower frequency was assigned to bonds with the O-
tion. For the pentamer one can construct various pyra- H group belonging to DAA. This frequency is red shifted
midal structures like the one shown in Fig. 13 and some by as much as about 550 cm−1 from the monomer’s sym-
of them are local minima; however, all of them are ener- metric stretch, even more than the largest red shifts in ice
getically significantly above the cyclic pentamer despite or liquid water (comparing peak values). The peak cor-
having more hydrogen bonds. This is because the dimer responding to the O-H stretch in a DDA monomer is red
configurations in those structures are far from the dimer’s shifted by only about 110 cm−1 (i.e., even less than in
minimum structure, which reduces the magnitude of the the water dimer). The free O-H stretch is at 3700 cm−1 ,
two-body component. midway between the two stretches in the monomer. The
In contrast to smaller clusters, there exist several en- splittings of the peaks are related to the symmetric and
ergetically close isomers for the water hexamer. The six asymmetric types of motion. Although the octamer struc-
hydrogen bonds in the cyclic structure may provide less ture of D2d symmetry shown in Fig. 14 agrees with the
stabilization than eight bonds that are possible in a cage- spectrum, it is not known at this point whether it is in-
like structure. Indeed, the latter structure has been shown deed the minimum structure since a similar isomer of S4
both by ab initio calculations and by experiments to be symmetry provides an equally satisfactory interpretation
the lowest one. However, the cyclic hexamer as well as of the spectrum. Quantum mechanical calculations [Lee
several other isomers shown in Fig. 13 are energetically et al. (2000)] predict that the two isomers have energies
very close, with only about 1% or smaller differences in close to within 0.1 kcal/mol. Buck et al. assumed that both
the binding energies. This process of forming more and isomers might be present in the beam. Calculations of Lee
more hydrogen bonds per molecule continues as the size et al. show that (harmonic approximation) spectra of the
of the cluster increases and at the limit of infinite clus- two isomers do differ significantly enough to distinguish
ter (i.e., in ice, each molecule participates in four hydro- between them, provided that higher resolution spectra are
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528 Hydrogen Bond

same types of hydrogen bondings. However, each spec-

trum has also distinctly different features. In the nanomer
spectrum one can clearly see that the lowest frequency
band is much broader than in the octamer. This can be
related to the fact that one of the water monomers in the
structure presented in Fig. 14 is of DA type. Calculations
of Lee et al. (2000) indeed predict a smaller red shift
for this monomer so the O-H vibration connected with
the DA monomer is responsible for the features around
3150 cm−1 . A further reason for the broadening of the
bands in the nanomer compared to the octamer is that the
DAA monomers are no longer equivalent. Notice also that
the position of the strongest peak in the hydrogen-bonded
OH band moves to lower frequencies for nanomer com-
pared to octamer and to still lower in the case of decamer,
indicating the increased strength of hydrogen bonding. For
decamer none of the theoretically predicted spectra agrees
well with the experimental spectrum. However, the “but-
terfly” structure (c) in Fig. 14 agrees much better than the
“cage” structure (a).

VIII. HYDROGEN BONDS IN SOLIDS

X-ray and neutron diffraction measurements on hydrogen-

bonded solids provide precise data on their structure, in-
cluding information about internuclear distances. These
distances can be compared to those found for dimers from
spectroscopic measurements. It should be realized, how-
ever, that the distances to be compared are in fact some-
what different quantities. The spectral information about
internuclear distances is obtained from rotational con-
−1/2
stants (i.e., the distances are defined as R −2 0 , where
the brackets denote averaging over the ground vibrational
wave function). The diffraction data give just R0 . Both
quantities are different from the equilibrium distances Re
−1/2
calculated ab initio. For the water dimer, the R −2 0 and
Re O-O separations are 2.98 and 2.91 Å, respectively. The
FIGURE 14 Spectra of water clusters from octamer to decamer. measured value of the O-O separation for ice is 2.75 Å.
The horizontal axis is frequency in cm−1 . The vertical axis is the The shortening of about 0.2 Å in ice compared to the
dissociation (Diss.) fraction of clusters. (From Buck et al., 1998.)
dimer is twice as large as the shortening of 0.1 Å between
the dimer and the trimer. The decrease of intermolecular
distances in solids compared to dimers is related to the
measured. This will also require, however, more accurate increase in the strengths of binding due to both pair-wise
ab initio calculations since although the overall agreement additive and nonadditive effects. For example, about 30%
of the ab initio spectrum generated by Lee et al. with the of the trimer shortening is due to two-body forces.
experimental spectrum is reasonable, some details are sig- Solids of hydrogen halides allow one to relate the ob-
nificantly different. For example, the splitting of the band served trends in vibrational spectra to the differences
at 3550 cm−1 is measured to be only 30 cm−1 , while the in their pairwise additive and nonadditive effects. The
computed splitting is about 80 cm−1 . different hydrogen halide crystals show fairly varying
Spectra of the two other clusters shown in Fig. 14 are properties. At low temperatures HF, HCl, and HBr have
similar to the octamer spectrum, indicating generally the the same type of crystal structure consisting of zig-zag
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Hydrogen Bond 529

TABLE III Intramonomer Vibrational Frequen- nonadditivity in HCl compared to HF (assuming monomer
cies of Hydrogen Halides (in cm−1 ). separations in crystal unchanged from the dimer separa-
HF HCl HBr tions). Overall, one can expect that the stabilization due
to the cooperative effects will be an order of magnitude
Monomer 3961a 2886a 2556b smaller for HCl than for HF crystals.
Dimer 3868a 2857a 2496b Let us now discuss the solid phase of water. Ice exists
3931a 2880a 2550b in several polymorphic phases. The one most commonly
Solidc 3065 2699 2395 investigated is the hexagonal form (ice Ih). The structure
3275 2715 2406 of ice Ih obtained from simulations with a SAPT potential
3404 2744 2431 is shown in Fig. 15. The oxygen atoms form a hexago-
3585 2754 2440 nal lattice, and each water molecule is in the center of a
a Pine and Howard (1986). tetrahedron, participating in four hydrogen bonds. There
b Maillard et al. (1979), in argon matrix. are several possible arrangements of the hydrogen atoms
c Kittelberger and Horning (1967) for HF and Savoie
in such a structure, and these are realized stochastically.
and Anderson (1966) for HCl and HBr. There are four different nearest neighbor water dimer con-
figurations in ice Ih.
An interesting property of ice is its response to an ex-
hydrogen-bonded chains, while the structure of HI is not ternal electric field. The dielectric constant of any polar
precisely known. The chains are loosely packed, the dis- medium is a measure of the ability of the molecules to
tance between chains being larger than the distance be- reorient in the electric field. It is believed that in ice the
tween the nearest halide atoms in a chain. The triples of
nearest heavy atoms form the angle of 116◦ for HF and 90◦
for HCl and HBr, close to the halide-halide-free hydrogen
angles in the corresponding dimers. The most striking dif-
ferences are in the red shifts of X-H vibrations displayed
in Table III. The HF crystal exhibits an extremely large
shift of 896 cm−1 , whereas for HCl and HBr the shifts
are only 187 and 161 cm−1 , respectively. The differences
are much smaller in the dimers, where the corresponding
shifts are 93, 29, and 60 cm−1 . The main reason for these
differences appears to be the significantly larger X-Y sep-
arations in HCl (and HBr) than in HF clusters, which lead
to much smaller nonadditive effects in the former case. In
the dimers the relevant separations are 3.8 and 2.7 Å. The
bond is longer for HCl simply because the chlorine atom
is larger than fluorine and charge-overlap repulsive effects
are larger for a given separation. Also the dipole moment
of HCl is about twice as small as that of HF—therefore the
electrostatic interaction is about a factor of four smaller in
magnitude at a given distance—but this loss of attractive
interaction is partly made up by the dispersion interaction,
which is larger for HCl. As a result, the strength of the hy-
drogen bond is only twice as small in HCl than in HF.
The increase in the heavy atom separation has, however, a
more significant impact on nonadditive effects. The lead-
ing nonadditive term is proportional to the product of the
square of the dipole moment and polarizability. Because
the polarizability of HCl is about twice that of HF, this
product is roughly twice as small for HCl than for HF at
a given separation. However, because the intermonomer
distance in HCl is almost 1 Å larger than in HF, the 1/R 6 FIGURE 15 The structure of ice Ih. The top view is along the
decay of the induction nonadditivity means that there will hexagonal axis, and the bottom one is from a perpendicular
be an additional sixfold decrease of the magnitude of the direction.
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530 Hydrogen Bond

reorientation is achieved by a collective proton transfer IX. HYDROGEN BONDS IN LIQUIDS

rather than by a true rotation of molecules. This mecha-
nism is supported by the properties of the dielectric con- The hydrogen-bonded liquids are much more difficult to
stant, as the time of the dielectric orientation in ice has describe than either the gas phase (where the ideal gas ap-
been found to increase rapidly with decreasing tempera- proximation provides a good zeroth-order description) or
ture. Such strong temperature dependence is characteristic the solid phase (with its lattice symmetries and long-range
of processes that require activation energy, as the collec- order). The hydrogen-bonded liquids, often called associ-
tive proton transfer does. ated liquids, are so different from simple liquids that their
As already discussed, the O-O distance in ice is 2.75 Å, properties are called anomalous. How profound the differ-
significantly smaller than in the dimer, showing the in- ences are can be illustrated by the fact that water would be
creased strength of binding due to cooperative effects. This expected, based on its molecular mass, to be a gas at room
increased binding is also demonstrated by the increased temperatures. Similarly, many organic compounds would
value of the red shift. The shift which in the dimer case not exist as solids were they not hydrogen bonded (e.g.,
is 127 cm−1 , becomes equal to 437 cm−1 for ice Ih (cf. the sugars glucose and sucrose). The anomalous behavior
Table II). The sharp transition line in the case of the water of the density of water as a function of temperature, with
monomer becomes a very diffuse band in ice, with a band- the maximum at 4◦ C, is another manifestation of hydro-
width of about 500 cm−1 . This broadening reflects the fact gen bonding. The fact that ice floats on water—the con-
that different environments of the O-H bond in the lattice sequence of this density dependence—is quite important
exhibit different shifts, as well as temperature broadening. for life on earth, since organisms survive winter in water
The H-O-H bend is seen as another broad band centered under a layer of ice.
at 1650 cm−1 (i.e., 55 cm−1 blue shifted compared to the Structural information about liquids can be obtained
monomer). The librational bend with peak at 840 cm−1 from neutron or X-ray diffraction experiments. This in-
extends from 400 to 1050 cm−1 . This range includes the formation is usually presented in the form of radial atom–
dimer’s out-of-plane bend and is close to dimer’s in-plane atom pair correlation (or distribution) functions g AB (R)
bend. However, the librational motions in ice are collec- giving the probability of finding an atom of type B at the
tive motions of the lattice and may be very different from distance R from atom A and vice versa. It is worth men-
the dimer’s dynamics. The same is true about the inter- tioning that the functions g AB (R) are not directly measured
monomer stretch band, which occupies the region from and result from a fairly complex processing of experimen-
50 to 360 cm−1 . Still, one of the peaks, at 164 cm−1 , is tal data involving several assumptions. Different methods
very close to the dimer’s stretch. of processing of the same set of data can give significantly
Some hydrogen-bonded crystals exhibit phenomena different pair correlation functions [Soper (2000)].
of (anti)ferroelectricity, which are analogues of (anti) Figure 16 shows the oxygen–oxygen pair correlation
ferromagneticity. At sufficiently low temperature a ferro- function for water at ambient conditions. This function is
electric crystal may show electric polarization, resulting in zero up to the distance of closest approach, about 2.6 Å,
one side of the crystal charged positively and the opposite and then increases rapidly, showing the strongest maxi-
one negatively. This polarization may exist in zero external mum at a value close to the equilibrium separation in the
electric field. In a ferroelectric crystal molecular dipole, dimer of 2.9 Å. This peak represents the first coordination
moments spontaneously orient themselves within small shell of the liquid and is followed by a minimum result-
but macroscopic regions of space called domains in such ing from geometrical restrictions. The integral of gOO (R)
a way that the domains are electrically polarized. Ferro- up to R = Rmin1 , the position of the first minimum, de-
electricity ceases in a given material above a characteristic fines the coordination number (i.e., the number of water
temperature called the Curie temperature for this crystal, molecules in the first shell). The experiments show that
because above this temperature the thermal motion over- this value is slightly larger than five molecules, while it is
comes the tendency of the dipoles to align. At the Curie four for ice. Thus, in liquid the water molecules can get
temperature a ferroelectric crystal has an order–disorder into the interstitial spaces (i.e., into the cavities formed
phase transition. The best known ferroelectric hydrogen- by the ice lattice, see Fig. 15). This explains why the wa-
bonded crystal is KH2 PO4 . Also one of the crystal forms ter density increases when ice melts. As we go to still
of water, ice IX, is ferroelectric with Curie temperature of larger R, the second peak arises—indicating the second
72◦ K. Below this temperature, the stochastic distribution coordination shell—and then the pair correlation function
of protons around oxygens characteristic of ice Ih changes oscillates with a decreasing amplitude around the limiting
into an ordered distribution, leading to an alignment of value of gOO (R) = 1—indicating a more and more random
dipole moments. distribution.
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Hydrogen Bond 531

FIGURE 16 The oxygen–oxygen pair correlation function for liquid water at ambient conditions.

The vibrational spectrum spectrum of liquid water is may actually not be due to an O-H stretch vibration but
presented in Fig. 17 and the centers of the peaks are listed may originate from the overtone of the H-O-H bend. In
in Table II. The most striking feature of this spectrum the dimer this overtone is around 3180 cm−1 . In addition
is that it consists of very broad bands. The band in the to the broad range of red-shifts of O-H stretching, there
region between 3000 and 3800 cm−1 corresponding to are a number of other factors contributing to the smooth-
the O-H stretching excitations is about 400 cm−1 wide at ness of the spectral band. One of them is the fact that an
half height and shows little structure. This lack of struc- excitation of the intramonomer transition is in most cases
ture is not due to insufficient spectral resolution (which coupled to some excitation of the intermonomer modes.
is about 0.5 cm−1 ) but is an inherent feature of this spec- The smallest of the latter excitations are of the order of
trum. The major reason for the large width of the band is 100 cm−1 , which is comparable to the width of the band.
the broad distribution of environments of the O–H bonds in Finally, the lines are broadened by thermal effects (i.e., by
liquid water. Some O–H bonds are in ice-like clusters and collisions with other water molecules).
therefore are strongly red shifted. The strongest peak at In addition to the O-H stretch band, Fig. 17 shows also
3233 cm−1 , red shifted by 424 cm−1 , is usually attributed the H-O-H bend region and the intramonomer vibration
to this type of environment. It is quite close to the strongest region. The frequency ranges not shown in Fig. 17 are rel-
peak at ice I at 3220 cm−1 . The Gaussian deconvoluted atively featureless. In the H-O-H bend region one may dis-
peak at about 3628 cm−1 , red shifted by 79 cm−1 com- tinguish two frequencies likely corresponding to bendings
pared to the average of the two stretching modes in the in molecules with the prevailing donor versus acceptor
monomer, corresponds likely to a water molecule playing character. Compared to the monomer, one of the frequen-
the role of a donor to only one other molecule or being cies is blue and another red shifted. The blue-shifted fre-
only an acceptor. In both cases such a molecule possesses quency is very close to the H-O-H bend frequency in ice I.
a “free” O-H bond whose frequency can be only little The intramonomer frequencies have been classified
shifted. One may also mention that the peak at 3051 cm−1 as either corresponding to stretches (translations) or to
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532 Hydrogen Bond

FIGURE 17 Raman vibrational spectrum of liquid water at temperature of 24◦ C and pressure of 128 bar. (From Carey
and Korenowski, 1998.) The figure shows also the Gaussian deconvoluted peaks.

librations. Comparison with the dimer frequencies may tions, which show a significant disorder of the hydrogen-
suggest that two of the librational peaks, at 430 and at bond network. The picture based on such simulations de-
650 cm−1 , may indeed be related to dimer’s in-plane and fines the current model of liquid water. While ice-like
out-of-plane bends. The frequency at 795 cm−1 may be an structures prevail, some molecules form less than four
overtone or may result from collective motions like in ice. and some do not form any hydrogen bonds at a given
One of the stretches, at 162 cm−1 , is close to the dimer instant. Neutron scattering measurements coupled with
stretch at 187 cm−1 . The other frequency, at 65 cm−1 , clas- Monte Carlo simulations indicate that on the average each
sified usually as a stretch, may also result from torsional water molecule participates in about 3.5 hydrogen bonds.
motions of donors, which have 86 cm−1 frequency in a During the thermal motion the hydrogen bonds are bro-
dimer. ken and made; thus a given molecule can move back and
Several models for the structure of liquid water have forth from an ice-like cluster environment with four hydro-
been proposed in the past. Some of them, like the bent- gen bonds, through intermediate hydrogen bond coordina-
bond model with all water molecules four-coordinated as tions, to a monomer not forming any hydrogen bonds. This
in ice, can be discarded based on the molecular simula- model explains the essential features of the pair correlation
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Hydrogen Bond 533

functions, the vibrational spectra of water, the decrease of hydrogen bond. At sufficiently low dilutions, spectral line
volume on melting, and several other anomalous proper- shifts characteristic of dimers can be observed. NMR tech-
ties of water. For example, the time constant of the di- niques are often used in such measurements because the
electric relaxation in water has been measured to be about small number of dimers in fairly well-defined geometries
six orders of magnitude shorter than in ice and much less produce spectra that are easy to interpret.
temperature dependent. This indicates that the response to Molecules of all nonpolar and certain polar compounds
the electric field is achieved in liquid water by partial ro- form aggregates in water. Because most of these molecules
tations of “free” water monomers and of small clusters— do not form aggregates in other solvents, the process is
processes that do not involve activation barriers. An open clearly related to the specific structure of water. Aggrega-
question about the structure of liquid water is whether it tion of molecules in water is commonly called hydropho-
contains one or a few predominant cluster sizes and struc- bic interaction. This aggregation is a process with interest-
tures. If there are a few such clusters, water should ex- ing thermodynamic properties. In some cases the change
hibit some characteristic properties of a multicomponent of energy due to the aggregation is positive; therefore,
liquid, and there is some experimental evidence for this. from this point of view the aggregation should not take
Among other structures, octamers and decamers shown place. Thus, the entropic change has to be the driving force
in Fig. 14 have been postulated. Other authors believe of the process. The entropy that is the measure of the disor-
that more likely structures are cyclic hexamers, as these der of a system is increased upon aggregation compared to
naturally result from ice Ih and have been the predomi- dispersion. If nonpolar solute particles are dispersed, wa-
nant structures observed in some molecular simulations. ter molecules tend to orient themselves around the solute
A snapshot from a Monte Carlo simulation with a SAPT molecules in an orderly fashion. Formation of aggregates
potential at ambient conditions is shown in Fig. 18. This leads then to a loss of order.
figure suggests that liquid water is a collection of a variety
of cluster structures.
Structures and properties of other strongly associated X. PROTON TRANSFER
liquids like hydrogen fluoride or carboxylic acids share
many features with liquid water. Therefore, a separate Proton transfer from one molecule to another is one of the
discussion of other pure liquids is not needed here. Spec- most studied phenomena in chemistry. It is the essence
troscopic techniques can also be applied to solutions of of acid–base chemistry. This process is related to hydro-
hydrogen-bonded species in solvents that do not form hy- gen bonding, as a hydrogen-bonded complex can be an
drogen bonds. This method is particularly useful for inves- intermediate step:
tigations of solutions, with two solutes forming a strong +
A-H + B   A− · · · H-B+ 
 A-H · · · B   A− + H-B ,
(22)
where A-H· · ·B is a hydrogen-bonded complex and
A− · · ·H-B+ is an ionic pair, bound mainly by the Coulom-
bic attraction between the charges. Proton transfer requires
breaking of the chemical bond, a highly energetic transi-
tion compared to energies of hydrogen bonds. Therefore,
the proton transfer processes are very distinct from the
processes considered in the rest of this article, which in-
clude breaking and making of hydrogen bonds only.
Almost all neutral dimers form only one stable com-
plex in the gas phase, the neutral complex A-H· · ·B. The
energy of the two ions is much higher than that of the
two neutral molecules, and the barrier along the proton
transfer path between the two minima may also be high.
The proton transfer will therefore be a rare event. The
situation changes in solution, where both complexes are
stabilized by solvation. Some solvents will stabilize the
ionic complex more than the neutral one, up to the point
FIGURE 18 A snap shot from a Monte Carlo simulation of liquid that it becomes the global minimum on the proton transfer
water at ambient conditions using a symmetry-adapted perturba- path. The extent of proton transfer is determined then by
tion theory (SAPT) potential. the acidity of A-H and the basicity of B. Experimentally
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534 Hydrogen Bond

the transfer from the neutral to the ionic form can be ob- hydrogen bonds is just right for biological applications.
served by a very significant increase of the dipole moment The energy needed to break such a bond is somewhat
of the complex. The neutral forms have dipole moments larger than the thermal energy at ambient temperatures;
in the range of 1–3 Debye, whereas the ionic ones have therefore, hydrogen-bonded structures are well-defined.
dipole moments around 10 Debye. The ionic complex can At the same time, in proper environments these bonds can
also be dissociated into free solvated ions. The whole pro- dissociate and associate quickly, allowing dynamical bi-
ton transfer process is a complicated many-step reaction. ological processes. The chemical bonds could not have
It involves more degrees of freedom than just the proton been used for this purpose because the energies required
motion because the reorientation of the solvent molecules to break them are much larger.
is critical. The rate of the proton transfer process depends Proteins are polypeptides (i.e., polymers formed from
on the barrier height on the reaction path. There is little amino acids). About 20 different amino acids appear in
reliable information available on the barrier heights for proteins. The sequence of amino acids determines the pri-
the proton transfer in solutions. In some solvents (e.g., mary structure of a protein. The peptide link between the
in water), the process is simplified since the solvent ef- adjacent amino acids; in other words, the group
fects are so strong that neither the neutral complex nor
O
the ionic complex are formed, except as very short-lived #
intermediates. Then the process can be well described as C#
❝
N
a single-step reaction. #
H
There are some charged dimers that exhibit an in-
trinsic symmetry on the proton transfer coordinate. All
those systems are strongly bound, typically by more than can act both as proton donor and acceptor (at the oxy-
10 kcal/mol. The best known example is F− · · ·HF (bound gen atom). The polypetide chains are connected by hydro-
by about 40 kcal/mol). Clearly, the structure FH· · ·F− gen bonds formed between different peptide link groups
must possess, the same energy. Early electronic structure as shown in Fig. 19. A single chain can form a helical
calculations were predicting that the intermolecular po- structure, the so-called α helix, where peptide link groups
tential for the proton motion along the transfer path is that are above each other form hydrogen bonds. Another
a symmetric double-well potential. This could give rise chain arrangement are the pleated sheets (β sheets), where
to interesting tunneling phenomena. However, more ac- chains of polypeptides placed next to each other are con-
curate calculations have found that there is only a single nected by hydrogen bonds. These spatial arrangements
minimum on this path. Thus, the structure of the system is are called secondary structures. All polypeptides have one
better described as [F· · ·H· · ·F]− . The potential is similar structure or the other and often have alternating regions of
for [H3 O2 ]− , [HCl2 ]− , and [HBr2 ]− . Only for weak pro- either one. The spatial arrangement of fragments consist-
ton donors like CH4 there probably is a double minimum ing of α helices and β sheets is called the tertiary structure
well with a small barrier. Also the cationic complexes like (see Fig. 19), and hydrogen bonds contribute to its stabil-
[H5 O2 ]+ usually have near-centrosymmetric potentials, ity as well. Enzyme molecules are a class of polypeptides
with barriers smaller than 1 kcal/mol. An exception could whose function in an organism is chiefly determined by
be [H7 N2 ]+ , where the barrier could be around 1 kcal/mol. their shape. In particular, the shape is critical near the cat-
alytic center of the enzyme (key and lock mechanism). Be-
XI. HYDROGEN BONDS IN cause these shapes are determined by hydrogen bonds, it
BIOLOGICAL STRUCTURES follows that hydrogen bonds are centrally important to the
functions of life. In some cases hydrogen bonds can also
Hydrogen bonds are of great significance in determin- directly participate in a catalytic reaction of an enzyme.
ing the structure of the biologically most important com- Of similar importance are hydrogen bonds in nucleic
pounds like proteins and nucleic acids. Since virtually acids, although they play a different role there than in pro-
all biological processes take place in aqueous solution, teins. These bonds are responsible for the specific pair-
equally important to the hydrogen bonds between biopoly- ing of the nucleic bases. There are only a few bases that
mers are hydrogen bonds between biopolymers and water are the building blocks of nucleic acids, and their spe-
and between water molecules surrounding biopolymers. cific sequence contains all the genetic information. Only
Water stabilizes biopolymers and, as discussed above, is certain pairs of bases, called complementary pairs, form
often the medium stimulating the formation of various strong hydrogen-bonded complexes binding the double
kinds of aggregates essential in living matter. Most bio- helix structure of nucleic acids. For example, cytosine con-
logical compounds simply do not exist in their biologically nects with guanine and thymine with adenine as shown in
functional form in nonaqueous solutions. The strength of Fig. 20. The double helix is stabilized by two backbone
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Hydrogen Bond 535

FIGURE 19 The structure of proteins. (a) The primary structure is the determined by the sequence of amino acids
in the polypeptide chain. Four of such acids shown are valine (Val), glycine (Gly), serine (Ser), and leucine (Leu).
(b) The secondary structures: α helix and pleated β sheet. Hydrogens or side chains connected to the carbon atoms
situated between the peptide link groups (Cα carbons) are not shown. The hydrogen bonds are indicated by dotted
lines. Most of the hydrogen bonds in proteins are N-H· · ·O = C bonds, but C-H· · ·O = C bonds are also present, and
one such bond is marked on the α helix. (c) Fragments of proteins built of pleated sheets and α helices connected
by additional hydrogen bonds (not shown) are creating the tertiary structure. (d) Well-determined units such as the
one shown in (c) may repeat a number of times in a large protein. Mutual arrangements of such units determine the
quaternary structure of a protein. The units can be linked to each other by hydrogen bonds.

strands on the outside consisting of sugar molecules to and uracil (U). DNA uses thymine (T) instead of uracil.
which the bases are attached and of phosphate groups Thus, a given nucleic acid alphabet contains to a very
linking the sugar molecules together, as shown in Fig. 21. good approximation just four letters. Only very exception-
Two such strands form a double helix displayed in Fig. 22. ally do some other bases appear, mainly methylated forms
The strands are connected by hydrogen bonds between the of major bases found in ribosomal RNA. The hydrogen-
nucleic bases. There are two classes of nucleic acids: ri- bonded pairs GC and AT (AU in RNA) are more stable
bonucleic acid (RNA) and deoxyribonucleic acid (DNA). than the other combinations and better fit into the geom-
RNA plays a function in the cellular synthesis of proteins, etry of the backbone, and for this reason they are called
whereas DNA is the carrier of the genetic information, complementary pairs. Their hydrogen-bonded configura-
except for some viruses that use RNA for that purpose. tions shown in Fig. 20 were proposed by Watson and Crick.
There are two main differences between RNA and DNA: The complementarity is the basis of the molecular mech-
the sugar of the backbone is ribose and 2-deoxyribose, re- anism of nucleic acid replication as well as transcription
spectively, and one of the bases is different. There are four from DNA to RNA and translation from RNA to proteins.
major bases appearing in either RNA or DNA. In the for- The genetic information coded by the sequence of the nu-
mer case these are guanine (G), adenine (A), cytosine (C), cleic bases is replicated when DNA separates into two
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536 Hydrogen Bond

TABLE IV Interaction Energies of Base Pairsa

∆H(T)
Base pair E int + E def T ∆H(T) experimentalb

GC −23.4 381 −20.5 −21.0

CC −17.5 381 −14.6 −16.0
AU −14.5
AT (Hoogsteen) −12.7 323 −10.3 −13.0
AT −11.8 298 −9.5
UU −9.5
TT −10.0 323 −7.8 −9.0
a Ab initio values from Hobza and Sponer (1996). Experimental en-

thalpies from Yanson et al. (1979). All energies in kcal/mol, temperature

in degrees Kelvin.
b The experiment in not sensitive to the geometry of the complex. As-

signments have been made assuming that the observed complexes cor-
respond to the minimum structures determined in ab initio calculations.

FIGURE 20 The adenine–thymine and guanine–cytosine com-

Interaction energies and enthalpies of formation for a
plementary pairs. Notice two types of hydrogen bonds:
N-H· · ·O=C and N-H· · ·N. few base pairs are listed in Table IV. The enthalpies have
to be computed in order to compare with measured val-
ues. Enthalpies of formation are related to the dissociation
single strands, each of which serves as a template for a
energies—under assumption of the complete separation of
new strand. The copying process producing a new strand
the rotational and vibrational motion—by the formula
is guided by the same pairs of hydrogen-bonded nucleic
bases that appeared in the original double-stranded DNA. H (T ) = −D0 + E vib (T ) + 4RT, (23)

FIGURE 21 A single strand of DNA. The sugar molecules are connected to each other by the phosphate groups
forming the DNA backbone. A nucleic base is attached to the other end of each sugar molecule.
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Hydrogen Bond 537

monomers to those in the complex. The ab initio enthalpies

of formation listed in Table IV agree well with the mea-
sured ones. One should point out, however, that due to
the size of the system, the ab initio calculations had to
be performed at a relatively low level of theory and used
small basis sets. Also the accuracy of the experimental
data is uncertain, and the measurement of Yanson et al. is
the only source of data available.
The complementary pairs GC and AT listed in Ta-
ble IV are in configurations shown in Fig. 20. Many other
hydrogen-bonded dimers are observed in crystal struc-
tures of nucleic acid bases, involving both homo and het-
ero pairs, and some of them are included in Table IV. The
Hoogsteen AT pairing can be obtained from the AT con-
figuration in Fig. 20 by rotating the adenine around the
N-C-N axis in the six-membered ring. The GC pair is the
strongest bond of all nucleic acid pairs. This is clearly
due to the fact that this is the only pair with three hy-
drogen bonds. The Watson-Crick AT pair is bound only
half as strong. The bond in the Hoogsteen AT pair is in
fact little stronger, but this pair cannot be used in DNA
due to steric reasons of connecting to the sugars of the
backbone.

SEE ALSO THE FOLLOWING ARTICLES

BIOPOLYMERS • BORON HYDRIDES • COHESION PARAM-

ETERS • ENERGY TRANSFER, INTRAMOLECULAR • HALO-
GEN CHEMISTRY • PERTURBATION THEORY • PROTEIN
STRUCTURE • QUANTUM MECHANICS
FIGURE 22 The DNA α helix consisting of two strands such as
those shown in Fig. 21. The sugar–phosphate backbones are
shown only schematically as blue ribbons. The two strands are
BIBLIOGRAPHY
connected by the hydrogen bonds between the nucleic bases.

Bentwood, R. M., Barbes, A. J., and Orville-Thomas, W. J. (1980).

J. Mol. Spectrosc. 84, 391.
where R is the gas constant, T is temperature in Kelvin, Braly, L. B., Liu, K., Brown, M. G., Keutsch, F. N., Fellers, R. S., and
and E vib (T ) is the vibrational thermal energy defined in Saykally, R. J. (2000). J. Chem. Phys. 112, 10314.
the harmonic approximation as Buck, U., Ettischer, I., Melzer, M., Buch, V., and Sadlej, J. (1998). Phys.
 ωi
Rev. Lett. 80, 2578 (1998).
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i
exp(ωi /RT ) − 1 A 103, 7322.
Camy-Peyret, C., Fland, J. M., Maillard, J. P., Guelachvili, G. (1977).
where ωi are the complex’s fundamental excitation en- Mol. Phys. 33, 1641.
Carey, D. M., and Korenowski, G. M. (1998). J. Chem. Phys. 108, 2669.
ergies. Enthalpy of formation accounts for the fact that
Chalasinski, G., and Szczesniak, M. M. (1994). Chem. Rev. 94, 1723.
in a given temperature the dimers can be created at var- Chemical Reviews (1994), 94, Issue 7. The American Chemical Society.
ious excited vibrational levels as well as for changes Curtiss, L. A., Frurip, D. J., and Blander, M. (1975). J. Chem. Phys. 71,
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the monomer deformation energies E def . These relatively Structural Chemistry and Biology,” Oxford Univ. Press, Oxford and
New York.
small (1–2 kcal/mol) destabilizing contributions describe Fland, J. M., Camy-Peyret, C., and Maillard, J. P. (1976). Mol. Phys. 32,
the change of monomers’ energies upon the deforma- 499.
tion of monomers’ geometries from the values in isolated Franks, F. (ed.) (1972). “Water, a Comprehensive Treatment,” Vol. 1.
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Groenenboom, G., Mas, E. M., Bukowski, R., Szalewicz, K., Wormer, Lee, H. M., Suh, S. B., Lee, J. Y., Tarakeshwar, P., and Kim, K. S. (2000).
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Ion Kinetics and Energetics

James M. Farrar
University of Rochester

I. History
II. Ion Energetics
III. Ion Kinetics

GLOSSARY Gas-phase basicity Gibbs free energy change associated

with the protonation reaction M,
Appearance energy (AE) Minimum energy required to
M + H+ −→ MH+ .
form a particular fragment ion A+ from a precursor
neutral molecule: Ionization energy (IE) Energy required to remove an
+ − electron from a molecule or atom:
AB −→ A + B + e , Hr×n = AE.
Breakdown diagram Graph of the relative abundance of M −→ M+ + e− , Hr×n = IE.
parent ion and fragment ion as a function of the energy
IEs are classified as adiabatic or vertical: The adia-
above the ionization threshold of the precursor neutral
batic IE is the lowest energy required to remove an
molecule.
electron from a molecule or atom and equals the tran-
Electron affinity (EA) For a neutral atom or molecule,
sition energy from the lowest electronic, vibrational,
equal to the energy difference between the enthalpy
and rotational level of the isolated molecule to the cor-
of formation of a neutral species and the enthalpy of
responding level of the isolated ion. The vertical IE
formation of the negative ion of the same structure.
is the energy change corresponding to ionization lead-
The EA is defined as the negative of the 0 K enthalpy
ing to formation of the ion in a configuration with the
change for the electron attachment reaction:
same equilibrium geometry as the ground-state neutral
M + e− −→ M− , Hr×n = EA. molecule. The vertical IE must always be greater than
Franck–Condon principle Principle that an electronic or equal to the adiabatic IE.
transition, such as that effected in ionization, takes KERD Kinetic energy release distribution—the proba-
place such that the positions and momenta of the nuclei bility distribution for observing product fragments in a
remain fixed. dissociative process with a particular value of the rela-
Gas-phase acidity For a molecule AH, the Gibbs free tive kinetic energy.
energy change (at 298 K) for the reaction MATI Mass-analyzed threshold ionization—the mass
spectrometry of ions produced in coincidence with
AH −→ A− + H+ . zero-kinetic energy (ZEKE) electrons.

65
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66 Ion Kinetics and Energetics

PEPICO Form of photoionization mass spectrometry in nuclei and are called cations, while negatively charged
which ions produced by photoionization are detected species are referred to as anions.
in coincidence with the accompanying energy-selected One of the early triumphs of the theory of atomic struc-
photoelectrons. ture was the correct description of the quantized energy
PFI Pulsed field ionization—the application of a short level structure of atoms formed by the Coulomb attraction
electric field pulse that induces long-lived Rydberg of a single electron to a positively charged nucleus. The
states of atoms or molecules just below the ionization 1/n 2 dependence of the energy levels on integer quantum
continuum to decay by tunneling through the electric number n in one-electron systems yielded an exact fit to
field-induced barrier. the emission spectra of such atoms that had been cataloged
Photoionization Production of atomic and molecular at the end of the nineteenth century by Balmer, Rydberg,
ions from precursor neutrals by absorption of photons. Bohr, and Ritz. The convergence of such Rydberg series
Proton affinity (PA) Negative of the enthalpy change of at large n to energy levels of the corresponding ion pro-
the protonation reaction: vided a sharp definition of the ionization energy of an
atom.
M + H+ −→ MH+ , Hr×n = −PA.
The PA is a quantity defined at a finite temperature,
A. Ion Energetics
usually 298 K.
Quasi-Equilibrium theory (QET) Theory of mass spec- Once the fundamental principle was established that mat-
tra based on rapid internal conversion of excited elec- ter exists as a collection of positively charged nuclei
tronic states produced by electron impact to the ground surrounded by negatively charged electrons, many ex-
electronic state. Statistical redistribution of energy on perimental observations confirmed that ionized matter is
the-ground state surface, followed by vibrational pre- present throughout the Universe. In addition to “cathode
dissociation, determines the rate of fragmentation. rays” produced by thermionic emission from metals or by
REMPI Resonance-enhanced multiphoton ionization— the photoelectric effect, “positive rays” were also gener-
the ionization process whereby an atomic or molecular ated in gases. The identification of the latter species as
species absorbs two or more photons through a tran- positive ions from the fact that their deflections in elec-
sition from an intermediate resonant bound state to a tric and magnetic fields were opposite to those of cathode
bound state. rays occurred quickly. The same experimental techniques
R2PI Resonance two-photon ionization—a variant of of focusing and deflection of charged particles in elec-
REMPI in which two photons are required to produce tric and magnetic fields, in conjunction with improved
ionization, with the first photon accessing a resonant methods for producing a high vacuum, led to the devel-
bound intermediate state. opment of mass spectrometers, devices that sorted these
ZEKE Zero-kinetic energy electrons, produced by field charged particles according to mass. The early history of
ionization of excited Rydberg states just below the ion- mass spectrometry focused on the determination of atomic
ization limit to a particular internal energy state of the and molecular masses of ions formed by electron impact-
resultant ion. induced removal of one (or more) electrons from a stable
molecule. The use of incident electrons with reasonably
well-characterized energies also led to systematic infor-
I. HISTORY mation on the threshold ionization energies of atoms and
molecules, forming the basis for the determination of en-
At the beginning of the twentieth century, ground- thalpies of formation of gaseous ions. In the case of sim-
breaking experiments by leading scientists of the day, ple electron removal to form the parent ion, the resul-
most notably J. J. Thomson and Ernest Rutherford, de- tant energy is the ionization energy, while bond cleavage
termined that the electrical nature of matter is fundamen- occurring in conjunction with ionization, so-called dis-
tally a property associated discrete particles. Thomson’s sociative ionization, yields the appearance energy of the
discovery of the “electron” as the particle that carries neg- corresponding ionic fragment. The systematic study of
ative charge in matter and Rutherford’s determination that ionization and appearance energies for parent and frag-
the positive charge in atoms is localized in a very small ment ion formation to yield enthalpies of formation for
volume called the “nucleus” provided the foundations of gaseous ions forms the heart of the subject of “ion en-
the modern atomic theory. In an electrically neutral atom ergetics.” The electron volt (eV) is the most frequently
or molecule, the number of electrons balances the posi- employed unit of energy in studies of ionization phenom-
tive charge of the constituent nuclei. Positively charged ena and corresponds to the energy acquired by a single
species have a deficiency of electron charge relative to the fundamental charge when accelerated by an electrostatic
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Ion Kinetics and Energetics 67

potential of one volt. The definition of the electron volt is reactions with ionic products observed in the radiation
as follows: 1 eV = 96.4845 kJ/mol or 23.06036 kcal/mol. chemistry of hydrocarbons. Pioneering work by Hamill
at the Notre Dame Radiation Laboratory suggested that
the ionic products formed in hydrocarbon mixtures irra-
B. Ion Kinetics
diated by ionizing radiation from the γ -emission of ra-
Concurrently with these studies of primary atomic and dioactive nuclei could be explained on the basis of simple
molecular ionization mechanisms in atoms and molecules ion-neutral collisions. It was the observation in 1958 by
under collision-free conditions, mass spectrometrists be- Field and Lampe that hydrocarbon cations were capable
gan to observe pressure-dependent phenomena in the ion of abstracting hydride (H− ) ions from neutral hydrocar-
sources of their instruments. One of the first such obser- bon collision partners that led Futrell to connect chem-
vations goes back to the beginning of the twentieth cen- istry occurring in γ -radiolysis with simple ion–molecule
tury, when J. J. Thomson discovered that operating his reactions. The determination of ionization potentials and
positive ray parabola apparatus in a hydrogen atmosphere appearance energies with instrumentation that developed
produced signals at a mass-to-charge ratio of 3. Although rapidly in the 1950s and 1960s led to additional studies of
he correctly attributed this signal to the species H3 , it was the reactivity and stability of gas-phase ions by pioneers
only in later high-pressure ion source mass spectrometer such as Franklin and Ausloos.
experiments by Hogness and Lunn that it was demon- The 1960s brought two major advances in the discipline
strated unequivocally that this species was produced by a of ion energetics and structure. The development of high-
reaction between the primary ionization product H+ 2 and pressure mass spectrometer ion sources led by Kebarle and
molecular hydrogen. This point of view concerning the co-workers allowed the measurement of equilibrium con-
rapidity of reactions between gaseous ions and molecules stants for gas-phase ionic systems at well-specified tem-
in the gas phase was supported by other pioneers in the peratures and, from temperature-dependent studies, the
emerging field of mass spectrometry, including Aston and enthalpy and entropy changes associated with gas phase
Dempster. equilibria. These concepts provided the foundation for cur-
Although theoretical work by Eyring, Hirschfielder, and rent studies of molecular recognition in the gas phase.
Taylor in the mid-1930s predicted that the rate of the ion– The development of the discipline of elementary re-
molecule reaction action dynamics as the foundation of chemical kinetics
also occurred in the 1960s. This subject addresses the
H+ +
2 + H2 −→ H3 + H (1)
fundamental question of energy disposal in a chemical
was limited only by the frequency with which the reactants reaction and the microscopic details of the collisions that
collide, a picture that was claimed to describe the rates of lead to reaction product formation by probing the features
many such ion–molecule reactions, systematic studies of of the potential energy surface (or surfaces) that governs
such rates were not carried out for another 15 years. The the conversion of reactants into products. The applica-
pioneering work of Tal’rose in Moscow on ion formation tion of the methods of collision kinematics and dynamics
in methane gas irradiated by electrons initiated the study exemplified in the molecular beam experiments of Datz
of ion–molecule reactions as a distinct discipline within and Taylor was a natural development, as the techniques
the field of chemical kinetics. In those studies, electron of mass spectrometry form the ionic reagents into a di-
impact ionization in methane produced CH+ 4 as a parent rected beam. The measurement of product energy and an-
ion and CH+ 3 by dissociative ionization. The bimolecular gular distributions that such an experimental geometry af-
reaction fords yielded a microscopic view of the kinds of collisions
that lead to chemical reaction. Some of the pioneering
CH+ +
4 + CH4 −→ CH5 + CH3 , (2)
applications of these techniques were accomplished by
occurring by a mechanism in which proton transfer from Mahan and co-workers at Berkeley, Herman in Prague,
CH+ +
4 to CH4 and hydrogen transfer from CH4 to CH4 are and Wolfgang at Yale, on collisions of atomic and diatomic
implicated, was observed to occur on every collision. In ions with hydrogen molecules.
addition, the carbon–carbon bond formation reaction By exploiting the state selectivity that ionization of
small molecules by ultraviolet radiation provided, ionic
CH+ +
4 + CH4 −→ C2 H5 + H2 (3)
collision dynamics made a central contribution to the
was also observed to occur at the collision frequency. emerging field of chemical dynamics. A key question in
Reactions (2) and (3) occurring in methane were also chemical dynamics is how energy that is placed in spe-
observed by Stevenson and co-workers in 1955 in the ion cific modes of reactant motion affects the outcome of a
source of a laboratory mass spectrometer and launched chemical reaction. The first example of a chemical reac-
an important era that connected elementary ion–molecule tant prepared in a quantized excited vibrational state and
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68 Ion Kinetics and Energetics

the observation that energy in this form allowed the system of the ionization threshold to cause fragmentation of the
to surmount a potential energy barrier occurred in an ionic parent ion. The threshold energies associated with frag-
system. By using a monochromatic light source in the ul- ments A+ formed through the reaction
traviolet region of the spectrum, Chupka and co-workers
AB −→ A+ + B + e− (5)
were able to produce H+ 2 ions in selected vibrational states
by photoionization of molecular hydrogen. The use of are the appearance energies, AE, for a given fragment.
photoionization methods to produce vibrationally state- Appearance energy values result in thermodynamic infor-
selected reagents both for bimolecular collision studies mation only when the reaction coordinate has no barrier
and for unimolecular decay of energy-selected ions played in excess of the endothermicity for dissociative ioniza-
a central role in contemporary developments in ionic re- tion, and the products appear promptly on the time scale
action dynamics. Along with more sophisticated methods of product detection in a particular instrument, i.e., there
for reagent preparation and product state-resolved detec- is no “kinetic shift.”
tion came advances in the production of chemically more The terminology introduced above for the formation
complex reagents. The field of ion kinetics has provided of cations may also be applied to anions, which may be
benchmark data for testing theories of chemical reaction formed either through heterolytic bond cleavage in AB,
dynamics in elementary atom–diatom systems. The field
AB −→ A+ + B− , (6)
has also provided a wealth of studies on more complex pro-
cesses at the microscopic level, including organometallic or by electron attachment to a suitable neutral precursor
chemistry related to catalysis, cluster ion studies relevant A having a positive electron affinity,
to atmospheric and materials chemistry, the ion chemistry
A + e− −→ A− . (7)
of electrical discharges and plasmas (relevant to the micro-
electronics industry), and reactions of biological species Some classes of ionic decomposition processes occur
that provide useful information on the nature of confor- via pathways requiring that the system surmount a barrier
mation as a function of solvation. on the potential surface in excess of the endothermicity.
The majority of ionic species are formed by the removal Simple bond cleavage processes generally occur without
(or the addition) of an electron from (or to) a stable atom or such a barrier, but rearrangements often occur with such
molecule. As a result, ionic species are highly reactive. Be- a barrier. The determination of accurate thermochemical
cause the environment in which ionic species are created information from fragmentation threshold energies is al-
is often chemically complex, special techniques for the ways subject to the uncertainty that the enthalpy of reac-
preparation and handling of such transients are required tion may differ from the observed threshold energy. The
for reliable determination of ionization and appearance presence of a potential barrier for a fragmentation process
energies, energetic thresholds for chemical reactions, and may result in excess product translational energy release,
unambiguous measurements of chemical reaction cross and measurement of the kinetic energy release distribution
sections and rates. The general techniques of mass spec- (KERD) often allows an estimate of the barrier height.
trometry form the basis for experimental methods that pro- The term “kinetic shift” refers to experimentally
vide information on ion energetics and kinetics. observed ionization thresholds that are higher than true
thermodynamic threshold energies because of the finite
lifetime of the decaying species. Most experimental appa-
II. ION ENERGETICS ratuses sample ions at a specific, instrument-dependent
time after ionization has occurred, typically about
A. Spectroscopic and Ionization Methods 10−5 sec, so that ions decaying on a time scale long com-
in Isolated Atoms and Molecules pared to this characteristic observation time will not be
detected at threshold. This situation results in an apparent
1. Threshold Determination
threshold for dissociation that is shifted to higher values
The ionization threshold energy for the process of the internal energy of the decaying parent ion by the
magnitude of the “kinetic shift.” The kinetic shift thus de-
M −→ M+ + e− (4)
pends on the time scale for observation and the sensitivity
is the minimum internal energy change accompanying the of the instrument for detecting low signal levels for ion
removal of an electron from a stable neutral precursor M. formation. Measuring the decay rate as a function of the
The term ionization energy generally refers to the adia- parent ion internal energy provides a way to correct experi-
batic ionization energy, denoted IEa . The species M+ is mental data for this kinetic shift. Time-resolved ionization
called the parent ion. When M is a molecular species, the methods employing pulsed ion production methods also
ionization process may impart sufficient energy in excess provide a way to estimate the kinetic shift.
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Ion Kinetics and Energetics 69

The most widely used technique for determination of Doppler broadening. These refinements make the deter-
ionization and appearance energies measures the mini- mination of ionization energies quite precise, in the fa-
mum energy required to form a parent or fragment ion vorable case where the neutral and ionic ground states
from its precursor neutral or to detach an electron from a do not involve significant geometric rearrangements. As
negative ion. Ionization of a given species may be effected with electron impact ionization, the Franck–Condon prin-
by absorption of a photon, by collision with electrons hav- ciple predicts that a large change in geometry upon single-
ing kinetic energy in excess of the ionization threshold, or photon absorption will result in an ionization threshold
by interaction with excited atoms or molecules having ex- that is gradual, making the exact ionization threshold dif-
citation energies in excess of the ionization energy of the ficult to locate accurately. In the case where ionization
neutral. Such measurements can be carried out by deter- is direct, the narrow bandwidth of modern photoioniza-
mining the coincidence between the ions and the electrons tion sources often provides a means to achieve the pro-
formed. duction of molecular ions with vibrational state selection.
The venerable technique of electron impact is the most At the lowest ionization threshold, ions are formed in the
widely employed in mass spectrometric determination of ground vibrational state. As the frequency of the photoion-
ionization and appearance energies. The development in ization radiation is increased, thresholds for the formation
the 1960s of electron monochromators, in which electron of molecular ions with vibrational excitation are encoun-
beams with kinetic energy spreads of as little as 0.005 eV tered, and the photoionization efficiency curve shows step-
are generated by passing the beam through deflection- function increases in ion production as excited vibrational
type electron energy selectors, led to important advances states become accessible. In the favorable case of pho-
in measuring ionization and appearance potentials. The toionization of H2 , rotational state selection of the resul-
incident electron excites the molecular precursor through tant molecular ions can also be achieved. At the threshold
an energy transfer collision in a vertical Franck–Condon for the formation of a molecular ion in a given excited
transition to excited electronic states. The Franck–Condon vibrational state, the product ion distribution will contain
principle states that the most probable ionizing transition contributions from all lower vibrational states that are en-
will be the one in which the positions and momenta of the ergetically accessible, degrading the quantum state purity
nuclei do not change. When the equilibrium geometries of the parent ions. In addition, the simple step-function
of a neutral precursor and its corresponding parent ion are behavior that accompanies direct ionization may be com-
similar, the energy dependence of the ionization threshold plicated by autoionization processes, in which the initial
will be a sharp step function, forming the ground vibra- optical excitation is to an excited Rydberg state of the neu-
tional state of the ion. However, when the equilibrium ge- tral molecule. As discussed below, energy analysis of the
ometry of the ion is significantly different from that of the electrons that accompany the ionization process can sort
neutral, e.g., is accompanied by a significant change in one out the details of such complex ionization processes.
or more bond lengths or angles, the transition to the lowest The rapid development of intense laser sources has
vibrational level of the ion is no longer the most proba- led to the development of ionization methods based on
ble one. The vertical ionization energy corresponding to the absorption of multiple photons. Ionization energies
the maximum transition probability will populate excited for molecules have been measured using resonant two-
vibrational levels of the ion preferentially. The geometry photon ionization (R2PI) or resonance-enhanced multi-
change upon ionization can be sufficiently large that ion- photon ionization (REMPI) of rotationally cooled species
ization to produce the lowest vibrational level of the ion in a molecular beam. In such studies, the internally cooled
at the adiabatic ionization energy will not be observed. beam of molecules is excited to a specific quantum state
In the mid-1960s, the availability of tunable ultraviolet with a tunable laser; while holding this excitation energy
radiation laboratory sources led to the replacement of elec- constant, a second, independently tunable laser ionizes the
tron beams with photon sources. Rare gas resonance lamps beam of excited molecules. By tuning the first excitation
producing continuum sources of radiation that could then laser to different transitions, the entire Franck–Condon
be passed through monochromators allowed the field of accessible region of the intermediate electronic state is
photoionization mass spectrometry to develop. The deter- probed, yielding the adiabatic ionization energy. The ex-
mination of photoion yield as a function of ionization en- periment thus contains an internal consistency check that
ergy, the photoionization efficiency curve, led to determi- leads to more reliable values of ionization threshold. The
nation of ionization potentials with accuracies exceeding production of ions by multiple photon absorption is com-
those of electron impact methods. Modern photoioniza- plicated by the loss of information on the Franck–Condon
tion experiments often utilize laser or synchrotron light factors for the initial photon absorption steps. However, in
sources with narrow bandwidths and may employ colli- cases where the ionization is an (n + 1)-photon process,
mated molecular beam sources that reduce the effects of with the first n photons providing access to a Rydberg
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70 Ion Kinetics and Energetics

state of the precursor neutral, the final photon absorption spectral resolution of conventional photoelectron spec-
process often occurs from a specific vibrational state of troscopy. When the full energy of the photon is ab-
the neutral to an ion with the same vibrational quantum sorbed in the optical transition leading to ionization, the
number. Under such conditions, vibrational state selection ejected electron has zero kinetic energy. As the photon
can be achieved by multiphoton absorption. The method energy is increased beyond an ionization threshold, the
has been applied successfully in the production of NH+ 3 atom or molecule continues to absorb light and electrons
cations with specific excitation in the ν2 umbrella-bending are ejected with nonzero kinetic energy. The resulting
mode. “hot” electrons can be discriminated from the zero ki-
The photoionization process is accompanied by the netic energy electrons by the fact that they are moving
emission of electrons. The technique of photoelectron in the center of mass coordinates, and the electrons with
spectroscopy is based on a measurement of the kinetic zero kinetic energy are stationary in this frame of ref-
energies of those electrons, either independently of the erence. The zero-kinetic energy-threshold electrons re-
ion formation process or in coincidence with it. In photo- main in the interaction region, and a small electric field
electron spectroscopy, the precursor atom or molecule is extracts them through a small aperture or a restricted
irradiated with light of a known energy sufficient to eject channel.
an electron from the material through the process An important variant of the threshold photoelectron
spectroscopy technique arises from a consideration of the
M + hν −→ M+ + e− (KE), (8)
nature of the Rydberg states of the precursor neutral that
where converge to the ground state of the ion, defining the ion-
ization energy. Additionally, each electronic, vibrational,
KE(e− ) = hν − I − E ∗ (vib,rot). (9)
and rotational (rovibronic) state of the ion has a unique
In this expression, I is the binding energy of the electron Rydberg series converging to that state of the ion. While
and E ∗ (vib,rot) is the internal energy of the product ion conventional TPES focuses on the zero-kinetic energy
M+ . The technique may also be employed to determine electrons in the ionization continuum, i.e., KE(e− ) → 0+ ,
the electron affinities of atomic or molecular anions. the technique of ZEKE spectroscopy is concerned with
Conventional photoelectron spectroscopy, invented by the detection of Rydberg states in a very narrow band just
Turner and Siegbahn, developed through the application below the ionization limit of each robronic state of the
of the helium or neon resonance lines (21.218 and 40.813 ion. These long-lived states are separated from the fast-
or 16.848 and 16.671 eV, respectively) from discharge decaying low-n Rydberg states by a simple time delay in
lamp photon sources. The development of synchrotron the detection process. The usual method for carrying out
radiation sources as well as tunable vacuum ultraviolet this delayed ionization is to apply a pulsed electric field of
laser sources has also enhanced the utility of photoelec- magniture ∼1 V/cm approximately 10 µsec after the pri-
tron spectroscopic methods. In an experiment, the ejected mary excitation step and after the “prompt” electrons from
electrons will be produced with a distribution of kinetic short-lived states have moved away. The small applied
energies degermined by the distribution of energy levels in field then ionizes the long-lived Rydberg states by field
the M+ ion product. The energy distribution of the emit- ionization. The lifetimes of such high-n Rydberg states are
ted electrons is called the photoelectron spectrum. The observed to be nearly two orders of magnitude longer than
photoelectron band shapes reflect not only the vibrational expected and arise from external perturbations that operate
energy level structures in the ground and excited elec- only on the Rydberg states lying extremely close to the ion-
tronic states of the ion, but also the M+ ← M transition ization threshold. The acronym “ZEKE,” referring to the
probabilities dictated by Franck–Condon factors. When detection of these zero-kinetic energy electrons, is com-
the equilibrium geometries of the ion and the correspond- monplace, although the term “ZKE” has also been used
ing neutral are similar, the observed threshold of the first in the literature, more correctly referring to the zero-field
photoelectron band generally yields the adiabatic ioniza- production of threshold electrons. The use of a pulsed elec-
tion energy. The ionization energies are thus determined tric field is referred to as “pulsed field ionization” (PFI).
with an energy resolution characteristic of the resolving ZEKE spectroscopy differs from other methods of pho-
power of deflection-type energy analyzers, or as low as toelectron spectroscopy because it is a multistep process.
0.005 eV. On an energy scale appropriate to optical mea- The successive steps are required to isolate the narrow
surements, this resolution corresponds to 40 cm−1 , signif- band of long-lived high-n Rydberg neutrals from the back-
icantly poorer than the subcentimeter value afforded by ground hot electrons and their counterions from the low-n
narrow-bandwidth optical sources. Rydberg states. The ions produced in coincidence with
Threshold photoelectron spectroscopy (TPES) was de- ZEKE electrons can also be detected, forming the basis for
veloped to overcome the inherent limitations in the mass-analyzed threshold ionization (MATI) spectroscopy.
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Ion Kinetics and Energetics 71

Owing to the kinematic restriction that results from by summing the enthalpy of formation of the precursor
detecting the ion, this method has an intrinsically lower molecule to the adiabatic ionization energy (IEa ) and sub-
energy resolution than detecting the corresponding ZEKE tracting the enthalpy of formation of the electron,
electron. However, that disadvantage is offset by the de-
f H 0 (M+ ) = f H 0 (M) + IEa − f H 0 (e− ). (10)
sirability of producing mass-selected ions with a known
vibrational excitation. The analogous expression for an anion requires the value
For the purpose of producing ions with well- for the electron affinity:
characterized levels of vibrational excitation, as well as
for studying the thermochemistry of ionic fragmentation f H 0 (M− ) = f H 0 (M) − EA + f H 0 (e− ). (11)
processes, the coincident detection of photoions and their Similarly, the enthalpy of formation of a positive fragment
corresponding electrons yields a powerful combination. ion A+ with appearance energy AE formed by dissociative
The technique known as photoelectron–photoion coinci- ionization of precursor molecule AB is given by
dence (PEPICO) correlates ejected electrons formed with
zero kinetic energy with their corresponding positive ions. f H 0 (A+ ) = f H 0 (AB) − f H 0 (B) − f H 0 (e− ) + AE.
Below the dissociation threshold, this method provides a (12)
way to produce parent ions with vibrational state selec- As we have already noted, this expression assumes that
tion. At energies where parent ions undergo dissociation the dissociation reaction coordinate has no barrier in ex-
to form one or more fragment ions, one measures the rel- cess of the dissociation energy and that the dissociation
ative probabilities for the formation of the daughter ions lifetime is rapid compared with the time scale of measure-
from parent ions with a well-specified internal energy, a ment in the specific instrument. The molecular quantities
quantity called the “breakdown diagram.” The ions can be of ionization energy, electron affinity, and appearance en-
detected at differing times after the ionization event for ergy refer to differences in zero-point energy levels of the
determination of the time dependence of the dissociation appropriate potential energy surfaces of reactants or prod-
process. By measuring the time-of-flight distributions for ucts and are, thus, internal energies. Their conversion to
state-selected ions, a detailed analysis of the lineshapes the corresponding enthalpies at finite, nonzero absolute
can yield the kinetic energy release distributions for state- temperatures requires correction factors that depend on
selected fragmentation processes occurring on the time how the free electron enthalpy is accounted for. The en-
scale of transit through the instrument. thalpy of formation of a chemical species is defined as
Photoelectron spectroscopy can also be carried out by the difference between the enthalpy of the compound and
measuring the distribution of flight times of photoemitted the sum of the enthalpies of the elements comprising it.
electrons. This method is useful in systems in which the In the case of a cation or anion, the balanced chemical
absorbing species are produced by a pulsed source and the reaction corresponding to its formation from the elements
photolysis radiation is also pulsed. These electron time of will also contain the electrons that are liberated or cap-
flight methods have been used to elucidate structures of tured in the ionization process. The enthalpy of forma-
transient species such as free radicals and clusters pro- tion of the free electron must therefore also be accounted
duced in pulsed photolysis sources and in assessing the for in the ionic enthalpy of formation. Although the nu-
vibrational-state purity of ions produced in multiphoton merical value of the enthalpy of formation of a given ion
ionization processes, particularly those in which the final should be independent of the convention whereby one ac-
photon absorption process is from a Rydberg state whose counts for the free electron enthalpy, two distinct pro-
geometry is similar to that of the ion. cedures for dealing with this issue have evolved in the
literature.
The computation of an enthalpy change at a finite tem-
2. Ion Enthalpies of Formation perature relative to the 0 K value requires the evaluation
from Threshold Energies of the following expression:
The methods for determining ionization and appear-  T
ance energies under collision-free conditions as described H 0T (K) = H00K + CP (T ) dT . (13)
above must be employed according to well-documented 0

procedures of chemical thermodynamics to yield the ap- The evaluation of this expression for an ionization pro-
propriate enthalpies. The conversion of the internal en- cess, in which an electron appears explicitly as a reactant
ergy changes for these primary ionization processes to or product, requires a consistent approach. In the “Electron
enthalpies of formation requires that attention be paid to Convention,” used predominantly in the thermodynamics
a number of important principles and conventions. The community, and the “Ion Convention,” employed in the
enthalpy of formation of a molecular cation is obtained ion physics/chemistry communities, important differences
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72 Ion Kinetics and Energetics

arise in the manner by which the integrated heat capacities Convention, the enthalpies of formation of cations and
of the elements are used to compute enthalpies at nonzero anions reduce to
absolute temperatures. The more widely used Electron
Convention defines the enthalpies of formation of ele- f H 0 (M+ )298 K = f H 0 (M)298 K − f H 0 (e− )298 K
ments in their standard states to be zero at all tempera-
tures. Under such a convention, the integrated heat ca- + IEa + C, (18)
pacities of the elements must be accounted for implicitly = f H 0 (M)298 K + IEa , (19)
in other parts of the calculation. The Ion Convention is
based on the definition of the enthalpy of formation of a and
given element at temperatures above absolute zero to be
equal to the integrated heat capacity of that species. At f H 0 (M− )298 K = f H 0 (M)298 K + f H 0 (e− )298 K
the zero of absolute temperature, the enthalpies of forma-
tion of a given ion are identical in both conventions. Be- − EA + C, (20)
cause standard tabulations of thermochemical quantities = f H 0 (M)298 K − EA. (21)
have historically used both conventions, there is a need
to define the conventions with clarity and caution users Note that in both expressions, the equality of C and the
of such data to be aware of the conventions. In the Elec- enthalpy of formation of the electron at temperature T
tron and Ion conventions, at 0 K the enthalpy of formation (=298 K) results in expressions that have no dependence
of the electron is zero and the enthalpies of formation of on the integrated heat capacity of the electron.
the ions are exactly equal to the 0 K enthalpy of forma- The calculation of C, the integrated heat capacity of
tion of the precursor molecule plus the ionization energy the electron, is based on treating the free electrons as an
of M. The following equations treat anions and cations ideal gas and computing the heat capacity according to
consistently: Boltzmann statistics. At 298 K, the heat capacity at con-
f H 0 (M+ ) 0 K = f H 0 (M) 0 K + IEa , (14) stant pressure is that of an ideal gas, C = 5/2 RT, or
−
6.197 kJ/mol. This computation allows data tabulated un-
f H (M ) 0 K = f H (M) 0 K − EA.
0 0
(15) der the Electron Convention to be rationalized with Ion
At temperatures above 0 K, e.g., 298 K, where many Convention data as follows:
standard thermochemical data are reported, the Electron
and Ion conventions differ in the following manner: in the f H 0 (M+ )298 K (IC) = f H 0 (M+ )298 K (EC)
Electron Convention, the electron is treated like a stan-
− 6.197 kJ/mol, (22)
dard chemical element, and its enthalpy of formation is
− −
constrained to be zero at all temperatures. However, the f H (M )298 K (IC) = f H (M )298 K (EC)
0 0

integrated heat capacity is not taken to be zero. Under this

+ 6.197 kJ/mol. (23)
condition, the expressions for the enthalpies of formation
of positive and negative ions reduce to
For the most precise work, however, the evaluation of
f H 0 (M+ )298 K = f H 0 (M)298 K + IEa + C, (16) the heat capacity of the free electron gas should be carried
out with Fermi–Dirac statistics, resulting in a value of
f H 0 (M− )298 K = f H 0 (M)298 K − EA − C. (17)
C = 3.145 kJ/mol. This value is recommended in all cases
In these expressions, C is the integrated heat capacity where the electron is explicitly a reactant or product in an
for the electron. The integrated heat capacities for the ionization reaction.
ion M+ and its precursor neutral M effectively cancel in While many earlier compilations of data have used
the above expressions. The Electron Convention has been the Electron Convention, the most recent tabulation of
used historically in the ion thermochemistry literature de- standard enthalpies described in the NIST Webbook
spite the fact that the additive correction to the enthalpy (http://www.nist.gov) employs the Ion Convention. It
of ionization from the integrated heat capacity of the elec- does not introduce any temperature dependence, however
tron is small and temperature dependent, thereby causing small, to ion enthalpies of formation and is, therefore,
confusion. considered a simpler and less confusing representation of
In contrast, the standard Ion Convention treatment of data. This convention is also consistent with the literature
ion enthalpies of formation that appears in much of the of the ion physics and chemistry community over the past
literature on ion physics/chemistry assumes that the inte- 50 years. In any application of tabulated thermochemical
grated heat capacity of the electron, C, equals the enthalpy data, investigators are cautioned to be exceedingly clear
of formation of the electron at temperature T . In the Ion about the conventions of the data they employ.
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Ion Kinetics and Energetics 73

B. Measurement of Equilibrium Constant and viscous flow, diffusion of neutral species leads to
Methods, Keq mass discrimination effects. Other systematic errors arise
from clustering of neutral molecules to the ions at low
The preceding methods may be characterized as collision-
temperatures and pyrolysis of the ions at high tempera-
less, i.e., they determine the properties of isolated atoms
tures. The high level of development of ab initio quantum
or molecules in the gas phase. In contrast, ion/molecule
chemistry calculations has resulted in reliable estimates
equilibrium processes maintained by collision and char-
of equilibrium geometries of polyatomic molecular ions,
acterized by a specific temperature
from which vibrational frequencies and rotational con-
−−−→
A± + B ←−−− C± + D (24) stants yield absolute entropies that rival or surpass the
accuracy of experimental determinations or provide valu-
may be established in a high-pressure mass spectrometer, able consistency checks.
flow tube, or ion cyclotron resonance spectrometer. By Thermochemical scales derived from equilibrium con-
determining the mass action equilibrium constant through stant determinations are relative values, and absolute as-
measurement of the relative abundances of the two ions A± signments for appropriate quantities require reliable cal-
and C± after equilibrium has been established by a large ibration values of ionization energy, electron affinity, or
number of collisions, the thermodynamic state variables proton affinity, for example. Moreover, because of the in-
for chemical reaction may be obtained. K eq is defined by terrelationships among the thermochemical data for struc-
the following expression: turally similar molecules, the scale must be evaluated as a
K eq = [C± ][D]/[A± ][B]. (25) whole, not just for individual molecules, and must demon-
strate internal consistency among the variables G, H ,
The neutral reactants B and D are present in great excess and S.
compared to the ionic reactants, yielding a ratio [D]/[B] A particularly important application of equilibrium
that does not change as equilibrium is established. A single methods in mass spectrometry arises in the phenomenon
measurement of K eq yields a value for the Gibbs free en- of “chemical ionization.” In analytical mass spectrom-
ergy change of reaction at the temperature of the measure- etry, the extensive fragmentation that accompanies
ment, while a series of measurements at different temper- the ionization of large molecules in electron impact
atures permits an experimental evaluation of the entropy ionization is a serious problem. The distribution of ions
and enthalpy changes associated with the reaction through in a high-pressure ion source at thermal equilibrium is
the relation illustrative of the so-called “soft” ionization techniques
that have been developed to circumvent the problem of
−RT ln K eq = G 0 = H 0 − T S 0 . (26)
fragmentation when a Franck–Condon distribution of
Accurate knowledge of the temperature is essential for species is created by electron impact or photoionization.
a correct application of equilibrium methods. Equilib- The chemical ionization (CI) method employs a chemical
rium measurements carried out in widely different pres- reaction between ions generated from a reactant gas and
sure regimes have been able to reproduce relative spectro- the species to be ionized to generate primary ions. The
scopic ionization energies quite reliably, demonstrating reactant gas in CI is usually chosen to be a species such
that equilibrium may be achieved readily in such experi- as CH4 or H2 which may be ionized by electron impact
ments. Such measurements produce only relative thermo- followed by reactions with the neutral gas that lead to
chemical data; consequently, the resulting thermochem- protonated species such as CH+ +
5 and H3 . These species
ical “ladders” must be calibrated to reliable comparison may then undergo proton transfer reactions with the
standards to yield absolute values. species M to be ionized. Such reactions generally lead
Extracting the more useful H 0 values from G 0 mea- to MH+ ions in thermodynamic equilibrium at the ion
surements requires determination of Third Law entropies, source temperature with very little fragmentation.
through either temperature-dependent methods, i.e., van’t
Hoff plots,
1. Proton and Electron Transfer Equilibria
d ln K eq −H 0
= , (27) Three important classes of gas-phase ion–molecule re-
d(1/T ) R action schemes demonstrate the value of thermochemi-
or applications of statistical mechanical methods. Sys- cal data deduced from equilibrium systems. The first of
tematic errors in such estimates arise from inaccurate these concerns the derivation of extensive scales of relative
determination of the reactive neutral pressure in pulsed proton affinities, gas-phase acidities, and electron affini-
high-pressure mass spectrometers. When such an instru- ties. These results derive primarily from measurements of
ment operates in the transition regime between molecular enthalpy changes for proton or electron transfer reactions:
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74 Ion Kinetics and Energetics

AH+ + B −→ BH+ + A (28) Aq+ · Bn yield equilibrium constants and thermodynamic

parameters as follows:
or   
ln K n,n+1 = ln(Cn+1 /Cn ) = −Hn,n+1
0
RT
AH + B− −→ BH + A− . (29)
 0  
+ Sn,n+1 R . (32)
The proton affinity of substance A is defined as the nega-
tive of the enthalpy change for attachment of a proton at a Many of the early studies focused on the thermochem-
particular temperature, usually 298 K; the gas-phase ba- istry of hydration and ammoniation of alkali metal cations,
sicity of A is the negative of the Gibbs free energy change Ag+ , H3 O+ , and NH+ 4 . These studies focused initially on
for that process. The negative of the Gibbs free energy the value of such data in understanding nucleation and gas-
change for the dissociation of a species HA into H+ and phase ion solvation phenomena but were quickly appreci-
A− defines the gas phase acidity of HA. ated as probes of solvation energies in the bulk solvent.
Another valuable system is that of charge transfer pro- Experimental data show that the ratio of the solvation
cesses energy in the liquid phase to the sum of the stepwise en-
A± + B −→ B± + A, (30) thalpies of solvation up to a given cluster size converges
with as few as five or six solvent molecules for many dif-
which provide information on relative enthalpies of ion- ferent cations clustered both to water and to ammonia.
ization or electron affinity at finite temperatures. Such These observations end support to the very simple Born
equilibrium determinations of relative ionization energies concept that to first order, solvation can be modeled by the
closely reproduce the equivalent scale of spectroscopic immersion of a sphere of fixed radius and charge in a struc-
ionization energies. The most useful application of this tureless dielectric continuum. Higher-order corrections to
equivalence is the determination of ionization energies this simple picture come from consideration of surface ten-
for species that undergo a large change of geometry upon sion effects. Convergence of these ratios to approximately
electron loss. The small Franck–Condon factors for ver- the same value is indicative of the fact that, beyond the first
tical transitions therefore result in poorly defined ioniza- solvation shell, the majority of the contribution to solva-
tion thresholds. The n-alkanes provide examples of such tion is from electrostatic interactions between the central
a system. The conventional view of thermal energy ion– ion cavity and the surrounding medium.
molecule equilibria is that electron transfer occurs in a
long-lived A± · B collision complex that survives for many
vibrational periods, allowing the ionic configuration cor- 3. Molecular Recognition
responding to the equilibrium geometry of the ion, i.e., the The study of ion energetics and equilibria in the gas phase
geometry corresponding to the adiabatic transition, to be has made valuable contributions to the subject of molec-
accessed. ular recognition. One of the fundamental characteristics
of systems that exhibit molecular recognition is the pres-
2. Solvation ence of significant noncovalent interactions. Such interac-
tions involve an interplay of entropic and enthalpic effects
Under high-pressure conditions in the ion source of a mass that are difficult to separate in the condensed phase but
spectrometer, it is possible to measure the equilibrium that can be sorted out in careful gas-phase studies using
constants for formation of solvated ionic species. Such methods described in preceding sections. The insight that
information provides insight into the thermochemistry of gas phase energetics studies can provide to this important
stepwise attachment of solvent molecules to selected ion field of inquiry is especially important in the develop-
cores. The high-pressure mass spectrometer technique al- ment of new analytical separations technology that can
lows the attainment of equilibrium cluster ion distribu- be applied to important environmental remediation issues
tions at specified partial pressures of a clustering ligand such as nuclear waste disposal. Gas-phase experiments
at well-specified source temperatures. The method de- provide the benchmark data that allow the development
pends on creating and measuring an equilibrium distribu- of computational methods capable of accurate predictions
tion for ligands, B, clustered to ions, Aq+ , of charge q, as of host–guest interactions in relevant condensed-phase
follows: environments.
A particularly important model system for understand-
Aq+ · Bn + B + M = Aq+ · Bn+1 + M. (31)
ing the microscopic details of molecular recognition is the
n is the number of solvent molecules, and M is a back- interaction of alkali metal ions with macrocyclic ligands
ground gas species that provides collisional stabilization such as crown ethers, c-(C2 H4 O)n . The n = 6 case, specif-
of the clusters. The measured intensities Cn of the species ically 18-crown-6, denoted 18c6, has generated much
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Ion Kinetics and Energetics 75

interest because of the fact that it binds K+ selectively over 1. Ion-Molecule Bracketing Experiments
Rb+ , Cs+ , and Na+ (in that order) in an aqueous environ-
Equilibrium in the ion source of a mass spectrometer
ment. In contrast, the gas-phase bond energies reported by
cannot be achieved in certain ion–molecule systems be-
Armentrout, using the thermokinetic method of collision-
cause of rapid competitive reactions or because one of the
induced dissociation, for the various alkali metal cations
species in the equilibrium of interest is an unstable species
with 18c6 clearly indicate that Na+ is most strongly bound,
such as a free radical. In such cases, it is sometimes pos-
as one expects from charge density models of electrostatic
sible to obtain an experimental estimate of the enthalpy
binding. A consideration of the competition between gas-
change of a particular reaction (charge transfer, proton
phase solvation of the cations by water and complexation
transfer, etc.) by use of a technique known as “bracket-
by the crown ether,
ing,” in which the ion of interest is reacted with a series of
M+ (H2 O)x + 18c6 −→ M+ (18c6) + xH2 O, (33) molecules selected to provide a range of values for the rele-
+ vant thermochemical parameter of interest, e.g., ionization
shows that complexation of Na by 18c6 is favored until
energy, electron affinity, gas-phase basicity, or acidity. Re-
the number of displaced water molecules corresponds to a
action is presumed to occur for exothermic processes and
complete solvent shell. At this point, K+ selectively binds
not to occur for endothermic processes.
to the crown ether, as observed in solution. In addition, for
For example, the proton affinity of a species B can be
all metal cations, the displacement reaction that liberates
“bracketed” between the know proton affinity of reference
six water molecules but binds a single 18c6 species is en-
compound A and that of reference compound C if the
tropically driven. Overall, this comparison demonstrates
following observations are made:
that the selective binding of K+ by 18c6 in aqueous me-
dia is a subtle balance of the solvation and complexation no reaction
BH+ + A −−−−→ AH+ + B, (34)
enthalpies, entropic effects, and the solvation of the resul-
fast reaction
tant complex. The results are consistent with a picture in BH+ + C −−−−−→ CH+ + B. (35)
which such selectivity is not an intrinsic property of the
metal cation–crown ether complex but depends critically The notation “no reaction” means either that the reaction
on solvation. This point of view makes it clear that a proper products are not observed or that the reaction efficiency,
understanding of molecular recognition in such systems i.e., the rate relative to the Langevin collision rate, is low.
must include details of the solvent itself. The observations lead to the relative ordering PA(A) <
PA(B) < PA(C).
C. Thermokinetic Methods
2. The Kinetic Method
In addition to the two general methods described above for
determination of thermochemical parameters, i.e., ioniza- The kinetic method is an approximate scheme to determine
tion under collision-free conditions and free energy mea- relative thermochemical properties based on the rates of
surements in systems at equilibrium at a well-specified competitive dissociation of mass-selected cluster ions. As
temperature, a third set of methods exists for determina- an example, consider the proton-bound dimer system:
tions of reaction enthalpies and enthalpies of formation. k1
These methods are collectively referred to as “thermoki- B1−H+−B2 −→ B1 H+ , (36)
netic” measurements and are based on the relative rates or k2
−→ B2 H+ , (37)
cross sections for the formation of reaction products under
single-collision conditions. The “ion bracketing method” with rate constants for competitive dissociation as indi-
puts constraints on the enthalpy of formation for a spe- cated. In its simplest form, the kinetic method deals with
cific species by observing the occurrence or nonoccur- systems in which the structures of B1 and B2 are suf-
rence of reactions of that species with known collision ficiently similar that it is reasonable to assume that the
partners. The collision-induced dissociation method deter- entropic factors in both decay processes are equal. With
mines bond energies in polyatomic ions by observing the the additional assumption that the dissociation processes
threshold energy at which collisions with a rare gas atom occur with no barriers in excess of the endothermicities,
fragments the parent ion. The “kinetic method” evaluates the following relationship holds:
the difference in enthalpies of reaction of two competi-    
k1 [B1 H+ ] (H )
tive reaction channels arising from decay of a common ln = ln +
≈ , (38)
precursor, usually a cluster ion. Each of these classes of k2 [B2 H ] RTeff
thermokinetic methods is based on underlying assump- where Teff is the effective temperature of the activated
tions that restrict the validity of a given method. proton-bound dimer. Perhaps the most difficult issue
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76 Ion Kinetics and Energetics

associated with the application of this method is the es- cessibility of methods for performing accurate ab initio
timation of the effective temperature, which describes a quantum chemical calculations has led to reliable esti-
Boltzmann distribution of activated dimer ions which frag- mates for the vibrational frequencies and rotational con-
ments to give the same fragment ion abundance ratio as stants of decaying molecules, as required for evaluation
observed for the non-Boltzmann population sampled in of rate constants computed according to statistical Rice–
the experiment. The assignment of Teff is made especially Ramsperger–Kassel–Marcus (RRKM) theory.
difficult because the distribution it describes is time depen- Threshold CID measurements have proven to be valu-
dent, a function of the observation time characteristic of able in determining thermodynamic information. By vary-
a particular instrument. Since the method determines dif- ing the kinetic energy of the AB+ ions in reaction (39) and
ferences in enthalpies of reaction, calibration data based observing A+ products as a function of incident energy, the
on the ion ratios of several species with energetics known threshold energy for CID can be determined, yielding the
from other methods, such as ion/molecule equilibria, are bond energy of AB+ . The accuracy of this method requires
necessary for absolute data determinations. The method that the probability for transferring all translational energy
may be applied to reactions other than relative proton affin- into the internal energy of the AB+ molecule is finite and
ity determinations, including electron affinities, ionization nonzero and that there is no activation energy in excess of
energies, gas-phase acidities, and cation affinities. In fa- the bond energy along the reaction coordinate for dissoci-
vorable cases, entropy changes associated with attachment ation. Accurate threshold determinations require attention
of an ion to a molecule may be determined from kinetic to the role of multiple collisions with the Rg collision gas,
method data, yielding information on bonding and frag- the effect of the internal energy content of the AB+ re-
mentation mechanisms in cluster ions, especially those of actant, and the metastability of the activated AB+ species
biological origin. on the timescale for detection. The generality of the
methods has been demonstrated through its application
to systems such as small organic molecules, solvated hy-
3. Collision-Induced Dissociation
dronium ions and metal ions, organometallic complexes,
This collisional method obtains bond energies by mea- atomic clusters, and metal–crown ether complexes.
suring the kinetic energy threshold for the dissociation of
AB+ ions, represented schematically as follows:
D. Sources of Evaluated Data
AB+ + Rg −→ A+ + B + Rg. (39)
The foregoing discussions of methods for determining
Formally, this process may be thought of as a superpo- thermochemical properties of gas-phase ions have focused
sition of bimolecular activation and unimolecular decay. on specific experiments that yield a particular observ-
The bimolecular step occurs in the collisional activation able parameter. New experimental methods that improve
of an AB+ ion above one (or more) of its dissociation the accuracy and precision of thermochemical determina-
thresholds; A+ fragment ions appear as products of the tions, as well as the fact that conventions for expressing
unimolecular decay of the activated ion. In the process such information change with time, make up-to-date criti-
noted above, Rg is often a rare gas atom. cal data compilations of prime importance for consumers.
A consideration of collisional dissociation near thresh- The National Institutes of Standards and Technology
old requires an understanding of the amount of energy (NIST) has continued its historical tradition of maintain-
transferred in a single encounter, the role of angular mo- ing a critical compilation of data, estimating error lim-
mentum in the decay of activated molecules, and the life- its in appropriate cases. The NIST compilations focus on
times for decay of such species. Accurate determination experimental determinations, but the importance of high-
of apparent thresholds has been achieved by modeling the quality ab initio calculation of enthalpies of formation of
threshold behavior of the system with a cross-sectional ionic compounds should not be ignored.
form as follows: As an example of this last point, the understanding of
  the structure of the seven-membered cyclic tropyl ion,
σ (E) = σ0 gi (E − E i − E 0 )n E, (40)
c-C7 H+ 7 , is particularly illustrative of the value of com-
where the summation extends over internal states labeled putations. Neither the tropyl ion, nor the isomeric ben-
by the index i and having degeneracy gi , σ0 and n are zyl, C6 H5 CH+ +
2 , and tolyl, C6 H4 CH3 , ions are stable in
adjustable parameters, E is the relative kinetic energy, the neutral precursor forms, forming in the gas phases
and E 0 is the 0 K reaction threshold. only through ionic dissociation reactions. Numerous re-
The dissociation rates of activated molecules close to actions produce the c-C7 H+ 7 ions, among them hydro-
threshold may be long in comparison with the observa- gen atom loss from toluene and halogen atom loss from
tion time window, leading to large kinetic shifts. The ac- benzyl halides and halotoluenes. The tolyl and benzyl ion
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Ion Kinetics and Energetics 77

structures can be produced at their thermochemical thresh- microcanonical equilibrium is achieved, and subsequent
olds, yielding well-established heats of formation. How- vibrational predissociation leads to fragmentation. The
ever, the tropyl ion is formed only through a process with breakdown diagram, the graph of fragment ion abundances
a substantial barrier. Thus, the only means for obtaining as a function of the internal energy of the ion, is computed
its energy directly is through ab initio quantum chemical from QET rate constants, and the mass spectrum is the
calculations, which have been carried out with the Gaus- convolution of the energy deposition function for the ion-
sian G2 methodology. The most current online source of ization process, e.g., the Franck–Condon factors for the
thermochemical data may be found in the NIST Web- primary ionization, with the breakdown diagram. QET has
book (http://webbook.nist.gov). In particular, the web site enjoyed considerable success in interpreting mass spectra.
http://webbook.nist.gov/chemistry/ion-ser.htm provides a The QET is formally identical to the Rice–Ramsperger–
searchable database for enthalpies of formation, electron Kassel–Marcus (RRKM) theory of unimolecular decay, in
affinities, ionization energies, gas-phase acidities and ba- which the rate constant for dissociation to reaction prod-
sicities, and appearance energies. The NIST data collec- ucts of an energized species with total angular momentum
tion includes only data derived from experimental deter- J and internal energy E ∗ over a barrier of E 0 is given by
minations, although the evaluation of the reliability of the the following relation:
data has been enhanced by using computational results,
σ N + (E ∗ − E 0 , J )
particularly for the proton affinity tabulation. k(E ∗ ) = . (41)
hρ(E ∗ , J )

III. ION KINETICS In this expression, N + (E ∗ − E 0 , J ) is the total number of

energy levels associated with the 3N − 7 bound internal
A. Unimolecular Reactions degrees of freedom of the critical configuration of total
angular momentum J and energy E ∗ − E 0 . The quantity
Decay of molecular ions activated above one or more dis- ρ(E ∗ , J ) is the density of internal energy states of the
sociation thresholds by photon absorption or electron im- activated ion at energy E ∗ , σ is the symmetry number of
pact and decomposition of an activated species prepared the reaction coordinate, and h is Planck’s constant. The
by a collisional excitation, are examples of unimolecular evaluation of rate constants by RRKM theory requires es-
reactions. Such reactions have played a central role in the timates of vibrational frequencies for activated molecules
subject of ion energetics and kinetics and have served as and critical configurations, all of which have been facil-
important testing grounds for statistical theories of uni- itated by ab initio calculations of the relevant potential
molecular decay. The fundamental assumption of all sta- energy surfaces. The barrier height, E 0 , is generally the
tistical theories of chemical reaction dynamics is that at least well-determined parameter in an RRKM calculation
some specified location on the reaction coordinate, all en- and is often the single parameter varied until the calculated
ergy microstates accessible to the system are populated rate constant is in agreement with the observed rate.
with equal probability. The manner in which this micro- The validity of the statistical approximation in QET–
canonical equilibrium is achieved is not specified in the RRKM–phase-space theories has been tested extensively
theory, but the implication of the assumption is that in- both experimentally and theoretically. Some of the most
tramolecular vibrational redistribution (IVR) is rapid on incisive tests of statistical theory have been performed
the time scale of reaction. All statistical theories have this with energy-selected ions, prepared as described pre-
assumption in common but differ in the point on the re- viously, using methods such as photoelectron–photoion
action coordinate at which the statistical approximation is coincidence (PEPICO). Particularly incisive tests of these
applied and in the manner in which angular momentum statistical models have been performed on isomeric C4 H+ 6
conservation is handled. Theories in which the statisti- systems by Baer and Bowers and their co-workers and
cal approximation is applied at a critical configuration are on C4 H+ 8 by Bowers and collaborators. The latter study
called transition-state theories, while those in which the provided validation of an important variant of statistical
product states accessible by energy and angular momen- theory called the “transition state switching” model.
tum conservation are populated with equal probability are
called phase-space theories.
One of the earliest statistical theories of unimolecular B. Bimolecular Reactions
decay of ionic species, developed explicitly to interpret
1. Ion-Neutral Collision Cross Sections and Rates
mass spectra, is the quasi-equilibrium theory (QET). In
the QET, the electronically excited molecular states that Langevin (1905) provided the first theoretical description
are accessed by the primary ionization event decay rapidly of the collision frequency between an ion and a neutral
by internal conversion to the ground state of the ion, where species in terms of the long-range potential between these
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78 Ion Kinetics and Energetics

species. The sum of the long-range attractive electrostatic below the LGS limit. The interpretation of such slow re-
potential and the repulsive 1/r 2 centrifugal potential re- actions has been the subject of numerous investigations.
sults in a barrier as the reactants approach. For every col- Brauman and co-workers have proposed a model of ionic
lision for which the relative kinetic energy exceeds this reactions that proceed on potential energy surfaces with
centrifugal barrier, reaction is assumed to occur. For an two minima separated by a barrier lower than the entrance
ion of charge e approaching a neutral collision partner channel energy. A schematic surface with these features
with polarizability α, the long-range potential behaves as is shown in Fig. 1. As the reagents approach under the
1/r 4 and the Langevin capture cross section is given by influence of the long range attraction, they enter the first
1/2
well, the electrostatically bound encounter complex. For
2α reaction to occur, this complex must undergo an atom or
σLangevin = πq , (42)
µE T functional group transfer over a barrier to a second bound
where the relative collision energy is E T and the reduced species that is a precursor to products. When this barrier
mass of the approaching reactants is µ. The thermal aver- height is below the energy of the approaching reagents,
age of this cross section over the relative speed distribution the barrier is not an energetic bottleneck to reaction, but
at a fixed temperature yields the Langevin–Gioumousis– the low density of states for crossing the barrier may re-
Stevenson (LGS) rate constant expression, duce the rate for this process below that for decomposition
of the initial encounter complex back to reagents. When
1/2
α the branching ratio for decay of this encounter complex
kLangevin = 2πe , (43) favors production of the reactants, the reaction efficiency
µ
drops significantly below the LGS prediction. By model-
a result that is independent of temperature. For neutral col- ing complex formation and decomposition reaction rates
lision partners with permanent dipole moments, the long- using statistical RRKM theory and computing reaction ef-
range potential also has a charge-dipole term that behaves ficiencies as a parametric function of the intermediate bar-
as r −2 cos θ, where θ is the angle between the relative rier height, one can determine barrier energies for many
velocity vector and the axis of the dipole. Several mod- potential surfaces, correlating them with structural fea-
els have been proposed to account for interaction of the tures of the reactants.
charge with the dipole, the most successful of which is the A particularly important reaction that has been exam-
average dipole orientation (ADO) model. This model pos- ined in the context of the double minimum potential model
tulates that the electric field of the approaching ion does is the gas-phase nucleophilic substitution reaction, written
not fully quench the rotational motion of the dipole and symbolically as
results in a partial locking of the dipole orientation. The
ADO cross section is given by the following expression: X− + CH3 Y −→ Y− + CH3 X, (45)

πq 2 α 2πqµD where X and Y are halogen atoms. Experimental work

σ (ν) = πrc2 + + cos θ. (44) from the research groups of Bowers, Johnson, and
rc2 µν 2 µν 2
Brauman has provided critical confirmation of this dou-
The quantity rc is the distance at the top of the centrifu- ble minimum potential model by trapping the electrostatic
gal barrier for the full effective potential, and the bar de- complexes, activating them, and observing their decom-
notes that the cross section is computed as an average over position to reactants or products. Experiments by Bowers
the orientation the permanent dipole µD makes with re- and collaborators have focused attention on the Cl− +
spect to the relative velocity vector of magnitude v. Both CH3 Br system, with overall reaction as follows:
the Langevin and the ADO models predict thermal en- −−→ −−→
Cl− + CH3 Br ← −
−
− [Cl · CH3 Br] ← −
−
− [Br · CH3 Cl]
ergy cross sections of magnitude 10−16 −10−15 cm2 , corre-
sponding to rates in excess of 10−9 cm3 molecule−1 sec−1 . A B
These predictions were tested in pioneering experiments −−
→ −
by Laudenslager and Bowers in the early 1970s that ←−− Br + CH3 Cl (46)
estimated the extent of dipole locking, demonstrating This reaction is known to occur with approximately 1%
the general validity of such capture theories at thermal efficiency at thermal energies. In addition, the height of
energy. the isomerization barrier separating intermediates A and
The capture hypothesis forms the basis for the LGS B, as estimated from RRKM calculations, lies approx-
model for ion-neutral reactions and many exothermic re- imately 0.085 eV below the energy of the approaching
actions appear to proceed at the collision frequency. De- reagents. In the experimental work, the electrostatically
spite the appeal and widespread validity of the LGS model, bound complex corresponding to the entrance channel is
a number of ion-neutral reactions have rates significantly produced in a high-pressure ion source with a narrow range
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Ion Kinetics and Energetics 79

FIGURE 1 Double-minimum reaction coordinate showing formation of complex A with rate k1 . The sparse level
density for crossing the intermediate isomerization barrier to B with rate constant k2 makes this rate low in comparison
with nonreactive decay to reactants, with rate constant k−1 .

of internal energies and is injected into a reverse geometry arly important testing ground for such concepts. Exper-
sector mass spectrometer. To be detected in the time win- imental methods employing liquid helium-cooled drift
dow of these experiments, the metastable ion Cl− ·CH3 Br tubes, Penning traps, and supersonic expansions such as
must be formed with internal energies between about 0.4 the CRESU (Cinetique de Reaction en Ecoulements Su-
and 0.5 eV. The lower limit corresponds to the height of personiques Uniformes) wind tunnel instrument have al-
the isomerization barrier, while ions produced with inter- lowed studies of ion-neutral interactions at temperatures
nal energies of more than 0.5 eV decay on a time scale as low as 3 K. At these temperatures, radiative association
very fast in comparison with the 10-µsec transit time to and three-body association reactions become important,
the second field-free region of the mass spectrometer. Ions as well as bimolecular processes. Recent low-temperature
with this distribution of internal energies yield the prod- studies of such collisional processes include the reaction
ucts Br− + CH3 Cl. The data also allow a determination of N+ with molecular hydrogen and its isotopomers. Al-
of the kinetic energy release distribution (KERD) for the though the magnitudes of the rotational energies of the
reaction, thus providing a test of the statistical assump- neutral reactants, the spin-orbit electronic energies of N+ ,
tion inherent in RRKM or phase-space treatments of the and the zero-point energy differences among H2 , HD, and
dynamics. D2 are fairly small, they are significant compared to the
magnitude of the collision energy at low temperatures
and provide sensitive tests of quantum theories of capture
2. Low-Temperature Dynamics
processes.
At very low temperatures, quantum mechanical effects Such quantum capture theories in three dimensions have
that classical electrostatic capture models fail to account been developed to solve the Schrödinger equation for the
for play a critical role in determining reaction rates. Ion long-range attractive entrance channel potential in a cou-
chemistry at temperatures below 80 K is especially im- pled rotational-states formalism. A rotationally adiabatic
portant in elucidating the role of such quantum effects; approximation to this theory has been developed by con-
molecule formation in the interstellar medium is a particul- structing potential curves that describe the evolution of
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80 Ion Kinetics and Energetics

isolated rotational states of molecular reagents into hin- v + = 3 and 4, agreement with the Langevin result is better.
dered rotor states of the ion–molecule complex. The re- At these levels of vibrational excitation, Franck–Condon
action probability of that reagent rotational state is unity factors make the charge transfer process less favorable,
when the collision energy lies above a particular adia- and the total cross section is more closely described by the
batic curve and zero when the curve rises above the col- N+2 + H2 long-range potential. Above a collision energy of
lision energy. The cross section is computed by summing 0.09 eV, the reactive cross section rises above the Lange-
over capture probabilities for the rotationally adiabatic vin value as endothermic charge transfer channels open.
curves. These theories yield improved agreement with ex- The most detailed probe of an ion–molecule reaction
perimental data on ion–dipole collision processes, at low is the state-to-state cross section. The measurement of
temperatures. angularly resolved state-to-state cross sections has been
achieved only for reactants in their ground state, but true
state-to-state total cross sections have now been measured
3. Vibrational-State Resolution
in a few favorable cases. A particularly novel method for
in Ion–Molecule Reactions
product state determination with reactant state selection
Since the pioneering experiments of Chupka and co- has been developed by Ng. In the differential reactivity
workers, which employed single-photon VUV ioniza- method, product vibrational states are distinguished by
tion of molecular hydrogen to prepare H+ 2 with a spe- their differing cross sections for charge transfer with se-
cific amount of vibrational excitation, the field of study lected molecules. The charge transfer reaction
of ion–molecule reaction dynamics with vibrationally
state-selected reactants has experienced a number of H+ + +
2 (v ) + H2 −→ H2 + H2 (v ), (48)
advances. Another important system in the history of in which H+ +
2 is prepared in v = 0 and 1 by VUV photoion-
ion–molecule reactions is the hydrogen atom transfer ization provides a particularly good example of its power.
process (47): The H+ 2 charge transfer products, formed in v = 0–3, are
N+ +
2 + H2 −→ N2 H + H. (47) first mass analyzed, accelerated to 10 eV, and then passed
through a collision cell containing N2 , Ar, or CO, where
A recent study of this system, in which the N+ reactant charge transfer occurs once again. The N+ + +
2 , Ar , or CO
2
is produced in the ground electronic state in a single ro- products are mass analyzed and the cross sections σm for
tational state (J = 2) and with vibrational quantum num- forming these ions by charge transfer from the H+ 2 reaction
ber v + varied between 0 and 4 has been performed by products are measured. The charge transfer cross sections
the group of Kompa. The reactant ions are produced by for H+2 with these gases have different dependences on v ,
(2 + 1) REMPI on nitrogen gas in a pulsed supersonic and therefore the gases can be used to probe the product
expansion. The spectroscopic method for ion production states of H+2 formed in the symmetric charge exchange
is a one-color scheme that employs high vibrational lev- reaction. Letting X v denote the fraction of H+ 2 formed in
els, v =10−14, of the two-photon allowed a 1 g state the vibrational state v , the following set of simultaneous
of N2 having a lifetime of 120 µsec, followed by absorp- equations can be solved for X v , since the cross sections
tion of a third photon to produce the desired N+ 2 reactant σv are known and the σm s are measured:
ions. This state-preparation scheme requires photons in the
wavelength range near 237 nm and is employed in con- X 0 + X 1 + X 2 + X 3 = 1, (49)
junction with octupole ion guides and a scattering gas cell
to determine total cross sections for chemical reaction of X 0 σ0 (N+ + +
2 ) + X 1 σ1 (N2 ) + X 2 σ2 (N2 )
N+ +
2 formed in vibrational states v = 0–4 over the trans-
lational energy range from 0.01 to 2 eV in the center of + X 3 σ3 (N+ +
2 ) = σm (N2 ), (50)
mass coordinates.
An unexpected result of this study was the observa- X 0 σ0 (Ar+ ) + X 1 σ1 (Ar+ ) + X 2 σ2 (Ar+ )
tion of a small activation barrier to reaction of magnitude
+ X 3 σ3 (Ar+ ) = σm (Ar+ ), (51)
0.01 eV. The data show a rise from this threshold and fol-
low an E −1/2 dependence over the collision energy range
from 0.02 to 0.09 eV. The cross sections appear to be larger X 0 σ0 (CO+ ) + X 1 σ1 (CO+ ) + X 2 σ2 (CO+ )
than the Langevin prediction, calculated with the polariz- + X 3 σ3 (CO+ ) = σm (CO+ ). (52)
ability of H2 , particularly for reactant ions with vibrational
excitation v + ≤ 2, and in fact are in much better agreement An extensive set of data at collision energies from 2 up
with the cross section computed for the attraction of the to 16 eV has been measured. When the reactant ions are
charge-transferred reactants H+ +
2 + N2 . For N2 ions with in the vibrational ground state, at low kinetic energies the
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Ion Kinetics and Energetics 81

charge transfer product is also in its ground state, indicat- C 2 H+ +

2 + CH4 −→ C3 H5 + H (H = −0.92 eV),
ing that resonant charge transfer is the dominant process.
At increasing collision energies, X 1 increases from 0.0 to (53)
0.17. For vibrationally excited H+ 2 reactants, inelastic re- −→ C3 H+
4 + H2 (H = −1.33 eV),
laxation to form H+ 2 in v = 0 is important at all collision
energies, increasing in magnitude with increasing colli- (54)
sion energy. Of particular interest is the fact that inelastic −→ C2 H+
3 + CH3 (H = +0.02 eV).
relaxation forming v = 0 is substantially more important
than inelastic excitation producing v = 1 or 2. This trend (55)
is predicted by theory but underestimated at lower colli- The condensation reactions (53) and (54) forming new
sion energies. C–C bonds are exothermic, proceeding through a colli-
More recently, methods based on laser preparation of sion complex, and, as expected, show very little effect of
reagent ions and laser-based detection of product ions have vibrational energy. The hydrogen atom transfer reaction
been accomplished for the thermal energy charge transfer (55), is mildly endothermic, however, and shows a sig-
reaction DBr+ + HBr → HBr+ + DBr. REMPI was used nificant vibrational effect. With bending excitation in the
to prepare DBr+ in specific vibrational and spin-orbit reactants, the cross section for C2 H+ 3 formation shows a
states, and the HBr+ product state was measured by laser- significant enhancement, with the data showing that this
induced fluorescence. The largest rate constants were ob- form of excitation increases the cross section at the lowest
served for near-resonant processes in which both the vi- collision energies by a factor of 30 relative to ground-state
brational and the spin-orbit quantum numbers remained ions. Moreover, excitation of the bending mode increases
unchanged. the selectivity of formation of the C2 H+3 product relative to
the C3 condensation products dramatically near threshold.
4. Mode-Selective Chemistry Anderson and co-workers hypothesize that the selective
enhancement of C2 H+ 3 production arises from the fact that
One of the objectives of quantum state selection is to en- formation of C2 H+ from C 2 H+
3 2 requires rehybridization
hance the rates of chemical transformation by exciting of the carbon atoms in C2 H+ from linear sp to trigonal sp2 ,
2
molecular motions correlated with the formation of par- and bending excitation facilitates that motion. This work
ticularly desirable (and perhaps non-statistically favored) represents one of the clearest demonstrations of the role
reaction products. In the H+ 2 + He system, the activation of selective vibrational excitation in promoting a specific
barrier occurs late, after the collision system has “turned reaction to date.
the corner” of the potential energy surface. Thus, H+ 2 vi- Another recent example of mode-selective chemistry
brational motion is directed along the reaction coordinate comes from the laboratory of Zare and co-workers on col-
at the saddle point and is effective in promoting reaction. lisions of state-selected NH+ 3 with ND3 , the products of
In polyatomic species, the issue of enhancement becomes which are shown below:
more complex because rapid intramolecular vibrational
relaxation may dissipate selective excitation on a time NH+ +
3 + ND3 −→ NH3 D + ND2 , (56)
scale fast compared to reaction. Vibrational energy may
also be expected to play specific roles that depend on the −→ NH+
3 + ND+
3, (57)
nature of the atomic motions in a given normal or local −→ NH2 + ND3 H+ . (58)
mode. Recent research by Anderson and co-workers on
C2 H+2 reactant ions produced by REMPI methods has pro- The ammonia cation, NH+ 3 , is readily prepared by
vided another example of mode-selective enhancement of (2 + 1) REMPI through the B̃ and C̃ Rydberg states of
chemical reactions. REMPI methods have been demon- NH3 . Because the ammonia molecule is pyramidal in the
strated to prepare C2 H+ 2 in the ground electronic and vi- ground state and planar in the B̃ and C̃ Rydberg states and
brational states, as well as with excitation in the ν2 C–C in the ion, (2 + 1) REMPI produces NH+ 3 in a progres-
stretching mode and with two quanta in the bending ex- sion in the ν2 umbrella bending mode. The ν1 breathing
citation. This state selection is accomplished with (2 + 1) mode corresponds to symmetric elongation and compres-
ionization through Rydberg states of gerade symmetry; sion of all three N–H bonds. By control of the excitation
bending modes promote vibronic coupling of neighboring wavelength, isoenergetic states of NH+ 3 with pure ν2 um-
Rydberg states and, therefore, become optically accessi- brella excitation or combinations of ν1 breathing and ν2
ble in the ionization process. State-selected reactant ions umbrella motion can be prepared. Two particular combi-
produced in this way have been studied in reaction with nations of states have been examined in detail: the state
CH4 as shown below: with one quantum of breathing excitation and two quanta
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82 Ion Kinetics and Energetics

of umbrella excitation (denoted ν1 = 1, ν2 = 2, or 11 22 ), attenuation of ions with a particular mobility and therefore
with 0.63 eV of internal energy, and the state with no in a particular electronic state.
breathing excitation and five umbrella quanta, denoted The reaction of Fe+ with propane, C3 H8 , is a particu-
10 25 , with a total internal energy of 0.60 eV. Because larly interesting system with rich chemistry. In ion chro-
the two state preparations have essentially the same in- matography experiments, the Fe+ ions are prepared by
ternal energy, their differential reactivities can address the electron impact on Fe(CO)5 , and the electronic state dis-
question of whether the magnitude the internal energy is tribution is controlled with the ionizing electron beam en-
sufficient to effect a particular reaction or if the form of the ergy. The 6 D (4s3d6 ) ground state of Fe+ exhibits a high
internal motion in the reactants plays an important role. rate for formation of the adduct Fe+ · C3 H8 without addi-
All three of the reactive channels of NH+ 3 with ND3 are
tional reaction, while the 4 D (4s3d6 ) and 4 F (3d7 ) excited
direct processes that do not involve the intermediacy of a states exhibit subsequent elimination of H2 and CH4 . The
transient complex and, thus, represent good opportunities system is particularly interesting in that it is one of a very
for demonstrating mode-specific dynamics. A compari- few that have been studied with all three methods of elec-
son of the reactive cross section for the isoenergetic states tronic state preparation, and agreement among the differ-
11 22 and 10 25 shows that deuterium abstraction and charge ing studies is excellent.
transfer are enhanced, and proton transfer is suppressed
by the 10 25 excitation, i.e., the state with enhanced um-
brella excitation. In addition to comparing the reactivity
SEE ALSO THE FOLLOWING ARTICLES
of different isoenergetic vibrational state preparations, the
CHEMICAL KINETICS, EXPERIMENTATION • DIELECTRIC
study also compares the effect of vibration with equiva-
GASES • ION TRANSPORT ACROSS BIOLOGICAL MEM-
lent amounts of translational energy, demonstrating that
BRANES • KINETICS (CHEMISTRY) • MASS SPECTROM-
ν2 umbrella excitation is four times more effective in pro-
ETRY • POTENTIAL ENERGY SURFACES
moting deuterium transfer than an equivalent amount of
translational energy.
BIBLIOGRAPHY
5. Electronic State Selection
Armentrout, P. B. (1990). “Electronic state-specific transition metal ion
Electronic excitation of atomic ions provides numerous chemistry,” Annu. Rev. Phys. Chem. 41, 313.
opportunities to observe dramatic effects in both the over- Armentrout, P. B., and Baer, T. (1996). “Gas phase ion dynamics and
chemistry,” J. Phys. Chem. 100, 12866.
all rates of reaction of such species and the distributions of Baer, T., Ng, C. Y., and Powis, I. (eds.) (1996). “The Structure, Energetics,
products in these reactions. Three fundamental methods and Dynamics of Organic Ions,” Wiley, New York.
have been applied to the production of electronically state- Bowers, M. T. (ed.) (1979, 1980). “Gas Phase Ion Chemistry,” Vols. 1–3,
selected ions. The first method compares the reactivities of Academic, Press, New York.
different distributions of electronic states resulting from Cooks, R. G., Koskinen, J. T., and Thomas, P. D. (1999). “The kinetic
methods of making thermochemical determinations,” J. Mass Spec-
ions produced in different ways, e.g., electron impact ion- trom. 34, 85.
ization and thermal ionization. The second method uses Farrar, J. M. (1995). “Ion reaction dynamics,” Annu. Rev. Phys. Chem.
REMPI for atoms whose Rydberg states are unperturbed 46, 525.
by configuration interaction and autoionization. The Farrar, J. M., and Saunders, W. H., Jr. (eds.) (1988). “Techniques for the
final method, referred to as “ion chromatography,” uses Study of Ion-Molecule Reactions,” Wiley–Interscience, New York.
Lias, S. G., and Bartmess, J. E. (1997). “Gas-Phase Ion Thermochem-
the differing mobilities of metal ions with different elec- istry,” National Institute of Standards and Technology, Washington,
tronic configurations in He. Particularly large differences DC. http://webbook.nist.gov/chemistry/ion/.
are observed when vacancies are created in valence s or- Ng, C. Y., and Baer, M. (eds.) (1992). “State-Selected and State-to-State
bitals. By injecting a short pulse of ions into a helium-filled Ion-Molecule Reaction Dynamics, Part 1: Experiment,” Vol. LXXXII
cell with a uniform drift field, the ions separate spatially in Advances in Chemical Physics, Wiley–Interscience, New York.
Ng, C. Y., Baer, T., and Powis, T. (eds.) (1994). “Unimolecular and
and temporally as they diffuse through the cell. Electronic Bimolecular Ion-Molecule Reaction Dynamics,” Wiley, New York.
state-specific chemistry can be examined by introducing Thomson, J. J. (1913). “Rays of Positive Electricity,” Longmans Green,
small amounts of a reagent gas and observing the selective New York.
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Kinetics(Chemistry)
Keith J. Laidler
University of Ottawa

I. Basic Kinetic Principles

II. Molecularity
III. Temperature and Reaction Rates
IV. Statistical Theories of Rates
V. Reaction Dynamics
VI. Reactions in the Gas Phase
VII. Reactions in Solution
VIII. Reactions on Surfaces
IX. Composite Reaction Mechanisms
X. Photochemical and Radiation-Chemical
Reactions
XI. Homogeneous Catalysis

GLOSSARY Composite (complex or stepwise) reaction A reaction

that involves more than one elementary reaction.
Activated complex Configuration of atoms correspond- Elementary reaction Reaction in which no reaction
ing to an arbitrarily small region near to the col in a intermediates (other than transition species) have been
potential energy surface. detected or need to be postulated in order to explain the
Activation energy Energy defined by the equation behavior.
d ln k Half-life Time required for a reactant concentration to
E = −R , reach a value that is the arithmetic mean of its initial
d(1/T )
and final values.
where k is the rate constant, T the absolute temperature, Inhibition Process by which a substance (called an
and R the gas constant. This energy is related to the inhibitor) reduces the rate of a chemical reaction.
heights of energy barriers to reaction. Molecularity Number of reactant particles (atoms,
Catalysis Substance that increases the rate of a chemical molecules, free radicals, or ions) that are involved in the
reaction without itself being consumed, and without microscopic event occurring in an elementary reaction.
affecting the energetics of the overall reaction, is called Order of reaction For some reactions the rate of reaction
a catalyst. The process is called catalysis. is expressible as

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178 Kinetics (Chemistry)

v = k[A]α [B]β concentrations, temperature, and pressure. The ultimate

objective of a chemical-kinetic investigation is to gain
where k, α, and β are independent of concentration information about the mechanisms of chemical reactions.
and time. The exponent α is the order with respect to Such information is also provided by certain nonkinetic
A, and β is the order with respect to B. These are partial studies, but little can be known about the mechanism of
orders; the sum of the partial orders, often written as n, a reaction until its kinetics have been investigated. Even
is the overall order. then, some doubt must remain about a reaction mecha-
Photochemical reaction Chemical reaction brought nism; an investigation, kinetic or otherwise, can disprove
about by electromagnetic radiation having insufficient a proposed mechanism but cannot establish a mechanism
energy to bring about ionization. with absolute certainty. Chemical kinetics has very far-
Potential energy surface Surface resulting from a plot of reaching implications in that it relates to many branches
potential energy against two parameters, such as two of biology, geology, engineering, and even psychology.
interatomic distances. If more than two parameters are Theories of chemical kinetics are also applicable to purely
used the term hypersurface is employed. physical processes, such as flow processes.
Pre-exponential factor The factor A when the rate con-
stant is expressed as
I. BASIC KINETIC PRINCIPLES
k = Ae−E/RT ,
where E is the activation energy. Several rates can be defined with reference to a chemical
Rate of reaction Rate of formation of a product, d[Z ]/dt, reaction. Substances whose concentrations decrease with
or the rate of consumption of a reactant, −d[A]/dt, time are known as reactants, and the rate of decrease of a
divided by the corresponding coefficient in the reactant concentration is known as the rate of consumption
stoichiometric equation. (removal or disappearance) of that reactant. Concentration
Rate constant For a reaction having an order, the rate is amount of substance (S.I. unit: mol) divided by volume
constant k is the constant appearing in the rate equation. (S.I. unit: m3 ), and the concentration of a substance A is
Radiation-chemical reaction Chemical reaction bro- conveniently written as cA or [A]. The rate of consumption
ught about by electromagnetic or particle radiation hav- of A is thus defined as
ing sufficient energy to bring about ionization. vA = −d[A]/dt. (1)
Reaction cross-section Quantity that is used in collision −3 −1 −3 −1
Its S.I. unit is mol m s , but mol dm s (also written
theory to give a measure of the rate of a bimolecular as mol L−1 s−1 or as M s−1 ) is more commonly used.
reaction; it is the probability of reaction multiplied by Rates of consumption of two reactants A and B are
π d 2 , where d is the collision diameter (i.e., the dis- only the same if 1 mol of A reacts with 1 mol of B. If, for
tance between the centers of two colliding reactant example, the stoichiometric equation is of the type
molecules).
Reaction (or molecular) dynamics A field that deals A + 2B → Y + Z,
with the intermolecular and intramolecular motion that the rate of consumption of B is twice the rate of consump-
occurs during the course of a chemical reaction and the tion of A.
quantum states of the reactant and product molecules. The rate of formation of a product of reaction is de-
State-to-state kinetics Study of the transformation of re- fined as the rate of increase in its concentration: thus for
acting molecules in specified quantum states into prod- a product Z
uct molecules in specified quantum states.
vZ = d[Z]/dt. (2)
Steady-state treatment Application of the hypothesis
that for an intermediate X present at very low con- Again, the rates of formation of different products are not
centrations, d[X]/dt = 0. always the same, nor are they necessarily equal to the rates
Transition-state theory Theory of rates that focuses of consumption of reactants. Thus if the stoichiometry of
attention on activated complexes and assumes them to the reaction is
have a concentration corresponding to equilibrium with 3A + B → 2Y + Z,
the reactant molecules.
Transition species Species having a state intermediate and this stoichiometry is preserved throughout the course
between reactants and products. of reaction,
vA vY
= vB = = vZ (3)
3 2
CHEMICAL KINETICS deals with the rates of chemi- The S.I. unit is the same for all of these rate expressions,
cal processes and how the rates depend on factors such as and mol dm−3 s−1 is most commonly used.
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Kinetics (Chemistry) 179

Sometimes, but not always, it is possible to define a α + β + · · · , is known as the overall order and is often
quantity, known as the rate of reaction, which is inde- given the symbol n.
pendent of the reactants and products. This can only be A simple case is when the rate equation is given by
done if the reaction is of known stoichiometry; for some
v = k[A] (6)
reactions there are numerous minor products and the sto-
ichiometry is uncertain. Another condition for defining a An example of such a first-order reaction is the conversion
rate of reaction is that the stoichiometric equation must re- of cyclopropane into propylene
main the same throughout the course of reaction: for some
reactions intermediates are formed in significant amounts,
and the stoichiometry varies as the reaction proceeds. If
these two conditions are satisfied (i.e., if the stoichiometry
is known and is time independent), the rate of reaction is A second-order reaction can involve a single reactant;
given by any of the expressions that appear in Eq. (3). In
v = k[A]2 , (7)
other words, the rate of reaction is the rate of consump-
tion or formation divided by the appropriate coefficient or two reactants,
that appears in the stoichiometric equation. In the case of
v = k[A][B]. (8)
products these coefficients are called the stoichiometric
coefficients; in the case of reactants the stoichiometric co- In the latter case the partial orders are unity, and the overall
efficients are the negatives of the coefficients in the rate order is two. The process
equation. As seen in Eq. (3), this division has made the
H2 + I2 2HI
four rates equal to one another, so that the rate of reaction
is unique for the reaction under the particular conditions is an example, being second order in both directions. Re-
of the experiment. action orders are not necessarily integral; in the case of
It is important to note that rate of reaction, unlike rates the acetaldehyde decomposition, for example,
of consumption and formation, only has meaning with
CH3 CHO → CH4 + CO
reference to a specified stoichiometric equation for the
reaction. Thus, if the stoichiometric equation had been the order is :
3
2
written as
v = k[CH3 CHO]3/2 . (9)
3
2 A+ B→Y+ Z
1
2
1
2
This failure of the kinetics to correspond to the stoichiome-
the rate of reaction would be try indicates that the reaction occurs by a composite mech-
anism, the nature of which is considered in Section IX.
v = 23 vA = 2vB = vY = 2vZ (4)
The constant k that appears in the preceding equations
and would therefore be twice the rate specified with refer- is known as the rate constant. Its units depend on the order
ence to the first form of the equation. of reaction. Thus, if a reaction is first order [Eq. (6)] and
Note also that some kineticists define rates with refer- v is expressed as mol dm−3 s−1 and [A] as mol dm−3 ,
ence to the rates of change of amounts of substances rather the unit of k is s−1 . Similarly, for the second-order reac-
than their concentrations; the S.I. unit is then mol s−1 , there tion the unit of k is usually dm3 mol−1 s−1 . Just as rates
being no division by volume. of consumption and formation depend, in general, on the
In general, rates depend on concentrations of reactants reactant or product under consideration, so do the cor-
and sometimes on concentrations of products and other responding rate constants. The rate constant that derives
substances. For some reactions the rate of reaction v can from the rate of reaction, for a specified stoichiometric
be expressed by an equation of the form equation, is unique.
By no means do all equations have rate equations of the
v = k[A]α [B]β , (5)
type shown in Eq. (5). Sometimes reactant concentrations
where k, α, and β, are independent of concentration and appear in the denominator of the rate equation, and this is
time. Similar equations apply to rates of consumption and indicative of a composite mechanism.
formation. The exponent α is known as the order of reac- If a chemical reaction is sufficiently slow it is possible
tion with respect to A. The term order was introduced in to mix reactants together or to raise the temperature of the
1887 by F. W. Ostwald (1853–1932), but the concept of or- reaction system very rapidly so as to start the reaction,
der had been used in 1884 by J. H. van’t Hoff (1852–1911). and then to measure concentrations of reactants or prod-
Similarly the exponent β is the order with respect to ucts at various times. Such concentrations may be mea-
B. When there is more than one such order, as in this sured by chemical methods or by physical methods such
example, each one is called a partial order, and their sum, as spectrophotometry. Two procedures are then available
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180 Kinetics (Chemistry)

for determining orders of reactions and rate constants. One called catalysis, this name having been coined in 1836
method is the method of integration, which involves inte- by J. J. Berzelius (1779–1848). Catalysis can be classi-
grating the differential equation for the rate and obtaining fied as homogeneous catalysis (Section XI) in which only
expressions for concentrations of reactants and products one phase is involved, and as heterogeneous or surface
as a function of time. This integrated equation, which de- catalysis (Section VIII) in which the reaction occurs at
scribes the time course of the reaction, is then fitted to the an interface between phases. In biological systems catal-
experimental results. ysis is brought about by enzymes, which are proteins: the
A second method, the differential method, involves de- action is sometimes homogeneous and sometimes hetero-
termining rates from the slopes of concentration–time geneous. A special type of catalysis, brought about by the
curves. An analysis is made of the way in which the rates product of a reaction, is known as autocatalysis. For ex-
depend on the concentrations of reactants, and the order ample, ester hydrolysis is catalyzed by acids, which are
and rate constant can then be deduced. products of the reaction; the process may therefore first
For rapid chemical reactions special methods must be accelerate. The term catalyst is sometimes applied to a
used. For reactions that are not extremely rapid, flow substance that is consumed but which in other ways acts
methods are useful. Reactants may be mixed together like a catalyst: such substances, however, are better called
in specially designed vessels and then passed along a pseudocatalysts or activators. Mechanisms of catalysis are
tube, concentrations being measured at various positions considered in Sections VIII and XI.
by physical techniques such as spectrophotometry which An inhibitor is a substance that reduces the rate of a
allow instantaneous determinations to be made. A com- chemical reaction. Such substances were formerly called
monly used technique is the stopped-flow method, in negative catalysts, but this terminology is not recom-
which reactants are mixed and the flow suddenly stopped, mended since their action is quite different from that of a
so that the mixture is trapped in a vessel in which, by phys- true catalyst. Inhibitors, in fact, act either by interacting
ical methods, concentrations can be studied as a function with a catalyst and rendering it less effective or by remov-
of time. The results can be analyzed by suitable adapta- ing active intermediates such as free radicals. The term
tions of either the method of integration or the differential inhibitor is often applied to substances that are consumed
method. during the course of reaction. If a reaction in the absence
Some reactions, however, are so rapid that mixing can- of an inhibitor proceeds with a rate v0 , and in the presence
not be achieved sufficiently rapidly. For such reactions of inhibitor with rate v, the degree of inhibition is defined
the relaxation methods, such as the temperature-jump as
(T-jump) method may be used. They were developed in v0 − v v
1954 by M. Eigen (b. 1927). In this technique a reaction εi = =1− . (10)
v0 v0
system at equilibrium is subjected to a very rapid rise in
temperature which causes the equilibrium to shift (relax)
to a new position of equilibrium. Physical methods are II. MOLECULARITY
available for following the concentration changes during
this relaxation, and the results can be analyzed to give the Chemical reactions can be classified as either elementary
rate constants and the order of reaction. or composite. An elementary reaction is one which, as far
A quantity that has proved useful for comparing rates as can be determined, goes in a single stage; the reactants
of different reactions is the half-life, or half-period. The pass smoothly through an intermediate state and then be-
half-life of a given reactant is the time that it takes for come products. If a reaction is elementary no specific inter-
half of it to be consumed during the reaction. The way mediates can be detected or need to be postulated in order
in which the half-life depends on reactant concentrations to explain the kinetic behavior. Composite reactions, also
varies with the order of the reaction; for the special case of known as complex or stepwise reactions, occur in more
a first-order reaction there is no dependence of half-life on than one stage, and therefore involve two or more ele-
reactant concentration. For a reaction of any order the half- mentary reactions; they are considered in more detail in
life is inversely proportional to the rate constant; half-lives Section IX.
are therefore useful in giving an inverse measure of the rate For an elementary reaction, but not for a composite
of a reaction and can be used for comparing reactions of reaction, the term molecularity can be employed. The
different orders. molecularity of an elementary reaction is the number of
Sometimes the rate of a chemical reaction is affected reactant particles (atoms, molecules, free radicals, or ions)
by the addition of a substance that is not consumed in the that are involved in each individual chemical event. For
process and does not affect the equilibrium constant for example, the cyclopropane isomerization appears to be
the reaction. When the rate is increased in this way the elementary, in that each chemical act involves a single cy-
added substance is known as a catalyst, and the effect is clopropane molecule: the molecularity is unity, and the
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Kinetics (Chemistry) 181

reaction is said to be unimolecular. For the elementary resolved in favor of equations for which there was a useful
reaction physical interpretation.
One of the earliest equations relating the rate constant
Br + H2 → HBr + H,
k to the absolute temperature T was
the molecularity is two, and the reaction is said to be bi-
k = Ae DT or ln k = ln A + DT. (11)
molecular. A reaction having molecularity of three, such
as This equation was proposed in 1862 by M. Berthelot
2NO + Cl2 → 2NOCl (1827–1907). The parameters A and D are empirical quan-
tities, and this equation requires that a plot of ln k against
is said to be trimolecular. Reactions of higher molecu- the absolute temperature T will be linear, as is approxi-
larities are unknown: it is unlikely for more than three mately true in many cases. It is of interest that recently
molecules to come together in a single chemical event, (1982–1985) C. M. Hurd and co-workers have shown that
and instead the mechanism is composite. this equation is obeyed when a process occurs by quantum-
It is important to distinguish clearly between the molec- mechanical tunneling (see Section IV), and they have pro-
ularity and the order. The latter is a purely experimental vided an interpretation in terms of atomic vibrations.
quantity, which is concerned with how the rate depends In 1884 J. H. van’t Hoff presented the equation, derived
on reactant concentrations; the concept of order applies to from thermodynamics, for the temperature dependence of
some composite reactions. The molecularity of an elemen- an equilibrium constant K :
tary reaction, on the other hand, is arrived at by inference
d ln K H◦
from all of the evidence available about the reaction. One = , (12)
such piece of evidence is the order. If a reaction in the dT RT 2
gas phase appears to be elementary and has an order of where R is the gas constant and H ◦ the standard change
one, it is reasonable to conclude that it is unimolecular. in heat constant (enthalpy) during the overall process. He
However, as will be seen in Section VI, unimolecular gas then noted that an equilibrium constant is the ratio of rate
reactions become second order at low pressures, and it is constants for the reaction in forward and reverse direc-
therefore unsafe to conclude that a second-order gas reac- tions, his argument being as follows: If a reaction
tion is bimolecular: it may be a unimolecular reaction in
A+B Y+Z
its second-order region.
With reactions in solution the question arises as to is elementary in both directions, the rate from left to right
whether the solvent should be included in the molecularity. is k1 [A][B] and that from right to left is k−1 [Y][Z]. At
It is usually considered that it counts in the molecularity equilibrium the two rates are equal so that
if it enters into the overall reaction but not if it exerts only  
[Y][Z] k1
an environmental effect. Thus, a process in aqueous solu- = = K. (13)
tion in which a compound was being hydrolyzed, with the [A][B] eq k−1
reaction of a water molecule with each solute molecule, This being so, van’t Hoff argued, k1 and k−1 must show the
would be regarded as bimolecular. The isomerization of same kind of temperature dependence as K , and therefore
cyclopropane in solution, however, is unimolecular. for a rate constant k
Similar conventions are applied to reactions on surfaces. d ln k E
If individual molecules undergo decomposition or isomer- = , (14)
dT RT 2
ization on a surface the reaction is usually described as
unimolecular, even though the surface atoms are also in- where E is some energy term. van’t Hoff did not as-
volved. This, however, would not be done if the material sume that E itself is temperature independent but consid-
of the surface entered into the final products. ered several possibilities. If E is temperature independent
Eq. (14) integrates to
E
III. TEMPERATURE AND ln k = ln A −
RT
REACTION RATES or

A considerable number of empirical equations have been k = Ae−E/RT , (15)

proposed to express the dependence of reaction rates on
where A is a constant. Another possibility considered by
temperature, and for over 60 years—from about 1850 to
van’t Hoff is that E is linear in temperature; in that case
about 1910—there was much uncertainty and confusion.
the equation reduces to the form
The difficulty was that several of the proposed equations
fitted the data equally well, and the problem was finally k = AT m e−E/RT , (16)
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182 Kinetics (Chemistry)

where m is a constant. Most kinetic data fit this equation

very satisfactorily, and it is often used in modern compi-
lations of kinetic data. The reason that equations of such
different forms fit data reasonably well is that in kinetic
work the temperature range is usually quite limited.
In 1889 S. A. Arrhenius (1859–1927) showed that van’t
Hoff’s simplest equation [Eq. (15)] applied satisfactorily
to a number of results, and he also suggested a very simple
interpretation for the equation; consequently this equation,
although first given by van’t Hoff, is now always called the
Arrhenius equation. Arrhenius pointed out that increasing
the temperature by 10◦ C often approximately doubles the
rate of reaction, but that the average molecular energies
do not increase to anything like that extent. He concluded
that reaction rates cannot depend on the average molec-
FIGURE 2 Schematic Arrhenius plot of In k against 1/T. The
ular energies, and he postulated that a pre-equilibrium slope is −E/R, and the activation energy E is thus defined by
is first established between reactant molecules and some E ≡ −R [d ln k/d (1/T)].
highly energized intermediate. Thus, for a bimolecular re-
action between A and B the process would be represented
as that only those colliding molecules having joint energy in
excess of E are able to undergo reaction; other collisions
A+B AB∗ → Y + Z are ineffective, the reactant molecules merely separating
The intermediate complex AB∗ , being of high energy, is unchanged.
formed only in very small amounts, and its concentration The energy E that appears in Eq. (15) is known as the
increases strongly with increase in temperature. The rate activation energy or the energy of activation. The param-
is proportional to the concentration of AB∗ , and the large eter A, which has the same units as the rate constant, is
temperature coefficients are therefore explained. called the pre-exponential factor (formerly the frequency
Arrhenius’s interpretation is essentially correct, and it factor). The activation energy is obtained experimentally
was later made more precise by the application of sta- by plotting ln k against 1/T and measuring the slope, as
tistical procedures to reaction systems. Figure 1 shows shown schematically in Fig. 2; the slope is equal to −E/R.
the distribution of energy in a system, as given by the On the basis of a statistical argument it was shown in 1939
treatments of J. Clark Maxwell (1831–1879) and L. E. by R. H. Fowler and E. A. Guggenheim that the activation
Boltzmann (1844–1906). The fraction of molecules hav- energy obtained in this way is the average energy of the
ing energy in excess of a specified value E (per mole) is molecules actually undergoing reaction minus the average
e−E/RT , which is the fraction that appears in the Arrhenius energy of all of the reactant molecules.
equation [Eq. (15)]. The interpretation of the equation is The activation energy is conveniently considered with
reference to a potential energy surface, in which potential
energy is plotted against bond distances and angles. A
simple type of surface is obtained for a reaction
A + B—C → A—B + C
in which A, B, and C are atoms. The system A . . . B . . . C
requires three parameters to describe it; these might be the
A–B, B–C, and A–C distances, or two of the distances and
an angle. The potential energy would therefore have to be
plotted against three parameters, which would require a
four-dimensional diagram. Since such a diagram cannot
be constructed or visualized it is necessary to use a series
of three-dimensional diagrams in which one parameter has
been fixed at a particular value. For example, the A–B–C
FIGURE 1 Distribution of energy in a gas, according to the treat- angle might be fixed at 180◦ , and for some systems this is
ments of Maxwell and Boltzmann. the most probable configuration.
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Kinetics (Chemistry) 183

represented as X‡ . The state of an activated complex is

known as the transition state. Activated complexes play a
very important role in theories of reaction rates, as will be
seen in Sections IV and V.
The preceding discussion has been confined to a sys-
tem of three atoms, with the angle A–B–C held constant.
If more atoms are involved, it is necessary to consider po-
tential energy hypersurfaces for which there are more than
three dimensions. These can be dealt with by extensions of
the methods outlined; the data for the hypersurfaces can be
stored in a computer, and activated complexes can again
be identified. Sometimes much more complicated reac-
tion systems are treated in an approximate way in terms
of three-dimensional surfaces such as that shown in Fig. 3,
and such treatments, although not precise, are very helpful
FIGURE 3 Schematic potential energy surface for a reaction in considering the course of reactions.
showing the minimal reaction path (dotted line) and a typical tra-
jectory (dashed line).

IV. STATISTICAL THEORIES OF RATES

This type of three-dimensional diagram is conveniently
represented on a two-dimensional surface as a contour Most measurements of rates of chemical reactions are
diagram, and an example of such a diagram is shown made on bulk systems in which the reacting molecules are
in Fig. 3. The course of the reaction is then represented distributed over a range of energy states (cf. Fig. 1). Some
by motion of the system from the top left-hand region theories of reaction rates therefore focus on the bulk, or
to the bottom right-hand region. In the top left-hand re- macroscopic, systems. This requires them to be statistical
gion the A–B distance is large, and the configuration treatments.
therefore corresponds to A + B—C; in the bottom right- It is useful to consider theories of reaction rates in terms
hand region the B–C distance is large and the system is of the Arrhenius equation [Eq. (15)] which has two pa-
A—B + C. Many calculations have been made to de- rameters, the pre-exponential factor A and the activation
termine the general shapes of potential energy surfaces, energy E. If each one of these can be calculated from first
some of them involving pure quantum-mechanical theory principles a complete theory of rates has been attained. If a
and others introducing a certain amount of empiricism. potential energy surface has been calculated the height of
All of the calculations have shown that the surfaces for the barrier to reaction is known, and the activation energy
A . . . B . . . C systems are of the general form shown in can be deduced from this height (although it is somewhat
Fig. 3. The course of an individual reaction involves the difficult to do this precisely). Progress is being made to-
motion of the system along the lower part of a rising val- wards the reliable calculation of potential energy surfaces
ley until it reaches a col or saddle-point; then the system by quantum-mechanical methods, but success has so far
descends into another valley and finally reaches the state only been achieved for systems involving few nuclei and
A—B + C. The dotted line in the diagram shows what is electrons; no doubt the problems for more complicated
called the minimal reaction path, which corresponds to the systems will be overcome in the future.
path of steepest descent from the col into the two valleys. For the treatment of the pre-exponential factor A there
If it were to follow this minimal reaction path the system have been several useful treatments, and there has been
would make the least expenditure of energy. In reality, much more success in calculating values that agree with
however, systems will follow a variety of reaction paths, experiment.
or trajectories, depending on the initial conditions of the The first of these was simple collision theory, in which
reactants A and B–C. A typical trajectory is illustrated by reacting molecules were treated as if they were hard
the dashed line in Fig. 3. This particular trajectory leads to spheres, and the frequencies of their collisions were
considerable vibrational energy in the product molecule calculated on the basis of kinetic theory. This treatment
B–C, a matter that is referred to further in Section V. leads to a collision frequency factor z, and the rate con-
Those configurations of atoms that correspond to an stant is then obtained by multiplying z by e−E/RT , which is
arbitrary small region near the col of a potential energy the fraction of collisions in which there is sufficient energy
surface are known as activated complexes, and are often for reaction to occur:
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184 Kinetics (Chemistry)

k = ze−E/RT . (17) face has been calculated. If it has not, the parameters can
usually be estimated sufficiently well to lead to useful ap-
A particularly clear formulation of this kind was presented proximate rate constants.
in 1918 by W. C. McC. Lewis (1885–1956), and on its basis The second procedure is to employ a thermodynamic
he calculated a value of the pre-exponential factor for the formulation. The equilibrium constant K ‡ can be ex-
reaction 2HI → H2 + I2 that was in excellent agreement ‡
pressed as e− G/RT , where ‡ G, known as the Gibbs en-
with experiment. ergy of activation, is the change in Gibbs energy when the
However, later work showed that rather large devia- reactants become activated complexes. The Gibbs energy
tions from experiment are obtained for reactions in which of activation can, in turn, be expressed as ‡ H − T ‡ S,
the reacting molecules are more complicated. This col- where ‡ H is the enthalpy of activation and ‡ S the en-
lision theory is evidently too simple and unlikely to be tropy of activation. The rate constant k can thus be formu-
generally reliable. One weakness is the assumption that lated as
molecules are hard spheres, which implies that any col- kT − ‡ G/RT
lision with sufficient energy will lead to reaction; if the k= e
h
molecules are more complicated, this is not the case. A
more fundamental objection to the treatment is that when KT ‡ S/R − ‡ H/RT
= e e . (19)
applied to forward and reverse reactions it cannot lead to h
an expression for the equilibrium constant that involves This equation is of the same form as Eq. (16); the factors
‡
the correct thermodynamic parameters. More recent work e− H/RT corresponds to e−E/RT , while the pre-exponential
‡
has involved a similar approach but has treated molecular factor (kT / h)e S/R shows dependence on temperature.
collisions in a more realistic and detailed way. ‡
However, H is not quite the same as the activation en-
The most successful of the later statistical treatments ergy E, but adjustments can easily be made for different
has been transition-state theory, first formulated simulta- types of reactions.
neously and independently in 1935 by H. Eyring (1901– Much effort has gone into testing the validity of the
1981) and by M. G. Evans (1904–1952) and M. Polanyi original formulation of transition-state theory (now often
(1891–1976). Transition-state theory treats the rates of referred to as conventional transition-state theory) and to
elementary reactions as if there were a special type of improving it or proposing alternative theories. Useful ex-
equilibrium, having an equilibrium constant K ‡ , between tensions of the theory have been suggested, some of them
reactants and activated complexes. The rate constant is involving locating the activated complex at a position other
then given by than at the col in the potential energy surface. Improve-
k = (kT / h)K ‡ , (18) ment has been achieved, but only at the cost of making very
extensive calculations and making assumptions the justi-
where k is the Boltzmann constant (the gas constant per fication for which is not always entirely clear. In addition
molecule) and h is the Planck constant. This assumption to these extensions of conventional transition-state theory
of equilibrium can be justified in most cases, but it breaks there have been some entirely different approaches, such
down for certain types of potential energy surfaces, and as the dynamical treatments to be considered in Section V.
particularly when the barrier is low so that the reaction is Imperfect as it is—as are all scientific theories—
rapid. An important and simplifying feature of transition- conventional transition-state theory is of importance in
state theory is that it focuses attention on the activated providing a conceptual framework with the aid of which
complex. How the system reaches the transition state and much insight is gained into how chemical reactions occur.
how it behaves after reaching the transition state, is not It is possible without even making any numerical calcu-
considered to affect the rate of reaction. lations to make qualitative predictions of many important
The equilibrium constant K ‡ can be treated in two kinetic effects. So far no alternative treatment has provided
different but equivalent ways. In the first procedure, the any such insight.
methods of statistical mechanics are used. Equilibrium Sometimes chemical reactions occur to some extent
constants can be calculated reliably in terms of partition by quantum-mechanical tunneling. Usually systems must
functions for the molecules involved, and the same can surmount the col in the potential energy surface (Fig. 3),
be done for the particular equilibrium constant K ‡ . What but quantum-mechanical theory allows the possibility of
are required are the masses of the reactant molecules and going from the initial state A + BC to the final state
the activated complex, their moments of inertia, and their AB + C without passage over the col. This arises when
vibrational frequencies. For the reactant molecules this is very light species, such as electrons and hydrogen atoms,
usually straightforward. These parameters are also known are involved in the reaction. For example, in a reaction
for an activated complex if a reliable potential energy sur- such as,
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Kinetics (Chemistry) 185

Tl2+ + Fe2+ → Fe3+ + Tl+ , the probability of reaction and d, the collision diameter, is
the distance between the centers of the reactant molecules
there is simply the transfer of an electron, which tunnels when they collide. In practice the reaction cross section,
through the potential energy barrier without going over it. given the symbol σ , is the quantity that has to be postu-
Tunneling is also important in a reaction such as lated in using collision theory to interpret calculated or
D + H2 → DH + H, experimental rates.
Much of the theoretical work in molecular dynamics has
where D is a deuterium atom. Here there is a transfer of a been based on potential energy surfaces that have been cal-
hydrogen atom H, and the reaction involves some passage culated for individual reactions. Dynamical calculations
over the energy barrier but also some tunneling. Since the are then carried out for various initial states of the re-
rate of tunneling increases much less with temperature acting molecules. For a reaction A + B—C, for example,
than the passage over the barrier, quantum-mechanical one chooses a particular vibrational and rotational state
tunneling is relatively more important at low temperatures, for the molecule B–C, and particular translational states
and it is at such temperatures that much of the evidence for A and B–C. Other details of the collision between the
for tunneling has been obtained. two are also selected. One then calculates, on the basis of
Quantum-mechanical tunneling is an important factor dynamics, the path that the system takes on the potential
that must be considered in connection with kinetic-isotope energy surface. A diagram or mathematical description
effects. Suppose, for example, that the reactions that describes the motion of a reaction system over a po-
D + H2 → DH + H tential energy surface is known as a trajectory. Ideally the
dynamical calculations are based on quantum mechanics,
and but this presents difficulty and more often classical calcu-
D + D2 → D2 + D lations are made; there is good reason to conclude that not
much error is then introduced. Even when the trajectories
are compared. The ratio of rate constants depends on cer- are obtained classically, the initial states of the reactants
tain factors that enter into the partition functions for the are usually selected on the basis of quantum theory.
reactants and activated complexes but also on the fact that A large number of trajectories have been calculated,
quantum-mechanical tunneling is important for the first and the results have provided considerable insight into
reaction but not for the second. The deuterium atom D how reactions proceed. Calculations by Karplus and co-
is twice as heavy as the H atom, and tunneling is quite workers on the reaction
unimportant when D, or any heavier atom, is transferred
H + H 2 → H2 + H
in a chemical process.
have revealed a number of interesting features. One is that
not all of the vibrational energy of H2 can contribute to
V. REACTION DYNAMICS allowing the system to surmount the potential energy bar-
rier. Another is that, as assumed in transition-state theory,
It is important to have knowledge, on the molecular or the system passes directly through the col and does not
microscopic level, of the elementary act that occurs dur- remain there and perform a number of vibrations. On the
ing the course of chemical change. Work in this field, basis of calculations made for a variety of initial condi-
referred to as-reaction dynamics or molecular dynamics, tions it was possible to compare calculated rates with those
deals with the intermolecular and intramolecular motions obtained from transition-state theory, and the agreement
that occur in a chemical reaction and the quantum states of was very good. For the reaction
the reactant and product molecules. There are two main
Br + H2 → HBr + H,
reasons for studying chemical dynamics. One is to test
the validity of the statistical theories that were outlined in the agreement is not as good. Other trajectory calculations
the preceding section. The other is that there are impor- have been made for potential energy surfaces that do not
tant applications (e.g., lasers) in which it is necessary to have the shape shown in Fig. 3 but instead have a basin at
have information about the energy states of products of the col. It is then found that the activated complexes are
reaction, information that is not provided by the statistical trapped for a short period in the basin, and perform several
theories. vibrations before they become products.
The results of dynamical calculations and experiments A number of trajectory calculations have been made,
are frequently expressed in terms of reaction cross sec- particularly by J. C. Polanyi (b. 1929) and co-workers,
tions rather than rate constants. The reaction cross section with the object of exploring how the slopes of potential
for a bimolecular reaction is defined as Pr πd 2 , where Pr is energy surfaces affect the transfer of energy during the
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186 Kinetics (Chemistry)

course of a chemical reaction. Three questions of particu- with each other. The primary purpose of these molecular-
lar importance are: beam studies is to determine the fate of the reactants and
products after the beams have come together.
1. If energy is released in a chemical reaction (i.e., if 2. Experiments carried out in bulk systems in which
the reaction is exothermic), what is the distribution of the the energy states of the reaction products are determined
energy among the translational, vibrational, and rotational by spectroscopic techniques. The reaction itself may oc-
states of the product molecules? cur in a static or flow system, and often the reactant
2. What type of energy is particularly effective in lead- molecules have been put into particular energy states. The
ing to a successful chemical reaction? term chemiluminescence is applied to such studies, since
3. If a collision occurs with substantially more than they are concerned with radiation emitted by the products.
enough energy to surmount the barrier, in what form is the
excess energy released? Ideally, in both types of investigation, the reactant
molecules are put into selected translational, vibrational,
The answers to all three questions depend on the form and rotational states, and the corresponding states of the
of the potential energy surface. In the schematic potential reaction products are determined. When this objective is
energy surface shown in Fig. 3 the energy level of the more or less achieved the expression state-to-state kinetics
products, A—B + C, is lower than that of the reactants is applied.
(i.e., the reaction is exothermic). Also, the surface was Molecular-beam studies have only been carried out to
drawn in such a way that at the activated state there is any extent since the 1950s, and the techniques have devel-
not much change in the B–C distance, but that the A–B oped considerably since that time. A particular advance
distance is considerably greater than it becomes in the has been the use of mass spectrometers for determining
product A–B. This type of surface is called an attractive the nature, speeds, and direction of the molecules after
or an early downhill surface. In the trajectory shown in the collision has occurred. Analysis of the results yields
Fig. 3 there is not much vibrational energy in the reactant detailed information about the distribution of angular mo-
B–C, but much more in the product A–B, and this is typical mentum among the reaction products, the reaction cross
of this type of surface. If, on the other hand, an exothermic sections, the quantum states of the product molecules, and
reaction has a late downhill surface, or a repulsive surface, the lifetime of the collision complex. Many reactions fall
the calculations showed that not so much of the energy into one of two main classes:
released passed into vibrational energy of A–B, most of it
becoming translational energy of A–B and C. 1. Reactions having high reaction cross sections (i.e.,
The answer to the second question can be appreciated occurring at relatively high rates) and in which the reaction
by considering the reverse processes. Suppose that the products are scattered forward with respect to the center
surface is as shown in Fig. 3 but that the reaction is of mass of the system. This type of process is said to occur
by a stripping mechanism.
A—B + C → A + B—C.
2. Reactions having small cross sections, in which there
The reverse of the trajectory shown in Fig. 3 therefore ap- is backward scattering of the reaction products. The mech-
plies, and the reaction absorbs energy (i.e., it is endother- anism is then said to be a rebound mechanism.
mic). Vibrational energy is now much more important than
translational energy in surmounting the barrier. If there is It has been found that reactions for which the potential en-
only translational energy the system is likely to bounce ergy surface is attractive (Fig. 3) tend to occur by a strip-
against the inner wall of the surface and return to the en- ping mechanism, while when it is repulsive there is a re-
trance valley. bound mechanism. The reasons for this have been worked
With regard to the third question, the disposition of out.
excess energy, there is a tendency for excess translational When a reaction occurs either by a stripping or a re-
energy to appear as translational energy in the products bound mechanism the lifetime of the activated complex
and for excess vibrational energy to appear as vibrational must be short; if it were long enough for rotation to occur
energy. This effect has been referred to as adiabaticity, and the products would separate in random directions and the
theoretical reasons for it have been proposed. reaction is then said to occur by an indirect or complex-
These conclusions have been amply confirmed by many mode mechanism. When the lifetime of the complex is
experimental results. Broadly speaking the experimental short, as in the stripping and rebound mechanisms, the
investigations fall into two main classes: expression direct or impulsive is used. The occurrence of
a reaction by a complex-mode mechanism appears to be
1. Experiments in which narrow beams of reactant associated with the existence of a basin in the potential
molecules, in preselected states, are brought into contact energy surface.
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Kinetics (Chemistry) 187

The chemiluminescence investigations of chemical re- ular entities having configurations between those of the
actions have as their origin some pioneering investigations reactants and products of a chemical reaction. The term
carried out in the 1920s and 1930s by M. Polanyi. In the transition species covers a much broader range of config-
course of these studies it was found, for example, that in urations than does the term activated complex, which is
the reaction defined as existing in an arbitrarily small region of space.
It has long been known that spectral lines are broadened
Cl + Na2 → NaCl + Na
when a gas is at higher pressures, and this was interpreted
a good deal of the energy liberated resides in the prod- in 1915 by H. A. Lorentz (1853–1928) as being due to
uct NaCl molecule in the form of vibrational energy, as collisions between the molecules. It was only in 1980,
indicated by the prime. These investigations have been however, that J. C. Polanyi and co-workers were success-
extended, particularly by J. C. Polanyi and co-workers, ful in detecting similar effects from molecules that were
who have introduced new experimental techniques and undergoing reactive collisions. For example, they studied
have studied reactions of a variety of types. It was these the reaction
investigations, together with parallel theoretical studies,
that led to the classification of different types of potential F + Na2 → F . . . Na . . . Na → NaF + Na∗
energy surfaces. The product Na∗ is in an electronically excited state and
Both the molecular-beam and chemiluminescence tech- emits the familiar yellow D-line. On both sides of this line
niques have been applied to the investigation of state-to- there was “wing” emission, and the evidence indicated
state kinetics. In a molecular-beam experiment the trans- that this was due to the transition species F . . . Na . . . Na.
lational energies of the reactant molecules can be well Techniques have now been developed for studying the
controlled, and by laser excitation the molecules can be course of chemical change in great detail. In particular,
put into particular vibrational and rotational states. In the femtosecond flash photolysis has been used to observe
chemiluminescence experiments the reactant molecules transition species, notably by Philip R. Brooks and by
are sometimes put into particular vibrational and rotational Ahmed H. Zewail.
states by forming them in prereactions.
State-to-state studies have been carried out only since
the early 1970s, but they have already revealed much im-
portant information. By and large they have confirmed VI. REACTIONS IN THE GAS PHASE
and amplified the previous theoretical and experimental
studies in reaction dynamics. One general result that has Reactions in the gas phase are in some respects easier
been obtained is that when reactions are substantially en- to understand than those in solution or on surfaces, and
dothermic, their barriers are usually late ones, so that they what is learned about gas reactions is valuable in leading
are enhanced more by vibrational than by translational en- to an understanding of the other types of processes. The
ergy. On the other hand, when reactions are only slightly most straightforward of gas reactions are those that are
endothermic or are exothermic, the barriers are generally elementary and bimolecular. There are few bimolecular
earlier, and translational energy then plays a more im- reactions involving molecules, as opposed to atoms and
portant role in leading to reaction. State-to-state studies free radicals, since most second-order reactions involving
have also led to some clarification of the influence of rota- molecules occur in more than one stage, i.e., they are
tional energy on reactivity, although the matter is still not composite. Such composite reactions are dealt with in
entirely clear. When the translational and vibrational ener- Section IX.
gies are held constant and the rotational quantum state of The prototype of all bimolecular reactions is the process
a reactant molecule is steadily increased, the rates some- H + H 2 → H2 + H
times first decrease and then increase. As rotational speeds
increase, the time that a molecule spends in a favorable The measurement of the rate of this reaction is made possi-
orientation decreases, and this factor leads to a decrease ble by the fact that H2 exists in two forms, designated ortho
in reaction probability. At higher rotational speeds, how- (o) and para ( p). To explain the kinetics of this reaction
ever, the preferred orientations are obtained again at short a large number of theoretical studies have been made. It
intervals during the approach of the reactants, and this can is now possible to calculate, by pure quantum mechanics,
give rise to higher rates as the rotational energies increase. an accurate potential energy surface for this reaction. For
Also, at the higher rotational speeds there is a greater pro- this particular reaction, which has a symmetrical potential
portion of energy in the form of rotational energy, and this energy surface, conventional transition-state theory is in
again can contribute to the effects observed. good agreement with the best of the dynamical treatments.
An important development has been the spectroscopic One matter of considerable interest is the kinetic isotope
detection of transition species, which are defined as molec- effect observed when H atoms are replaced by deuterium
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188 Kinetics (Chemistry)

(D) or tritium (T) atoms in this system. These kinetic iso- suggestion made in 1921 by F. A. Lindemann, later Lord
tope effects still cannot be treated completely satisfac- Cherwell (1886–1957).
torily, largely because the theory of quantum-mechanical Lindemann’s hypothesis, as later interpreted and devel-
tunneling is by no means satisfactory. The effects are, how- oped by C. N. Hinshelwood (1897–1967) and others, is as
ever, broadly understood in a semiquantitative way. follows. In a unimolecular process an energized molecule
Among other bimolecular gas reactions that have been A∗ is first formed by a collision between two molecules
extensively investigated are so-called abstraction or meta- of the reactant A:
thetical reactions involving atoms and free radicals. An
A+A A∗ + A
example is
The energization process is second order, the rate being
CH3 + C2 H6 → CH4 + C2 H5 .
k1 [A]2 , and the rate of the reverse de-energization process
In this process the free methyl radical CH3 abstracts a is k−1 [A∗ ][A]. The energized molecule A∗ may undergo
hydrogen atom from the ethane molecule. There has also de-energization, but it may also undergo a process in which
been much study, by mass spectrometric techniques, of the reaction products are formed:
bimolecular reactions involving ions, such as the reaction
A∗ → products
+ +
O + N2 → NO + N.
The rate of this first-order process is k2 [A∗ ].
For most such reactions conventional transition-state the- If the pressure is high enough the de-energization pro-
ory provides a useful, but not always precise, interpretation cess will be more rapid than the reaction to form products.
of the results. This being so, the energized molecule A∗ is essentially in
A few trimolecular reactions in the gas phase have also equilibrium with normal molecules, and its concentration
been investigated; examples are [A∗ ] is proportional to the first power of the concentra-
tion [A]. Since the rate is proportional to [A∗ ] it is also
2NO + Cl2 → 2NOCl
proportional to [A]; i.e., the kinetics are first order.
and At sufficiently low pressures, on the other hand, the
time between successive collisions between A∗ and A be-
2NO + O2 → 2NO2 .
comes longer than the time that elapses before A∗ can
The interpretation of these reactions was a considerable become products. The removal of A∗ molecules by chem-
triumph for conventional transition-state theory. Simple ical change then seriously diminishes the concentration of
collision theory proved unsatisfactory for trimolecular re- activated molecules. At extremely low pressures the en-
actions, owing to the difficulty of defining a collision be- ergized molecules A∗ almost inevitably become products,
tween three molecules, and usually led to very serious as there are few collisions to inactivate them. The rate of
overestimations (by several powers of ten) of the rate con- reaction is then equal to the rate of energization and is thus
stants. Similar difficulties are encountered with dynami- proportional to the square of the concentration.
cal treatments, and these have still not been satisfactorily If this Lindemann–Hinshelwood hypothesis is correct,
resolved. Conventional transition-state theory, by regard- unimolecular gas reactions should be first order at high
ing the activated complex as being in equilibrium with pressures and should become second order at low pres-
the reactants, leads to a very simple formulation of the sures. This behavior has now been confirmed for a large
rate constant and to values in good agreement with ex- number of reactions. In its original form the hypothesis
periment. It also very neatly explains the rather marked had some difficulty in interpreting results quantitatively,
negative temperature dependence of the pre-exponential but a number of extensions of the original hypothesis have
factors for these reactions. been made, notably by R. A. Marcus whose treatment is
The elucidation of unimolecular gas reactions proved consistent with transition-state theory.
to be much more difficult than that of bimolecular and
trimolecular reactions. Whereas the rates of the latter re-
actions can be interpreted in terms of collisions between VII. REACTIONS IN SOLUTION
two and three molecules respectively, no such treatment
appears at first sight to be possible for unimolecular reac- Reactions in solution or in the liquid phase are intrinsi-
tions. At one time it was widely held that collisions are not cally more difficult to understand than reactions in the gas
at all involved in unimolecular reactions, and that instead phase because of the complications arising from the effect
the reactions occur as a result of the absorption of radia- of the liquid. When a solvent is present there are two pos-
tion emitted by the vessel walls. However, this proved to sibilities: the solvent may exert purely an environmental
be incorrect, and the problem was resolved as a result of a effect on the reaction, or it may also enter into the reaction.
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Kinetics (Chemistry) 189

The latter case is exemplified by the hydrolysis of an or- the pre-exponential factors of such reactions. In water at
ganic compound in aqueous solution; water molecules are 25◦ C, for example, the pre-exponential factor of a reaction
chemically involved in the reaction. of the type A+ + B+ is apt to be about two orders of mag-
Some understanding of solvent effects has been nitude lower than for the corresponding reaction between
provided by comparisons of the same reaction in the gas neutral molecules. By contrast, for a reaction in aqueous
phase and in solution. Some reactions, however, do not solution between singly charged ions of opposite signs,
occur at all in the gas phase, and one must then be con- A+ + B− , the pre-exponential factor at 25◦ C is usually
tent with comparing their rates in different solvents. When about 102 greater than that between neutral molecules.
such comparisons are made it is sometimes found that the Similar considerations allow useful predictions to be
solvent does not have much effect on the rate. When, on the made about the effects or different solvents on reaction
other hand, ions are involved as reactants or products, sol- rates. If a reaction is of the type A+ + B+ the forces are
vents usually have a much greater effect on rates, because repulsive and will be smaller the higher the dielectric con-
of the rather strong electrostatic interactions between ions stant of the solvent. The reaction therefore proceeds more
and solvent molecules. rapidly in aqueous solution than in alcohol, since water
Theoretical studies have also contributed to an under- has a higher dielectric constant than alcohol and reduces
standing of reactions in solution. For reactions between the repulsions to a greater extent. When on the other hand
neutral species the frequencies of collisions are of the same the reaction is of the type A+ + B− , the rate will be greater
order of magnitude in solution and in the gas phase. How- in alcohol than in water, since water greatly reduces the at-
ever, there are important differences between the distribu- tractions between the reactants. Quantitative formulations
tion of collisions. When two molecules collide in solution of these effects have been worked out.
they are “caged” in by surrounding molecules and within Another matter of considerable importance in connec-
a very short period of time they are likely to undergo one tion with ionic reactions in solution is the effect on rates
or more additional collisions before they separate. Such a of the ionic strength. This property, introduced in 1921 by
set of collisions, occurring in rapid succession, is known G. N. Lewis (1875–1946), is defined as
as an encounter. This tendency for collisions in solution to 1 2
occur in sets has no effect on reactions involving an activa- I = z ci , (20)
2 i i
tion energy, because reaction may occur on any collision
within the set. However, atomic and free-radical combi- where ci is the concentration of each ion in solution and
nations do not involve an activation energy and occur on z i is its charge number (e.g., +1 for Na+ , −2 for SO−24 ):
every collision. They therefore occur at the first collision the summation is made over all of the ions present in
in the set, so that the remaining collisions in the encounter the solution. Qualitatively the ionic strength has the same
do not contribute to the rate. The pre-exponential factor kind of effect as the dielectric constant; increasing I re-
is therefore not related to the frequency of collisions but duces the forces between ions. Thus for a reaction of the
rather to the frequency of encounters. type A+ + B+ , increasing the ionic strength increases the
This cage effect, also known as the Franck– rate by reducing the repulsion. For a reaction A+ + B− ,
Rabinowitch effect, has other important consequences. In increasing the ionic strength decreases the rate by reduc-
a photochemical reaction in solution, for example, a pair of ing the attraction. These ideas were put into quantitative
free radicals produced initially may, owing to their being form in 1922–1924 by J. N. Brønsted (1879–1947), N. J.
caged in by the surrounding molecules, recombine before Bierrum (1879–1958), and J. A. Christiansen (1888–
they can separate from each other. This effect is known as 1969).
primary recombination. Special effects arise for a solution reaction that is
When reaction occurs between ions in solution some extremely rapid, in which case the rate may depend on the
rather special effects become important. These can be rate with which the reactant molecules diffuse through the
understood in an approximate but very useful way by solvent. Two effects are to be distinguished, macroscopic
focusing attention on the dielectric constant of the solvent. diffusion control and microscopic diffusion control. If a
The forces between charges, whether they are attractive rapid bimolecular reaction in solution is initiated by mix-
or repulsive, are inversely proportional to the dielectric ing solutions of the two reactants, the observed rate may
constant of the medium. The dielectric constant of wa- depend on the rate with which the solutions mix, and one
ter, for example, is about 78 at room temperature, and the then speaks of mixing control or macroscopic diffusion
force of repulsion between two ions A+ and B+ in wa- control.
1
ter is only 78 of that in the gas phase. Even in aqueous Even if this effect has been eliminated the rate of a
solution the forces are still strong enough to have a sub- reaction may be influenced by the rate with which the
stantial effect on the collision frequencies and therefore on reactant molecules diffuse towards each other. This effect
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190 Kinetics (Chemistry)

is known as microscopic diffusion control or encounter sorbed molecules, so that 1 − θ is the fraction that is not
control. If the measured rate is almost exactly equal to the covered. If [A] is the concentration of gas molecules, then
rate of diffusion one speaks of full diffusion control. An the rate of adsorption, which can only occur on bare sur-
example of this is provided by the combination of H+ and face, is ka [A](1 − θ ), where ka is a constant. The reverse
OH− ions in solution, a reaction that is so fast that the desorption process is a unimolecular process and its rate
rate is almost entirely controlled by the diffusion of the is kd θ. At equilibrium the two rates are the same so that
ions towards each other. For some reactions the rates of ka [A](1 − θ ) = kd θ (21)
chemical reaction and diffusion are similar to each other,
and one then speaks of partial diffusion control. from which it follows that
Quantitative formulations have been worked out for the K [A]
θ= , (22)
rate constants for both full and partial diffusion control. 1 + K [A]
Diffusion rates do not vary greatly from one system to where K is equal to ka /kd .
another and for uncharged reactants in aqueous solution Equation (22) leads at once to kinetic equations that
at 25◦ C diffusional rate constants are approximately 7 × apply to unimolecular processes on surfaces. The rate is
109 dm3 mol−1 s−1 . If the chemical rate constant is sub- proportional to θ and is therefore given by
stantially greater than this there is therefore appreciable
k K [A]
diffusion control. Most reactions, however, have much v= (23)
smaller rate constants because of an energy barrier to re- 1 + K [A]
action, and are therefore not affected by diffusion. For If [A] is sufficiently small that k[A] 1, this reduces to
reactions between ions the diffusion rates and chemical v = k K [A] (24)
rates are increased if the ions are of opposite signs, and
they are decreased if they are of the same sign. and the reaction is first order. If [A] is sufficiently large
that K [A] 1 the rate is
v=k (25)
VIII. REACTIONS ON SURFACES and is now independent of concentration; the order of
the reaction is thus zero. One example of a reaction that
Many reactions are affected by the surface of the vessel in changes from zero-order kinetics at high concentrations
which they occur, with an increase in rate. The effect is of- to first-order kinetics at low concentrations is the decom-
ten a catalytic one, the surface remaining unchanged, and position of ammonia on the surface of a metal such as
substances are often deliberately introduced into reaction tungsten or iron.
systems with the object of increasing the rates. Surface When two substances are undergoing reaction at a sur-
catalysis is of very great importance in technical work. face there are two possibilities. The reaction may be an
The fact that the enhanced rates are due to adsorption interaction between two molecules that are adsorbed side-
at the surface has long been known. An important ad- by-side on a surface, or it may be an interaction between
vance was made in 1916 by I. Langmuir (1881–1957) who an adsorbed molecule of one kind and a gas molecule of
showed that in many cases of adsorption the gas molecules the other. The kinetics are satisfactorily interpreted by an
are held to the surface by bonds of the same character as extension of Langmuir’s isotherm [Eq. (22)], which for
covalent chemical bonds, and the term chemisorption has two gases A and B gives the following expressions for the
been applied to this type of adsorption. Langmuir also de- fractions of surface covered by A and B respectively:
veloped adsorption isotherms that relate the fraction of
K A [A]
surface covered to the pressure or concentration of a gas. θA = (26)
Later H. S. Taylor (1890–1974) emphasized the fact 1 + K A [A] + K B [B]
that surfaces are never smooth on the atomic scale, and K B [B]
θB = (27)
that surface sites are therefore of variable activity. Certain 1 + K A [A] + K B [B]
sites, which he called active centers, are particularly active Reactions involving interaction between two adsorbed
and it is on these that catalysis occurs for the most part. molecules are said to occur by Langmuir–Hinshelwood
Taylor also showed that the process of chemisorption itself mechanisms, and their rates are proportional to the product
is accompanied by an activation energy, and he referred θA θB :
to this type of adsorption as activated adsorption.
k K A K B [A][B]
The kinetic equations that apply to reactions on sur- v = kθA θB = (28)
faces are given to a good approximation on the basis of (1 + K A [A] + K B [B])2
the Langmuir isotherm, which can be derived as follows. If either concentration is held constant and the other
Let θ be the fraction of a surface that is covered by ad- one increased, the rate passes through a maximum. The
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Kinetics (Chemistry) 191

most favorable situation is for equal numbers of A and B described as composite, complex, or stepwise. One indica-
molecules to be on the surface, since then the number of tion that a reaction is composite is that the kinetic equation
A–B pairs is a maximum. If the concentration of either does not correspond to the stoichiometric equation. A sim-
is then increased, the other is displaced from the surface, ple example is the gas-phase reaction between nitric oxide
and the number of A–B pairs diminishes. and hydrogen, the stoichiometric equation for which is
Mechanisms in which a gas molecule reacts with
2NO + 2H2 → N2 + 2H2 O
an adsorbed molecule of the other kind are known as
Langmuir–Rideal mechanisms. If, for example, the inter- If the process were elementary it would be second order in
action is between gaseous A and adsorbed B the rate is NO and second order in H2 , with an overall order of four.
proportional to [A]θB and is therefore In fact, the rate is proportional to [NO]2 [H2 ]. The reason
k K B [A][B] is that the reaction occurs in two steps,
v= (29)
1 + K A [A] + K B [B] 2NO + H2 → N2 + H2 O2
There is therefore no longer a maximum in the rate, which H2 O2 + H2 → 2H2 O
now approaches a limiting value if the concentration of
one reactant is increased with the other held constant. The second reaction is rapid compared with the first, so
This difference in kinetic behavior allows a discrimination that the overall rate is that of the first reaction and is pro-
between the two mechanisms, both of which sometimes portional to [NO]2 [H2 ].
occur simultaneously. Because reactions can occur in steps, the order of a
Since about 1970 there have been many important reaction is often less than corresponds to the stoichiome-
advances in experimental techniques for the study of try. A reactive collision between three molecules is much
surfaces and adsorbed layers of molecules on surfaces. less likely than one between two, and one between four
Techniques that have been particularly valuable in the molecules is exceedingly unlikely; indeed it is doubt-
investigation of solid surfaces are field-ion microscopy ful whether elementary reactions between four molecules
(FIM) and low-energy electron diffraction (LEED). These ever occur. A reaction whose stoichiometric equation in-
techniques have shown that surfaces have different types volves more than three molecules always proceeds more
of surface sites, such as atoms at terraces, atoms at steps, rapidly by two or more processes of lower molecularity.
atoms at kinks, and adatoms which project out of the Even if the kinetics of a reaction does correspond to the
surfaces. stoichiometry it may still be the case that the mechanism
A technique that has provided valuable information is composite. For example, the reaction
about adsorbed films is infrared spectroscopy. As an ex- H2 + I2 → 2HI
ample of its use we mention some work on the adsorption and the reverse decomposition are both second order, and
of ethylene (C2 H4 ) on various surfaces. It has been found the processes were formerly thought to occur in a single
that the manner in which ethylene is adsorbed depends stage. Later work, however, has shown that reactions in-
on the availability of hydrogen. If no hydrogen is avail- volving I atoms are also involved. The decomposition of
able the adsorption tends to be of the dissociative type; ethane,
the ethylene splits into C2 H2 and 2H, all of which are
adsorbed separately. With hydrogen present, however, ad- C2 H6 → C2 H4 + H2 ,
sorbed H atoms add on to C2 H4 and ethyl radicals (C2 H5 ) is first order and was long thought to be elementary; how-
become attached to the surface. Evidence of this kind is of ever it occurs entirely by a free-radical mechanism, to be
great importance in understanding the kinetics and mech- considered later.
anisms of the hydrogenation of ethylene and many other Composite mechanisms can be classified in a number
processes. of different ways. First, there is the usual classification
Reactions on surfaces frequently undergo inhibition by according to whether the process occurs in the gas phase,
added substances, which themselves become adsorbed on the liquid phase, or on a surface. Another classification is
the surface and reduce its catalytic activity. This effect is according to whether the process is thermal, photochemi-
commonly referred to as poisoning of the surface. cal, or radiation chemical. A thermal reaction occurs sim-
ply by virtue of the heat energy present in the system;
molecules can pick up more energy on colliding with other
IX. COMPOSITE REACTION MECHANISMS molecules, and eventually an energetic collision will lead
to reaction. Photochemical and radiation-chemical reac-
Many of the reactions familiar to the chemist occur in tions are brought about as a result of radiation absorbed
more than one stage, and their mechanisms are therefore in the system.
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192 Kinetics (Chemistry)

Another characterization of composite mechanisms is

in terms of the types of elementary reactions occurring.
Sometimes reactions occur in parallel, such as
A→Y
A → Z,
and are called simultaneous reactions. When there are si-
multaneous reactions, there is sometimes competition, as
in the scheme
A+B→Y
A + C → Z,
where B and C compete with one another for A.
Reactions occurring in forward and reverse directions
are called opposing: FIGURE 4 Variations with time of the concentrations of A, X, and
Z for the mechanism A → X → Z.
A+B Z
Reactions occurring in sequence, such as
A→X→Y→Z in Fig. 4. The rate of formation of Z is proportional to [X],
and since [X] starts at zero and passes through a maximum,
are called consecutive reactions. Reactions are said to ex- the initial rate of formation of Z is zero. This rate, how-
hibit feedback if a substance formed in one step affects ever, increases, and passes through a maximum when [X]
the rate of a previous step. For example, in the scheme is at its maximum.
A→X→Y→Z In a composite mechanism it is sometimes possible to
identify a rate-determining or rate-controlling step. An
the intermediate Y may catalyze the first reaction (positive example is provided by the mechanism previously given
feedback) or inhibit it (negative feedback). More than one for the 2NO + 2H2 reaction. Since the first step is slow
of the above features may of course occur in a composite and the second rapid, the first step determines the rate.
mechanism. The rate may also be controlled by a step that is not the
Sometimes a composite reaction mechanism involves first; in that case the overall rate is not equal to the rate of
a cycle of reactions such that certain reaction intermedi- the slow step but is proportional to it.
ates consumed in one step are regenerated in another. The Only in the case of very simple reaction mechanisms
intermediates may be atoms, free radicals, or ions. For ex- is it possible to obtain explicit expressions for concentra-
ample, the reaction between hydrogen and bromine, to be tion changes as a function of time. In some situations a
considered later, includes the steps reliable solution to the problem may be obtained by ap-
Br + H2 → HBr + H plication of the steady-state treatment. The condition for
this to be valid is that the intermediates are present only at
H + Br2 → HBr + Br. concentrations that are very low compared to those of the
reactants. If this condition is satisfied by an intermediate
When this feature exists, and the cycle is on the average
X, the rate of change of its concentration is always much
repeated more than once (as it is in this reaction under
less than those of the reactants, and to a good approxima-
usual conditions), the reaction is called a chain reaction,
tion can be set equal to zero:
and the active intermediates (here H and Br) are referred to
as chain carriers. The preceeding two reactions are referred d[X]/dt = 0 (30)
to as chain-propagating steps.
Substances that are formed during the course of a reac- This approximation can be safely applied to intermediates
tion but do not remain to any extent as final products are such as atoms and free radicals.
known as transient intermediates, or transients. A simple The reaction between hydrogen and bromine provides
reaction scheme is a good example of a composite mechanism to which the
steady-state treatment can be applied, since the interme-
A→X→Z
diates are the atoms Br and H. If the back reaction is
and if the reaction goes to completion the way in which the prevented from occurring (by removal of the product HBr
concentrations of A, X, and Z vary with time is illustrated as it is formed) the mechanism is
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Kinetics (Chemistry) 193

(1) Br2 → 2Br The solution for [CH3 ] is

 1/2
(2) Br + H2 → HBr + H k1
[CH3 ] = [CH3 CHO]1/2 . (37)
(3) H + Br2 → HBr + Br k4
The rate of formation of the product CH4 is k2 [CH3 ]
(−1) 2Br → Br2 .
[CH3 CHO] and is therefore
Reactions (2) and (3) constitute chain-propagating reac-  1/2
tions. Reaction (1) is referred to as chain-initiation process k1
vCH4 = k2 [CH3 CHO]3/2 . (38)
and reaction (−1) as a chain-ending step. Application of k4
the steady-state treatment to the Br atoms gives The three-halves-order kinetics actually observed for this
k1 [Br2 ] − k2 [BF][H2 ] + k3 [H][Br2 ] − k−1 [Br] = 0.
2 reaction is thus explained.
(31) Ethane decomposition is also a chain reaction, and the
main features have now been elucidated. The initiation
For H atoms the steady-state equation is
process is the dissociation of the ethane molecule into two
k2 [Br][H2 ] − k3 [H][Br2 ] = 0. (32) methyl radicals:
There are thus two equations in the two unknowns [Br] C2 H6 → 2CH3 .
and [H], and the solution for [Br] is These, however are not chain carriers; they abstract a hy-
 
k1 1/2 drogen atom from a C2 H6 molecule
[Br] = [Br2 ]1/2 . (33)
k−1 CH3 + C2 H6 → CH4 + C2 H5 .
The rate of consumption of H2 is k2 [Br][H2 ], and therefore Methane (CH4 ) is, in fact, found as a minor product of
 
k1 1/2 the reaction. The C2 H5 radical is a chain carrier, since
vH2 = k2 [H2 ][Br2 ]1/2 . (34) it decomposes into C2 H4 and H, which then abstracts a
k−1
hydrogen atom from an ethane molecule:
This is also the rate of consumption of Br2 . Experimentally
the reaction is, in fact, first order in H2 and one-half order C2 H5 → C2 H4 + H
in Br2 . Much work has shown this mechanism to be almost H + C2 H6 → H2 + C2 H5 .
certainly close to the truth.
Many organic decompositions in the gas phase occur In this pair of chain-propagating steps the major products
by composite mechanisms involving the participation of of the reaction, ethylene (C2 H4 ) and hydrogen, are formed
atoms and free radicals, and in 1934 F. O. Rice (b. 1890) without any loss of chain carriers.
and K. F. Herzfeld (1892–1978) proposed several types There is a special class of reactions in which there is
of chain mechanisms to explain the kinetic behavior ob- chain branching, a concept suggested in 1927–1928 by
served. The acetaldehyde decomposition appears to occur N. N. Semenov (1896–1946) and by C. N. Hinshelwood.
largely by a mechanism that can be simplified to When a pair of ordinary chain-propagating steps occurs
there is no change in the number of chain carries. When
(1) CH3 CHO → CH3 + CHO there is chain branching, however, there is an increase in
(2) CH3 + CH3 CHO → CH4 + CH3 CO the number of carriers. An example is the pair of reactions

(3) CH3 CO → CH3 + CO H + O2 → OH + O

(4) 2CH3 → C2 H6 . O + H2 → OH + H.
The radical CHO produced in reaction (1), the initiation In each of these reactions two carriers have been formed
reaction, breaks down into CO + H, and H atoms combine from one; if the two reactions are added together the result
to form H2 which is found as a minor product. The C2 H6 is
formed in the termination reaction is also a minor product. H + O2 + H2 → 2OH + H,
Reactions (2) and (3) are chain-propagating steps. The
steady-state equations are now, for CH3 : so that the H atom is regenerated but has produced two
OH radicals which can undergo further reactions. When
k1 [CH3 CHO] − k2 [CH3 ][CH3 CHO] + k3 [CH3 CO]
such chain branching occurs the number of chain carriers
−k4 [CH3 ]2 = 0 (35) in the reaction can increase extremely rapidly. The rate of
reaction thus increases, and the result may be an explosion.
and for CH3 CO:
Mixtures of oxygen with substances such as hydrogen,
k2 [CH3 ][CH3 CHO] − k3 [CH3 CO] = 0. (36) carbon monoxide, and various organic substances do in
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194 Kinetics (Chemistry)

fact explode under certain conditions, and the reason is In order for a photochemical reaction to occur the radi-
that chain branching is involved. ation must be absorbed, and with the advent of the quan-
Reactions in which substances react together with the tum theory it became possible to understand the relation-
formation of much larger molecules known as polymers ship between the amount of radiation absorbed and the
are frequently chain reactions. Thus, a substance contain- extent of the chemical change that occurs. It was first re-
ing a carbon–carbon double bond may be caused to poly- alized by A. Einstein (1879–1955) that electromagnetic
merize by introduction of a free radical R which adds on to radiation can be regarded as a beam of particles, which
the double-bonded compound to form another free radical: G. N. Lewis (1875–1940) later called photons: each of
these particles has an energy equal to hν, where ν is the
frequency of the radiation and h is the Planck constant.
In 1911 J. Stark (1874–1957) and independently in 1912
Einstein proposed that one photon of radiation is absorbed
by one molecule. This relationship, usually referred to
as Einstein’s Law of Photochemical Equivalence, applies
The resulting free radical adds on to another monomer
satisfactorily to electromagnetic radiation of ordinary in-
molecule and the process continues with the eventual for-
tensities but fails for lasers of very high intensity. The
mation of a much larger molecule.
lifetime of a molecule that has absorbed a photon is usu-
ally less than about 10−8 sec, and with ordinary radiation it
is unlikely for a molecule that has absorbed one photon to
X. PHOTOCHEMICAL AND absorb another before it has become deactivated. In these
RADIATION-CHEMICAL REACTIONS circumstances there is therefore a one-to-one relationship
between the number of photons absorbed and the number
There are two kinds of radiation, electromagnetic and par- of excited molecules produced. Because of the high in-
ticle. The former behaves in some experiments as if it were tensity of lasers, however, a molecule sometimes absorbs
a beam of photons, but these have no mass and can be re- two or more photons, and one then speaks of multiphoton
garded as packets of energy. Particle radiation, on the other excitation.
hand, consists of beams of particles having mass. Cath- Even with ordinary radiation it may appear that the law
ode rays and β radiation, for example, consist of beams of photochemical equivalence is not obeyed, and this arises
of electrons, and α radiation consists of a beam of helium because of two factors. One is that a molecule that has ab-
nuclei. Particle-generating machines such as cyclotrons sorbed a photon may become inactivated before it has had
produce beams of protons, deuterons, and other particles. time to enter into reaction. When this alone is the case
All of these types of radiation are capable of bring- the ratio of the number of molecules undergoing reaction
ing about chemical reaction provided that the energies are to the number of photons absorbed (a quantity known as
sufficiently high. Reactions induced in this way are re- quantum yield or photon yield) is less than unity. The sec-
ferred to as either photo-chemical or radiation-chemical ond factor is that the reaction may occur by a composite
reactions. The distinction between the two types is not mechanism. For example, in the photochemical decompo-
sharp and is sometimes made on the basis of whether ions sition of hydrogen iodide (HI) into hydrogen and iodine,
are produced in the reaction. With radiation of lower en- the quantum yield is 2; that is, one photon brings about
ergies, such as electromagnetic radiation in the visible the decomposition of two molecules of hydrogen iodide.
and near-ultraviolet regions of the spectrum, there is no The reason is that the mechanism is
ion formation, and the resulting reaction is referred to as
photo-chemical. With ultraviolet radiation of higher fre- (1) HI + hν → H + I
quencies, with X-rays and γ -rays, and with high-energy (2) H + HI → H2 + I
particle radiation, ions are usually formed, and the pro-
cess is then described as radiation-chemical.1 Sometimes (3) I + I → I2 .
a distinction is based on specificity. With radiation of lower In the first step one photon, designated by its energy hν,
energy the resulting reaction is often of simple stoichiom- breaks apart an HI molecule, and the H atom produced
etry and can then be called photochemical. Higher-energy interacts with a second HI molecule [reaction (2)]. The
radiation, however, breaks up molecules into a number of sum of reactions (1), (2), and (3) is
fragments which lead to a variety of products; the term
radiation-chemical can then be applied. 2HI + hν → H2 + I2 ,
1 They should not be called “radiochemical,” which would cause which explains the quantum yield of 2.
confusion with radiochemistry, which is concerned with radioactive This mechanism is not a chain reaction, since no cy-
substances. cle of reactions is repeated. When chain processes are
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Kinetics (Chemistry) 195

involved the quantum yields may be very large. In the ions, and free radicals which undergo further reactions.
photochemical reaction between hydrogen and chlorine, For example, if hydrogen is irradiated with α particles
quantum yields of over 106 have been reported, and it was the overall primary process is largely the production of
this fact that led W. Nernst (1864–1941) to propose, in hydrogen atoms, and the process is usually written as
1918, the following chain mechanism for the reaction: α
H2
2H.
(1) Cl2 + hν → 2Cl
Several elementary processes lead to this dissociation. One
(2) Cl + H2 → HCl + H is the ejection of an electron by the α particle, the hydro-
gen molecule becoming an H+ 2 ion which dissociates into
(3) H + Cl2 → HCl + Cl
H + H+ :
(4) 2Cl → Cl2 . α + H 2 → H+ −
2 +α+e
Reactions (2) and (3) are chain-propagating steps, and H+ +
2 → H + H.
since they occur rapidly they are repeated many times,
leading to high quantum yields. The H+ ion produced is then likely to pick up an electron
One important photochemical technique is flash photol- with the formation of a hydrogen atom.
ysis, in which an intense flash of radiation of very short du- In radiation chemistry the analog of flash photolysis is
ration initiates a reaction by producing excited molecules, pulse radiolysis. For example, linear electron accelerators
atoms, and free radicals. The method, first used in 1950 by have been used to give pulses of very high energy with
G. Porter and R. G. W. Norrish (1887–1978), has been ap- durations of a few microseconds, and with special tech-
plied extensively to the study of fast reactions, both in the niques much shorter pulses, of the order of a nanosecond
gas phase and in solution. Extremely rapid processes can (10−9 sec), have been achieved.
be studied by the use of pulsed lasers, which can have a The term chemiluminescence is used to describe the
duration of less than 1 psec (10−12 sec). This is sufficiently radiation emitted as a result of a chemical reaction.
short to allow the study of the fastest of chemical reactions, Some of the radiation emitted by flames is produced
and even molecular relaxation process in which molecules in this way, although some of it is blackbody radiation
are changing their vibrational and rotational states. resulting from the high temperature of the burnt gases.
Some molecules do not absorb radiation at convenient The radiation emitted by fireflies and by certain tropical
wavelengths, and the technique of photosensitization is fish is chemiluminescence.
then useful. This term applies to the absorption of radia-
tion by a substance known as a photosensitizer, which then
transfers energy to a colliding molecule, causing it to un- XI. HOMOGENEOUS CATALYSIS
dergo chemical change. For example, hydrogen does not
absorb in the near ultraviolet, but mercury vapor does so at Catalysis at surfaces, or heterogeneous catalysis, has been
a wavelength of 253.7 nm which corresponds to an energy outlined in Section VIII, and the present section deals with
of 469.4 kJ mol−1 . If hydrogen saturated with mercury homogeneous catalysis, where only one phase is involved.
vapor is irradiated at this wavelength, the mercury atoms, Substances whose reactions undergo homogeneous
normally in a 61 S0 state, are excited to the 63 P1 state: catalysis are commonly known as substrates. There are
    several different types of homogeneous catalysis. Exam-
Hg 61 S0 + hν → Hg 63 P1 . ples in the gas phase sometimes involve chain mecha-
On collision with a hydrogen molecule an excited Hg nisms. Reactions in solution are commonly catalyzed by
atom can bring about dissociation into atoms: acids and bases, and many reactions in biological systems
    are catalyzed by enzymes, which are proteins. Reactions
Hg 63 P1 + H2 → Hg 61 S0 + 2H. in aqueous solution are often catalyzed by ions of variable
valency.
The dissociation of a mole of H2 atoms requires 432 kJ
No single mechanistic pattern applies to all cases of
of energy, so that the excited Hg atoms have more than
catalysis, but several different types of catalysis occur ac-
enough energy for this process to occur. Other molecules,
cording to the following scheme:
such as hydrocarbons, can be decomposed by similar
photosensitization processes. C+S X+Y
Radiation-chemical reactions have mechanisms simi-
X + W → P + Z.
lar to photochemical reactions, the difference being in
the nature of the radiation-chemical primary process. Un- Here C is the catalyst and S the substrate, while X is a
like photochemical primary processes, these processes are reaction intermediate which forms the product P in the
usually composite, leading in a series of steps to atoms, second step. The species Y, W, and Z undergo further
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196 Kinetics (Chemistry)

processes that do not affect the kinetics. In the case of The protonated acetone then gives up a different proton to
a unimolecular surface-catalyzed reaction the scheme is a basic species B present in solution:
simplified to:
C+S X
X → P.
The intermediate X is now an addition compound formed
from C and S, and in the second step it forms products. This is a very common pattern in acid catalysis. In the first
This scheme also applies to many reactions catalyzed by step the acid transfers a proton to the substrate, which in
enzymes. For reactions catalyzed by acids and bases, how- the second step transfers another proton, the product being
ever, it is necessary to include the additional species Y, W, formed either simultaneously or in a subsequent step. In
and Z. basic catalysis (which also occurs with the iodination of
Suppose, for example, that the reaction of a substrate S acetone), the substrate molecule first transfers a proton to
is being catalyzed by an acid HA. A typical mechanism is the basic catalyst, and in a second step accepts a proton at
another position.
HA + S SH+ + A−
Sometimes when reactions are catalyzed by acids and
SH+ + B → P + BH+ . bases there is little sign of any effect other than catalysis
by hydrated hydrogen ions (usually written as H3 O+ ) or
In the first step a proton H+ is transferred to the substrate,
by hydroxide ions. One then speaks of specific acid–base
with the formation of the intermediate SH+ . In the second
catalysis, and the rate of reaction might be of the form
step this intermediate SH+ transfers a proton to a basic  
species B (which may be identical with A− or may be a v = k0 [S] + kH+ [S] H3 O+ + kOH− [S][OH− ]. (39)
water molecule), and in this step the product P is formed.
The coefficient k0 relates to any uncatalyzed reaction, and
For example, the reaction between acetone and iodine,
kH+ and kOH− are catalytic coefficients.
CH3 COCH3 + I3 → CH3 COCH2 I + HI, It is sometimes found that acidic species other than hy-
drogen ions and basic species other than hydroxide ions
is catalyzed by acids, and the rate is proportional to the ace- are capable of catalyzing reactions. One then speaks of
tone concentration and also to the concentration of acid. general acid–base catalysis. For example, in an aqueous
The rate is, however, independent of the concentration of solution containing acetic acid and sodium acetate the rate
iodine, and indeed the rate remains the same if iodine is coefficient k(=v/[S]) can be expressed as
replaced by bromine. This suggests that the slow and rate-  
determining step does not involve iodine at all, but is the k = k0 + kH+ H3 O+ + kOH− [OH− ]
conversion of the ordinary form of acetone (known as the + kHA [HA] + kA− [A− ], (40)
keto form) into another form (the enol form) which can
react with iodine or bromine very rapidly: where HA is acetic acid and kHA the corresponding cat-
alytic coefficient; A− is the acetate ion and kA− its catalytic
coefficient.
If an acid has a large dissociation constant, for its dis-
sociation into ions, it tends to have a large catalytic coef-
ficient; similarly the catalytic strength of a base is greater
the larger the base dissociation constant. In 1924 J. N.
Brønsted proposed the following relationship between ka ,
the catalytic coefficient of an acid, and K a , its acid disso-
ciation constant:
The way in which an acid HA catalyzes the formation ka = G a K aα , (41)
of the enol form is believed to be as follows. First the
acid transfers a proton to the oxygen atom on the acetone where G a and α are constants. A similar relationship ap-
molecule: plies to a base catalyst.
Catalysis by enzymes, the biological catalysts, is much
more specific than that by acids and bases. Some enzymes
show absolute specificity, in that they are only known to be
able to catalyze a single chemical reaction. Others show
a lower specificity, in that they are able to catalyze only a
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Kinetics (Chemistry) 197

certain type of reaction, such as ester hydrolysis. Enzymes

commonly show stereochemical specificity, being capable
of catalyzing a reaction of one stereochemical form of a
substance and not the other.
All enzymes are proteins, and they are often associ-
ated with nonprotein substances, known as co-enzymes
or prosthetic groups. Some enzymes require the presence
of certain metal ions. The catalytic action of an enzyme
appears to involve only a small region of the enzyme sur-
face, known as the active center.
The mechanism of action of enzymes is similar in some
respects to that of acids and bases but shows some impor-
tant differences. One difference relates to the influence of
the pH of the solution. If there is catalysis by acid and base FIGURE 5 Variation of rate v with substrate concentration [S] for
the rate passes through a minimum as the pH is varied, be- a reaction obeying Michaelis–Menten kinetics [Eq. (42)].
cause there is acid catalysis at low pH and base catalysis
at high pH. With enzymes the rate passes through a max- may be less than the total concentration [E]0 , since some
imum as the pH is varied. This is explained as due to the enzyme has been converted into the enzyme–substrate
presence of at least two ionizing groups at the active cen- complex ES; thus
ter. For catalysis to be possible one of these groups must
be in its acidic form and the other in its basic form, and this [E]0 = [E] + [ES] (43)
combination can only occur at intermediate pH values. Application of the steady-state treatment to the reaction
The rates of enzyme-catalyzed reactions also pass scheme gives
through a maximum as the temperature is varied. The
increase at lower temperatures is the normal effect, due to k1 [E][S] − k−1 [ES] − k2 [ES] = 0 (44)
there being an activation energy for the enzyme-catalyzed and elimination of [E] through Eq. (43) gives
reaction. Enzymes, however, like all proteins, become  
denatured at higher temperatures and lose their catalytic k−1 + k2
[E]0 = [ES] +1 (45)
activity. k1 [S]
Many patterns of behavior are found for the effect of The rate is k2 [ES], and thus
substrate concentration on the rate of an enzyme-catalyzed
k2 [E]0
reaction. For a reaction involving a single substrate the v= k−1 +k2
(46)
simplest behavior, described as Michaelis–Menten kinet- k1 [S]
+ 1
ics, is when there is a hyperbolic relationship between the or
rate v and the substrate concentration [S]: k2 [E]0 [S]
v= k−1 +k2
(47)
V [S] + [S]
v= (42) k1
K m + [S] This is equivalent to Eq. (42) with V = k2 [E]0 and
Here K m is called the Michaelis constant and V is the K m = (k−1 + k2 )/k1 .
limiting rate at high substrate concentrations. Figure 5 This is the simplest mechanism leading to Michaelis–
illustrates this behavior and notes that K m is equal to the Menten kinetics, but many other mechanisms also do
concentration at which v is equal to V /2. so. To investigate mechanisms in more detail it is nec-
This type of kinetics was explained by L. Michaelis essary to use special techniques for studying very rapid
(1875–1949) and M. L. Menten (1878–1960) in terms of reactions, such as the stopped-flow and temperature-jump
the formation of an addition complex between the enzyme methods (Section I). Various factors give deviations from
and the substrate, the complex breaking down in a second Michaelis–Menten kinetics. For example, sometimes the
step into products with release of the enzyme: complex ES adds on an additional substrate molecule to
give ES2 ; if this does not react as rapidly as ES there is a
E+S ES falling off of the rate at higher substrate concentrations.
ES → E + P Many enzyme-catalyzed reactions involve two sub-
strates, one of which for example may oxidize the other.
Under usual conditions the substrate is greatly in excess of In such cases several mechanisms have been identified.
the enzyme, so that the concentration of free enzyme [E] Sometimes one substrate A first forms a complex EA with
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198 Kinetics (Chemistry)

the enzyme, and EA then reacts with the other substrate It is almost always the case that a catalyst exerts its
B to form a ternary complex EAB which then gives prod- action by reducing the activation energy, which means
ucts: this is the ordered ternary complex mechanism. Al- that it introduces the possibility of an alternative reaction
ternatively, in the random ternary complex mechanism the path involving less energy and therefore a higher rate of
ternary complex EAB may be formed either via EA or reaction.
EB. In another mechanism the reaction of enzyme with
one substrate A leads to one product of reaction, together
with an intermediate which reacts with B to give another SEE ALSO THE FOLLOWING ARTICLES
product. All of these mechanisms lead to similar types
of kinetic behavior, and discrimination between them re- ATOMIC AND MOLECULAR COLLISIONS • CATALYSIS,
quires careful investigation. INDUSTRIAL • CHEMICAL KINETICS, EXPERIMENTATION
In recent years there has been much interest in immobi- • ION KINETICS AND ENERGETICS • LASERS • MULTI-
lized enzymes, where the enzyme has been attached to a PHOTON SPECTROSCOPY • PHARMACOKINETICS • PHO-
solid support. This has the advantage in technical work of TOCHEMISTRY, MOLECULAR • POTENTIAL ENERGY SUR-
allowing an enzyme preparation to be used many times. FACES • RADIATION PHYSICS • STATISTICAL MECHANICS
The study of the kinetics of immobilized enzymes is also
valuable in leading to an understanding of how enzymes
behave in living systems, where they are often immobi-
lized. Kinetic studies have shown that in such systems the BIBLIOGRAPHY
rate is sometimes diffusion controlled (Section VII).
Other types of homogeneous catalysis do not follow Bamford, C. H., and Tipper, C. F. H., eds. (1969). “Comprehensive Chem-
a general pattern. Sometimes, for example, substances ical Kinetics,” Elsevier Publishing Co., Amsterdam. This series of
many volumes, begun in 1969 and still appearing, is a valuable source
bring about catalysis in gas reactions by bringing about of reference to all aspects of chemical kinetics.
chain-initiation processes, or by becoming involved in Laidler, K. J. (1987). “Chemical Kinetics,” 3rd ed., Harper & Row, New
chain-propagating processes. Ions of variable valency are York.
good catalysts for certain solution reactions. For example, Laidler, K. J. (1996). “Glossary of Terms used in Chemical Kinetics,
singly charged silver ions (Ag+ ) can bring about a reduc- Including Reaction Dynamics,” Pure Appli. Chem., 68, 149.
Pilling, M. J., and Seakins, P. W. (1995). “Reaction Kinetics,” 2nd edi.,
tion with the formation of Ag2+ , which then can bring Oxford University Press, Oxford, UK.
about an oxidation; the Ag+ − Ag2+ system can therefore Zewail, A. H. (1990). “The birth of molecules,” Scientific American,
act as a mediator in oxidation–reduction systems. November, p. 76.
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Membranes, Synthetic
(Chemistry)
Michael E. Starzak
State University of New York, Binghamton

I. Membranes
II. Membrane Modifiers
III. Membrane Characterization
IV. Membrane Phenomena

GLOSSARY either of the two bulk phases, its utility often arises from its
selectivity, i.e., its ability to facilitate the transport of spe-
Amphipathic Having both hydrophilic and hydrophobic cific materials between the two bulk phases. The net flux
regions in distinct regions of the same molecule. through the membrane is characterized by a permeability
Ionophore An organic molecule that binds a polar ion to coefficient P with units of velocity. The net flux of a ma-
create a membrane soluble complex. terial through the membrane is often proportional to this
Casting Solvent is evaporated from solvated membrane permeability coefficient and the concentration gradient of
material on a support to produce a membrane. permeant between the two bulk phases.
Permeability coefficient The proportionality factor with Naturally occurring materials like β-alumina can con-
units of velocity that relates concentration gradient to duct ions like Na+ , Ag+ and H+ , and water. Sections of
flux through a membrane. this material can then be used as membranes to regulate
Selectivity Membrane ability to pass certain species the flow of these ions without modification of the basic
while rejecting others. solid structure. More often, the goal is the preparation of
Ultrafiltration Water permeation through a membrane— synthetic membranes with specific properties that permit
reverse osmosis. the membrane to be used in a particular application. For
example, a synthetic membrane permeable only to water
would be useful for reverse osmosis where pure water is
A MEMBRANE is a special structure or phase that sep- separated from an aqueous solution. The state of the art in
arates two macroscopic phases. The membrane normally membrane research is often defined by methods of prepa-
forms a thin barrier between the macroscopic phases so ration that give a membrane with the qualities desired.
that its total volume is small relative to the separated A membrane with few desirable permeability proper-
phases. Although the membrane is generally insoluble in ties can also be modified by adding molecules that impart

345
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346 Membranes, Synthetic (Chemistry)

the proper selectivity or permeability. The membrane sur- surface layer toward a high pressure limit where the hy-
face might be modified to produce a useful membrane. drocarbon chains are forced parallel and normal to the
Special molecules might be added to or formed with the surface. This more ordered monolayer has some of the
membrane to produce the desired properties. For example, properties of a liquid-crystal. The hydrocarbon chains are
special protein channels can be inserted into membranes parallel but observation of the top surface of the monolayer
to produce a membrane selective to a specific ion. The would reveal a random liquidlike structure.
membrane is then permeable only to this species. In most This ordered monolayer is used as an air/solution bar-
cases, the ultimate goal is the development of a selective rier or as a medium for selective extraction of organic
membrane optimal permeability or adsorption. material from the aqueous phase. The ordered mono-
Membranes are available for a large number of research layer also serves as the building block multilayer mem-
and industrial applications including gas separation, fuel branes. A glass slide or other support is passed through
cells, reverse osmosis, dialysis, sensors, and purification. the monolayer. With each pass, a monolayer membrane is
They also serve as the support for special processes like the transferred from the surface layer to the support. If done
oxidation reduction processes in photosynthesis or cell- properly, this monolayer is stable and is not disturbed as
cell communication. additional monolayers are added with additional passes
The synthesis and production of membranes with struc- through the ordered surface monolayer.
tures that control material flow are presented in Section I. A biological membrane separates two aqueous phases.
Section II surveys special molecules incorporated into The outer surfaces of the membrane must be hydrophilic
membranes to impart specific properties to these mem- to stabilize the two membrane/solution interfaces. This is
branes. Section III describes some techniques and instru- accomplished with a bilayer membrane, in which the or-
mentation used to characterize membranes and pore struc- dered hydrocarbon chains from two monolayers merge to
ture. Section IV illustrates some special equilibrium and form a stable central hydrocarbon region approximately
kinetic physical phenomena most conveniently observed twice the length of the hydrocarbon chains. The opposed
with membrane systems. polar head groups form outer hydrophilic surfaces to sta-
bilize the structure and the solution/membrane interfaces
(Fig. 1).
I. MEMBRANES
The bilayer structure, which is the most common mem-
brane in biological systems, was originally revealed by
A. Monolayer Membranes
experiments that first determined the total membrane area
Biological systems are protected by membranes with in a specific number of red blood cells. The cells were
molecular structures that serve as models to illustrate then destroyed, phosopholipid was separated and spread
the structure and behavior of more complicated mem- on a surface balance. The area occupied by the lipid on the
branes. Monolayer membranes are made from amphi- surface balance was exactly twice the total surface area of
pathic molecules that have a polar, water-soluble, or hy- the red blood cells.
drophilic terminal region and a hydrocarbon, nonpolar or A lipid or soap membrane of large area is inherently
hydrophobic, region that usually contains long hydrocar- unstable. A soap bubble is a good example. Research
bon chains whose length dictates membrane thickness and membranes are often formed over very small pinholes
stability. Hydrocarbon chains of 16–20 carbons generate by applying solutions of the membrane material using a
a self-stabilizing hydrocarbon phase that is insoluble in
water. Soap molecules with a weak acid terminal group or
phospholipids with two hydrocarbon chains and a polar
phosphate-centered head group united on a glycerol base
can spontaneously form membranes.
If these amphipathic molecules are spread on a water
surface, the polar groups dissolve in water to “root” the
molecules. Since the polar heads are insoluble in hydro-
carbon, the molecules normally spread to form a mono-
layer membrane on the surface of the water. In this state,
the long hydrocarbon chains can be parallel to the wa-
FIGURE 1 Ion channels in the plasma membrane. The mem-
ter surface to create an extended, random monolayer. A
brane phospholipids are arranged in a bimolecular layers with their
more-ordered, liquid crystalline monolayer is generated polar heads on the outside and their hydrophobic tails inside. The
by applying surface pressure to the monolayer. A surface bilayer is about 30 Å thick. Sitting in it are various intrinsic proteins,
balance has floating barriers that move to compress the including the channels shown here.
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Membranes, Synthetic (Chemistry) 347

pipette or brush. Bilayers are also created as hemispherical reagents, often enhances reaction rates. Zeolites with par-
bubbles at the end of a Teflon™ tube. Pressure is applied allel pores suitable for transport are formed by allowing
to the solution phase within the tube to expand membrane the zeolite structure to develop around regularly spaced
material painted across the tube outlet into a hemispheri- organic molecules that function as templates. The organic
cal bubble. In each case, solvent moves toward the support material is then purged to produce membrane with regular,
walls to form a Gibbs plateau, a ring of solvent and mem- parallel pores. Pore diameters can be controlled accurately
brane surrounding the bilayer membrane. With the proper by the choice of template molecule.
concentrations, purity, and overall cleanliness, such mem-
branes are quite stable. However, a biological cell must C. Silica Membranes
remain stable for the life of a cell. Biological lipid mem- Many glass, i.e., silicon dioxide, membranes have some
branes are believed to act as stabilizing filler between the intrinsic porosity and selectivity. The pH “glass” electrode
proteins scattered throughout the membrane. The proteins selectively absorbs H+ ions to give a potential proportional
provide the support while restricting the area needed for to the logarithm of the H+ concentration. Other mem-
an integral bilayer. Larger synthetic bilayers might be sta- branes have been developed as ion-specific electrodes
bilized using membrane molecules that crosslink to form where the membrane is selectively permeable to ions to
a more durable structure. give a potential difference proportional to the concentra-
Solvent-free bilayer membranes are formed by form- tion of that ion.
ing monolayers on water surfaces on either side of a Sensors function in a similar manner. A membrane is
Teflon™ sheet containing a pinhole. As the water (and formed directly on an electrode support so ions or so-
monolayer) level is raised slowly past the pinhole, mono- lute reaching the sensor can induce changes at the support
layers from opposite sides merge to form the solvent-free electrode that can be detected electrically. The basic prin-
bilayer across the pinhole. ciple remains the same; the membrane facilitates transport
A vesicle or liposome is a spherical bilayer that encloses of a selected material between two bulk phases and the
solution and separates it from an external solution. They transport is reduced to some observable signal that can be
might be considered synthetic cells with integral bilayer measured to establish the presence and concentration of
membranes. Vesicles form spontaneously when a solution the species selected.
is agitated with ultrasound. Vesicles formed in this man- Glass membranes can be formed with small pores that
ner are called small, unilamellar vesicles, (SUV). Larger permit separation of hydrogen from other gases. For ex-
vesicles (large unilamellar vesicles, LUV) are formed by ample, the naturally occurring pores in Corning’s Vycor
repeated freeze thaw cycles of a lipid solution. Vesicles of glass are filled with additional silicon dioxide to produce
a specific diameter are formed by high-pressure extrusion pores of a size suitable for gas separation using chemical
of the lipid solution through polycarbonate membranes. vapor deposition. SiH4 and oxygen gas, flowing across op-
The membrane pores must be homogeneous of relatively posite surfaces, diffuse into the pores and react to create
constant diameter. SiO2 with a structure containing pores suitable for the gas
A vesicle can fuse with another vesicle or a planar bi- separation.
layer to create a new homogeneous membrane. Lipid bi- Colloidal silica can also be cast, i.e., aggregated on a
layer fusion is often mediated by a polyvalent ion like Ca2+ suitable surface, to form silica membranes. The colloids
which reduces the Debye lengths of the charged double aggregate into sols on the substrate to form protomem-
layer to permit the two membranes to reach a separation branes that can be calcined to stable, gas-permeable glass
distance where attractive forces can mediate the fusion. membranes.
Membrane fusion might facilitate the transfer of drugs in
the vesicle interior to biological cell. It might also per- D. Capillary Membranes
mit drug delivery to specific cells or act as a time-release
transfer mechanism. Silica membranes with homogeneous pores are also made
The molecules within a bilayer can aggregate into dif- by heating and drawing bundles of capillaries. As the cap-
ferent phases with different degrees of order. Phase for- illary length increases, the inner capillary diameter de-
mation has been studied using fluorescence imaging. creases. The process is repeated to create capillaries with
the appropriate inside diameter. The bundles are then cut
laterally to produce planar membranes.
B. Zeolite Membranes
E. Chemical Etching
Zeolites are aluminum-silicon compounds that form struc-
tures with random pores and cavities. The environment Homogeneous channels with a narrow size distribution
within the cavities, which can be selective for specific are created by irradiating 10–20 µm polymer films such
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348 Membranes, Synthetic (Chemistry)

as polyethylene terephthalate with heavy ions like Ar+9 the cooling rate, polymer solution concentration, and the
produced by a cyclotron. The ions create damage tracks composition of the polymer or polymers selected.
that can be expanded by chemical etching to pores of the Hollow fiber (tubular) membranes are made by spinning
proper diameter. The density of pores is dictated by the or extruding the polymers. The hollow fiber membranes
time and intensity or radiation while the pore diameter is provide a large surface area for transfer and are ideal for
determined by the etching time. separations in flow systems.
Membrane polymers include polypropylene, poly
(vinylidene difluoride), polysulfone, poly(ether sulfone),
F. X-Ray Lithography poly(ether ether ketone), polyvinyl alcohol, polyacryloni-
A surface covered with a photoresist and a gold mask can trile, polycarbonate, and poly(ethylene terephthalate).
be irradiated with high-intensity, well-collimated X-rays These “tortuous pore” membranes resemble porous
that degrade the exposed regions of the polymer. The de- sponges where permeant moves through a convoluted path
graded polymer is removed to create a primary template. as it passes between bulk phases. Membranes are consid-
Galvanoforming produces a secondary metallic template ered dense when they have less than 50% void volume.
that is used as a mold for a polymer membrane with ho- However, even dense membranes can be relatively porous
mogenous pores (Fig. 2). and might require additional treatment to produce a more
selective membrane. The membrane characteristics are of-
ten altered by treating the membrane surface to produce a
G. Cast Dense Membranes region with the requisite properties. The bulk of the mem-
Polymer membranes are also formed by casting. The or- brane then functions simply as a porous support.
ganic polymer that will constitute the membrane is dis- The properties of the membrane skin might depend on
solved in a solvent and spread on a support. The solvent the composition of the casting mixture. The surface might
evaporates leaving an integral membrane with the requi- be modified by high-temperature annealing or by plasma
site properties. Membranes are also formed without sol- treatment, where a discharge in an oxygen atmosphere
vent by spreading polymer melts on the surface to leave a produces the desired changes in membrane properties. The
membrane when the system cools to ambient temperature. surface might also be modified by covalently grafting new
The final membrane structure is controlled by factors like molecules with the desired properties to the surface. All
such treatments attack the surface rather than the interior
support region of the dense membranes.

H. Porous Membranes
A membrane is classified as porous when the void vol-
umes within the membrane exceed 50% of the membrane
volume. The porous membranes can be generated from
the dense membranes by addition of a solvent that in-
duces swelling. The solvent can be evaporated from some
membranes to leave large, stable voids within the porous
membrane. The surfaces of these porous membranes can
also be modified to produce a skin with the desired selec-
tivity and permeability properties.
The fibrous membranes are porous membranes based
on materials derived from cellulose. These fibrous mem-
branes often have pores that permit small biological en-
tities like small cells or viruses from aqueous solution.
Cellulose-based materials include cellulose acetate and
cellophane.

I. Liquid Membranes
A membrane can be formed by inserting a thin layer of in-
FIGURE 2 Schematic diagram showing the preparation of a soluble liquid between two phases. This liquid membrane
metal structure by galvanoforming. might be flowed onto one aqueous phase. The second
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Membranes, Synthetic (Chemistry) 349

aqueous phase is then carefully flowed onto the membrane and solute with equal facility, i.e., the solution flows
phase to complete the system. A porous membrane might through the membrane.
also be impregnated with the membrane liquid to function Semipermeable membranes are used for reverse osmo-
as a support for this liquid membrane. Solutes that dissolve sis where an applied pressure selectively forces water from
in the membrane are absorbed and transported between the a solution through the membrane to separate it from solute.
bulk phases if there is a concentration gradient. Strong synthetic membranes are required for effective, i.e.,
high pressure, purification.
J. Ion Exchange Membranes Membranes with pores that permit a flow of small so-
lute molecules and ions as well as water can separate these
The beads of an ion exchange resin have fixed ionized sites
species from much larger protein or polymer molecules.
of common charge. The sites retain ions of opposite charge
Dialysis membranes with this property are used to purge
for variable times to permit a separation in the eluent. The
small ions from a protein solution, leaving a protein with
classical example is the separation of the lanthanide series
neutralized charge sites. The neutralized semipermeable
of ions with very similar chemical properties.
membrane can be dialyzed with a semipermeable mem-
An ion exchange membrane must have pores that con-
brane where water is transported from the protein solution
tain fixed surface charge. This fixed charge attracts coun-
to a concentrated solution leaving a more concentrated
terions into the pores for transport while rejecting co-ions,
protein solution.
ions with the same charge as those in the surface.
The ion exchange membranes are made for modify-
ing polymers to have ionizable groups that can function L. Gold-Sulfur Bonded Membranes
as the fixed charge. Anionic fixed charge is normally in-
Metal surfaces are difficult to clean to produce surfaces
troduced with sulfonic acid or carboxylic acid groups.
as supports for homogeneous membranes. Patches of ox-
Cationic fixed charge for an anion exchange membrane
idized surface can reject membrane binding to produce
uses positive groups like alkyl ammonium. For example,
gaps in the membrane barrier to spoil the effectiveness of
Nafion 117 has a polytetrafluoroethylene backbone with
the membrane. Membrane monolayers can be bound to
regularly spaced fluorovinyl ether pendant side chains that
intrinsically clean gold surfaces using a gold-sulfur link-
terminate in a sulfonic acid. The concentration of fixed
age. Long hydrocarbon chains with a terminal sulfur bind
charge is high and, when the pores and channels within
densely and homogeneously on the fold surface to produce
the membrane are filled with water, the system functions
an integral membrane. Since the gold substrate functions
as a high concentration electrolytic system.
as an electrode, the combination is particularly suited to
The ion exchange membranes are used in systems where
the development of chemical sensors. The monolayer is
ions of specific charge must be transported. They are used
impregnated with molecules that permit selected species
as separators in fuel cells and for electrodialysis where
to react to the electrode for oxidation or reduction and,
ions must move between phases.
through those chemical changes, detection.
K. Semipermeable Membranes
Semipermeable membranes that transport only water II. MEMBRANE MODIFIERS
while blocking solute flow were discovered by Nollet
200 years ago. They are relatively common in biological While both selectivity and high permeability are charac-
systems. For example, frog skin is often used as a semi- teristic of an ideal membrane, it might be worthwhile
permeable membrane. Synthetic membranes such as to sacrifice high permeability for excellent selectivity.
cellophane and membranes made with polyvinyl alco- This condition can be reached by impregnating an im-
hol, polyurethane, and polytrifluorochloroethylene sele- permeable membrane with molecules that provide highly
ctively transmit water. Their ability to transport water is selective pathways through the membrane. Biological evo-
quantified with their ultrafiltration coefficient, the pro- lution has produced a large number of protein molecules
portionality constant that relates the concentration gradi- that are highly selective to specific chemicals. Although
ent to the net water flux through the membrane. The reflec- their densities in natural cells are often quite low, molec-
tion coefficient measures the relative selectivity of the ular biology provides the means to produce large samples
membrane for water and solute. A reflection coefficient of such proteins. If a large number of such highly selective
of one represents the ideal semipermeable membrane proteins are incorporated into a synthetic membrane, both
where all solute is rejected and only water flows through high selectivity and permeability are possible. The pro-
the membrane. A reflection coefficient of zero signifies a teins transport material across the membrane by several
membrane with pores that permit the flow of both solvent distinct mechanisms.
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350 Membranes, Synthetic (Chemistry)

A. Carrier Molecules central core lined with polar groups. An ion, approaching
this molecular channel, replaces some of its waters of hy-
A hydrophobic membrane like a lipid bilayer blocks the
dration with channel binding groups so that the channel
passage of both metal ions and water since they are in-
interior becomes a continuation of the aqueous solution.
soluble in the nonpolar central region formed from the
Transport across the membrane is then a series of transi-
hydrocarbon chains of the lipids. Ionic solubility is in-
tions between the charged intrachannel binding sites until
creased, however, if the metal ion is encased in organic
the ion is released on the opposite side of the membrane.
ligands which mitigate the effects of the ion charge in the
Biological protein channels can be extremely selective.
membrane. The tetraphenylborate anion, with the boron
A variety of special channels exist to transport sodium,
charge center surrounded by four bulky, nonpolar phenyl
potassium, and calcium ions, the most common biologi-
groups is soluble in the membrane and enters with a single
cal cations. Other channels exist to transport anions like
negative charge. The tetraphenylarsenate cation dissolves
carbonate and chloride.
in the membrane with a net positive charge. The ions are
The number of known ion-selective channels has grown
stabilized in sites near the membrane/solution interfaces.
exponentially with the development of the patch-clamp
Because the bilayer membrane is thin, a small electri-
technique. A specially polished pipette tip is brought care-
cal potential in the millivolt range can produce extremely
fully into contact with the membrane of a biological cell.
large electric fields (ca. 107 V/m) in the membrane. These
Suction is applied to the pipette to hold the cell to the
fields are sufficient to induce a transition in which the ion
pipette tip. Binding occurs between the glass of the tip and
passes through the hydrophobic central region to a site
the cell membrane to produce a high-resistance “gigohm”
at the opposite membrane/solution interface. The motion
seal. The seal is extremely strong and the pipette can be
of the ions produces an observable current in an external
retracted carrying a small section of the cell membrane
circuit. The current decay is exponential indicating inde-
across the tip. This patch membrane can be inserted into a
pendent transitions of the ions.
second solution to produce a tiny area of membrane sep-
Membrane-soluble carrier molecules can bind an ion
arating two aqueous phases. The small membrane area
from aqueous solution to create a charged ion/carrier com-
contains very few channels and the system is studied us-
plex within the membrane. This soluble ion then moves
ing single channel techniques which can monitor the small
down a concentration or electrical gradient to the opposite
currents through a single open channel. The properties of
interface where the ion is released to that solution. Carrier
the channel are deduced from the kinetic behavior of the
transport is modeled in four kinetic steps: (1) the carrier
channel.
absorbs an ion from solution 1; (2) the ion/carrier com-
Early studies on channels were restricted to a limited
plex moves down its gradient to the opposite interface;
number of biological systems that could be probed ex-
(3) the ion dissociates from the carrier or ionophore; and
perimentally with internal electrodes. For example, the
(4) the carrier (without ion) diffuses back to the first in-
squid axon, the portion of the nerve cell which transmits
terface to bind another ion and repeat the four step cycle.
a nervous impulse to the muscles that contract the ani-
For each cycle, one carrier transports one ion across the
mal’s mantle for flight, is roughly ten times larger than a
hydrophobic membrane.
human axon. Piggy-back electrodes with voltage-sensing
A carrier molecule can have structure or binding sites
and current-carrying electrodes glued together were in-
that make it suitable to transport a specific ion or class of
serted axially into the axon. A voltage clamp was then
ions. Valinomycin, for example, binds univalent K+ ion to
used to maintain a constant transmembrane potential while
initiate the four-step carrier/ion cycle. A class of macro-
current through channels in the axon membrane was mon-
cyclic molecules, the crown ethers, absorbs ions into the
itored. The patch-clamp technique has largely supplanted
central cavity of their crown-like structure to produce the
these more restricted membrane systems since a patch of
membrane-soluble ion complexes. Special ionophores like
membrane can be excised from almost any cell.
lasalocid and A23187 with judiciously placed carboxyl
The gramicidin channel, formed by dimerization of two
groups are selective for polyvalent ions such as Ca (II) or
molecules in a loose helical conformation (Fig. 3), has
lanthanide ions like Eu (III). The ionophore wraps around
been studied extensively as a model system. The helical
the ion as the carboxyl groups bind to produce the mem-
dimer spans the membrane to produce a channel through
brane soluble complex ion.
the hollow center of the helix with anionic sites or re-
gions to facilitate cation transport. The channel transmits
only univalent cations. Divalent calcium ion blocks ion
B. Channel Molecules
flow through the channel. The channel exhibits the anoma-
Ions can be transported across a hydrophobic membrane lous mole fraction effect. Both univalent thallous ion and
if this membrane is traversed by molecules with a hollow sodium ion are very permeable when gramicidin dimers
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Membranes, Synthetic (Chemistry) 351

FIGURE 4 The arrangement of helical regions of a single protein

molecule embedded in a membrane. Several such units aggregate
FIGURE 3 Molecular model of the gramicidin A channel. The two to create an operational channel.
monomers are placed head-to-head with their N termini in near
contact. (From Ury, D. W., Jing, T. L., Luan, C. H., and Waller, M.
(1988). “Current Topics in Membranes and Transport,” 33, 51–90.) had to undergo the conformational change to produce an
open channel.
The sodium channel is transient. On excitation, three
are present. However, in mixtures of the two ions with proteins change conformation to produce an open channel
a small Tl+ cation mole fraction, channel currents fall while a fourth protein changes conformation to initiate a
significantly. Depending on conditions, the thallous ion subsequent closing of the channel.
functions either as a permeant cation or a blocking ion.
Channels like alamethicin form when several molecules
aggregate to form a structure with a central pore. Alame- III. MEMBRANE CHARACTERIZATION
thicin is a simple example of a gated channel where an
applied transmembrane potential induces aggregation of The effectiveness of a membrane is often determined by
the molecules to form the conducting channel. Channel how well it performs the function for which it is developed.
formation might be viewed as the aggregation of several However, any membrane can be improved if the structure
long rods that span the membrane. The aggregated “rods” which results from its preparation is known. The structure
leave a central void space that functions as a channel. Ag- can suggest changes in the mode of preparation or con-
gregation of a larger number of rods produces a larger ditioning that enhance the overall quality. Some physical
central channel. techniques used to characterize the size, shape, size dis-
The rod analogy has proved to be an accurate descrip- tribution, and density of pores and the molecular structure
tion of the more complicated biological channels. Molecu- of the membrane surface follow.
lar biology studies of the primary protein structure, i.e., the
amino acid sequence, reveals sequences that are stable in
an α-helix conformation. A channel-forming protein then A. Atomic Force Microscopy
consists of regions of α-helix of length roughly equal to the An atomic force microscope uses the deflection produced
membrane thickness punctuated by regions of random pro- in a fine tip by interactions with atoms in the surface of
tein chain. The protein inserts through the membrane as a a membrane to reconstruct the surface structure of that
series of parallel rods where one rod ultimately forms part membrane. A piezoelectric drive moves the sample sur-
of the pore wall (Fig. 4). The protein sections that connect face under the tip. The motions of the tip are converted into
the helical rods organize for different channel functions. a three-dimensional image of the surface. Atomic force
The operational channel might consist of 4–6 of these par- microscopy requires no surface preparation so that the
allel rod proteins which aggregate to form the central pore. membrane can be observed in its normal environment.
The need for four separate channel molecules to pro-
duce an operational channel is consistent with the earli-
B. Electron Microscopy
est kinetic models for a channel. Hodgkin and Huxley, in
1952, postulated a model for the potassium channel with Moving electrons demonstrate wave behavior. With the
four independent channel proteins that could change con- proper electron velocity, produced by moving the electron
formation on the millisecond time scale. All four channels in an electric field, wavelengths in the nanometer range
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352 Membranes, Synthetic (Chemistry)

are possible. These wavelengths permit resolution of brane capacitance. The capacitance then determines the
structures on the nanometer scale. Transmission elec- membrane thickness if the area of the membrane is known.
tron microscopy (TEM), where the electrons penetrate If the membrane under study also contains channels or
through thin cross-sectional samples (50 nm) that have pores that transmit ions, the current also contains an ohmic
been freezedried and sectioned, uses the wave interference component and the electrical properties of the membrane
patterns to establish the structure of the sample. are modeled as a parallel resistor-capacitor combination.
Scanning electron microscopy (SEM) utilizes scattered Liposomes or vesicles in solution can be modeled
electrons to generate the image and has higher resolu- as nonconducting spheres embedded in a conduc-
tion than TEM. However, both techniques require sample tive medium. The measured capacity of the ensemble of
preparation which might alter the structure of the sample vesicles is converted to a capacitance per unit area of mem-
under observation. In addition, the high voltages required brane surface which, in turn, determines the membrane
to accelerate the electrons to the proper wavelength can thickness.
also cause damage to the surfaces.

IV. MEMBRANE PHENOMENA

C. Computer-Aided Image Analysis
An optical microscope can be used to observe surfaces if Membranes display some physical phenomena that might
it is interfaced with a computer system that can be used not normally be observed in bulk phases.
to enhance images of the surface. The computer corrects
for the image degradation that occurs when the light wave- A. Equilibrium Phenomena
length is comparable to the dimensions of the object being
1. Osmotic Pressure
measured. The computer system resolves the light image
by computationally removing the interference effects. A semipermeable membrane that permits only water flow
facilitates the flow of water from a higher to lower concen-
tration, e.g., from pure water to a saline solution. The pro-
D. The Bubble Point Method
cess could continue indefinitely unless the driving force
The size of pores in a membrane can be established by forc- for this flow is counterbalanced with an equal and opposite
ing liquid through the membrane under pressure. The time force. For osmotic pressure equilibrium, the hydrostatic
for the appearance of the bubble determines the largest pressure head resulting from the water flow will exactly
pore size in the membrane. The pressure necessary to pro- balance the concentration gradient driving force of the
duce a bubble can be reduced by using liquid mixtures that water. To a good approximation, the osmotic pressure is
minimize the surface tension within the pore. directly proportional to the molar concentration of the so-
The surface tension is lower if mercury is used as the lution when opposed by a bath with pure water and can be
bubble-forming solvent. In mercury porosimetry, how- used to determine the molar concentration of the solution.
ever, some mercury might be retained within the pores If the solute weight and solution volume are known, the
to cancel some advantages of this liquid. molecular weight of the solute can be determined.
The hydrostatic pressure can be increased to reverse the
flow of water so that it flows from the solution phase to the
E. Other Techniques
pure water phase. This reverse osmosis or ultrafiltration
A number of related techniques use adsorbance of a gas or provides a convenient way to purify water.
solid at a membrane surface to determine the total surface
area. Adsorption techniques can be used to determine the 2. The Donnan Equilibrium
density and size of the pores within the membrane as well.
Planar bilayer membranes are characterized by their If a membrane is permeable to small cations and anions,
electrical response since the insulating bilayer membrane the presence of a large membrane-impermeable molecule
and the two conducting ionic solutions are electrically with counterions can produce a salt concentration gradi-
equivalent to a capacitor with the membrane as the di- ent across the membrane. For a salt C+ A− , the Donnan
electric. The current through a capacitor is directly pro- equilibrium requires that the product of cation and anion
portional to the rate of change of the voltage on the capaci- concentrations in each bulk phase be equal
tor, i = C d V /dt. The capacitance, in turn, is related to the
[C+ ]1 [A− ]1 = [C+ ]2 [A− ]2
thickness of the membrane and its dielectric constant. The
membrane capacitance is determined by applying a ramp If an impermeable anion, P z− with z cations C+ is present
potential with a constant d V /dt across the membrane to on side 1, the total concentration of C+ in that bath in-
give a constant current that can be converted to the mem- creases and CA must move through the membrane to the
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Membranes, Synthetic (Chemistry) 353

opposite bulk phase to reestablish the equilibrium condi- because the fixed negative charge in membrane channels
tion. The net effect is a reduction of salt CA in Bath 1, the excludes anions from the pores so that only cations move
solution with the protein, and a CA concentration gradient with the electrial potential gradient; the flow of anions in
across the membrane. the opposite direction is reduced significantly by the fixed
charge. The waters of hydration on the moving cations are
carried through the pores as well to produce the observed
3. The Electrochemical Potential
water flow that characterizes electroosmosis.
An ion exchange membrane that can pass ions of one po-
larity while rejecting those of opposite polarity will pro- 3. Streaming Potential and Current
duce an electrical potential to balance the permeable ion
In electroosmosis, an applied voltage produces a flow of
concentration gradient. For example, channels with an-
neutral water, i.e., the ion flow and water flow are coupled.
ion charge will encourage the passage of cation while re-
The reciprocal process occurs when solution is forced
pelling anion to produce a charge separation and electrical
through the membrane with charged pores under a hy-
potential
drostatic pressure. Ions of charge opposite to that fixed in
V = V2 − V1 = −(RT )/(z F) ln[c2 /c1 ] the pore walls are carried along with the water while the
co-ions are repelled from the pores. The flow of one type of
where RT /F ∼ 25 mV and z is the charge on the permeant
charge produces a net current through the channels. This
ion.
streaming current would appear in a closed electrical cir-
A strong, cation permeable membrane might tap the the
cuit. If the electrical circuit is open, a streaming potential
Na+ concentration gradient as a fresh water river reaches
appears across the pore or channel.
the ocean to produce electrical power.
4. Oscillations
B. Dynamic Phenomena
Oscillatory behavior is the exception in homogeneous
1. Ultrafiltration phases although there are some special chemical reac-
tions that do produce oscillatory behavior. A membrane
A water concentration gradient or an externally applied
system is a multiphase system and oscillations can be gen-
hydrostatic pressure can force water through a semiperme-
erated with a judicious choice of external forces on the
able membrane. The flux of water through the membrane
membrane.
is directly proportional to the concentration gradient. This
One basic oscillatory system uses the kinetic behavior
is an example of Fick’s first law for a flux J
of protein channels for sodium and potassium ion in
J = P(c1 − c2 ) a nerve membrane. Before electrical excitation, the
sodium channels are closed to sodium ion flow and
where P is the permeability coefficient.
the electrochemical gradient of 110 mV possible with
A membrane permeable to both water and solute re-
the sodium ion gradient does not develop. The more per-
quires flux equations for both the water and the solute.
meable potassium channels tap the potassium ion gradient
The fluxes of water and solute are directly proportional to
to produce an internal electrical potential of −60 mV
their respective concentration gradients. In addition, the
relative to the external solution as ground. On excitation,
flows can be coupled so that a hydrostatic pressure also
the transient channels open and then close. As the sodium
produces a solute flux while a concentration gradient, pro-
channels open, the sodium electrochemical potential of
portional to osmotic pressure π , produces a water flux. The
110 mV appears to produce a peak internal potential
linear equations
of −60 + 110 = + 40 mV, The one-shot oscillation is
Jw = L 11 P + L 12 π completed as the sodium channel closes, the sodium-ion
induced potential is lost, and the internal potential returns
Js = L 21 P + L 22 π
to the potassium channel dominated potential of −60 mV.
obey the Onsager reciprocal relations The entire oscillation is controlled only by the sodium
and potassium channels and the sodium and potassium
L 12 = L 21
ion concentration gradients across the membrane.

2. Electroosmosis
SEE ALSO THE FOLLOWING ARTICLES
For a membrane with pores containing fixed negative
charge, the flow of ions through these pores produces a BATTERIES • CRYSTALLIZATION PROCESSES • DIS-
concomitant flow of water. This electroosmosis results TILLATION • ELECTROCHEMICAL ENGINEERING • ION
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354 Membranes, Synthetic (Chemistry)

TRANSPORT ACROSS BIOLOGICAL MEMBRANES • Hiemenz, P. (1986). “Principles of Surface and Colloid Chemistry,”
MEMBRANES, SYNTHETIC, APPLICATIONS • SOLVENT Marcel Dekker, New York.
EXTRACTION • SURFACE CHEMISTRY • WASTEWATER Kesting, R. (1971). “Synthetic Polymer Membranes,” McGraw-Hill,
New York.
TREATMENT AND WATER RECLAMATION Lloyd, D. R., ed. (1985). Materials Science of Synthetic Membranes,
ACS Symposium Series No. 269, Am. Chem. Soc., Washington, DC.
Sorensen, T. S. (1999). “Surface Chemistry and Electrochemistry of
Membranes,” Marcel Dekker, New York.
BIBLIOGRAPHY Starzak, M. (1984). “The Physical Chemistry of Membranes,” Academic
Press, New York.
Aideley, D., and Stanfield, R. (1996). “Ion Channels,” Cambridge Univ. Starzak, M. (1994). “Kinetics of Permeation and Gating in Membrane
Press, Cambridge. Channels,” 46: 61.
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Micelles
Srinivas Manne L. K. Patterson
University of Arizona University of Notre Dame

I. Brief History
II. Micelle Formation
III. Micellar Structure
IV. Micellar Kinetics
V. Solubilization
VI. Micellar Catalysis
VII. Micelles at Interfaces
VIII. Surfactant Aggregates at Solid-Liquid
Interfaces
IX. Conclusion

GLOSSARY indicates a completely ionized Stern layer while a

value of 0 denotes that all headgroups are bound to
Aggregation number Number of monomeric surfactant counter ions.
units per micelle. Hydration number Number of water molecules moving
Amphiphilic Term denoting the dual nature of a molecule with a micelle as a kinetic entity. Generally expressed
that has both a water-insoluble hydrocarbon group and in terms of water molecules per surfactant molecule.
a polar headgroup. For examples, see Fig. 2. Solubilization Inclusion of normally hydrophobic or
Critical micelle concentration (cmc) Concentration of only slightly polar materials (solubilizates or sub-
a surfactant in solution above which the formation of strates) into micelles in aqueous solution.
micelles occurs. It is generally the concentration above Surfactant Amphiphilic molecule generally perceived as
which a physical property associated with surfactant having a polar headgroup, either charged or neutral, and
aggregation changes markedly (e.g., surface tension, a long-chain hydrocarbon tail.
light scattering, or conductivity). The concept of a crit-
ical micelle concentration carries the implication of a
phase separation, which is not rigorously true; however, MICELLE is derived from the Latin term micella meaning
the cmc remains a good working measure of micelle “small bit.” In aqueous solution, micelles are aggregates
formation. of surfactant molecules that form spontaneously when ap-
Degree of ionization (α) Fraction of dissociated ionic propriate conditions, such as concentration, temperature,
headgroups at the micelle surface. A value of 1.0 and ionic strength, are met. Depending both on such

661
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662 Micelles

although evidence for systematic study of such properties

appears only in the nineteenth century. In 1846, Peroz
reported that soap solutions have the power to increase
the solubility of various substances; W. Kuehne noted
in 1868 that cholesterol, which is essentially insoluble
in water, aqueous mineral acids, and alkali solutions, is
soluble in soap and solutions of bile salts. Oil-soluble
dyes were reported by E. Pfluger in 1899 to be solubil-
ized in aqueous soap solutions and bile salts. As early as
1892 C. Engler and E. Dieckhoff noted that the effective-
ness of a soap in inducing solubility was related to the
length of the paraffin chain in the soap. The concept of
an aggregate as responsible for these unusual properties
was not suggested until the twentieth century. With
FIGURE 1 Highly simplified pictorial model of a spherical ionic the early work of investigators such as J. W. McBain
micelle. Symbols indicate counterions (x), headgroups (), and (1913), whose conductivity measurements on stearate
hydrocarbon chains (vvv). [From Fendler, J. H., and Fendler, stimulated the investigation of aggregation in soap solu-
E. J. (1975). “Catalysis in Micellar and Macromolecular Systems,” tion, and who demonstrated the reversible character of
Academic Press, New York.]
micelle formation, numerous studies related the unusual
physical properties of surfactant-bearing solutions to the
conditions and on surfactant structure, these aggregates
characteristics of micelles. It was McBain who intro-
may be composed of only a few or up to more than 1000
duced the term micelle in 1913 to describe colloidal parti-
monomeric units. A naive representation of the aggregate
cles of detergents and soaps. C. R. Bury and E. R. Jones in
is given in Fig. 1. This very simplistic approach is nev-
1927 related the marked change in activity coefficient for
ertheless useful for orientation to the discussion that fol-
butyric acid solutions to micelle formation and suggested
lows. The thermodynamic constraints of water exclude
that the dual nature of the fatty acid (hydrophobic and
the hydrophobic moieties of the surfactant into a princi-
hydrophylic) leads to micelle formation. Bury and Davies
pally hydrocarbon microregion while leaving the charged
in 1930 proposed the concept of the critical micelle
or polar headgroups in contact with the aqueous phase.
concentration (the surfactant concentration above which
This ordering of the micelle constituents produces an in-
micelles form); their work noted that this number is a
terfacial region of high polarity or, in the case of charged
function of the length of the hydrocarbon moiety. The
surfactants, high surface potential. The interfacial region
correct interpretation of the role of water in forces respon-
may involve water–hydrocarbon interaction. Although it
sible for micelle formation (i.e., the hydrophobic effect)
is discussed in terms of distinct regions, the micelle is
was proposed by G. S. Hartley in 1936. He was also
viewed as a highly dynamic structure with rapid exchange
responsible for suggesting the roughly spherical model for
of surfactant material between the aqueous bulk solution
the micelle, a suggestion that gained general favor later.
and the hydrocarbon pseudo-phase. The presence of mi-
The development of readily available instrumentation
celles in solution can dramatically alter the solubility of
for optical spectroscopy, light scattering, NMR, ESR, and
otherwise water-insoluble materials, and their electrostatic
so on, has provided possibilities for investigation of many
properties may strongly mediate the distribution and ki-
micelle properties at the molecular level. Especially dur-
netics of polar species. There has emerged a literature
ing the decades of the 1960s and 1970s, application of
concerning associated catalytic effects for specific types
such techniques, along with a wide variety of theoretical
of reactions. Additionally, the overall structure has evoked
studies, enhanced manyfold the information on micellar
comparison with certain biological entities for which mi-
aggregates in solution.
celles have been used as simple models. While there are
other molecular assemblies that bear the term micelle (bile
salts and surfactants in nonpolar media), these systems are
II. MICELLE FORMATION
not included in this discussion.
The micellar behavior of any surfactant is determined by
I. BRIEF HISTORY the molecular structure of the surfactant. All surfactants
have in common both a hydrophilic headgroup, which may
Many of the properties of soap in water, used by humans or may not be charged, and a hydrophobic moiety that
for centuries, may be ascribed to the presence of micelles, would exhibit little water solubility alone. Formulas for
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Micelles 663

FIGURE 2 Examples of several micellar surfactants.

typical micellar surfactants are given in Fig. 2, in which consideration of the driving forces for molecular organiza-
the dual, or amphiphilic, nature of these molecules may tion in this type of aggregate. Two principal factors govern
be easily seen. For example, in the case of sodium dode- such organization: (1) tailgroup–tailgroup interactions, in
cylsulfate (SDS), one of the most widely used surfactants which the hydrophobic effect (see Section II.A) causes the
in micelle studies, the molecule consists of a charged sul- nonpolar entities to coalesce; (2) headgroup–headgroup
fate headgroup (hydrophilic) and a 12-carbon aliphatic and headgroup–water interactions which oppose the total
chain (hydrophobic). Such chains are commonly termed separation of surfactant into a nonpolar phase. The in-
hydrocarbon or hydrophobic tails. Also among the most terplay of these two factors determines the concentration
extensively studied groups of surfactants are the tertiary onset of micelle formation, the micelle size distribution,
amines (e.g., hexadecyltrimethylammonium bromide, and subsequent physical and chemical properties.
CTAB). For uncharged surfactants, the molecule may have
a hydroxyl headgroup, but normally it includes a region
A. The Hydrophobic Effect
of linked ethoxy groups that may undergo some hydration
to compensate for the lack of charge on the OH. See the The marked insolubility of nonpolar molecules in wa-
polyoxyethylene alcohol (or ethyleneglycolmonoether) in ter is essentially an entropic effect and arises, not from
the figure. energy of association between hydrocarbon molecules,
It was established early that surfactants dissolve as sin- but rather from the unique hydrogen-bond character
gle molecules in water up to a given concentration (de- of water structure. Simply stated, the hydrogen-bonded
pendent on temperature and ionic strength), beyond which structure of bulk water must be distorted to accommodate
they are no longer soluble in water as monomeric units but hydrocarbon molecules. H2 O forms an ordered, cagelike
form aggregates. The monomeric surfactant concentration
beyond which added surfactant forms micelles is termed
the critical micelle concentration (cmc). Micelle forma-
tion is not a matter of simple phase separation. There is a
region over which both monomer concentration increases
and aggregation takes place. Experimentally, this region
is determined by plotting measurements of some physical
or spectroscopic property that changes markedly with mi-
celle formation as a function of surfactant concentration.
Data from low and high concentrations are extrapolated
to an intersection point that is taken as the cmc. Some of
the properties that exhibit such behavior are illustrated in
FIGURE 3 Concentration-dependent behavior of some physi-
Fig. 3. cal properties for a micelle-forming surfactant in solution. [From
Any understanding of effects produced in aqueous so- Lindman, B., and Wennerström, H. (1980). Top. Curr. Chem. 87,
lution by the presence of micelles must be preceded by a 1–83.]
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664 Micelles

structure around nonpolar solutes (an effect known as

hydrophobic hydration) in an effort to give up as few
H-bonds as possible. This constraint therefore leads to sig-
nificantly restricted mobility of H2 O in the hydration layer.
The thermodynamic barrier to solubility in water is
therefore largely dependent on the surface area of the cav-
ity created in the water for water–hydrocarbon contact,
which is proportional to the length of the hydrocarbon.
For n-alkanes, it is known that the chemical potential for
transfer from pure liquid hydrocarbon to aqueous solution
is linearly dependent on the number of CH2 groups in the
molecule (n C ) and has been written as FIGURE 4 Plots of ln cmc versus hydrocarbon chain length at
25◦ C, unless otherwise stated: A, alkyl hexaoxyethylene glycol
µ0HC − µ0aq = (−2436 − 884)n C cal/mol. (1) monoethers; B, alkyl sulfinyl alcohols; C, alkyl glucosides; D, alkyl
trimethylammonium bromides in 0.5 M NaBr; E, N-alkyl betaines;
Introduction of a double bond causes the first term to and F, alkyl sulfates in the absence of added salt at 40◦ C. [Com-
drop from 2436 to 1503. For dialkenes it falls further to posite from Tanford, C. (1980). “The Hydrophobic Effect: Forma-
903, indicating that the double bonds increase the overall tion of Micelles and Biological Membranes,” Wiley, New York.]
solubility but do not perturb the essentially linear depen-
dence on the number of CH2 groups present. These con-
hibits several features contributing to micelle character.
siderations, then, provide a measure of the hydrophobic
While the headgroups provide water solubility to an oth-
character of the surfactant hydrocarbon chain in isolation
erwise insoluble entity, their localization in the surface
from the headgroup.
region of the micelle (see Fig. 1) introduces large charge–
The coalescence of hydrocarbon chains allows the
charge repulsions that limit the number of surfactant
ordered hydration layers to be expelled into the bulk
monomers that may come together. The influence of the
phase, resulting in a considerable net gain in entropy.
headgroups may be seen in the effects of counterion con-
Indeed, micelle formation is primarily an entropy-driven
centration on both cmc and micellar size. By reducing the
process; the enthalpy of hydrocarbon association is com-
repulsive forces, the cmc is markedly reduced as may be
paratively weak and can even be endothermic (opposing
seen in Fig. 5, which provides data for cmc versus ionic
association). As an example, dimethyl-n-dodecylamine
strength. Further, reduction in headgroup–headgroup re-
oxide (illustrated in Fig. 2) undergoes or free energy
pulsions also raises the limit to the number of monomers
change of micellization of G = −6.2 kcal/mol (a
per micellar unit and the aggregation number. This
fairly typical value), of which the enthalpic contribution
behavior also is illustrated in Fig. 5. The effects upon
H = +1.7 kcal/mol and the entropic contribution
cmc and micelle size, produced by changing various
−T  S = −7.9 kcal/mol.
of the parameters that alter hydrophobic and headgroup
Because hydrocarbon structure plays a marked role in
alkane and alkene solubility, it also influences strongly
the solubility of surfactants. To express aggregation data
in thermodynamic terms by analogy with the hydrocarbon
data discussed earlier, it is necessary to consider ln cmc as
the measure of free energy (the difference in free energy
for a surfactant in the micelle and in water may be shown
proportional to ln cmc). Indeed, for a group of surfactants
with a common headgroup, a linear relationship between
hydrocarbon chain length and ln cmc can be observed
(Fig. 4). The addition of a double bond in the chain has an
effect equivalent to a reduction in chain length of 1–1.5
carbons. Typical examples are the fatty acid soaps, (e.g.,
salts of stearic, oleic, and linoleic acids). FIGURE 5 Dependence of the cmc and average micelle size on
ionic strength and counterion at 25◦ C. Curve 1, Na dodecyl sulfate
with added NaCl; curve 2, dodecyltrimethylammonium bromide
B. Electrostatic Interactions with added NaBr; and curve 3, dodecyltrimethylammonium chlo-
ride with added NaCl. [Composite from Tanford, C. (1980). “The
The counterbalancing influence to the hydrophobic char- Hydrophobic Effect: Formation of Micelles and Biological Mem-
acter of the surfactant is the polar headgroup, which ex- branes,” Wiley, New York.]
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Micelles 665

TABLE I Effect of Physical and Structural Properties on the as well. The absence of highly repulsive headgroups in
Critical Micelle Concentration (cmc), Aggregation Number nonionic systems is expected to affect both cmc and micel-
(n), and Degree of Ionization (α)a
lar size. And as expected, it is found that the cmc is about
Surfactant cmc (mM) n α two orders of magnitude lower for a nonionic surfactant
than for an ionic one having the same-length aliphatic
Chain length
group. With the nonionic polyoxyethylene surfactants,
C10 N(CH3 )3 Br 63 52 0.18
micelle size exhibits a marked dependence on the size of
C12 N(CH3 )3 Br 15 73 0.16
the polyoxyethylene chain. With C12 H25 (OEt)8 OH, only
C14 N(CH3 )3 Br 3.6 107 0.15
small micelles with aggregation numbers up to about
Surfactant branching
120 are seen at room temperature, even at high concen-
C14 OSO3 Na 1.7 — —
tration, while with the (OEt)6 analog, size can grow to
C12 CH(CH3 )OSO3 Na 3.3 — —
quite large values.
C11 CH(CH2 CH3 )OSO3 Na 5.8 — —
Surfactant head size
C10 NH3 Br 16 1100 0.07
III. MICELLAR STRUCTURE
C10 NH2 CH3 Br 20 670 0.07
C10 NH(CH3 )2 Br 12 69 0.08
As a consequence of the interactions discussed previ-
C10 (CH3 )3 Br 18 48 0.13
ously, the micelle can be visualized as being composed
C14 N(CH3 )3 Br 3.5 71 0.14
of three regions: (1) the hydrocarbon core, (2) the polar
C14 N(n-Pr)3 Br 2.1 48 0.11
surface layer, and (3) the diffuse double layer. These may
Counterion type
be considered separately along with the tools that have
C12 N(CH3 )3 Br (0.5 M NaF) 8.4 59 0.21
been used to give us our present perception of the overall
C12 N(CH3 )3 Br (0.5 M NaCl) 3.8 62 0.20
structure.
C12 N(CH3 )3 Br (0.5 M NaBr) 1.9 84 0.17
C12 N(CH3 )3 Br (0.5 M NalO3 ) 5.1 38 0.24
Temperature A. The Hydrocarbon Core
C12 N(CH3 )3 Br (25◦ C) 15 43 0.17
In early work, Hartley suggested that the hydrocarbon in-
C12 N(CH3 )3 Br (35◦ C) 15 34 0.18
terior of the micelle must be liquidlike if one is to under-
C12 N(CH3 )3 Br (45◦ C) 17 28 0.19
stand its extensive solubilization properties. Very little has
C12 N(CH3 )3 Br (55◦ C) 17 24 0.20
happened that would alter that view. Since alkanes with
Salt concentration
structures analogous to the hydrocarbon tails found in sur-
C14 OSO3 Na (0.0125 M NaCl) 1.7 120 0.12
factants exhibit freezing points generally much lower than
C14 OSO3 Na (0.050 M NaCl) 1.1 144 0.11
the temperatures at which micelles are studied, the liquid-
C14 OSO3 Na (0.10 M NaCl) 0.32 153 0.11
like nature of the core is to be expected.
Surfactant concentration
Many studies have been directed at reaching some quan-
C12 OSO3 Na (0.012 M) — 83 0.26
titative view of the micellar interior. Thermodynamic data
C12 OSO3 Na (0.020 M) — 87 0.26
taken from partial molal properties indicate that these
C12 OSO3 Na (0.129 M) — 110 0.26
properties in micelles are comparable to those found in liq-
Nonelectrolyte additive
uid hydrocarbons. Several spectroscopic approaches have
C12 OSO3 Na (pure H2 O) 5.7 — —
been used including fluorescence depolarization and ESR
C12 OSO3 Na (6 M urea) 9.5 — —
measurements involving nitroxide spin labels. Both of
C12 OSO3 Na (0.06 mole fraction MeOH) 7.9 64 0.19
these measure the mobility of the probe within the micelle.
C12 OSO3 Na (0.12 mole fraction MeOH) 9.0 23 0.22
A somewhat lower mobility than in pure hydrocarbon is
a From Menger, F. M. (1977). In “Bioorganic Chemistry III. Macro- found for the fluorescence probes, and a lower mobility has
and Multimolecular Systems” (E. E. van Tamelen, ed.). Academic Press, been observed for the nitroxide than in aqueous solution.
New York. Such measurements have been criticized by suggesting
that the probes themselves significantly perturb the mi-
interactions, are summarized in Table I for various ionic celle and, in monitoring probe motion, do not give a true
systems. picture of the liquid character of the core. Further, some of
With nonionic surfactants, for example, the poly- these probes are, indeed, of a size significant on the scale
oxyethylene alcohol in Fig. 2, the solubility of the of a micelle. Additionally, there is evidence that some such
headgroup comes from hydration, and the headgroup probes tend to localize near the micelle surface where flu-
repulsions are much smaller. Steric factors may play a role idity can differ from that found near the micellar center.
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666 Micelles

An approach that involves no such perturbations is the is found, that the cmc is lowest for I− , increasing as one
use of 13 C NMR, from which one may gather information goes to the left in the series. For sulfates and sulfonates, the
about the conformation of the chains and chain motion. counter-cations bind in the order Li+ < Na+ < K+ < Cs+ .
It has been suggested that, on average, the chains tend to In both cases, smaller counterion size correlates with
be somewhat more extended in the micelle than in pure weaker binding to headgroups. This is because small and
liquid; the measurements of motion also give indication energetic ions such as Li+ and F− strongly bind dipolar
of a liquidlike structure. H2 O molecules, greatly inflating the (now hydrated) ion
size and shielding the charge within the hydration shell. If
the counterion is made hydrophobic, one has, in addition
B. The Micellar Surface Region
to electrostatic effects, hydrophobic interactions between
It is normal to think of the surface of the micelle as the re- surfactant and counterion. An example is the salicylate
gion in which one finds not only the surfactant headgroup anion, which binds very strongly to cationic surfactants,
but also bound counterions (in the case of ionic head- decreasing the cmc manyfold and α to near zero.
groups) and water molecules. This region is also referred
to as the Stern layer. The outer edge of this layer defines the
C. Hydration in the Micelle
shear surface of the micelle as it moves and is only a few
angstroms thick, roughly the diameter of the headgroup Because there is effectively a hydrocarbon–water inter-
(see Fig. 1). As stated above, the headgroups are always face at the micelle surface, several possibilities must be
partially associated with counterions in the Stern layer, considered for hydration in the micelle. These involve
which diminishes the surface potential. A number given counterions, headgroups, and the portion of the hydro-
for concentration local to the Stern layer is about 3 M. carbon chain near the Stern layer. The bound counterions
These counterions are subject to both coulombic and ther- themselves may differ considerably in extent of hydration;
mal forces, one serving to attract them to the headgroup the cations noted above maintain a higher degree of hy-
and the second to disperse them. The extent to which coun- dration than do the anions. There has been considerable
terions are unbound from headgroups in the Stern layer is evidence that much of the water of hydration is maintained
defined as the degree of ionization α and has a profound upon binding. From viscosity and diffusion studies, hydra-
effect not only on micelle structure but on the whole range tion numbers for micelles have been deduced for a variety
of properties that depend on electrostatic interactions. The of charged surfactants; these fall into the range of 5–10
region beyond the shear surface in which the dissociated water molecules per surfactant molecule. For uncharged
counterions lie is called the Gouy–Chapman double layer micelles with variable numbers of oxyethylene groups,
and may be several hundred angstroms thick. Here the the hydration number can vary considerably, as seen from
counterions may exchange with the bulk phase. Fig. 6.
The perception of bound versus dissociated counteri- The extent to which water interacts with the hydrocar-
ons, of course, depends on the method used to measure it. bon chains of the surfactant is a question yet unsettled;
Spectroscopic techniques, such as fluorescence quench- various workers have suggested complete, partial, or no
ing or NMR, measure changes in properties affected by water penetration into the micellar core. For aliphatic
the presence of ions in the surface region; thermodynamic
measurements are sensitive to ion concentrations well
away from the Stern layer. Transport techniques, on the
other hand, measure the quantity of ions that move through
solution with the micelle. These approaches give results
that agree only qualitatively; however, α generally falls
in the region 0.1–0.4. By and large, it is little changed by
temperature, total surfactant concentration, or alkyl chain
length for micelles of the same shape. (Exceptions are fatty
acid sodium salts, for which α decreases from 0.43 for C7
to only 0.26 for C12 .) For systems with amine and sul-
fate headgroups, a compilation of dependences on various
surfactant parameters is included in Table I.
The effectiveness of binding has been shown to be
FIGURE 6 Dependence of the number of water molecules per
dirrerent for different counterions. For alkyl ammonium polyoxyethylene chain on the number of oxyethylene units for mi-
headgroups, anions bind more effectively in the sequence celles of sodium dodecylpolyoxyethylene sulfates. [From Takiwa,
F− < Cl−  Br− < No− −
3  I . It is to be expected, and F., and Ohki, K. (1967). J. Phys. Chem. 71, 1343–1349.]
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Micelles 667

surfactants, persuasive evidence has been given to sug- D. Surfactant Organization in Micelles
gest that the core of the micelle contains no substantial
Developing a three-dimensional model that accurately
amount of water and that if there is penetration it proba-
takes into account all the characteristics experimentally
bly involves no more than two carbons. Surfactants con-
defined for the micelle—surface structure, water pene-
taining oxyethylene moieties appear to be substantially
tration, fluidity of the core, solubilization, and dynamic
hydrated in the region of these groups. This is implied in
character—is not a trivial task. The initial picture given in
Fig. 6. A number of studies involving probes solubilized
Fig. 1, while providing an elementary concept with which
in the micelle or attached to the surfactant itself (e.g., car-
to work, does not reflect either the dynamic character of
bonyl groups) indicate the presence of water around such
micelles or the effect this should have on surface regu-
probes. It is possible that perturbation of the system by the
larity. Further, it does not reflect any randomness in the
included probe can lead to significant water–hydrocarbon
coiling of the hydrocarbon chains.
contact and/or that many such probes lie near the surface.
Attempts have been made to construct micelle struc-
Of course, as has been shown, the dynamic equilibrium
tures along the lines suggested by Fig. 1, with molecular
between surfactants in bulk phase and micelle assures con-
models in which some kinks are introduced to provide a
siderable motion of material across the micelle boundary.
much more rugged micelle, but one in which considerable
Additionally, it is quite likely that the micelle surface is
water penetration is suggested. The representation in Fig. 7
not a simple two-dimensional interface but involves some
approximates this approach. Other more geometrically
protrusion of surfactants into the bulk where hydrocarbon
simple models using square-lattice packing suggest al-
wetting could occur (Fig. 7). In summary, one should note
ternate ways of arranging surfactants: first using parallel
that whether there are 5–10 water molecules associated
correlation with headgroups separated at right angles and
with each surfactant of a simple micelle or whether there
then with the introduction of gauche conformations near
is penetration to several carbons depth in the presence of
the headgroup to release headgroup contact. The results of
solubilized material, a substantial fraction of material as-
such efforts are given in Fig. 8. Averaging arrangements
sociated with the micelle is, indeed, water.
of this type can yield an approximation to the ideal micro-
scopic oil drop shown in Fig. 8b.
Statistical theory employing a three-dimensional lattice
model has also been developed. The model emerging
from such an approach (Fig. 9) provides constant radial

FIGURE 8 Space-filling model of 64 SDS units: (a) bilayer

fragment model, (b) compact droplet by coalescing volume of
FIGURE 7 Schematic of the dynamic protrusion of surfactant tails up to a carbon, (c) parallel correlation of units with head-
monomers from spherical and rod-shaped micelles into surround- groups at right angles, and (d) release of headgroup interaction
ing bulk phase to enhance hydrocarbon–water content. [From by gauche kinks near headgroup. Average wetting is two car-
Lindman, B., and Wennerström, H. (1980). Top. Curr. Chem. 87, bons per unit. [From Fromhertz, P. (1980). Chem. Phys. Lett. 77,
1–83.] 460–466.]
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668 Micelles

crease the repulsion between headgroups: (1) the addition

of a tightly binding counterion, which decreases the degree
of ionization and the effective headgroup charge; (2) the
addition of an electrolyte, which increases the degree of
electrostatic screening; or (3) a significant increase in the
concentration of surfactant itself, which has the same ef-
fect. A sphere-to-rod transition manifests itself by, among
other things, a sudden increase in the solution viscosity
due to entanglement between the rodlike micelles. Some
authors denote the surfactant concentration at which the
viscosity jumps as a “second cmc.” The value and even
existence of the second cmc depends on the degree of
counterion binding; strongly binding counterions (e.g., in
FIGURE 9 Two-dimensional representation of lattice model from
statistical treatment. [From Dill, K. A., and Flory, P. J. (1981). Proc.
CTAB) display far lower second cmc’s than those with
Natl. Acad. Sci. 78, 676–680.] weaker binding (e.g., CTAC).
As surfactant solutions approach large concentrations
interlayer spacing and equal volumes for lattice sites. (of order 1 M), the micelles themselves begin to self-
Each site can accommodate one alkyl chain segment. organize into higher-order structures termed lyotropic
Configurational freedom in the surface sites considerably liquid crystals. These complex structures are highly de-
exceeds that of those near the core, implying an ordered pendent on surfactant geometry in ways that are not com-
center and a disordered surface region. It would also pletely understood. For surfactants with highly repulsive
allow considerable water–hydrocarbon contact since the headgroups, the first observed lyotropic phase is typically
statistics suggest that a deep-lying CH2 could contact the the “discontinuous cubic” phase, which is thought to con-
water surface. While these proposed models provide us sist of discrete micelles in a cubic lattice. Surfactants with
with images with which to work, it is not generally agreed less repulsive headgroups, which undergo a sphere-to-
that any one of them yields a totally accurate picture, for rod transition at a second cmc, give rise to a “hexagonal
example, in the matter of water penetration. It is further phase” consisting of hexagonally close-packed cylindrical
difficult to portray the dynamic character of the micelle micelles. Surfactants with weakly repulsive headgroups
from such static representations even though they may be (or double tails), which tend to form sheetlike bilayers,
reported as time averages. give rise to “lamellar phases” consisting of stacked bi-
layer sheets separated by water. If surfactant concen-
tration is increased past the first lyotropic phase, more
E. Nonspherical Micelles
complex bicontinuous and inverted phases are often ob-
For most conventional surfactants, the delicate balance served, culminating finally in hydrated crystals of the solid
of repulsive forces (between headgroups) with attractive surfactant.
forces (between tailgroups) results in discrete, quasi-
spherical micelles at the cmc. Changing this balance in ei-
ther direction can have a pronounced effect on the micelle IV. MICELLAR KINETICS
shape and aggregation number. Increasing the intermolec-
ular repulsion—using, for instance, bulky or multivalent Although the micelle may appear to be a clump of mate-
headgroups or very short alkane chains—increases the rial, insoluble in the water phase, the exchange of material
cmc, decreases the aggregation number, and can sup- with the bulk phase is actually very fast. While early ex-
press micelle formation altogether. Conversely, increasing perimental measurements seemed to indicate two differ-
the intermolecular attraction—e.g., by using double-chain ent time domains—one in the microsecond and one in the
tailgroups, or by screening out the headgroup repulsion— millisecond region—for material exchange rates between
decreases the cmc, increases the aggregation number, and micelle and solution, it is now agreed that overall micelle
can favor micelles that are continuous along a single di- kinetics are governed by the mechanism
mension (cylindrical rods, cf. Fig. 7) or along two dimen- k+
sions (bilayer sheets, cf. Fig. 8a). The growth of rodlike S1 + Sn−1  Sn , (2)
k−
and sheetlike micelles is not self-limiting, so these shapes
no longer have well-defined aggregation numbers. where k + and k − are rate constants for inclusion of a
For ionic surfactants, the micellar sphere-to-rod transi- surfactant molecule into and loss of a surfactant from the
tion can be induced in a number of ways, all of which de- aggregate, and n indicates the number of monomers in the
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Micelles 669

TABLE II Rate Constants and Micelle Size Distribution for a

Series of Sodium Alkyl Sulfates at 25◦ Ca
Surfactant cmc (M) nb σ c k− (s−1 ) k+ (M−1 s−1 )

NaC6 SO4 0.42 17 6 1.32 × 109 3.2 × 109

NaC7 SO4 0.22 22 10 7.3 × 108 3.3 × 109
NaC8 SO4 0.13 27 — 1.0 × 108 7.7 × 108
NaC9 SO4 6.10−2 33 — 1.4 × 108 2.3 × 109
NaC10 SO4 d 3.3 × 10−2 41 — 9 × 107 2.7 × 109
NaC11 SO4 1.6 × 10−2 52 — 4 × 107 2.6 × 109
NaC12 SO4 8.2 × 10−3 64 13 1.0 × 107 1.2 × 109
FIGURE 10 Distribution of a representative micelle population
as a function of aggregation number i. The dashed curve indi- NaC14 SO4 2.05 × 10−3 80 16.5 9.6 × 105 4.7 × 108
cates the redistribution after a small perturbation of the system NaC16 SO4 e 4.5 × 10−4 100 11 6 × 104 1.3 × 108
that leads to dissociation and decrease of the mean aggregation
a Data from Aniansson, E. A. G. et al. (1976). J. Phys. Chem. 80,
number of micelles. The dotted line is the final equilibrium dis-
tribution, t 1 and t 2 are the characteristic relaxation times of the 905–917, as compiled by Lindman, B., and Wennerström, H. (1980).
process indicated by the arrows. [From Schelly, Z. A. et al. (1979). Top. Curr. Chem. 87, 1–83.
b Mean aggregation number.
In “Solution Chemistry of Surfactants,” pp. 323–325. Plenum, New
c Standard deviation for the micelle size distribution.
York, as discussed in Fendler, J. H. (1982). “Membrane Mimetic
d 40◦ C.
Chemistry,” Wiley, New York.]
e 30◦ C.

aggregate. Because multiple equilibria are involved there

is certainly a range of micelle sizes, but the cooperative equilibrium. The relaxation time τ2 is heavily dependent
nature of micelle formation produces size distributions for on the sum of dissociation rates kn− × Sn for aggregation
micelles that cluster about optimum values. This behav- numbers (n) between monomer and proper micelles. Char-
ior is illustrated in Fig. 10. This mechanism allows one acteristically, τ2 values range from 10−3 to l s−1 , increasing
to neglect the interaction of submicelle aggregates: say, with temperature and decreasing with added salt. The ef-
S j + Sk → S j+k in the kinetic description. When a micelle fects of both relaxation steps on micelle size distribution
close to its thermodynamically optimal size is perturbed, are illustrated in Fig. 10.
the initial step in relaxation to the new equilibrium level
reflects the process described in Eq. (2) and exhibits a
relaxation time τ1 that may be expressed by V. SOLUBILIZATION
τ1−1 −
= k /σ + ak /n,
2 −
(3)
In terms of utility, the most important feature of the mi-
where σ is the variance of micelle size distribution and a celle is its ability to take up or solubilize nonsurfactant
the equilibrium ratio of micellar and monomeric surfac- materials. A large number of substances not readily solu-
tant. This represents a change in the size of micelles but ble in water may be dissolved in surfactant solutions (e.g.,
not in number. Measurements of τ as a function of a can hydrocarbon substances). A principal application of this
yield the other parameters if n is known independently. characteristic is to household detergent, by which water-
Under the condition where concentrations Sn Sn+1 , that insoluble “dirt and grease” are suspended in the micel-
is, σ > 1, the relationship k − /k + = cmc may be used to lar pseudo-phase and separated from the material to be
extract both forward and reverse rate constants. In Table II, cleaned. One technological variation of this use involves
values of k + and k − are given for a series of sodium alkyl the recovery of petroleum, adherent to underground rock
sulfates, along with values of σ, n, and the cmc. It shows a surfaces, by pumping detergent solutions into oil wells.
quite dramatic dependence of exitrate constants on chain Under appropriate economic conditions, this could bring
length. On the other hand, k + values are slower than would into production once more, sites that have been abandoned
be predicted by simple diffusion considerations, and it has when conventional techniques ceased to give adequate
been suggested that this is due to long-term repulsions by yield.
the surface potential field. The measurements of such pro- It may be seen that in surfactant solutions, the solubil-
cesses may be made by various techniques, (e.g., p-jump ity of various hydrophobic substances can increase rapidly
and ultrasonic absorption). only above the cmc and that association does not occur sig-
After the initial process (relaxation to the quasi- nificantly with individual surfactant monomers. Figure 11
equilibrium state) just described, a change in the num- illustrates changes in decanol solubility as a function of
ber of micelles occurs, representing relaxation to the true surfactant concentration in several systems. Solubility of
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670 Micelles

FIGURE 11 Solubility of decanol in solutions of (a) sodium octanoate (20◦ C), (b) sodium decanoate (40◦ C), (c)
sodium dodecanoate (40◦ C), and (d) sodium tetradecanoate (40◦ C). [From Ekwall, P. et al. (1969). Mol. Cryst. Liq.
Cryst. 8, 157–213.]

such substances in aqueous solution has been used as a of a solubilizate. As an illustration, solute near the surface
measure of the cmc. Because the extent of solubilization can produce a gain in energy by decreasing the ratio of
is dependent upon the quantity of micellar surfactant, such gauche to trans configurations in hydrocarbon chains in
behavior has been interpreted in terms of the phase sep- that region. Rigid molecules such as planar aromatic hy-
aration model where the surfactant is considered to be a drocarbons may perturb packing in the core, which may
separate or pseudo-phase. Indeed, various spectroscopic contribute to their unfavorable location in that domain.
observations indicate that many solubilizates move in a While various techniques, such as stopped flow, have
liquidlike environment, an observation that is consistent been used to follow substrate kinetics, many kinetic mea-
with the idea of a separate phase. One consequence of this surements have involved the photophysical properties of
approach has been to show the validity of a relationship solubilized probes. Because of the luminescent properties
analogous to Henry’s law: of their excited states, the aromatic hydrocarbons provide
opportunities for monitoring movement of such probes
cmc(Xa) = cmc(Xa = 0) − k · Xa (4)
across the micelle boundary. For example, long-lived
for micellar systems, where Xa is the mole fraction of the phosphorescence of aromatic hydrocarbons has been mon-
material to be solubilized. itored in micellar solutions containing ionic quenchers that
As described previously, the micelle exhibits a surface themselves are repelled by the surfactant head groups.
region with significant polar character, while the interior is Since quenching must take place in the aqueous phase,
essentially hydrocarbon in nature. It is to be expected that phosphorescence lifetimes may be interpreted to provide
materials associating with micelles would distribute them- rate constants for exit of the probe from the micelle. Some
selves between these two regions depending on polarity typical values obtained by this technique are given in
or polarizability. Indeed, those materials such as aliphatic Table III. Fluorescence data have also been used to obtain
hydrocarbons that have no surface activity are to be found such information.
in the micellar core while the more polarizable aromatic
hydrocarbons have been found to associate with the sur-
face region. Many such species give evidence of lying in an VI. MICELLAR CATALYSIS
alcohol-like environment. There are further energetic con-
siderations related to the effects of surfactant packing on It has been shown that a number of chemical processes can
the micellar structure itself that influence the distribution be kinetically altered in the presence of micelles. Either
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Micelles 671

TABLE III Solubilizate Entry and Exit Rate

Constants in Micellar SDSa

Solubilizate k+ (M−1 s−1 ) k− (s−1 )

Oxygen 1 × 1010 5 × 107

Benzene 4.4 × 106
Naphthalene 2.5 × 105
Anthracene 1.7 × 104
Pyrene 4.1 × 103
1-Bromonaphthalene 3.3 × 104
Perylene 4.1 × 102 FIGURE 12 Plots of kobs for the hydrolysis of p-nitrophenyl ac-
etate (curves A), mono- p-nitrophenyl dodecanedioate (curves B),
aCompilation taken from Fendler, J. H. (1982). and p-nitrophenyl octanoate (curves C) versus (a) concentration
“Membrane Mimetic Chemistry,” Wiley, New York. of sodium dodecanoate at pH 9.59 = 0.1 and 50◦ and versus (b)
concentration of n-dodecyltrimethyl ammonium bromide (LTAB)
at pH 10.49 = 0.2 and 50◦ . Values of kobs for the reaction of A
rates of reaction or the distribution of products can be with sodium laurate have been divided by 2.0 to bring the curve
significantly altered when either reactants or products as- on scale. [From Menger, F. M., and Portnoy, C. E. (1967). J. Am.
sociate with surfactant micelles. This recognition has led Chem. Soc. 89, 4698–4703.]
to increased investigation into such behavior, and some
simple examples are presented here.
The data presented by such reactions were analyzed in
Several aspects of micelle–reactant interaction are
terms of the simple kinetic scheme
suggested as responsible for the phenomenon called mi-
cellan catalysis. It is suggested that the micellar medium Sn  E SnE
can affect transition states of reactions, thereby altering
kw km , (6)
their rates; and some cases are cited in the literature.
Seemingly, however, the most important effect in micellar
P P
catalysis relates to the control of local concentrations
of components in bimolecular reactions. If a reactant where Sn is the micelle, E is the substrate, and P is the
exhibits some hydrophobic character, it may preferen- product. It may be shown that the rate constant for the
tially solubilize in the micellar pseudo-phase where its reaction in the absence of micelles kw and the observed
concentration can be controlled. For charged micelles, rate of reaction kobs may be related to the concentration of
ionic reaction components can be localized at or repelled micelles by the expression
from the micelle surface. One may note, for example, that
1 1 1
experiments with pH-sensitive dyes have shown that pH   (7)
at the micelle surface can be lowered by a couple of units k w  kobs k w  km (k w  km)K[Sn] ,
for negatively charged micelles such as SDS and raised
which, it may be noted, bears resemblance to treatments
by two units in positively charged systems such as CTAB.
of enzyme kinetics. Under the right conditions, plots of
One of the most widely discussed processes involving
(kw + kobs )−1 versus [Sn ]−1 may be seen to yield rate con-
micellar catalysis deals with hydrolysis reactions of the
stants for the micelle catalyzed reaction km and the binding
form
constant, K s , for the equation. However, the simple con-
O O ditions defined in Eq. (6) are not met under conditions
|| || (5) described by Fig. 12b where both OH− and substrate can
−
R C O R + OH R C O− + R OH
bind to the micelle. One should note that overall parallels
Of course, for esters that solubilize, it is expected that re- drawn between micellar catalysis and enzyme behavior
action rates will depend on concentrations of OH− local must be treated with care because enzymes exhibit a de-
to the micelle. One would expect that such concentrations gree of site selectivity not seen in micellar systems. It may
will be enhanced in the presence of positively charged mi- be noted that such a simple unimolecular treatment holds
celles and inhibited by negatively charged ones. Figure 12 when we consider partitioning one reaction component. In
gives examples of systems that follow those expectations. the late 1980s, much effort has been expended to develop
It may be seen that the response to concentrations of sur- sophisticated models for catalysis that deal with bimolec-
factant depend on the length of the hydrocarbon chain in ular reactions and address kinetic dependencies on surface
the ester, suggesting some variation in extent to which the charge, pH, buffers, chain length, and specific salt effects.
esters are solubilized. The literature in this area has become rather extensive.
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672 Micelles

In systems where more than one reaction pathway is effects on reaction rates of excited states and radiolyti-
possible, localization of reactant by micelles may govern cally generated radicals. While these might appear to be
the kinetics and determine product yield. An example of highly specialized measurements, the time resolution that
this may be nicely seen in the photolysis of ketone: may be achieved provides insight into the catalysis of
many micelle-related events on a very short time scale.
O
For example, the movement of charged radicals, such as
CH2 C CH2 CH3 hydrated electrons, to reaction sites at positively charged
micellar surfaces has been shown to increase up to two
orders of magnitude over diffusion control. Dispropor-
For convenience, one may use the notation tionation of Br− 2 radicals has been shown to occur much
more rapidly on a CTAB micelle surface than in solu-
A CH2 tion. Initial steps in the radical processes governing lipid
peroxidation, a mechanism of particular biological inter-
est, have been studied in micelles to determine the effects
and of a membrane-mimic environment on radical behavior.
Micellar influence on kinetics of excited-state quench-
B CH2 CH3 ing by adsorbed anions, photoionization of sequestered
chromophores, and many other photoprocesses have been
investigated.
and write the reaction

h
ACB AA  AB  BB (8) VII. MICELLES AT INTERFACES
O
For all the structural and behavioral complexity that mi-
The distribution of products in homogeneous solution celles present, they are the simplest assembly of am-
is governed by simple statistics as shown in Fig. 13. How- phiphilic molecules with which to deal experimentally.
ever, with the addition of surfactant up to a concentration In most cases one merely dissolves the surfactant of inter-
that localizes each reactant molecule in a micellar “cage,” est in water, and the gods of thermodynamics do the rest.
the yield of AB is totally dominant. While only a limited number of biological amphiphiles ac-
A large number of studies have been carried out with tually aggregate in this way (bilesalts, fatty acid salts, and
fast-reaction kinetics techniques to characterize micellar lysolecithin), micelles do present accessible model sys-
tems with which to approach phenomena governing more
complex, extended assemblies such as biological mem-
branes. Although the limitations of micelle–membrane
comparisons must be kept in focus, a wide range of infor-
mation characterizing hydrophobic interaction and water–
lipid interfacial phenomena, which are highly relevant to
biological systems, has been built up from the collective
study of micelles.

VIII. SURFACTANT AGGREGATES

AT SOLID-LIQUID INTERFACES

Surfactants are generally attracted to solid-liquid and

liquid-air interfaces, and this interfacial enrichment is vi-
tal to a large number of industrial applications. (Even the
term surfactant—short for surface-active agent—betrays
the central importance of interfaces.) One such applica-
tion is foam flotation in the mining industry, in which
FIGURE 13 Dependence of product distribution from photolysis
of dissymmetrical dibenzylketones on CTACI concentration. [From surfactant adsorption to ore microparticles causes them to
Turro, N. S., and Cherry, W. P. (1978). J. Am. Chem. Soc. 100, flocculate at the surfaces of air bubbles and rise to the foam
7431–7432.] layer, where they are skimmed from the remaining matrix.
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Micelles 673

(hydrophilic
surfaces)

(hydrophobic
surfaces)
Adsorption density

CMC

Surfactant concentration
FIGURE 14 Schematic of “two-step” absorption isotherms for surfactants on hydrophobic surfaces (dashed line, right
vertical scale) and on hydrophilic surfaces (solid line, left vertical scale). The absorption models are inferred from the
measured amounts of surfactant absorbed per unit surface area.

Another is particulate detergency, in which surfactant in- ety of hydrophobic and hydrophilic surfaces. At the risk of
filtration between a soil particle and the substrate eventu- overgeneralizing, adsorption isotherms typically follow a
ally desorbs the soil and prevents its readsorption. A final two-step pattern (Fig. 14) for both hydrophobic and hy-
example is tertiary oil recovery, in which oil is dislodged drophilic surfaces. In both cases, a low-density plateau at
from the microchannels of porous rocks by competitive low concentrations gives way to a high-density plateau as
surfactant adsorption at the pore surfaces and by emul- the concentration approaches the cmc; this final adsorp-
sification of the oil. Despite the importance of these ap- tion density remains approximately constant up to very
plications, knowledge of surfactant behavior at interfaces high surfactant concentrations. The surfactant organiza-
has historically lagged far behind that in bulk solutions. tion at each plateau is inferred from the measured surface
Which morphologies surfactant aggregates assumed at in- density and from known interaction sites. Hydrophobic
terfaces, or even whether well-defined aggregates analo- surfaces, which interact with tailgroups via hydrophobic
gous to bulk micelles existed at interfaces, remained open interactions, display a low-density plateau consistent with
questions until fairly recently. a horizontal monolayer and a high-density plateau con-
The first evidence for hydrophobic association at in- sistent with a vertical monolayer, with tailgroups facing
terfaces came from adsorption isotherms—i.e., measure- the surface. This is in contrast with charged hydrophilic
ments of surface adsorption density as a function of surfaces, which interact electrostatically with oppositely
surfactant concentration in solution. In a landmark 1955 charged headgroups. Here the low-density plateau approx-
paper, A. M. Gaudin and D. N. Fuerstenau noted that the imately corresponds to a vertical monolayer (headgroups
surface density of SDS on alumina increased sharply as the facing the surface), whereas the high-density plateau is
concentration approached the cmc, and they interpreted consistent with a vertical bilayer above the cmc.
this as evidence for hydrophobic association into interfa- However, while these flat morphologies served as the
cial aggregates termed hemimicelles. standard models of interfacial aggregation, uncertain-
Confirming evidence for interfacial aggregation has ties in surface area determination (which can approach
since come from hundreds of adsorption studies on a vari- 30%) could not definitively exclude curved interfacial
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674 Micelles

aggregates resembling bulk micelles. (Indeed, many work-

ers found in adsorption isotherms consistent evidence for
defective or incomplete layers or even for adsorbed mi-
celles.) While hydrophobic association was agreed to be
the mechanism for interfacial adsorption near the cmc,
the corresponding surfactant structure was unknown until
recently.

A. Imaging Interfacial Aggregates

by Atomic Force Microscopy
In 1995, the high-density structures above the cmc were
imaged directly by atomic force microscopy (AFM) for
both hydrophilic and hydrophobic surfaces. These results
showed for the first time that interfacial micelles existed
in well-defined shapes and sizes, that they generally pos-
sessed spherical or cylindrical curvature (in contrast to the
standard models), and that this curvature was a compro-
mise between the spontaneous curvature of bulk micelles
and the constraints imposed by the flat surface.
Briefly, AFM is a technique that maps the topography
of a surface by plotting (on a color scale) the measured
force between the surface and a small tip attached to a
sensitive cantilever spring. In most applications, the tip is
in direct contact with the surface, and the AFM performs
as a sensitive contact profilometer. For imaging interfa-
cial surfactant structures, however, contact forces disrupt
the liquid crystalline aggregates. Therefore the repulsive
colloidal stabilization forces between the surfactant lay-
ers adsorbed to the tip and sample are used as the contrast
mechanism during imaging.
A simplified schematic of the imaging mechanism is
shown in Fig. 15 for ionic surfactants. The tip and sam-
ple are immersed in surfactant solution above the cmc
(where the high-density plateau occurs in the adsorption B
isotherm). Surfactant adsorption on the tip and sample
FIGURE 15 AFM imaging mechanism for interfacial surfactant
charges both with the same sign, resulting in a long- aggregates. (a) Surfactant adsorption on the tip and sample cre-
ranged, screened electrostatic repulsion between the two ates a long-range repulsion between the tip and sample, down to
(Fig. 15a). By fixing the imaging force (using a feedback separations (around 5 nm) where the opposing surfactant layers
loop) in this noncontact regime, the AFM “flies” the imag- touch and fuse together. Imaging in the noncontact regime allows
ing probe above the aggregate layer while obtaining a “sur- the AFM tip to obtain a map of the surfactant aggregate structure.
(b) A sample AFM image (200 × 200 nm) of spherical micelles in
face map” of the colloidal stabilization force. This map of a hexagonal pattern at the mica-solution interface. The surfactant
the tip-sample repulsion reveals the surfactant aggregate is a divalent cationic surfactant with a C18 tail.
structure at the interface (Fig. 15b). Comparing AFM im-
ages with other data (e.g., adsorption isotherms) usually most popular substrates have been layered crystals, owing
fixes the interfacial micelle structure uniquely. to the ease of surface preparation (cleaving by adhesive
AFM imaging has been used to identify interfacial ag- tape) and the variety of available surface properties. A
gregate structure above the cmc for a variety of ionic, summary of observed aggregate structures follows.
nonionic, and zwitterionic surfactants on both hydropho-
bic and hydrophilic surfaces. (Structures far below the
B. Aggregates at Hydrophobic Surfaces
cmc, corresponding to the low-density adsorption plateau,
cannot be imaged readily because the tip-sample force is AFM results (Fig. 16a) show that the morphology of
strongly hydrophobic and attractive in this regime.) The surfactant aggregates at hydrophobic surfaces depends
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Micelles 675

B
FIGURE 16 AFM images and schematics of alkyltrimethylammonium surfactant aggregates on (a) the hydrophobic
graphite surface and (b) the hydrophilic mica surface. In (a), the bottom row of tails are aligned parallel to a surface
symmetry axis, orienting the half-cylinder perpendicular to this axis. In (b), the smaller contact area between the
aggregate and surface allows the cylindrical aggregate to meander over the surface.

heavily on the crystalline anisotropy of the substrate, with micelles in bulk. The orientation of the aggregates with
the surfactant geometry itself playing a comparatively respect to the surface lattice suggests that the crystalline
minor role. Almost all surfactants—ionic, nonionic, and anisotropy of the substrate plays a central role in deter-
zwitterionic, with tail lengths ranging from 12 to 18 car- mining this curvature. This has been further confirmed
bon atoms—aggregate in the form of half-cylindrical ag- by control experiments on amorphous hydrophobic
gregates on cleaved crystals of graphite and MoS2 . This surfaces; these show half-spherical micelles above the
is evidenced by AFM images in the form of rigid, paral- cmc, in agreement with the spontaneous curvature in bulk
lel stripes, separated by a little over twice the surfactant solution.
length, with stripe axes running perpendicular to the un- The current understanding of the adsorption and aggre-
derlying lattice symmetry axes. Parallel half-cylinders are gation process is as follows. At very low concentrations,
consistent with the observed stripe spacing and with the hydrophobic attraction causes the tailgroup to adsorb hor-
known adsorption density (roughly equivalent to a vertical izontally on the surface, and an anisotropic interaction
monolayer) from isotherms. with the surface lattice causes the tailgroup to orient it-
The cylindrical curvature is, however, initially sur- self parallel to an underlying symmetry axis. Because the
prising considering that these surfactants form spherical tail-surface interaction for this configuration is typically
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676 Micelles

stronger than that between two tails, the molecule does not structure than close-packed spheres and a flatter curvature
gradually desorb to a vertical orientation (as in Fig. 14) than is found for bulk micelles. The mica surface has been
as the surfactant concentration is increased. Instead, each likened to a highly charged “planar counterion,” which in-
strip of horizontal molecules, arranged head-to-head and duces a sphere-to-rod transition at the interface, in a simi-
tail-to-tail along a symmetry axis, serves as a founda- lar way that multivalent counterions induce sphere-to-rod
tion for a half-cylindrical aggregate above the cmc (see transitions in bulk micelles. In cases where the surfac-
the schematic of Fig. 16a). Apparently, the original align- tant headgroups are highly repulsive or bulky, even the
ment of tails parallel to a symmetry axis not only deter- mica surface is unable to bring headgroups close enough
mines the direction of the final half-cylindrical aggregate, to effect a sphere-to-cylinder transition, and interfacial
but also the fact that half-cylinders are the favored ar- micelles remain spherical. This is the case for divalent
rangement. Where the lattice alignment is absent—i.e., surfactants, as shown in Fig. 15b.
for isotropic substrates such as hydrophobized silica—the In summary, the geometry of surfactant aggregates at
same surfactants form half-spherical aggregates. charged surfaces is highly sensitive to “charge density
Both graphite and MoS2 —despite marked differences matching” between the surface and free (unperturbed)
in lattice symmetry, spacing, and surface groups—give micelles. The interfacial aggregate can have a flatter
rise to similar half-cylindrical aggregates at the same per- curvature than free micelles in cases where the adsorp-
pendicular orientation relative to the underlying lattice. tion density becomes comparable to the micelle charge
This suggests that strong tailgroup alignment, leading to density.
half-cylindrical aggregates, may be a feature common to
all crystalline hydrophobic adsorbents. Since hydrophobic
surfaces interact with the entire length of the tailgroup, this IX. CONCLUSION
large interaction area evidently leads to a high degree of
surface control of the aggregate structure. In the technological realm, an application that has gen-
erated much excitement is the synthesis of mesoscopic
C. Aggregates at Hydrophilic Surfaces materials using surfactant micelles as templates, as first
reported in 1992 by Beck et al. This process relies on in-
Hydrophilic surfaces, on the other hand, interact with the organic polymerization at the interfacial region between
much smaller surfactant headgroup. It is therefore natural a surfactant aggregate and a solution in which the inor-
to expect “full” aggregate structures, whose curvature is ganic precursors (usually silicate ions) are initially dis-
controlled as much by intermolecular interactions as by persed. By restricting the polymerization reaction to the
the surface. This is exactly what is observed by AFM. micelle–solution interface, a complex nanocomposite is
The vast majority of experiments in this category have formed consisting of surfactant micelles embedded in an
investigated ionic surfactants on oppositely charged sur- ordered array within a continuous inorganic (e.g., silica)
faces. On the anionic surface of silica, single-chain “scaffold.” Pyrolyzing the surfactant finally results in a
cationic surfactants self-assemble into spherical aggre- mesoporous material, with pore sizes of order 5 nm, which
gates (resembling bulk micelles) above the cmc. These can serve as, for example, a molecular filter, catalytic
are thought to originate from the electrostatic binding be- support, or laser waveguide.
tween charge sites on the surface and individual surfac- However, aside from such applications and, of course,
tant molecules; the latter then serve as nucleation sites for the industrial interest in detergent action, one should note
micellar aggregation above the cmc. Similar results have that of the wide range of experimentalists and theoreticians
been observed with anionic surfactants on the cationic that have been drawn to investigation of micelles, most
surface of alumina. In both cases, the spherical interfacial have been attracted by the unique intellectual challenge
aggregates are consistent with the curvature found in bulk such systems offer. The literature provides ample evidence
solution. Micelle curvature is expected to be relatively that they have not been disappointed.
unperturbed as long as the substrate charge density (i.e.,
adsorption site density) falls short of the charge density
on the outer surface of the micelle. Most surfaces satisfy
this requirement. SEE ALSO THE FOLLOWING ARTICLES
A notable exception is the anionic cleavage plane of
mica, where exchangeable surface ions give rise to a far CHEMICAL KINETICS, EXPERIMENTATION • CHEMICAL
higher adsorption density than on silica. Alkyltrimethy- THERMODYNAMICS • ELECTROPHORESIS • HYDROGEN
lammonium surfactants on mica self-assemble into paral- BOND • KINETICS (CHEMISTRY) • MACROMOLECULES,
lel cylindrical aggregates (see Fig. 16b)—a higher-density STRUCTURE • PRECIPITATION REACTIONS • SILICONE
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Micelles 677

(SILOXANE) SURFACTANTS • SURFACTANTS, INDUSTRIAL Klafter, J., and Drake, J. M. (1989). “Molecular Dynamics in Restricted
APPLICATIONS • SURFACE CHEMISTRY Geometries,” Wiley, New York and Chichester.
Lindman, B., and Wennerström, H. (1980). Top. Curr. Chem. 87,
1–83.
Manne, S., and Gaub, H. E. (1995). Science 270, 1480–1482.
BIBLIOGRAPHY Manne, S., and Warr, G. G. (1999). In “Supramolecular Structure in
Confined Geometries” (S. Manne and G. G. Warr, eds.), pp. 2–23.
Beck, J. S., et al. (1992). J. Am. Chem. Soc. 114, 10834–10843. American Chemical Society, Washington DC.
Fendler, J. H. (1982). “Membrane Mimetic Chemistry,” Wiley, New Menger, F. M. (1977). In “Bioorganic Chemistry III. Macro- and Multi-
York. molecular Systems” (E. E. van Tamelen, ed.), pp. 137–152. Academic
Fendler, J. H., and Fendler, E. J. (1975). “Catalysis in Micellar and Press, New York.
Macromolecular Systems,” Academic Press, New York. Tanford, C. (1980). “The Hydrophobic Effect: Formation of Micelles
Gaudin, A. M., and Fuerstenau, D. W. (1955). Trans. AIME 202, 958– and Biological Membranes,” Wiley, New York.
962. Wennerström, H., and Lindman, B. (1979). Phys. Rep. 52, 1–86.
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Physical Chemistry
Douglas J. Henderson Charles T. Rettner
Brigham Young University IBM Almaden Research Center

I. Classical Mechanics
II. Quantum Mechanics
III. Statistical Thermodynamics
IV. Kinetics and Dynamics

GLOSSARY Kinetics Study of how chemical systems change, conce-

rning the rate at which change occurs and the factors on
Activated complex Short-lived transition state that oc- which this rate depends. Also used to refer to the seq-
curs at the point of maximum energy along a reaction uence of reactions by which a complex reaction occurs.
path when the molecules in a chemical reaction can no Molecular beam Stream of molecules all traveling in
longer be considered as reactants or products. the same direction in vacuum, used in studies of iso-
Adsorption Adhesion of a gas or liquid at a surface lated molecules and to examine the dynamics of single
resulting in an increased concentration of the gas molecular collisions.
in the vicinity of the surface; to be distinguished Normal mode One of a set of coordinates of a system
from absorption, which occurs throughout the solid or that can be excited while the others remain at rest.
liquid. Order of a transition Transition from one thermody-
Critical point Point where two phases become identical namic phase to another is of order n if the first dis-
and form one phase. continuous derivative of the free energy with respect to
Degrees of freedom Variables which must be determined the thermodynamic variables is of order n.
to specify the state of a system. Phase, thermodynamic Region of the space specified by
Elementary reaction Reaction concerning a single the thermodynamic degrees of freedom of system sep-
chemical step, such as dissociation or recombination, arated from the remainder by a clearly defined surface
as distinct from complex reactions which occur through and within which the thermodynamic properties differ
a series of separate elementary reactions. from those of the remainder.
Equation of state Relation between the thermodynamic Rate constant Constant that gives a measure of the rate
properties of a system. of a chemical reaction; the proportionality constant be-
Equilibrium State of an isolated system which is speci- tween the rate of product formation and the product
fied by quantities which are independent of time. of the reagent concentrations. If the rate expression
Isotherm Curve joining states for which the temperature involves N molecules of the same reagent, the concen-
is constant. tration must be raised to the power of N .

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160 Physical Chemistry

Reversible process A process in which a system changes I. CLASSICAL MECHANICS

from one thermodynamic state to another is reversible
if the thermodynamic variables in the inverse process The dynamics (i.e., motion and energetics) of molecules
pass through the same values but in the inverse order and atoms and, at a more fundamental level, electrons, are
and in which all exchanges of heat, work, etc., with the origin of chemical phenomena. Prior to the twentieth
the surroundings occur with reverse sign and in inverse century it was believed that all of the dynamics of a sys-
order. tem, whether astronomical or molecular, were described
Spectroscopy Analytical technique concerned with the by Newton’s equation of motion.
measurement of the interaction of energy and mat-
dv
ter, the development of instruments for such measure- F=m , (1)
ments, and the interpretation of such information for dt
analysis of the structure or constituents of a system. where F is the force, v the velocity, t the time, and the
Techniques, such as mass spectrometry, which do not proportionality factor, m, the mass of the particle or object.
involve energy are often called spectroscopic because The force and velocity are vectors, whose direction and
they also yield output scans in the form of spectra. magnitude are both of importance. In complex problems
Spectrum Intensity of a signal due to a process such as it is often preferable to reformulate classical mechanics in
optical absorption or emission displayed as a function terms of a scalar, such as the energy, which is characterized
of some varying characteristic such as wavelength, en- only by its magnitude. This gives rise to the Lagrangian
ergy, or mass. Also used in quantum mechanics and ap- and Hamiltonian equations of motion. The latter equations
plied mathematics to specify the pattern of eigenvalues are of most interest here and are
of a linear operator and in electrodynamics to specify ∂qi ∂
the range of frequencies of electromagnetic radiation. = ,
∂t ∂ pi
State function In thermodynamics a variable is a state (2)
function if, when all the thermodynamic variables are ∂ pi ∂
=− ,
specified, it has a unique value. As a result, the change ∂t ∂qi
in any state function in a reversible cyclic process must where pi and qi are generalized momenta and positions,
be zero. respectively, and , the Hamiltonian, is the total energy
Thermodynamics Study of the changes in the properties of the system using momenta and position as variables.
of a system, usually as a result of changes in tempera- The space spanned by the pi and qi is called phase space.
ture or pressure. The dynamics of a system are described by a path in phase
space. If the system is periodic, as is the case for electrons
in an atom or molecule, then the path is a closed orbit
PHYSICAL CHEMISTRY is the branch of chemistry in in phase space. The advantage of the Hamiltonian formu-
which experimental and theoretical techniques of physics lation in physical chemistry is the fact that all variables
are used to investigate and interpret chemical phenomena. are treated on an equal footing. However, the Hamiltonian
Physical chemistry has its origins in the late nineteenth and Newtonian formulations of classical mechanics are
century, where it was largely concerned with the appli- completely equivalent.
cation of classical thermodynamics to chemistry. Modern
physical chemistry is based more on quantum and statis-
tical mechanics, which were developed only during the
II. QUANTUM MECHANICS
twentieth century. The branch of physical chemistry that
employs twentieth century physical techniques is some-
A. Duality of Matter and Energy;
times called chemical physics, with physical chemistry be-
Uncertainty Principle
ing regarded as concerned only with classical techniques.
However, the distinction is artificial. Physical chemistry During the nineteenth century it was established that mat-
and chemical physics are really the same field and are ter consists of atoms and chemically bound aggregates
considered as such here. Experimental physical chemistry of atoms called molecules. At first, it was thought that
has been revolutionized by relatively recent advances in atoms were structureless. However, by about the turn of
electronic instrumentation, vacuum technology, and by the century, it was shown that atoms were miniature so-
the introduction of lasers. Equally, advances in computer lar systems consisting of a positively charged nucleus,
power have had a great impact on theoretical studies, with whose structure is irrelevant for chemical phenomena,
an increasing emphasis on computer simulations and the which contains nearly all the atomic mass, and negatively
detailed modeling of chemical systems. charged “planetary” electrons which orbit the nucleus.
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Physical Chemistry 161

Because of this, nuclei are slow moving, virtually mo- B. Wave Equation
tionless, on the timescale of electronic motions. For many
In the earliest formulation of quantum mechanics, classi-
chemical phenomena, the nuclei can be regarded as fixed
cal mechanics was assumed valid with the exception that
in space. Only the electronic dynamics need be consid-
some periodic variables were quantized (i.e., had discrete
ered. This simplification is called the Born–Oppenheimer
values). Their values could be determined by integrating
approximation.
the pi over their orbits in phase space, according to
At first it was thought that the electronic motions could 
be described by classical mechanics. However, it is im- pi dqi = n i h, (7)
possible to describe the microscopic world by classical
mechanics. It became apparent, from for example the pho- where n i is an integer called a quantum number. The inte-
toelectric effect, that electromagnetic radiation was not al- gral in Eq. (7) over a closed path is called a phase integral.
ways wavelike, but, in some circumstances, consisted of However, as the implications of the duality of matter
discrete, particle-like, units of magnitude called quanta, and energy and the uncertainty principle were accepted,
it became apparent that one could refer only to the proba-
E = hν, (3) bility of finding the system in some configuration. Just as
the wave nature of radiation meant that there was a wave
where ν is the frequency of the radiation and h =
equation for radiation, the wave nature of matter implied
6.626 ×10−34 J sec is Planck’s constant. Conversely, it
the existence of a new wave equation. This wave equa-
became apparent, through for example the diffraction of
tion, called the Schrödinger equation, is formulated as
electrons, that matter was not always particle-like but, in
an eigenvalue equation (eigen ≡ characteristic or proper)
some circumstances consisted of waves of wavelength
where the Hamiltonian operator “operates” on the prob-
λ = h/ p. (4) ability function or wave function or eigenfunction, ψ, to
give the energy eigenvalue, E, times ψ. Thus, the wave
Such waves can be used to probe the structure of crystal equation is
surfaces, through low-energy electron diffraction (LEED) ψ = Eψ (8)
or atomic beam diffraction. The latter is usually confined
to He atoms, but even Ar atom diffraction can be discerned The wave function has the property that |ψ|2 gives the
in favorable cases. probability of the system having the eigenstate whose en-
In other words, there is a duality of matter and energy. ergy is E. The Hamiltonian operator is formed by re-
Whether the particle-like or the wavelike character of mat- placing p j in the classical Hamiltonian by √ the opera-
ter/energy is dominant depends on the experiment. In fact, tor −(h/i)(∂/∂q j ), where h = h/2π and i = − 1. The
the experiment itself interacts with the matter/energy and q j remain unchanged. Interestingly, the earlier phase in-
defines some aspect of the system at the cost of indefinite- tegral formulation [Eq. (7)] becomes the approximate
ness of some other aspect. This uncertainty principle was Wentzel–Kramers–Brillouin (WKB) method of solution
made precise by Heisenberg who showed that even under of Schrödinger’s equation and remains useful in many
the most ideal circumstances problems in the sense that differences between quantized
values of a phase integral are integral multiples of h except
pi qi = h/4π. (5) that there may be a zero point value of the phase integral
given by a fractional value of h.
If the experiment defines the particle character of the sys-
tem, the uncertainty of the positions, qi , is small and the
C. Hydrogen-Like Atom; Electronic Transitions
uncertainty in momenta, pi , or frequency is large. How-
ever, if the experiment defines the wave character of the One of the first systems to which quantum mechan-
system, the reverse is true. The momenta pi and positions ics was applied was the hydrogen-like atom consisting
qi are called conjugate variables. Energy and time are also of a single electron orbiting a nucleus of charge Z e0 .
conjugate variables so that The energy eigenvalues or levels are obtained by solving
Schrödinger’s equation and are given by
Et = h/4π. (6)
2π 2 m 0 Z 2 e04 hc R Z 2
E =− = − , (9)
Classical mechanics, where there is no uncertainty, is a n2h2 n2
limiting case in which the magnitudes of the variables are where e0 is the charge of an electron, n is an integer, c is
large compared to h. As a result, classical mechanics is the velocity of light, and R is called Rydberg’s constant.
appropriate for large macroscopic bodies. Strictly speaking we should not use the electronic mass m 0
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162 Physical Chemistry

is an active research field today. However, an understand-

ing of the electronic structure of atoms can be understood
in terms of the aufbau (building up) principle whereby
electrons are added one at a time to the atom.
However, two additional facts should be mentioned.
First, the quantum numbers n, l, and m are not sufficient
to specify the state of an electron. The spin of an electron
must also be specified. Electrons can have one of two spins
(say, up or down). This is specified by the spin quantum
number, s = ± 12 (so that there are 2|s| + 1 = 2 spin states).
Thus, the state of an electron is specified by n, l, m, and
s. For historical reasons the values l = 0, 1, 2, 3, 4, . . . are
specified by the spectroscopic notation s, p, d, e, f, . . . .
Thus, an electron might be said to be in a 1s(n = 1, l = 0)
or a 2 p(n = 2, l = 1), state. Similarly, states for the
whole atom are termed, S, P, D, E, . . . corresponding to
L = 0, 1, 2, 3, . . . , where L is the total orbital angular mo-
mentum for the atom, which is arrived at by combining
the orbital angular momenta of the individual electrons.
Second, electrons obey the Pauli exclusion principle.
This means that only one electron can occupy a quantum
FIGURE 1 Energy-level diagram for the hydrogen atom showing state. Thus, as the aufbau principle is employed, the elec-
allowed transitions. Insert displays the Balmer series spectrum trons are added one at a time to the state of lowest energy,
that can be observed in the visible.
each state being filled by one electron.
From these principles a simple understanding of the
in this formula but the reduced electronic mass. However, periodic table is gained. Each electronic shell is specified
the effect is small. by n and contains 2n 2 states. Thus, the first row of the
This means that electronic transitions between states periodic table corresponds to n = 1 and contains 2 ele-
characterized by n 1 and n 2 emit or adsorb energy or radia- ments (H and He). The electronic configurations of these
tion whose wavelength is given by elements are denoted 1s (H) and 1s 2 (He). The super-
 
1 1 1 script indicates the number of electrons with the given
=Z R 2− 2 .
2
(10)
λ n1 n2 value of l. The second row corresponds to n = 2 and
contains 8 elements with configurations 1s 2 2s, 1s 2 2s 2 ,
An energy-level diagram for the hydrogen atom is shown
1s 2 2s 2 2 p, . . . , 1s 2 2s 2 2 p 6 . The subsequent rows contain
in Fig. 1, which also displays some of the allowed transi-
8 columns even though 2n 2 exceeds 8 because the en-
tions.
ergy of the electronic states is ordered (approximately)
The energy levels of the hydrogen-like atom are degen-
1s/2s 2p/3s 3p/4s 3d4p/5s 4d 5p/6s 4f 5d 6p/7s . . . so
erate because more than one state corresponds to a spe-
that the third row is still filled with 8 elements. With potas-
cific value of n (the principal quantum number). These de-
sium (Z = 19) the nineteenth electron goes into a 4s rather
generate states are characterized by the quantum numbers
than a 3d level. The transition elements are regarded as
l and m, which characterize the spherical harmonics of the
occupying one position in the table since the outer shell
wave function. For each value of n there are n values of
configuration does not change as the d electrons are added
l(l = 0, . . . , n − 1) and for each value of l there are 2l + 1
and, as a result, they have similar chemical properties. As
values of m(m = − l, −l + 1, . . . , 0, . . . , l − 1, l) giving
n increases, not only must the d electrons be accommo-
n 2 values of l and n for each value of n.
dated in single positions, but the f electrons must also be
accommodated in a single position, so that the table be-
D. Many-Electron Atoms; Pauli Principle;
comes more complex. However, the underlying principles
Electron Spin
are simple.
To understand more complex atoms containing many elec-
trons, we must solve the many-electron Schrödinger equa-
E. Molecular Systems: Chemical Bond
tion. Even in classical mechanics, many-body problems
are difficult, so it is not surprising that many-electron Many-electron molecular systems are even more com-
quantum mechanics, usually called quantum chemistry, plex than atomic systems. The theory of such systems
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Physical Chemistry 163

is an active field of research. The potential energy terms and they are termed doublet states. The former three have
in the wave equation for the molecule involve not only zero spin, a multiplicity of 1, and are termed singlet states,
the Coulomb repulsions between the electrons and the while states with a multiplicity of 3 and 4 are termed
Coulomb attractions of the electrons and nuclei but also triplet and quartet states, respectively. Thus, the ground
the Coulomb repulsion between the nuclei. electronic state of NO is written as 2 1/2,3/2 , where the 2
Given the repulsion between the nuclei, we are inclined refers to the doublet nature of the state, the  to = 1, and
to ask how atoms form a chemical bond in a molecule. the 12 and 32 refer to values of  which arise from the two
A simple answer can be obtained by considering the one possible ways that the spin and orbital angular momentum
electron hydrogen molecule ion H2+ . The wave functions can add.
of each H atom separately are ψls (A) and ψls (B). An ap- In addition to electronic energy states, molecules posses
proximation to the H2+ wave function can be obtained by both rotational and vibrational energy levels. Assuming a
forming a molecular orbital from a linear combination of fixed distance between two atoms (rigid rotor approxi-
these two wave functions mation), the Schrödinger equation yields for the allowed
rotational energy levels of a diatomic molecule
ψb = ψls (A) + ψls (B)
h2
or Er ≈ J (J + 1), (12)
8π 2 I
ψa = ψls (A) − ψls (B). (11) where I is the moment of inertia of the molecule, J the
In the first (bonding) orbital, the electron is concentrated rotational quantum number and the quantity (h 2 /8π 2 I ) is
between the nuclei, and is simultaneously attracted by both termed the rotational constant for that particular electronic
nuclei resulting in a lower electronic energy which more state of the molecule (usually given the symbol B).
than offsets the repulsion of the nuclei. In other words Vibrational energy levels can be estimated by inserting
when the electron is between the nuclei it acts as a cement the Hooke’s law potential energy, U (r ) = 0.5k(r − re )2 ,
holding them together. There is zero probability of finding in the Schrödinger equation (harmonic oscillator approx-
the electron between the nuclei in the second (antibonding) imation). This yields eigenvalues, E v , for the permissible
orbital. As a result, a chemical bond is not formed by this energy levels, of
orbital.     
E v = (h/2π ) k/µ v + 12 = hν0 v + 12 , (13)
where µ is the reduced mass of the system [µ =
F. Molecular Systems; Energy Levels m 1 m 2 /(m 1 + m 2 )] and ν0 is known as the fundamental
When atoms combine to form molecules, the individ- vibrational frequency. The smallest amount of vibrational
ual atomic energy levels give rise to discrete electronic energy a molecule can possess is thus ν0 /2, termed the
energy levels or states of the molecule. The number of zero-point energy. Rather than the simple Hooke’s law
these molecular electronic states far exceeds those of potential we may consider more realistic molecular po-
the individual atoms because of the many different ways tential energy curves such as a Morse potential given by
in which the atomic states can be combined. Electronic
U (r ) = De {1 − exp[−β(r − re )]}2 , (14)
states of molecules are classified in terms of several
molecular quantum numbers in a manner analogous to where De is the dissociation energy of the molecule and β
atomic electronic states. For a diatomic molecule these is related to De and ν0 . This leads to a similar expression
include the electronic orbital angular momentum, l, its for E v , but with an additional quadratic term in (v + 12 ),
component along the internuclear axis, λ, and the corre- which is negligible for low vibrational energies. Similarly,
sponding quantities for the molecule as a whole, L and an accurate treatment of molecular rotation leads to addi-
. Just as l = 0, 1, 2, . . . gives rise to s, p, d, . . . elec- tional terms in higher powers of the quantity {J (J + 1)}.
tron states and L = 0, 1, 2 . . . gives S, P, D, . . . atomic
states, so λ = 0, 1, 2 . . . yield σ, π, δ . . . electron states
G. Spectroscopy
and = 0, 1, 2 . . . correspond to , ,  . . . molecu-
lar states. The component of the total electronic angu- Atoms and molecules can adsorb and emit radiation
lar momentum along the internuclear axis, , is also of to change their internal energy states. The electronic
importance. transitions of the hydrogen-like atoms have already been
The ground electronic states of H2 , O2 , and N2 are  mentioned. The quantization of the energy levels restricts
states, while those of OH and NO are  states. These latter the possible wavelengths of the radiation to discrete
two molecules have open valence shells with net spin of 12 , spectral lines. Only certain transitions are allowed and
so that the multiplicity, S, of these states is 2 (S = 2S + 1), these are given by separate selection rules for electronic,
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164 Physical Chemistry

vibrational, and rotational transitions. For example, in radiation, while nuclear magnetic resonance (NMR) is a
atomic transitions l can only take values of ±1. In add- radio-frequency technique.
ition, each allowed transition has an associated transi- 5. Mössbauer spectroscopy, which involves the reso-
tion linestrength. In electronic spectroscopy involving nant absorption of a γ -ray photon by a nucleus. The res-
transitions between electronic states, these are termed onant condition is achieved via the Doppler effect, by
transition moments, Franck–Condon factors and Hönl– sweeping the velocity of a sample relative to the source.
London factors for electronic, vibrational, and rotational The chemical environment of the nucleus causes charac-
transitions, respectively. teristic frequency shifts.
The spectrum of absorption lines associated with a given
species can be used as a fingerprint for identification and
quantification in the process of absorption spectroscopy. III. STATISTICAL THERMODYNAMICS
An absorption spectrum is usually recorded with an ab-
sorption spectrometer or, more recently, with a laser. Sim- A. First and Second Laws of
ilarly, emission spectroscopy is concerned with the radia- Thermodynamics; Entropy
tion that is emitted by an excited atom or molecule. Here
The first law of thermodynamics states the conservation
radiation is generally spectrally resolved using a spectro-
of energy,
graph. In the various spectral regions, these techniques
may be referred to as vacuum ultraviolet (VUV), ultravi- δ Q = dU + δW, (15)
olet (UV), infrared (IR), and microwave spectroscopies.
Microwave photons have energies of less than 1 meV and where δ Q is the heat absorbed by the system, dU is the
are associated with rotational transitions, while infrared change in internal energy of the system, and δW is the
photons have energies of up to 1 eV and are involved with work done by the system. The second law of thermody-
vibrational transitions. More energetic radiation from the namics states that heat cannot pass from a cold reservoir
visible to VUV is usually associated with electronic tran- to a hot reservoir without the application of work.
sitions. In addition to identifying species, these and re- The change in entropy, d S, is just δ Q/T , where T
lated spectroscopic techniques are frequently employed is the temperature. The factor 1/T is an integrating factor
to obtain detailed structural information, such as bond that transforms δ Q into an exact differential just as 1/v 2
lengths and bond angles, and to study the flow of energy transforms vdu − udv into the exact differential d(u/v).
in chemical reactions. Because the change in entropy, d S = δ Q/T , is an exact
Other spectroscopic techniques include: differential, the change in entropy in a reversible cyclic
process is zero. The entropy of a thermodynamic state is
a well-defined single-valued function and the entropy is
1. Raman spectroscopy, which concerns the spectral
said to be a state function. An equivalent statement of the
analysis of radiation scattered by an atom or molecule.
second law of thermodynamics is
Recent developments are coherent anti-Stokes Raman
spectroscopy (CARS) and surface enhanced Raman spec- S ≥ 0, (16)
troscopy (SERS), both of which are sensitive laser-based
techniques, and examples of laser spectroscopy. where the change in entropy is zero for a reversible cyclic
2. Photoelectron spectroscopy, which is based on ki- process. The entropy increases in an irreversible process.
netic energy analysis of electrons ejected from an atom
or molecule by an enegetic photon and provides informa- B. Free Energy; Experimental Measurements
tion on the binding energies or ionization potentials of
the ejected electrons. Recent developments include X-ray The first and second laws of thermodynamics can be
photoelectron spectroscopy (XPS) of surfaces, and the use combined to give
of lasers as radiation sources. T d S = d E + δW. (17)
3. Auger electron spectroscopy (AES), which involves
the electron impact ionization of an atom to give an ex- If the only work done by the system results from an expan-
cited electronic state that decays by emission of a second sion d V or a change in the amount d Ni of the constituents,
electron whose energy is characteristic of the atom. This then Eq. (14) becomes
is most commonly used in surface analysis. 
m
4. Spin resonance spectroscopy, which concerns the ap- T d S = dU + pd V − µi d Ni , (18)
plication of a magnetic field to split energy states associ- i=1

ated with electron or nuclear spin orientations. Electron where p is the pressure, V the volume, µi the chemical po-
spin resonance (ESR) involves absorption of microwave tential of constituent i, and Ni the amount or concentration
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Physical Chemistry 165

of constituent i. The chemical potential of a gas is the value the so-called gas constant (R) divided by Avogadro’s num-
of the Gibbs function for one mole. In a purely mechanical ber, N A = 6.022 × 1023 mol−1 , the number of molecules
system, equilibrium is achieved when the energy is a min- in a mole.
imum. In a thermodynamic system, entropy changes as The thermodynamic properties are related to the energy
well as energy changes must be considered. At constant levels E i through the partition function Z defined by
temperature, volume, and concentration, the Helmholtz 
Z = e−β A = exp(−β E i ), (23)
free energy, i
A = U − T S, (19) where the sum is over all the energy levels of the system.
is a minimum at equilibrium, whereas at constant pressure Thus, to obtain the thermodynamics of a system, all that
and temperature the Gibbs free energy is required is that Schrödinger’s equation for the system
be solved and the partition function summed. For most

m
systems this is a difficult task, often impossible without
G = A + pV = µi Ni (20)
i=1
some approximations.
There is also a relation between the entropy and the
is a minimum at equilibrium.
microscopic configurations of the system. The entropy is
For a dilute gas, where the perfect gas law ( pV = n RT )
proportional to the logarithm of the number of accessible
applies, the value of µ per mole at a pressure p is
states, , of the system. Thus,
µ( p) = µ◦ + RT ln( p/atm), (21)
S = k ln . (24)
where µ◦ is the value of µ at 1 atmosphere, which is the
Equation (24) is called Boltzmann’s relation. At absolute
pressure at which the standard state is established. The
zero, the system is in its ground state, and the number
value of µ◦ is often taken as zero for the elements. In Eqs.
of accessible states is unity. Thus, the entropy of a system
(20) and (21) R( = 8.3144 J mol−1 K−1 ) is the so-called
tends to zero as the temperature goes to zero. This is called
gas constant. A mole of any substances is the amount with
the third law of thermodynamics.
a mass in grams equal to its molecular weight in atomic
The Boltzmann relation provides a statistical interpre-
mass units, so that a mole of molecular hydrogen has a
tation of the entropy. The greater the number of accessible
mass of 0.002 kg. The value of G or µ can be determined
states, the less our knowledge of the system and the more
for some pressure p by measuring the volume of the gas
randomness or disorder in the system. This entropy is a
as a function of pressure up to p and integrating. Thus,
 measure of disorder. The tendency of the entropy to in-
1 p crease reflects the tendency of thermodynamic systems to
µ( p) = µ◦ + V ( p)d p, (22)
n p0 increase in disorder just as an initially ordered deck of
cards increases in disorder during a game of cards.
where p0 is the pressure of the standard state (usually 1
If the system is classical, the energy levels merge into
atm). The free energy of a condensed phase can be re-
a continuum and an important simplification results. The
lated to that of a dilute gas through the vapor pressure,
sum in the partition function becomes an integral. More-
the pressure of the gas in equilibrium with the condensed
over, if the kinetic energy degrees of freedom (i.e., the
phase. Once the free energy of the condensed phase has
momenta) are independent of the potential energy or in-
been established, values for other states can be obtained
ternal degrees of freedom (i.e., the generalized positions)
by measuring pressure or energy through a sequence of
then the momenta can be integrated immediately. For
states leading to the desired state.
the particular case in which there is only translational
motion.
C. Statistical Mechanics; Partition Function 
λ− 3N
Z= exp(−β) dr1 · · · dr N , (25)
The thermodynamic properties of a system result from N!
the dynamics of its molecules. Since even a three-body
where λ = h/(2π mkT )1/2 , N is the number of molecules
system is difficult, statistical methods must be employed
in the system, and  = (r1 , . . . , r N ) is the potential en-
to treat the large number of molecules in a thermodynamic
ergy. The factor N ! is required because states that differ
system.
only by an interchange of molecules are not distinguish-
The fundamental result in statistical mechanics is the
able.
fact that the probability of a system occupying the en-
From Eq. (20), it follows that the average kinetic energy
ergy level E i is proportional to the Boltzmann factor,
of the system is
exp(−β E i ), where β = 1/kT and k = 1.3804 ×10−23 J
K−1 is the Boltzmann constant. The Boltzmann constant is KE = 32 N kT (26)
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166 Physical Chemistry

In other words, there is a statistical relation between the computer simulations show that it will freeze and exist as
temperature and the average motion of the molecules. The a close-packed solid.
greater the temperature, the more rapidly the molecules
move and the greater their kinetic energy.
E. Liquids; van der Waals Theory; Critical
The problem of predicting the thermodynamic proper-
Point; Renormalization Group
ties of such a classical system becomes the problem of
evaluation of the configuration integral, the integral over In contrast to a gas, a liquid need not fill space but can exist
exp(−β). This is still a difficult task. In general, it can in equilibrium with its vapor with a surface separating the
be done only through computer simulations (Monte Carlo liquid and vapor. The pressure at which the equilibrium
and molecular dynamics methods). However, there are a occurs is called the vapor pressure. Below the vapor pres-
few simple approximations which are helpful. sure, liquid will evaporate until equilibrium is reached. For
pressures greater than the vapor pressure, there is no inter-
face between liquid and vapor. The liquid fills the container
D. Perfect and Imperfect Gases
and there is no clear distinction between liquid and gas.
The simplest system is the perfect gas in which the The liquid under pressure can be heated at constant volume
molecules do not interact, i.e.,  = 0. Thus, the config- to a temperature greater than the critical temperature (the
uration integral is just the volume raised to the power N . highest temperature at which liquid–vapor coexistence can
Using Stirling’s approximation, N ! = (N /e) N , occur), then allowed to expand and cool to the original
temperature and pressure without any transition from liq-
Z = λ− 3N (eV /N ) N (27)
uid to gas being observed. A continuity of states between
and liquid and gas is said to exist. This is illustrated in Fig. 2.
The liquid–gas phase can be referred to by the single
pV = N kT. (28)
term fluid. Thus, a theory of the liquid state is of necessity
If the molecules interact, then the problem is more com- also a theory of an imperfect gas. The earliest theory of
plex. The gas is called imperfect because there are devia- the liquid state is that of van der Waals. Although more
tions from the perfect gas result. These deviations can be than a century old, with slight modifications it is viable
written as a power series in the density, ρ = N /V , called a today. The idea of van der Waals was that a liquid behaved
virial series. For example, if the molecules are hard spheres as a hard sphere gas except that the pressure must include
such that the molecules collide elastically but exert no at- the internal pressure due to the attractive forces of the
tractive forces on each other, then molecules in the liquid. It is reasonable to assume that the
contribution of the internal pressure to the free energy is
βp /ρ = 1 + ρb + 58 (ρb)2 + · · · . (29)
proportional to the density. Thus,
For hard spheres, the coefficients of ρ , called virial co-
n

efficients, are independent of the temperature. For more

complex gases the virial coefficients are temperature
dependent.
The virial coefficients can be related to the forces be-
tween the molecules. However, both the relation itself and
the evaluation of the resultant integrals rapidly become
complex as the power n of ρ n increases. In general, it is
difficult to go beyond n = 4.
The pressure of the hard-sphere gas exceeds that of
the perfect gas at the same temperature and density. To a
first approximation, this can be thought to be a result of a
reduction in the volume available to the molecules because
of the volume occupied by the molecules themselves. The
hard spheres can be said to have less free volume than the
perfect gas.
The hard-sphere gas cannot be liquified. Liquification
requires attractive forces. Attractive forces can also cause
the pressure to be less than the perfect gas result. Interest-
ingly, attractive forces are not required for the existence FIGURE 2 Phase diagram of a typical simple liquid. The shaded
of a solid phase. If the hard sphere gas is compressed, region is not thermodynamically stable.
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Physical Chemistry 167

p = p0 − ρ 2 a , (30)
where p0 is the pressure of the hard-sphere gas and a is a
constant depending on the nature of the attractive forces.
In its original formulation, the van der Waals theory was
only qualitatively successful because van der Waals ap-
proximated p0 by the perfect gas expression with a re-
duced free volume, i.e.,
βp0 1
= . (31)
ρ 1 − ρb
This expression gives only the second hardsphere virial co-
efficient correctly and seriously overestimates p0 . Much
more satisfactory results can be obtained from the approx-
imation
βp0 1
= (32)
ρ (1 − η)4
where η = 14 ρb. The van der Waals theory predicts that
the equation of state of a liquid can be expressed in
a universal form if the following reduced variables,
T ∗ = bkT /a, p ∗ = b2 p/a, and ρ ∗ = ρb, are used. This is
called the law of corresponding states. As is illustrated in
Fig. 3, the theory also predicts that below the critical tem-
perature there is a first-order phase transition between the FIGURE 3 Typical pressure isotherms as a function of the vol-
liquid and vapor accompanied by a discontinuous change ume V in the van der Waals theory. The shaded region is not
in the density ρ. At the critical temperature the transition thermodynamically stable. Here Tc is the critical temperature.
becomes second order since the liquid and vapor have be-
come identical. For temperatures above the critical tem-
perature, there is no phase transition. In the van der Waals reaching is the renormalization group approach in which
theory, the critical point occurs when a group of successive transformations is applied to the
   2  liquid, yielding ultimately a renormalized system in which
∂p ∂ p only the long-range correlations typical of the critical point
= = 0, (33)
∂ρ T ∂ρ 2 T remain. In this system the critical point properties can be
i.e., the pressure isotherms have a point of inflection at the examined.
critical point.
Modern theories show that the van der Waals theory F. Mixtures
is a first approximation to a systematic approach, called
perturbation theory, in which the pressure is obtained as a Mixtures of two gases or liquids can be treated by the
power series in 1/T . same techniques as liquids. The analog of a perfect gas is
In the van der Waals theory, the first two derivatives the ideal mixture, where molecules of the components are
of p at constant T with respect to the density vanish at very similar so that the partition function can be written
the critical point. This is not just a prediction of the van (for the two-component case) as
der Waals theory. Any theory in which the equation of N!
state is analytic at the critical point will yield this result. Z= Z1 Z2
N1 !N2 !
By analytic, it is meant that the pressure can be expanded
as a power series about the critical point. Experimentally, where N = N1 + N2 and Ni is the number of molecules
the equation of state is not analytic at the critical point. of species i. From this, it can be deduced that the par-
The exponents in an expansion near the critical point are tial pressures of the components are proportional to their
generally not integers. At least one, and possibly two, more concentrations. This result is known as Raoult’s law. The
derivatives of p with respect to the density at constant factor N !/N1 !N2 ! gives rise to the entropy of mixing
T vanish near the critical point. There has been a great S = −N k[x1 ln x1 + x2 ln x2 ], (34)
deal of work on the fascinating properties of the equation
of state in the vicinity of the critical point. The most far where xi = Ni /N .
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168 Physical Chemistry

For a nonideal mixture, the original approach of van der produce a diffraction pattern, which can be analyzed to re-
Waals is still useful. In this approach veal the crystal structure of the sample. All crystal lattices
can be classified into 14 Bravais lattices belonging to seven
N!
Z= Z  (35) systems. For example, the simple cubic, face-centered cu-
N1 !N2 ! bic and body-centered cubic lattices are the 3 lattices of the
where Z  is obtained from the van der Waals equation cubic system. Cubic and hexagonal close-packed struc-
of state of a liquid, preferably with the more satisfac- tures have the structure of tightly packed spheres where
tory expression for p0 , with a and b replaced by the each sphere touches 12 neighbors, 6 in the same plane and
concentration-dependent quantities 3 above and 3 below. These two close-packed structures
 differ in the placement of successive planes or layers. For
a  = xi x j ai j (36) the cubic case, a third layer is laid down to reproduce
ij
the first layer, so that the structure could be represented
and by ABABAB. . . . For hexagonal close packing, the third
 layer is again displaced, corresponding to ABCABC. . . .
b = xi x j bi j (37) No theory of freezing exists. That is, there is no par-
ij tition function that encompasses both the solid and fluid
√ phases. However, separate theories of solids and fluids can
with ai j  aii a j j taken as a parameter. Assuming that
the spherical cores of the molecules do not overlap, then be developed and their solid–fluid coexistence examined.
To that extent theories of melting or freezing exist. Since
 1/3 1/3 3
bii + b j j freezing can occur in the hard-sphere system, no critical
bi j = . (38) point is expected for freezing. This transition is expected
2
to be first order at all temperatures, as illustrated in Fig. 1.
This approach is satisfactory for mixtures of nonelec- If a solid were classical, the heat capacity would be 3N k.
trolytes. The situation is a little more complex for mixtures This is indeed the case at high temperatures and is called
of electrolytes because of the long range of the Coulomb the law of Dulong and Petit. However, the experimental
potential. However, each ion in the mixture tends to be heat capacity goes to zero at low temperatures. This can be
surrounded by ions of opposite charge, which causes the explained by regarding the solid as a collection of quan-
potential to decay exponentially with a decay factor, κ, tized oscillators. The only difficulty is to determine the
the Debye parameter, which is proportional to the square spectrum of frequencies of the oscillators. For many pur-
root of the product of the density and T −1 . As a result, an poses, the solid can be regarded as an elastic continuum.
appropriate expansion parameter for electrolytes is κ, or The result is the Debye theory. If something more sophis-
T −1/2 , which is different from nonelectrolytes, where T −1 ticated is needed one must solve for the normal modes of
is the expansion parameter. These ideas become quantita- the crystal, i.e., the method of lattice dynamics.
tive in the Debye–Hückel theory. The conduction of electricity in a metal is due to the
presence of free or quasi-free electrons in the metal. Clas-
sically, free electrons would contribute 3nk/2 to the heat
G. Solids
capacity, n being the number of free electrons. However,
In contrast to the disorder of gases and liquids, there is experimental evidence indicates that the electrons do not
translational order in crystals. Disordered or amorphous contribute significantly to the heat capacity of a metal.
solids (i.e., glasses) exist which lack this order. However, The reason for this is the exclusion principle. Although
they are really highly viscous liquids. This translational the electronic gas is in its ground state, because of the ex-
order is such that the entire structure, or lattice, can be clusion principle the electrons can each occupy one energy
generated by repeated replication of a small regular figure, level. The electrons occupy the levels up to a maximum en-
termed the unit cell. The planes of any crystalline structure ergy, called the Fermi energy, εF . Only the small number
can be specified using Miller indices, which also serve to of electrons with energies near εF can be thermally ex-
identify single crystal faces. Miller indices are obtained cited and, as a result, the electronic heat capacity is small.
by determining the intercepts of the plane with the unit If the exclusion principle is taken into account, treating
cell axes in terms of the length of the cell in that direction, the conduction electrons as free describes many of the
taking the reciprocal, and normalizing so the indices are electronic properties of a metal. To treat metals in a more
all integers. sophisticated manner and to account for semiconductors,
The ordered structure, or lattice, of a solid can be deter- the structure of the solid must be included. If this is done,
mined by X-ray or neutron diffraction studies, in which a the electrons are not free but are restricted to bands of
beam of X-rays of neutrons is scattered from the sample to energy.
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Physical Chemistry 169

an electrolyte, for example, electrons may leave it to re-

duce cations in the solution, giving it a net positive charge
and making the solution slightly negative. These charges
arrange themselves at the interface in two layers, known
as the double layer. The most important property of this
double layer is the variation of potential in its vicinity.
The potential governs the rate at which ions can be trans-
ported through the interface, and so controls the rate of
electrochemical processes.

FIGURE 4 Image of a single atom of xenon sitting on the surface IV. KINETICS AND DYNAMICS
of a platinum single crystal at 4 K, obtained with a scanning tunnel-
ing microscope. Xenon has an atomic radius of ∼1.2 × 10−10 m.
Picture provided by Don Eigler of the Almaden Research The previous sections have dealt only with the equilib-
Center. rium properties of a system of molecules. Such properties
tell us nothing of the time required for equilibrium to be
reached or about the dynamical properties of these sys-
H. Interfaces tems. The rate at which change occurs is the province of
kinetics. The detailed manner in which chemical forces act
The study of interfaces is becoming an increasingly impor- to bring about atomic and molecular motion is the province
tant area of physical chemistry. Of particular interest are of chemical dynamics. This section deals with the motions
gas–solid and gas–liquid interfaces. Both of these can now of atoms and molecules and the processes associated with
be imaged directly with scanning tunneling microscopy chemical change.
(STM). Here the contours of a surface may be determined
by sensing the small current that tunnels across a vacuum
gap to an atomically sharp tip as it is scanned across it. A. Kinetic Theory of Gases
Figure 4 illustrates the remarkable resolution of this in-
The kinetic theory of gases assumes that molecules have
strument. It shows a single atom of xenon sitting on the
negligible size compared to their separation, are in contin-
surface of a platinum crystal at 4 K. For the case of the
uous random motion, and interact only via elastic scatter-
liquid–solid interface, STM can be used to study biolog-
ing. These postulates permit the calculation of molecular
ical samples or the electrodes of an electrochemical cell.
speed and velocity distributions. The probability that a
Other important interfaces are those between a liquid and
molecule has a speed between v and v + dv is found to be
its vapor and between two imiscible liquids.
Consider, for example, the physical adsorption of a gas d F(v) = 4π (m/2π kT )3/2 v 2 exp(−mv 2 /2kT )dv, (40)
by a solid. If the solid is regarded as a giant sphere, the
adsorption of the gas can be regarded as the interaction of where T is the gas temperature and m the molecular mass.
a gas with a single infinitely large molecule dissolved in This is the Maxwell distribution of molecular speeds.
that gas. If the simplest form of the van der Waals theory Figure 5 displays this distribution for nitrogen gas at 25
of mixtures is applied to that system, then the adsorption and 500◦ C. Notice that the velocities are in the range of
isotherm is just hundreds to thousands of meters per second, which are
typical of those for small molecules at ambient tempera-

a12 tures. Recent experiments using light pressure from lasers
 = ρβ , (39)
β(∂ p /∂ρ)T to slow down atoms have resulted in atoms moving with
 velocities comparable to walking speed (1 m/s) and be-
where a12 is a constant. At low densities β(∂ p /∂ρ)T = 1
low. Such slow species are ideal for spectroscopic stud-
and the adsorption is proportional to the density (Henry’s
ies, since their adsorption spectra are not blurred by the
law). However, at higher densities β∂ p /∂ρ is a function of
Doppler effect due to their motion.
the density, and deviations from Henry’s law are observed.
The Maxwell distribution of molecular speeds permits
Especially interesting is the region near the critical point
the evaluation of such important quantities as the pressure
of the gas where (∂ p /∂ρ)T → 0 and singularities in the
p exerted by a dilute gas and the collision frequency Z in
adsorption are observed.
the gas under given conditions. The pressure is then given
Interfaces between dissimilar materials may also be-
by
come electrically polarized, with a separation of charge
occurring at the interface. When a metal is placed into p = 13 ρmvrms
2
, (41)
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170 Physical Chemistry

metals, obtaining the result that the ratio of the thermal

and electrical conductivities is a universal constant times
the temperature (the Wiedemann–Franz law).

B. Transport Properties
The kinetic motion of molecules may cause them to
change their spatial distribution through successive ran-
dom movements. This is the process of diffusion, which
is a transport property. Other transport properties include
viscosity, electrical conductivity, and thermal conductiv-
ity. While diffusion is concerned with the transport of mat-
ter, these are associated with the transport of momentum,
FIGURE 5 Maxwell distributions of speeds for molecular nitrogen
at 25◦ C (298 K) and 500◦ C (773 K). Arrows indicate v̄ and vrms for
electrical charge, and heat energy, respectively. Transport
each case. The most probable velocity has been arbitrarily scaled is driven in each case by a gradient in the respective prop-
to unity in each case. erty. Thus, the diffusion rate of species A is given by Fick’s
law,
while the collision frequency for a one-component gas is Jz (A) = −D[dρ(A)/dz] (45)
given by
√ where Jz (A) is the net flux of A molecules crossing unit
Z = 2σ v̄ρ, (42) area in the z direction and D is the diffusion coefficient;
simply kinetic theory leads to
where ρ is the number of molecules per unit volume and
σ is the collision cross section. The quantity vrms is the D ≈ 13 v̄λ (46)
average square speed and is related to the average kinetic
energy and thus to the temperature, so that Derivation of other transport properties follow from sim-
ilar relationships.
 3kT
vrms = v 2  =
, (43) The viscosity coefficient or viscosity of a gas is given
m by
where m is the molecular mass. This quantity differs from
η ≈ 13 v̄ρmλ, (47)
the average speed,
while the thermal conductivity coefficient κ is given by
8kT
v̄ = v = .
πm κ ≈ 13 v̄ρλCv = ηCv /m, (48)
Equation (43) is equivalent to Eq. (26).
where Cv is the molar heat capacity of the gas at constant
Knowing the collision frequency and the molecular
volume. Notice that since λ is inversely proportional to ρ,
speed, it is possible to estimate the mean free path be-
both η and κ are independent of the gas density. This will
tween collisions, λ = v/Z , so that
√ be true so long as λ is small compared to the dimensions
λ = 1/ 2ρσ, (44) of the apparatus.
In solution, D is given by the Stokes–Einstein relation
which shows the expected behavior that λ must decrease which relates D to the viscosity coefficient of the solution,
as the diameter of the molecule increases or as the density η, and the effective hydrodynamic radius a, where
of the gas increases.
Helium and nitrogen have estimated self-collision cross D = kT /6π ηa (49)
sections of 0.13 and 0.31 nm2 and at a pressure of
1 Torr ( = 133.3 N m−2 = 1.32 × 10−3 atm) there are and by the Einstein–Smoluchowski relation:
about 3 × 1022 molecules m−3 , giving mean free paths D = d 2 /2τ, (50)
of ∼1.8 × 10−4 and 7.6 × 10−5 m for helium and nitro-
gen, respectively. At 25◦ C, these species have respective where τ is the characteristic time between jumps of dis-
velocities of v̄ = 1254 and 474 m/sec, giving collision fre- tance d.
quencies of 6.9 and 6.2 × 106 sec−1 per molecule. More elaborate theories of transport phenomena make
The kinetic theory of gases can also be applied to the use of the Boltzmann transport equation or computer sim-
free-electron gas to describe the transport properties of ulations.
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C. Chemical Kinetics; Activated in a prior step. The species concerned is often a highly
Complex Theory reactive molecule with a vacancy in its outermost shell
of electrons, termed a free radical. Such processes are
The quantitative study of chemical reaction rates and the
termed chain reactions. Chain reactions are very important
factors on which these rates depend constitutes the field
in polymerization reactions, where a radical may add to
of chemical kinetics. Chemical reaction rates can be ex-
another reactant to form another (larger) radical. In cases
pressed in terms of the rate of production of any reaction
where more than one reagent species is formed as a product
product or as the rate of decrease in the concentration of
of a later step, the chain is said to be branched, and such
any reactant. The individual steps in a chemical reaction
branching chain reactions often lead to explosions. In other
sequence are termed elementary reactions. A number of
cases, explosions may occur as a result of a fast exothermic
consecutive elementary reactions may be responsible for a
reaction which yields a net excess of energy in the form of
given chemical change. If the observed rate is found to be
heat and in a time too short for the energy to be dissipated.
proportional to the concentration of a given reactant raised
The increase in temperature then causes an increase in
to some power, α then α is said to be the order of the re-
rate, and the cycle ends in a thermal explosion.
action with respect to that reagent. The sum of the orders
In some mechanisms a species may be consumed in one
over all reagents gives the overall order of the reaction. A
step of a reaction only to be regenerated in a subsequent
complex reaction, involving a number of elementary steps,
step. In cases where the presence of this species increases
may have a noninteger order. Thus the order should not be
the overall reaction rate, it is termed a catalyst, which is
confused with the molecularity of an elementary reaction,
defined as a species that increases the rate of a reaction
which is the number of reagent molecules involved in a
without being consumed or changing the reaction prod-
single reaction step. The sequence of elementary reactions
ucts. A catalyst must increase the rate of both forward and
by which a reaction proceeds is termed the reaction mech-
backward reactions in any system at equilibrium and can
anism, a term also used to describe the detailed process of
be thought of as lowering E 0 (see below).
bond breaking and formation in a single reactive collision.
An expression for bimolecular rate constants can be
By way of illustration, consider the formation of nitro-
obtained by observing that along a reaction coordinate
gen dioxide from nitric oxide and oxygen. This reaction
the energy surface consists of two wells, representing the
is found to be third order, corresponding to
reactants and products, separated by a saddle point, rep-
2NO + O2 = 2NO2 (51) resenting the maximum energy required to pass along the
minimum energy path between reactants and products. If
with a third-order rate law corresponding to
the height of this maximum, relative to the reactant well, is
d[NO2 ] E 0 then only collisions where the energy exceeds E 0
= keff [NO]2 [O2 ]. (52)
dt can lead to reaction. Integrating the Boltzmann distribu-
Here the constant keff is the reaction rate constant and tion of energies over all energies exceeding E 0 , shows
square brackets indicate concentrations. If concentrations that probability of a collision with energy in excess of
are given in moles per liter, the rate constants will have E 0 is proportional to exp(−βE 0 ). This is consistent
units of (mol/L)1−n sec−1 , where n is the order of the re- with the rate law of Arrhenius:
action. A likely mechanism for this process can be written k = A exp(−E 0 /kB T ), (54)
in terms of the elementary steps:
where A is known as the pre-exponential factor, and the
k1
NO + NO → N2 O2 (53a) Boltzmann constant is written as kB here to avoid con-
k−1 fusion; A can readily be estimated from collision theory,
N2 O2 → NO + NO (53b) using the expression for the collision frequency for one
k2 reagent with another, Z 12
N2 O2 + O2 → 2NO2 , (53c)
Z 12 = ρ1 ρ2 σ12 [8kB T /µπ ]1/2 (55)
which leads to the observed rate law if the first two steps
are assumed to come to equilibrium prior to the third reac- which leads to
tion, or if the steady-state approximation, which assumes
A = Pσ12 N A [8kB T /µπ ]1/2 , (56)
that the rate of change of all concentrations is zero, is in-
voked. Reaction (53a) has a molecularity of 2 and is a where NA is Avogadro’s number, which converts ρ to mo-
bimolecular reaction, while reaction (53b) is an example lar units, and P is the so-called steric factor, which ac-
of a unimolecular reaction, involving a single species. counts for the fact that not all collisions lead to reaction.
An important class of reaction mechanisms are those Alternatively, we can replace the product Pσ12 with σreac ,
in which a reaction product from one step is a reagent where σreact is termed the reactive cross section.
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172 Physical Chemistry

A more general treatment of detailed reaction rates is sis experiments, including discharge lamps, flash lamps,
available in the activated complex theory of Eyring, which and synchrotrons. However, most recent studies have con-
assumes that there is an intermediate state between the re- cerned laser photolysis. The photofragments are detected,
actants and the products, called the activated complex or for example, by emission or laser spectroscopy, which
transition state which can be regarded as at least some- provides information on the velocity and quantum-state
what stable and which is in thermodynamic equilibrium distribution of the fragments, with respect to rotational,
with the reactants, thus permitting thermodynamics to be vibrational, and electronic states. It is even possible with
applied. Instead of an energy, we must use the free energy the aid of femtosecond lasers to follow the photofragmen-
G (because the pressure is constant) in the exponential. tation process in real time. Such measurements can pro-
This treatment yields vide information on the shape of the excited state potential
  energy surface. In the last decade, researchers have taken
kT G ‡0 these ideas one step further to use the coherent nature of
k=κ exp −
h RT laser light to control the outcome of a photochemical reac-
    tion such as photodissociation. In this work, one or more
kT S0‡ H0‡
=κ exp − exp − , (57) pulse of laser energy is used to drive a reaction to a de-
h R RT sired outcome, opening up exciting possibilities for new
where R is the gas constant, κ is the transmission coef- methods of chemical synthesis.
ficient and G ‡0 S0‡ , and H0‡ refer to differences be- Bimolecular reactions are often studies by firing col-
tween the activated complex and the reactants. limated streams of reagents at each other in the form
Extensions of this statistical thermodynamical ap- of crossed molecular beams. The scattered reagents and
proach to estimating reaction rates include the RRK and products can be detected by a rotatable mass spectrome-
RRK M theories of unimolecular decay rates, and the ter in order to measure angular distributions. Such experi-
information theoretic formulation of reaction dynamics. ments have shown that many reactions occur in essentially
These theories are remarkably successful, although gen- a single encounter in a direct mechanism, while others pro-
erally more successful at interpreting experimental data ceed through a long-lived complex mechanism. In other
and correlating results than at deriving results a priori. experiments, spontaneous light emission from the unre-
laxed, or nascent, products, termed chemiluminescence,
has been analyzed to yield quantum-state distributions.
D. Reaction Dynamics; Inelastic Collisions
Lasers are often used to probe internal states of products,
Kinetic measurements and knowledge of reaction prod- for example, by inducing emission as in laser-induced flu-
ucts and yields can provide only rather limited insight into orescence (LIF) detection, and to prepare molecules in
the molecular dynamics of chemical reactions. To under- specific states and with chosen orientations. Vibrational
stand the detailed manner in which atoms and molecules energy is often found to be more efficacious in promoting
move together and come apart in the process of a chemical reaction than is translational or rotational energy, since it is
reaction, it is necessary to study the isolated elementary re- more strongly coupled to the reaction coordinate, or path
actions in as much detail as possible. Such isolation is most in phase space along which reaction takes place. Product
often provided by a dilute gas environment. Ultimately, the distributions are frequently observed to be far from equi-
hope is to understand reaction dynamics in terms of elec- librium. For example, in direct reactions, high vibrational
tronic structure and to be able to calculate this for a cho- levels are often found to be more populated than low ones.
sen system. The electronic structure or potential energy This so-called population inversion forms the basis of the
surface is the meeting ground between theory and exper- chemical laser.
iment. Currently most studies seek to probe those factors, Reaction rate constants cannot be used to describe
or states, which influence the rate of chemical reactions, such detailed processes.  Instead the differential  reac-
such as vibration and translational energy, and to examine tion cross section, σreact n 1 , n 2 , n 3 , . . . n 1 , n 2 , n 3 , is em-
the manner in which energy and angular momentum are ployed, where n i are various quantum numbers and the
disposed among the product states for various processes. primed quantities refer to reaction products. Such cross
This is the area known as state-to-state chemistry. sections represent the effective collision area for reagents
Molecular photodissociation is an ideal process for such with given n 1 , n 2 , . . . , to give specific products. Rate con-
studies and has been examined in considerable detail. This stants represent the effective average of the product of the
unimolecular event is sometimes considered as a “half cross section with the approach velocity taken over the
collision,” where the absorption of a photon excites the calculated distribution of reagent quantum states.
system to a repulsive state that flies apart. A number of Cross sections can be predicted from semiclassical tra-
radiation sources have been employed for such photoly- jectory calculations, in which equations of motion are
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Physical Chemistry 173

solved by numerical integration, or they can be ob- often catalyzed, for example, by protons in acid catalysis
tained from quantum calculations via the time-dependent and by enzymes in many biological systems. Moreover,
Schrödinger equation. Both approaches require a previ- interactions with solvent molecules may grossly alter the
ously calculated potential energy surface. However, accu- potential energy surface on which reaction occurs, com-
rate potentials are currently available only for the H + H2 pared to the isolated gas-phase system. Such interactions
reaction and its isotopic analogues, for which precise are strongest for polar reagents and solvents.
quantum calculations can be made. For other systems ap- Reactions in solution are often diffusion controlled,
proximate surfaces can be obtained either semiempirically where the limiting step is the rate at which reagents can
(e.g., using the LEPS or BEBO functions), or from approx- find each other. In the absence of strong interactions such
imate a priori calculations. Statistical theories are also em- as those between ions, the rate constant may be esti-
ployed. These are based on the assumption that different mated from Fick’s law [Eq. (45)] together with the Stokes–
reaction channels are populated in proportion to the vol- Einstein relation [Eq. (49)] giving:
ume of phase space with which they are associated, which
k = 8RT /3η, (58)
is consistent with conservation of energy and linear and
angular momentum. Dynamical factors may cause devia- where R is the gas constant. Since reactants are also slow
tions from such statistical behavior, providing information to drift apart, the time-averaged collision frequency per
on the reaction mechanism. This is recognized in the in- molecule may be close to the gas-phase value, so that re-
formation theoretic approach where the fully statistical actions with rate constants much smaller than given by
outcome, or prior distribution, is compared with observa- Eq. (58) may be relatively insensitive to diffusion effects
tions in so-called surprisal plots which indicate the degree (in practice this means E 0 ≥ 40 kJ/mol). Reaction prod-
to which the data deviate from statistical behavior. This ucts may also be slow to move apart, thus in liquid-phase
approach has proven very valuable in the correlation and photodissociation, where the adsorption of light causes a
extension of a wide body of data. molecule to fall apart, the surrounding solvent cage may
Since reaction rates can depend not only on reagent hold the products together long enough for recombination
energy, but also on the form in which it is available, a to occur.
full understanding of chemical behavior requires knowl- If two reactions are in equilibrium with an equilibrium
edge of the manner in which energy in various forms is constant K , and the back reaction is held constant at the
redistributed by collisions. This information must be ob- diffusion limit, kd , then the forward rate constant will be
tained by studies of energy transfer associated with in- equal to K kd . More generally, it is often found that for a
elastic collisions. Experimental studies vary from kinetic given reaction involving a series of similar reagents,
measurements of decay rates, to full state-to-state stud-
ies. It is found that rotational energy is readily trans- k ∝ K α, (59)
ferred from one molecule to another, occurring on al- log k = b + α log K . (60)
most every collision. Transfer from rotation to transla-
tion can be 102 times slower, while transfer to vibration This is the Brønstead equation, and is an example of a
may be 104 times slower. Transfer between translation linear free-energy relationship, since log K ∝ G 0 and
and vibration occurs only about once in a million colli- log k ∝ G ‡0 , then Eq. (60) could be written as
sions at room temperature. In general, the rate of energy G ‡0 = b + αG 0 (61)
transfer decreases rapidly as the amount of energy trans-
ferred increases, following an approximate exponential Related to the Brønstead equation is the Hammett equa-
gap rule. tion, which expresses the rate constant k of one of a series
of related reactions in terms of a specific reference reaction
with rate k0 , giving
E. Reactions in Solution
log(k/k0 ) = ρσ, (62)
In principle, reactions in solution occur in a similar man-
ner to those in the gas phase and in some favorable cases where ρ is a characteristic of the type of reaction and σ is
the observed rate constant is the same in both phases. For a characteristic of the specific system. Expressions such
example, the unimolecular decomposition of N2 O5 yields as the Brønstead and Hammett equations are particularly
similar A and E 0 values in the gas phase and in a large useful since the complex nature of the environment makes
range of solvents. However, there are many important dif- absolute rate theories such as the activated complex theory
ferences. Reactions of ionic species and of large molecules difficult or impossible to apply in solution.
such as proteins and polymers are rare in gas-phase stud- The rate constant for a bimolecular reaction in solution
ies but are common in solution. Reactions in solution are can be expressed in terms of the activity coefficients of
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174 Physical Chemistry

the reagents, γ (A) and γ (B), and of the transition state, (see above). In this method, the STM current shows fea-
γ (AB)‡ , by tures associated with the vibration frequencies of chemical
bonds. Figure 6(A) shows an STM image of the molecule
k = k0 [γ (A)γ (B)/γ (AB)‡ ], (63) HC2 D on a copper surface. Figure 6(B) shows an image
where an activity coefficient is defined as the ratio of the of the CD bond of this molecule.
effective concentration to the actual concentration, as re- The fraction of a surface covered by a gas, , is given
quired to obey Raoult’s law. The Debye–Hückel limiting in terms of monolayers (ML), where 1.0 ML represents
law gives γ in terms of the ionic charges z of the species: complete coverage by a single layer. The pressure depen-
√ dence of  at a given temperature is termed an adsorp-
log γ (i) = −sz i2 I , (64) tion isotherm. If the rate of adsorption is ka p(1 − ), and
the rate of desorption is kd , we obtain the Langmuir
where I is the ionic strength: isotherm:
1 i
=∞
=
Kp
(67)
I = xi z i2 , (65) 1 + Kp
2 i =0
where K = ka /kd . Thus, when K p is small,  is simply
in which xi indicates molar concentration, giving:
proportional to the pressure. An adsorption dependence on
√
log k = log k0 + 2sz A z B I . (66) 1 −  arises in the ideal case in which each molecule ad-
sorbs at and occupies a single surface site. If two adjacent
This indicates that the rate constant for reactions in solu- sites are required for adsorption, a (1 − )2 dependence
tion depends on the ionic strength of the solution, behavior might hold. The probability of adsorption for a single col-
referred to as the kinetic salt effect. Thus, addition of inert lision is termed the sticking probability, which usually
ions will increase the rate of reaction between ions of like implies chemisorption and may range from unity, for say
charge and vice versa. oxygen on a clean metal surface, to close to zero for an in-
Recent advances in theory√ have shown that log k ceases ert system. At low temperatures, even inert gases may trap
to be a linear function of I at large ionic strength. The into a physisorption state, in proportion to their trapping
reaction rate continues to increase with increasing ionic probability.
strength, but less rapidly than that predicted by the above With a sticking or trapping probability of unity, a mono-
relation. A careful examination of the experimental data layer will form in about 1 sec at 10−6 Torr, which means
confirms this prediction. that studies of clean surfaces must be carried out under
conditions of ultra high vacuum (UHV), or below ∼10−9
Torr.
F. Reactions at Surfaces; Heterogeneous The ability of surfaces to promote chemical reactions
Catalysis; Corrosion stems largely from their ability to cause dissociation.
Atoms and molecules frequently adsorb on surfaces, Consider the decomposition of ammonia to nitrogen and
where they may decompose and/or react with other ad- hydrogen:
sorbed species. Modern technology is increasingly depen- 2NH3 → N2 + 3H2 (68)
dent on surface chemistry which underlies many industri-
ally important processes as well as destructive processes In the gas phase, this process has an activation energy of
such as corrosion. It is useful to distinguish two types ∼330 kJ mol−1 , whereas in the presence of on a tung-
of adsorption: physical adsorption, or physisorption, and sten surface this falls to ∼160 kJ mol−1 . By providing
chemical adsorption, or chemisorption. Physisorption is an alternative low-energy path for reaction, the surface
similar in nature to condensation and involves little chem- causes a large increase in the reaction rate. This is an ex-
ical interaction with the surface, being associated with van ample of heterogeneous catalysis. (See Section IV.C for
der Waals forces. Chemisorption involves a true chemical a definition of catalysis.) For such a reaction to occur at
interaction with the surface, with the formation of a chem- a surface, the ammonia must first diffuse to the surface,
ical bond. Thus, the enthalpy of physisorption is usually of it must dissociatively chemisorb, the hydrogen and ni-
the order of 20 kJ mol−1 , while for chemisorption values trogen atoms must then recombine, and they must desorb
are in the region of 200 kJ mol−1 . A chemisorbed molecule and diffuse away from the surface. The recombination and
may either remain intact in molecular chemisorption, or desorption may actually occur as one step, as the reverse
fall apart in dissociative chemisorption. In an important of dissociative adsorption. Either the adsorption or des-
recent development, it is now possible to identify individ- orption steps are rate-limiting in gas–surface reactions,
ual molecular bonds of adsorbed molecules using STM although fast liquid–surface reactions may be diffusion
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Encyclopedia of Physical Science and Technology
EN012A-573
July 25, 2001
17:10

FIGURE 6 Scanning tunneling microscope image of a singly deuterated acetylene molecule (HC2 D) molecule on a
Cu(100) surface. (A) An image of the C–D bond obtained by setting the second differential of the tunneling current
to 269 meV. [See Stipe, B. C., Rezaei, M. A., and Ho, W. (1999). Phys. Rev. Lett. 82, 1724; courtesy B. C. Stipe, with
permission.]
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176 Physical Chemistry

limited. This is consistent with the fact that dissociative SEE ALSO THE FOLLOWING ARTICLES
chemisorption and recombinative desorption are often ac-
tivated processes. ADSORPTION • ATOMIC SPECTROMETRY • CHEMICAL
Chemical reactions at the gas–surface interface can be THERMODYNAMICS • CRYSTALLOGRAPHY • KINETICS
followed by monitoring gas-phase products with, for ex- (CHEMISTRY) • LIQUIDS, STRUCTURE AND DYNAMICS •
ample, a mass spectrometer, or by directly analyzing the MECHANICS, CLASSICAL • PERIODIC TABLE (CHEMISTRY)
surface with a spectroscopic technique such as Auger • QUANTUM CHEMISTRY • QUANTUM MECHANICS • STA-
electron spectroscopy (AES), photoelectron spectroscopy TISTICAL MECHANICS • SURFACE CHEMISTRY
(PES), or electron energy loss spectroscopy (EELS), all
of which involve energy analysis of electrons, or by sec-
BIBLIOGRAPHY
ondary ionization mass spectrometry (SIMS), which ex-
amines the masses of ions ejected by ion bombardment.
Adamson, A. W. (1980). “Physical Chemistry of Surfaces,” Wiley, New
Another widely used surface probe is low-energy electron York.
diffraction (LEED), which can provide structural infor- Adamson, A. W. (1979). “A Textbook of Physical Chemistry,” 2nd ed.,
mation via electron diffraction patterns. At the gas–liquid Academic Press, New York.
interface, optical reflection ellipsometry and optical spec- Atkins, P. W. (1982). “Physical Chemistry,” 2nd ed., Freeman, San Fran-
cisco.
troscopies are employed, such as Fourier transform in-
Bernstein, R. B. (1982). “Chemical Dynamics via Molecular Beam and
frared (FTIR) and laser Raman spectroscopies. Laser Techniques,” Oxford Univ. Press, New York.
Elastic and inelastic collisions of atoms and molecules Berry, R. S., Rice, S. A., and Ross, J. (1980). “Physical Chemistry,”
at surfaces are also of importance. The scattering of hydro- Wiley, New York.
gen and helium from surfaces leads to diffraction patterns Eyring, H. (1944). “Quantum Chemistry,” Wiley, New York.
Eyring, H., Henderson, D., and Jost, W. (1967). “Physical
in the same manner as with LEED, but since the atoms
Chemistry—An Advanced Treatise,” 15 vols., Academic Press, New
penetrate the surface far less deeply than even low-energy York.
electrons, the structures obtained reflect the very surface of Eyring, H., Henderson, D., Stover, B. J., and Eyring, E. M.
the sample. The inelastic surface scattering of molecules (1982). “Statistical Mechanics and Dynamics,” 2nd ed., Wiley, New
can be examined in detail using laser and mass spectromet- York.
Herzberg, G. (1950). “Molecular Spectra and Molecular Structure: I.
ric detection for the scattered molecules. Such measure-
Spectra of Diatomic Molecules,” 2nd ed., Van Nostrand-Reinhold,
ments can be used to model the form of the gas–surface New York.
interaction potential, knowledge of which is a prerequisite Kauzmann, W. (1957). “Quantum Chemistry,” Academic Press, New
for any detailed picture of gas–surface reaction dynamics. York.
Not all surface chemistry is catalytic. In many cases Laidler, K. J. (1965). “Chemical Kinetics,” 2nd ed., McGraw-Hill, New
York.
the surface itself may be consumed, in processes such
Levine, R. D., and Bernstein, R. B. (1974). “Molecular Reaction Dy-
as etching and corrosion. Etching is employed to fabri- namics,” Oxford Univ. Press, New York.
cate devices where it provides for the controlled removal Levine, R. D., and Bernstein, R. B. (1987). “Molecular Reaction
of material. In the semiconductor industry, for example, Dynamics and Chemical Reactivity,” Oxford Univ. Press, New
discharges containing fluorine are used to etch silicon by York.
Linnett, J. W. (1960). “Wave Mechanics and Valency,” Methuen, Lon-
volatilization as silicon fluorides. Corrosion is generally
don.
an unwanted process whereby items are destroyed through McQuarrie, D. A. (1976). “Statistical Mechanics,” Harper and Row, New
dissolution and/or oxidation. Metals may corrode through York.
many different (usually electrochemical) processes. For Moore, W. J. (1983). “Basic Physical Chemistry,” Prentice Hall, New
example, in the presence of oxygen, a metal may displace York.
protons as water or reduce oxygen to OH− , in acid and Partington, J. R. (1954). “An Advanced Treatise on Physical Chemistry,”
5 vols., Wiley, New York.
alkaline environments, respectively. In principle, this pro- Rowlinson, J. S. (1982). “Liquids and Liquid Mixtures,” 3rd ed., But-
cess requires the additional presence of a second metal, terworths, London.
with a lower electrochemical potential. However, all sam- Smith, I. W. M. (1980). “Kinetics and Dynamics of Elementary Gas
ples have regions of high and low strain, which will have Reactions,” Butterworths, London.
Smith, R. A. (1961). “Wave Mechanics of Crystalline Solids,” Wiley,
slightly different potentials. A given metal can be pro-
New York.
tected by contact with another (sacrificial) metal with a Steinfeld, J. I. (1974). “Molecules and Radiation: An Introduction
more negative potential, which will be preferentially cor- to Modern Molecular Spectroscopy,” MIT Press, Cambridge, Mas-
roded. This is applied in the galvanizing of iron by zinc. sachusetts.
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Encyclopedia of Physical Science and Technology EN013C-606 July 26, 2001 17:34

Potential Energy Surfaces

Donald G. Truhlar
University of Minnesota

I. Introduction
II. Quantum Mechanical Basis for Adiabatic
Potential Energy Surfaces
III. Topology of Adiabatic Potential Energy Surfaces
IV. Breakdown of the Adiabatic Approximation
V. Shapes of Potential Energy Surfaces

GLOSSARY Glancing intersection Case in which two potential en-

ergy surfaces intersect such that their separation de-
Adiabatic representation Representation in which the creases to zero quadratically in the relevant nuclear
electronic wave functions are calculated for fixed coordinates.
(i.e., nonmoving) nuclei. Ionization energy Energy required to remove an electron
Avoided intersection Case in which two potential energy from an atom or molecule.
surfaces come together but do not intersect.
Conical intersection Case in which two potential en-
ergy surfaces intersect such that their separation A POTENTIAL ENERGY SURFACE is an effective po-
decreases to zero linearly in the relevant nuclear tential function for molecular vibrational motion or atomic
coordinates. and molecular collisions as a function of internuclear co-
Diabatic representation Representation in which the ordinates. The concept of a potential energy surface is
electronic wave function is not adiabatic. basic to the quantum mechanical and semiclassical de-
Dunham expansion Taylor series expansion of a poten- scription of molecular energy states and dynamical pro-
tial energy curve in the vicinity of its minimum. cesses. It arises from the great mass disparity between
Electron affinity Binding energy of an electron to a neu- nuclei and electrons (a factor of 1838 or more) and may
tral atom or molecule. be understood by considering electronic motions to be
Equilibrium configuration Geometry of a molecule’s much faster than nuclear motions. (When we say nuclear
nuclear framework corresponding to the minimum adi- motions and nuclear degrees of freedom in this article, we
abatic energy. refer to motions of the nuclei considered as wholes, i.e.,
Force field The gradient of the potential energy to atomic motions.) This difference in timescales leads
surface. to the so-called electronic adiabatic approximation and to

9
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10 Potential Energy Surfaces

electronic adiabatic potential energy surfaces. Under some II. QUANTUM MECHANICAL BASIS
circumstances, however, it is convenient to use more gen- FOR ADIABATIC POTENTIAL
eral definitions; this results in potential energy surfaces ENERGY SURFACES
variously known as diabatic or nonadiabatic, the latter ad-
jective being a useful double negative (it is convenient The Schrödinger equation for a system of N nuclei and n
to use this term because, except for a few small terms, electrons is
adiabatic surfaces may be defined uniquely but in gen-
eral diabatic surfaces are not; nonadiabatic has the useful (H − E)(r, R) = 0, (1)
connotation then of “anything except the adiabatic”). The where H is the Hamiltonian or energy operator of the
concept of potential energy surfaces may be generalized molecule:
to systems in liquids, in which case one obtains potentials h2 2 h2 2
of mean force. H =− ∇ − ∇ + V (r, R) + Hrel (r, R). (2)
2M R 2m r
In these equations, h is Planck’s constant divided by 2π,
and R denotes a 3N -dimensional vector of scaled nuclear
coordinates:
 
I. INTRODUCTION M1 1/2
R1 = X 1, (3a)
M
The separation of electronic and nuclear motions accord-  
ing to time scales and the consequent introduction of M1 1/2
R2 = Y1 , (3b)
an effective potential energy surface for nuclear motion M
was first considered by Born and Oppenheimer. Although
..
their method is seldom used in modern work, the modern .
equivalents are still commonly called Born–Oppenheimer  1/2
MN
approximations and Born–Oppenheimer potential energy R3N = ZN, (3c)
surfaces. The modern form of the derivation, which is M
summarized below, dates to a later paper by Born and where M j , X j , Y j , and Z j are the mass and Cartesian co-
to work by Born and Huang. Occasionally the phrases ordinates of the nucleus j, M is any of the nuclear masses
Born–Oppenheimer and Born–Huang are used to specify or a convenient reduced nuclear mass, m is the electronic
whether certain small terms are included in the poten- mass, r is a 3n-dimensional vector of electronic Cartesian
tial energy surfaces, although, as mentioned above, it is coordinates {xk , yk , z k }nk=1 :
more common to refer to any adiabatic surfaces as Born–
r1 = x 1 , (4a)
Oppenheimer surfaces.
A potential energy surface is an effective potential en- r2 = y1 , (4b)
ergy function for the relevant nuclear degrees of freedom. ..
The latter are usually defined as all nuclear degrees of .
freedom minus three overall translations and two or three
r3n = z n , (4c)
rotations of the nuclear subsystem. If an atom has N nu-
clei, it is common to consider the potential energy as a V (r, R) is the sum of all coulomb forces between the par-
function of 3N − 5 coordinates for N = 2 (since two nu- ticles, Hrel (r, R) is the energy operator for relativistic ef-
clei always lie on a line and therefore, when considered as fects including mass-velocity and spin–orbit coupling, E
point masses, have only two rotational degrees of freedom) is the total energy, and ψ(r, R) is the wave function. Notice
and 3N − 6 coordinates otherwise. Thus for N = 2 we ac- that the first two terms in Eq. (1) represent the nonrelati-
tually have a potential energy curve (i.e., a function of one vistic kinetic energy of the nuclei and the electrons. Usu-
variable), whereas for N ≥ 3 we have a potential energy ally the change in ψ(r, R) is about the same order of mag-
hypersurface (i.e., a function of three or more variables). nitude when we move a nucleus a small amount as when
A potential energy surface would strictly speaking denote we move an electron the same small amount. When this
the potential energy as a function of two coordinates in is the case, ∇R2 ψ(r, R)/M is smaller than ∇r2 ψ(r, R)/m
a two-dimensional cut through the (3N − 6)-dimensional by a factor of order m/M, which is less than about 10−3 ;
internal-coordinate space. In this article, however, we fol- thus the first term in Eq. (2) may be neglected to a first
low the very common language by which any potential en- approximation.
ergy hypersurface or potential energy function is referred The physical interpretation of this is that because of
to as a surface. their larger masses, the nuclei move so slowly compared
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Potential Energy Surfaces 11

with the electrons that the dependence of the wave function By the same argument given above for the variation of
on electronic coordinates is essentially the same as if the ψ(r, R) with respect to r and R, we expect that the terms
nuclei were completely stationary (i.e., as if their mass containing Fαβ (R) and G αβ (R) are usually much smaller
were infinite so that their kinetic energy was zero). Then than the term containing Uα (R). When this is so, we may
Eq. (1) becomes neglect the small terms, and the set of coupled Eqs. (8) sim-
  plifies to a separate uncoupled equation for each χα (R),
h2 2
− ∇r + V (r, R) + Hrel (r, R) − Uα (R) namely,
2m  
h2 2
× ψα (r; R) = 0, (5) − ∇ + Uα (R) − E χα (R) = 0. (11)
2M R
where Uα (R) and ψα (r; R) denote the eigenvalue and
eigenfunction, respectively, with index α. Notice that both This has the form
of these depend parametrically on the nuclear positions R (Hnuc − E)χα (R) = 0, (12)
and also that the ψα (r, R) form a complete set of functions
of r for any particular value of R. In general the spectrum where Hnuc is an effective Hamiltonian for nuclear motion
{Uα (R)} contains a continuous part as well as a discrete given by
part, but the discrete part is the important part for the h2 2
concept of potential energy surfaces. We shall therefore Hnuc = − ∇ + Uα (R). (13)
2M R
use only a discrete index α. This is adequate for almost
all practical work since the continuous part is usually ne- Since a Hamiltonian is usually the sum of a kinetic energy
glected in calculations. For a more rigorous derivation, operator and a potential energy operator, we may interpret
however, all sums over discrete α in the equations below Uα (R) as an effective potential for nuclear motion. In fact,
must be replaced by a sum and an integral. Uα (R) is the potential energy surface that we sought to
To obtain the complete system wave function we choose derive. Recalling the origin of Uα (R), we see that it rep-
a trial function resents the total energy of the electrons, both kinetic and
 potential, plus all the rest of the potential energy, when
ψ(r, R) = ψα (r; R)χα (R). (6) the electrons are in state α. Alternatively, it represents
α
the entire (coulombic plus relativistic) potential energy of
Since the {ψα (r; R)} are complete, this trial function yields all particles plus the electrons’ kinetic energy. When the
the exact ψ(r, R) if we retain the complete set and solve equations for the χα (R) decouple, as in Eq. (12), the elec-
for {χα (R)} by the variation method. The best {χα (R)} by tronic state is preserved during the nuclear motion. The
this method satisfy the equation resulting quantized energy requirement of the electrons
  plus the rest of the potential energy (given in the absence
dr ψβ∗ (r; R)(H − E) ψα (r; R)χα (R) = 0, of relativistic effects by the nuclear–nuclear coulombic in-
α
teraction energy) together constitute an effective potential
β = 1, 2, . . . , ∞. (7) for nuclear motion.
If we carry out the indicated operations, using Eq. (5) When nuclear motion can be approximated by classical
and the orthogonality of the {ψα (r; R)} in r at fixed R, mechanics (which is often reasonable, especially for atoms
Eqs. (7) become heavier than hydrogen), Eqs. (12) and (13) are replaced by

h2  M R̈ = −∇R Uα (R), (14)
− ∇R2 χα (R) + 2 Fαβ (R) · ∇R χβ (R)
2M β where R̈ is the nuclear acceleration, and the right-hand
 side is the force on the nuclei. Since Uα (R) generates the
+ G αβ (R)χαβ (R) + [Uα (R) − E]χα (R) = 0, force function, it is sometimes called the force field.
β Inclusion of the spin–orbit and other relativistic terms
α = 1, 2, . . . , ∞, (8) in Eq. (5), as we have done, is, strictly speaking, the
most correct approach. This yields, as we have seen, a
where
 set of nuclear wave functions χα (R) whose uncoupled
motion is governed by the potentials Uα (R) and which
Fαβ (R) = dr ψα∗ (r; R)∇R ψβ (r; R) (9)
are coupled only by the nuclear-derivative terms Fαβ (R)
and and G αβ (R). In practice, though, Hrel (R) is difficult to
 treat on an equal footing with the coulombic terms in the
Gαβ (R) = dr ψα∗ (r; R)∇R2 ψβ (r; R). (10) Hamiltonian. Therefore one sometimes works with
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12 Potential Energy Surfaces

nonrelativistic adiabatic potential surfaces, although the

adjective nonrelativistic is seldom stated explicitly. In
this approximation one temporarily neglects Hrel (r, R) to
solve Eq. (5). This yields a new set of nuclear wave func-
tions χα (R) and Uα (r, R) that are easier to work with, but
the effect of Hrel (r, R) must be included later. The matrix
elements

Hrel,αβ (R) = dr ψα∗ (r; R)Hrel (r, R)ψβ (r; R) (15) FIGURE 1 An avoided crossing for a diatomic molecule. Ua is
the potential energy for electronic state a , R the internuclear
provide both a perturbative correction to the nonrelativis- distance, and R ∗ the distance corresponding to an avoided
crossing.
tic potential energy surfaces, for α = β, and an additional
coupling mechanism that must be considered along with
Fαβ (R) and Uαβ (R) for α = β. In the rest of this article at isolated values of R if they correspond to different
we restrict our attention to the nonrelativistic approxima- symmetry but not if they correspond to the same symme-
tion, and we assume that Hrel (r, R) has been neglected in try. When two Uα ( R) are equal, that is called a curve
solving Eq. (5). crossing. Sometimes two Uα ( R) approach very closely
as if they are about to cross but then avoid crossing. This
is called an avoided crossing. An example is shown in
Fig. 1. When the system has an odd number of electrons
III. TOPOLOGY OF ADIABATIC POTENTIAL and exists in a magnetic-free region, the possibilities are
ENERGY SURFACES the same except that all Uα ( R) occur in degenerate pairs.
Imposition of a magnetic field removes the degeneracy.
As shown in Eq. (5), an adiabatic potential energy surface Now consider the case of N ≥ 3 for which the potential
is an eigenvalue of a Hermitean operator, that is, one that energy surfaces depend on three or more variables. Here
has only real eigenvalues. In most cases these eigenvalues we also find potential surface intersections of states be-
are nondegenerate. At some geometries R, however, longing to different symmetries and avoided intersections
two or more eigenvalues may be equal, which is called of states belonging to the same symmetry, but there is also
a degeneracy. Such degeneracies may be mandated by a third possibility, namely, intersections even of potential
symmetry or may be accidental. Points where two or more energy surfaces belonging to the same symmetry. Such
eigenvalues are equal are particularly interesting, and we intersections in general occur in subspaces of dimension
may categorize some features of the potential energy sur- 3N − 8 or lower. If we consider a subset of two degrees
faces in the neighborhoods of these points on the basis of of freedom in which the intersection occurs at a single
symmetry. point, the shape of the surfaces in the vicinity of the
The nuclear configuration R, which appears as a param- intersection is as shown in Fig. 2, that is, the two surfaces
eter in the eigenvalue Eq. (5), may be classified by a sym- form a double cone. Such intersections are called conical
metry point group, for example, D∞h for a homonuclear intersections. Another shape of intersection may occur at
diatomic molecule or another symmetric linear molecule, linear geometries of polyatomic molecules. In this case,
C∞v for a heteronuclear diatomic molecule or other non- the two surfaces may have zero slope at the point of inter-
symmetric linear molecule, Td for a tetrahedral molecule, section. Such intersections are called glancing rather than
C2v for a symmetric nonlinear triatomic molecule, and conical.
Cs for a planar molecule. Since the operations of such a
group commute with −(h 2 /2M)∇r2 + V (r, R), the eigen-
functions ψα (r, R) of this operator can be taken to trans-
form as irreducible representations of the group. We may
thus classify both the eigenfunctions ψα (r, R) and eigen-
values Uα (R) by these irreducible representations, e.g.,
+
g , u , or g for D∞h or A1 or B2 for C 2v .
First consider the case of two nuclei. As already men-
tioned, the potential energy surfaces in this case are really
curves; they depend on only one scalar variable, the inter-
nuclear distance, which we may call R. One can show, FIGURE 2 Portions of two potential energy surfaces exhibiting
on general grounds, that for a system with an even num- a conical intersection. Ua is the potential energy for electronic
ber of electrons, two Uα ( R) may be accidentally equal state a .
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Potential Energy Surfaces 13

In general, for systems of three or more nuclei, some adiabatic approximation is expected to break down in the
potential energy surfaces that intersect when one neglects vicinity of any avoided crossing or avoided intersection,
spin–orbit coupling avoid intersecting when one includes and also at actual intersections for which the symmetry of
it. the two states is the same at the intersection.
There are other circumstances under which the adiabatic
approximation may break down. We have considered the
IV. BREAKDOWN OF THE ADIABATIC case where ψ(r, R) varies rapidly with R because of the
APPROXIMATION factor ψα (r; R). A second case where the term containing
Fαβ (R) in Eq. (8) may be significant occurs when χα (R)
We are now in a position to understand the limitations of varies unusually rapidly, for instance, in highenergy col-
the adiabatic potential energy surface concept. First, how- lisions of Na+ with Cl− . When the nuclear speed is large,
ever, we should understand the physical origin of avoided χα (R) must vary significantly on the scale of a very small
crossings and avoided intersections. We begin by consid- de Broglie wavelength.
ering the diatomic molecule NaCl, and we let R denote We may summarize the two cases in a simple but ap-
the distance between the nuclei. At R = ∞, the energy proximate way as follows: When the nuclear kinetic en-
of two neutral atoms is lower than the energy of a Na+ ergy is much smaller than the spacings between the adi-
ion and a Cl− ion by the difference E of the ioniza- abatic electronic energy surfaces Uα (R), these surfaces
tion potential of Na and the electron affinity of Cl− . As serve as potential energy surfaces for nuclear motion.
R is decreased, however, the energy of the ionic state When the nuclear kinetic energy is comparable to or larger
decreases rapidly because of the long-range coulomb at- than the spacings between the Uα (R), the adiabatic ap-
traction, which may be represented by −e2 / R where proximation may, and often does, break down.
e is the electronic charge, while the energy of the neu- The adiabatic potential energy surfaces need not be
tral state stays approximately constant until much shorter abandoned completely when the adiabatic approxima-
distances where the covalent interaction becomes appre- tion breaks down, especially if the region of breakdown
ciable. Thus at some distance R ∗ given approximately is fairly localized, as it often is when the breakdown is
by due to an avoided or conical intersection. If the nonadi-
abatic behavior is localized to a small region, we often
e2
E∼ = (16) employ the model of surface hopping. In this model the
R∗ nuclear motion is assumed to be governed by an adia-
the hypothetical purely ionic state and the hypothetical batic potential energy surface until a nonadiabatic region
purely covalent state would have the same energy. Actu- is reached. In such a region there is a nonzero quantum
ally though, at this R the corresponding eigenfunctions mechanical probability that the system “hops” to another
of Eq. (5) have mixed character, partly covalent and partly surface. Based on this probability one portion of the quan-
ionic, with about 50% partial ionic character. Since both tum mechanical probability density exits the nonadiabatic
states have 1 + g character, their eigenvalues are different. region in one of the adiabatic electronic states, and the
We call the energies of the hypothetical states with pure other portion exits in the other one or more coupled adi-
valence characteristics U1d ( R) and U2d ( R), where d de- abatic electronic states. After this the nuclear motions
notes diabatic (or nonadiabatic). Although U1d ( R) and again proceed independently as governed by single po-
U2d ( R) cross, the adiabatic curves U1 ( R) and U2 ( r ) tential energy surfaces until another nonadiabatic region
avoid crossing, having the shapes shown in Fig. 1. For is reached. Although this model neglects certain coherency
this case α = 1 corresponds to a covalent state to the right effects that may be important for quantitative work, it is of-
of R ∗ but to an ionic state to the left of R ∗ and vice ten useful for qualitative discussions and semiquantitative
versa for α = 2. Now recall the argument given above for calculations.
neglecting F12 (R) and G 12 (R). At R = R ∗ , the wave Another concept often invoked for qualitative discus-
function is changing character very rapidly as a function sions and for calculations when the adiabatic approxima-
of R, and the action of ∇R on ψ(r, R) is unusually large; tion breaks down is that of diabatic potential energy sur-
this means that F12 ( R) and G 12 ( R) need not be negligi- faces. There are several nonequivalent ways of defining
ble. In such a case, the dynamics governed by the nuclear- such surfaces, each of which may be useful under some
motion wave functions χ1 (R) and χ2 (R) do not decouple circumstances. The simplest way is that already illustrated
into independent motions governed by effective potentials above in conjunction with the NaCl example: namely, a
(i.e., the adiabatic potential energy surface concept breaks diabatic state is the effective potential energy function for
down). Although we have given the argument for a par- nuclear motion when the electronic state is artificially con-
ticular diatomic molecule, the effect is general, and the strained to a state of prespecified pure valency.
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14 Potential Energy Surfaces

 
A second way to define diabatic electronic states and po- h2 2
tential energy surfaces is more mathematical. Notice that − ∇r + V (r, R) − Uαn (R) ψαn (r, R) = 0, (22)
2m
the valency-character prescription leads to states coupled
by the operator where the superscript n denotes nonrelativistic. The
true adiabatic states are coupled only by −(h 2 /2M)∇R2 ,
h2 2 but these nonrelativistic adiabatic states are coupled by
Hel = − ∇ + V (r, R) + Hrel (r, R) (17)
2m r both this operator and Hrel (r, R). Because of the latter
and also by −(h 2 /2M)∇R2 . From the point of view of the coupling, the nonrelativistic adiabatic electronic states
nuclear motion, the former is sometimes called potential ψαn (r; R) and their associated potential energy curves
coupling (since it involves only multiplicative operators Uαn (R), which are the most widely employed states and
in the nuclear coordinates), and the latter is called deriva- potential energy surfaces in quantum chemistry, are ac-
tive coupling. Since electronically adiabatic states have tually diabatic. They are nevertheless usually called adi-
derivative coupling but no electronic coupling, a natural abatic although nonrelativistic is adiabatic is technically
question is whether useful diabatic states can be defined to more appropriate.
have potential coupling but not derivative coupling. Un-
fortunately, this leads to states that are completely inde-
pendent of R and are not useful. It is possible, however, to V. SHAPES OF POTENTIAL
make one component (in one or another coordinate sys- ENERGY SURFACES
tem) of the vector coupling operator Fαβ (R) vanish for all
α, β. Furthermore, if Fαβ (R) is approximated as the gradi- A. Diatomics
ent of a scalar (which can be a good approximation when
nonadiabatic effects are dominated by a narrowly avoided A schematic illustration of some typically shaped adia-
intersection), then it is possible to make all components of batic potential energy curves for a diatomic molecule is
Fαβ (R) vanish for all α, β. Both of these prescriptions are shown in Fig. 3. All five curves shown become large and
sometimes employed to obtain diabatic states. Consider, positive at small internuclear distance R. This repre-
for example, the case where Fαβ (R) is the gradient of a sents a repulsive force between the nuclei and is due to
scalar for all R; then it has zero curl. We define diabatic internuclear repulsion and the unfavorability of overlap-
electronic states by ping the atomic charge clouds of the two different centers.
 All five curves tend to constants at large R. This is be-
φαd (r; R) = φβ (r; R)Tβα (R). (18) cause the atomic interaction energy eventually decreases
β to zero as the distance between the atoms is increased.
The states {φαd (r; R)χαd (R)} will be uncoupled by nuclear The constant spacings between the curves at large R are
derivative operators if we choose Tβα (R) for all β and α equal to the atomic excitation energies. Curves 1 and 2
such that are effective potentials for the interaction of ground-state
 atoms, and curves 3–5 represent effective potentials for the
∇R Tαβ (R) = Fαγ (R)Tγβ (R), (19) case where at least one of the atoms is excited. The figure
γ shows an avoided crossing between curves 2 and 3 and
and this set of coupled partial differential equations does
have a solution if Fαβ (R) has zero curl. Furthermore, if
the state expansion α, β, . . . is truncated to a finite num-
ber of computationally important states, then the diabatic
electronic basis is not independent of R. In this way, one
can define a diabatic basis by a transformation from an
adiabatic one, and it spans the same space. The diabatic
potential surfaces are given by

Uααd
(R) = |Tγ α (R)|2 Uγ (R), (20)
γ

and the potential couplings are given by


Uαβ (R) = Tγ∗α (R)Uγ (R)Tγβ (R). (21)
γ
FIGURE 3 Typical potential energy curves for a diatomic
As mentioned in Section II, the usual treatments of po- molecule ordinarily thought of as bound. Ua and R are as in
tential energy surfaces neglect Hrel (r, R) in Eq. (5). Thus Fig. 1; De is the equilibrium bond energy of the ground state.
one solves Curves 1–5 are discussed in the text.
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Potential Energy Surfaces 15

true crossings of curves 3 and 4 by curve 5. Curves with

deep enough minima, such as 1 and 3, may possess bound
states of nuclear motion. Classically, a pair of nuclei whose
motion is governed by one of these curves could show sim-
ple, almost-harmonic motion in the vicinity of the mini-
mum of the curve. Quantally, there could be bound vibra-
tional states localized in these regions of R. Curve 1 has
the typical shape for the ground electronic state of a stable
molecule such as H2 , N2 , or HCl. Such a curve is often
represented in the vicinity of the minimum by a quadratic
potential:
1
Uα ( R) ∼
= k( R − Re )2 , (23) FIGURE 4 Typical potential energy curves for a pair of atoms
2 ordinarily thought of as unbound. Ua and R are as in Fig. 1.
where k is the force constant (actually the quadratic force See text for discussion of the curves.
constant) and Re the equilibrium internuclear distance. An
analytic representation valid over a wider range of R is
where ε is the well depth and σ the collision diameter.
given by
Notice that the minimum of Uα (R) occurs at R = Rm
1 1 where
Uα ( R) ∼
= k11 ( R − Re )2 + k111 ( R − Re )3
2 2
Rm = 21/6 σ (27)
1
+ k1111 ( R − Re )4 + · · · , (24) and that
2
where k has been renamed k11 , and k111 and k1111 are anhar- Uα ( R = Rm ) = −ε. (28)
monic (cubic and quartic) force constants. Sometimes the
When the minimum of a predominantly repulsive poten-
constant coefficient of ( R − Re ) j is written 1/j! instead
tial curve is considered negligible, it may be represented
of 12 so care must be exercised when using anharmonic
by a so-called anti-Morse curve:
force constants. Equation (24) is called a Dunham expan-
sion. An approximate representation of a potential curve Uα ( R) = D AM {exp[−2β( R − R AM )]
like curve 1 in Fig. 3 that gives its approximate shape over
+ 2 exp[−β( R − R AM )]} + C AM , (29)
the full range of R is
where D AM , β, R AM , and C AM are constants, or even by
Uα ( R) = De {1 − exp[−α( R − Re )]}2 . (25)
the simpler
This is called a Morse curve, De the equilibrium disso-  
β
ciation energy, and α the Morse range parameter. More Uα ( R) = exp(−α R). (30)
complicated analytic forms with more parameters are also R
used. Equation (29) or (30) could be applied to curve 4 of Fig. 3,
Information about the various parameters (Re , k11 , to curve 1, 3, or 4, of Fig. 4, or even to curve 2 of Fig. 3,
k111 , . . . , De , and α) comes primarily from spectroscopy, for which it might be useful in the region to the right of the
scattering or kinetics experiments, and quantum macha- avoided crossing and to the left of the shallow, large- R
nical electronic structure calculations. These are also the minimum.
sources for information about potential energy surfaces of Notice that the zero of energy is arbitrary for poten-
systems with three or more atoms. tial energy surfaces as long as it is chosen consistently
Figure 4 shows, to about the same scale as Fig. 3, some throughout a given calculation. In Fig. 3 we placed the zero
typically shaped potential curves for a diatomic system of energy at the bottom of the lowest potential curve. In
usually thought of as unbound (e.g., He2 , HeNe, or ArH). Fig. 4 we placed it at the energy of two separated ground-
Notice that the lowest potential energy curve has only a state atoms.
very small minimum at large R. When this minimum
is important for the problem at hand, such a potential en-
B. Larger Molecules
ergy curve is often represented by a Lennard–Jones 12–6
potential: Potential energy surfaces for systems with three or more
    atoms are harder to illustrate because they depend on three
σ 12 σ 6
Uα ( R) = 4ε − , (26) or more internal coordinates. Analytic representations are
R R also more complicated than for diatomics.
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16 Potential Energy Surfaces

Potential energy surfaces may be roughly classified

into those with deep enough minima to support one or
more strongly bound vibrational states and those with-
out such minima. We shall call the former attractive sur-
faces because of the role played by the attractive forces
between the atoms in creating the minimum. The latter
will be called repulsive surfaces. Because spacings be-
tween potential energy curves are usually much larger
than thermal energies, most molecular motions under or-
dinary conditions are usually governed by the lowest en-
ergy potential surface. Thus molecules that usually exist
as bound, stable entities (e.g., H2 O, CO2 , or CH4 ) have at-
tractive surfaces in their ground (i.e., lowest energy) elec-
tronic states, whereas molecules usually observed only as
transient species during collisions (e.g., FH2 which exists
during F + H2 or H + HF collisions or NeH2 O, which ex-
ists during Ne + H2 O collisions) have repulsive surfaces.
Systems like Ne2 or NeH2 O may exist as stable but very
weakly bound (and thus easily and usually dissociated)
species because of shallow potential wells in predomi-
nantly repulsive potential energy surfaces. Such weakly FIGURE 5 Perspective view of potential energy surface for
bound species are called van der Waals molecules. Sys- collinear H + HCl → H2 + Cl. The vertical axis is potential energy,
and axes in the horizontal plane are nearest-neighbor distances.
tems with attractive surfaces in their ground electronic
states may have repulsive surfaces in excited (i.e., higher-
energy) electronic states, and vice versa. Examples of van if i = j). If this is done and cross terms vanish in the kinetic
der Waals wells and repulsive excited states for the easily energy operator as well, Eq. (31) is called a normal-mode
illustrated special case of diatomic molecules may be seen expansion.
in Figs. 3 and 4. In the vicinity of the minimum of the surface, a two-
The most well understood region of attractive potential dimensional cut through an attractive potential energy sur-
energy surfaces is usually the region near the minimum. face has the shape of a distorted paraboloid of revolution.
One usually describes the potential energy surface in such Figure 5 shows a perspective view of a cut through a
a vicinity by a Taylor’s series about the minimum: potential energy surface for a chemical reaction; in par-
ticular it is based on an approximate surface for the reac-
1 
Uα (R) = Ue + k i j qi q j tion H + HCl → H2 + Cl. To represent the potential as a
2 i j function of two internal coordinates, the three atoms are
1  restricted for this figure to lie on a straight line. If the
+ ki jk qi q j qk hydrogens are labeled Ha and Hb , the left–right axis is
2 i j k
the Hb -to-Cl distance with large values at the left, and the
1  front–back axis is the Ha -to-Hb distance with large values
+ ki jkl qi q j qk ql + · · · , in the foreground; the third interpair distance is the sum of
2 i j k l
(31) these two. The vertical axis is potential energy. The figure
clearly shows the existence of a minimum-energy reaction
where Ue , ki j , kik j , . . . are constants, and the {q j } are suit- path from reactants in the foreground to products at the
able internal coordinates defined to vanish at the location back left. The highest energy point along the minimum-
of the minimum. As written, Eq. (31) contains no terms energy path is a saddle point. This point is sometimes
linear in the {q j }, but if these are not related to Cartesian called the transition state, and it primarily determines the
coordinates by a linear transformation, it may be neces- threshold energy for reaction to occur. The shape of the
sary to include linear terms. Equation (31) is called an reaction path is important for determining the reaction
anharmonic force field. If the coordinates are linear com- probability as a function of the vibrational and relative
binations of Cartesians and terms beyond the quadratic are translational energy of the reactants.
neglected, it becomes a harmonic force field. In the har- Figure 6 shows the same information as in Fig. 5 but
monic approximation it is always possible to define the in the form of a contour map (i.e., a set of isopotential
{q j } in such a way that the cross terms vanish (i.e., ki j = 0 contours). The horizontal axis is the distance from Cl to
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Potential Energy Surfaces 17

the center of mass of H2 , and the vertical axis is [(MCl + function of the solute coordinates by adding the free en-
2MH /4MCl ]1/2 times the Ha -to-Hb distance. Because of ergy of solution to the gas-phase potential surface. The
the mass scaling factor, the nuclear-motion Hamiltonian, resulting potential function may be used in Eq. (14), and
Eq. (13), in this coordinate system becomes it is called a potential of mean force.
 
h2 ∂ 2 ∂2
Hnuc = − + + Uα (x , y), (32)
2µ ∂ x 2 ∂ y2
SEE ALSO THE FOLLOWING ARTICLES
where
2MCl MH ATOMIC AND MOLECULAR COLLISIONS • ORGANIC
µ= . (33)
(MCl + 2MH ) CHEMICAL SYSTEMS, THEORY • QUANTUM MECHANICS
Since the coefficient of both derivative operators is the • SURFACE CHEMISTRY
same, this Hamiltonian is the same as that for a single par-
ticle in two dimensions under the influence of a potential
function Uα (x , y). This analogy is very helpful in mentally BIBLIOGRAPHY
visualizing the motion of a polyatomic system whose dy-
namics are governed by a multidimensional potential sur- Gao, J., and Thompson, M. A. (1998). “Combined Quantum Mechani-
face. In Fig. 6 the H + HCl reaction is initiated at the lower cal and Molecular Mechanical Models,” American Chemical Society,
right, and products are formed when the system, having Washington, DC.
Herzberg, G. (1966). “Molecular Spectra and Molecular Structure. III.
passed through or near the saddle point (denoted + in the
Electronic Spectra and Electronic Structure of Polyatomic Molecules,”
figure), reaches the top. Van Nostrand Reinhold, New York.
For solutes in the liquid phase (e.g., an organic molecule Kondratiev, V. N., and Nikitin, E. E. (1981). “Gas-Phase Reactions:
in aqueous solution), one can obtain an effective potential Kinetics and Mechanisms,” Springer-Verlag, Berlin.
Löwdin, P.-O., and Pullman, B., eds. (1983). “New Horizons of Quantum
Chemistry,” D. Reidel, Dordrecht, Holland.
Maitland, A., Rigby, M., Smith, E. B., and Wakeham, W. A. (1981).
“Intermolecular Forces,” Clarendon, Oxford.
Michl, J., and Bonačić-Koutecký. (1990). “Electronic Aspects of Or-
ganic Photo Chemistry,” John Wiley & Sons, New York.
Murrell, J. N., Carter, S., Farantos, S. C., Huxley, P., and Varandas,
A. J. C. (1984). “Molecular Potential Energy Functions,” Wiley,
Chichester.
Salem, L. (1982). “Electrons in Chemical Reactions: First Principles,”
Wiley-Interscience, New York.
Simons, J. (1983). “Energetic Principles of Chemical Reactions,” Jones
and Bartlett, Boston.
Smith, I. W. M. (1980). “Kinetics and Dynamics of Elementary Gas
Reactions,” Butterworths, London.
Truhlar, D. G., ed. (1981). “Potential Energy Surfaces and Dynamics
FIGURE 6 Contour map of a potential energy surface for collinear Calculations: For Chemical Reactions and Molecular Energy Trans-
H + HCl → H2 + Cl. x is the distance from H to the center of fer,” Plenum, New York.
mass of HCl and y the mass-scaled distance from Cl to its Truhlar, D. G., and Morokuma, K., eds. (1999). “Transition State
nearest H. Both axes are given in units of a 0, where 1a 0 = Modeling for Catalysis,” American Chemical Society, Washington,
1 bohr = 0.5292 × 10−10 m. DC.
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Solid-State Chemistry
Bahne C. Cornilsen
Michigan Technological University

I. The Structure–Property Relationship

II. Solid-State Structure and Structural
Characterization
III. Preparation Techniques and Property Variation

GLOSSARY The syntheses and fabrication procedures themselves of-

ten play a key structure-controlling role in the preparation
Condensed matter sciences Include solid-state physics, of materials with optimum properties. Detailed character-
ceramic science and engineering, metallurgical engi- ization of the structure and bonding is of major concern to
neering, polymers, and materials science, as well as the solid-state chemist. Control of structure and bonding
solid-state chemistry. during preparation and processing allows control of the
Sintering General process by which powders react and critical, technologically important properties. Such con-
densify to form polycrystalline compacts or ceramics. trol is necessary to optimize material performance.
Such compacts densify by grain growth and porosity
reduction. Sintering can be reactive, i.e., involve the
reaction of two or more solid components to form a I. THE STRUCTURE–PROPERTY
product or products. RELATIONSHIP
Structure Used herein to refer to the molecular-level,
crystallographic, three-dimensional arrangement of Solid-state chemists characterize materials with respect
atoms, as controlled by the chemical bonding. Both to their chemical and physical properties, structure, and
long-range and short-range order/disorder, including bonding, as well as define how these properties are con-
crystal imperfections and defects, must be considered. trolled by the chemical bonding and microscopic struc-
ture. They Vplay an increasingly important role as part
of a team of condensed matter specialists whose com-
SOLID-STATE CHEMISTRY concerns the preparation, mon goal is to design materials with optimum properties
structure, and properties of solid materials, often focus- for critical applications. Improved economic performance
ing on the relationship between structure and proper- in a globally competitive economy is strongly dependent
ties. Unique solid-state properties are taken advantage of upon materials development. Materials problems limit
for numerous practical, technological applications. Many the development of a variety of technologies, including
properties are structure sensitive, i.e., they are controlled high-temperature superconductors, high-energy density
by the chemical bonding and molecular-level structure. batteries, structural and insulating materials able to

295
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296 Solid-State Chemistry

withstand extremely high temperatures, improved hetero- charge, and the number of lattice sites must be conserved,
geneous catalysts, improved electronic materials, optics unusual oxidation states can be introduced (in dopants
compatible with very high laser intensities, stabile nu- or predominant cations) and nonstoichiometric composi-
clear waste containment materials, and longer lasting elec- tions stabilized. For example, Ni(III) can be formed in
trodes for fuel cells and magnetohydrodynamic genera- NiO, which nominally contains Ni(II) ions, and nickel va-
tors. To solve such problems and to optimize performance, cancies (VNi ) are formed according to Eq. 1.
it is necessary to control the molecular-level structure and 
Ni2+ 3+
Ni(1−3x) NiNi(2x) VNi(x) (1)
bonding and to understand the structure–property relation-
ship. The syntheses and fabrication processes themselves Point-defect ordering (e.g., vacancy-dopant pairs) leads to
are therefore critical for preparation of solid-state mate- interesting complications. Preparation conditions them-
rials which display the desired properties. Properties of selves (e.g., oxygen partial pressure and temperature in
interest include the chemical reactivity as well as the elec- oxides) thermodynamically define and control this defect
tronic, magnetic, optical, and mechanical properties. content and structure. It is important to realize that point
defects are thermodynamically allowed and defined; they
are not anomalous in the least. Therefore, undoped, high-
II. SOLID-STATE STRUCTURE AND purity compounds may exhibit sizable nonstoichiometry
STRUCTURAL CHARACTERIZATION due to intrinsic point defects. Doping (intentional addi-
tion of an impurity) allows one to precisely control the
Characterization of the detailed chemical structure and point-defect content and nonstoichiometry and, thereby,
bonding of a solid is a prerequisite to the understanding the properties. Transport properties are influenced by the
and control of the chemical and physical properties. In point defects. Electrical conduction (hole or electron trans-
general the properties of a solid are controlled by the port) and solid state diffusion of atoms generally vary with
macroscopic and the microscopic structures. The macro- the quantity and type of point defects.
scopic characteristics (e.g., dislocations) predominantly The determination of how nonstoichiometry is accom-
influence the mechanical properties, such as strength modated (i.e., by what type and amount of defect) is
for metals and ceramics. The microscopic structure an active research area. Nonstoichiometry can also be
(interatomic or molecular-level structure) is controlled accommodated by subtle changes in structure known as
by the chemical bonding. Solids are classified according extended defects or crystallographic shear. Crystallinity,
to their chemical bonding as metals, semiconductors, or impurity levels, point-defect structure, and nonstoichiom-
insulators. etry are each controlled by or influenced by the preparation
Complete structural characterization of a material in- method; therefore, it is discussed further in Section III.
volves not only the elemental composition for major com- Surface properties can differ from the bulk structurally,
ponents and a study of the crystal structure, but also the both as clean surfaces or because of products formed on re-
impurity content (impurities in solid solution and/or addi- active surfaces (physisorbed or chemisorbed). The former
tional phases) and stoichiometry. Noncrystalline materials can experience relaxation, that is, surface reconstruction
can display unique behavior, and noncrystalline second due to the distortion in bonding for surface atoms which
phases can alter properties. Both the long-range order and are lacking bonds. Impurity segregation at a surface can
crystal imperfection or defects must be defined. For ex- further alter properties, as can second phases formed on a
ample, the structural details which influence properties of surface. The activity of heterogeneous catalysts and cor-
oxides include the impurity and dopant content, nonstoi- rosion is controlled by such surface properties and by the
chiometry, and the oxidation states of cations and anions. bulk and surface point-defect structures.
These variables also influence the point-defect structure, Phases formed on semiconductor surfaces can change
which in turn influences chemical reactivity, and electri- the electrical properties in an uncontrolled, deleterious
cal, magnetic, catalytic, and optical properties. fashion. Oxide passivation layers on compound semicon-
Point defects are imperfections in the actual crystalline ductors (e.g., mercury cadmium telluride IR detectors or
architecture as compared to the ideal lattice in which each gallium arsenide solar cells) can be grown to impart pro-
atom site is filled with the appropriate element. They tection to the surfaces and to stabilize electrical properties
can influence properties at extremely low levels (ppb or by preventing uncontrolled reactions.
ppm). Typical point defects include crystal sites with miss- Interfaces between two bulk phases, between the bulk
ing atoms (vacancies), atoms positioned in sites that are and a surface, or at grain boundaries can further com-
not filled by the crystal structure in question (intersti- plicate the chemistry. Grain boundaries in polycrystalline
tials), crystal sites containing impurity atoms (dopants), materials can contain second phases (crystalline or non-
and cations with different oxidation states. Because mass, crystalline) and have significant width. This is termed an
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Solid-State Chemistry 297

interphase. On the other extreme, highly ordered (coher- ing varying degrees of order. Powders may be used as cata-
ent) interfaces can occur between two microcrystallites lysts or as precursors for crystal growing, glass formation,
(or grains). A second phase in a boundary can impart or ceramic formation. Numerous technologically useful
unique electrical properties, significantly influencing the components are produced by sintering powders, taking
characteristics of a capacitor, for example. Furthermore, advantage of the unique electrical, magnetic, optical, or
dopants may segregate to a grain boundary phase, affecting mechanical properties.
boundary and bulk phase properties. Positive temperature Particle size is also an important powder variable. Pro-
coefficient (PTC) resistors and boundary layer capacitor duction of powders with a controlled particle size distri-
operation are based on such effects. bution allows production of ceramics with uniform mi-
Characterization of the preceding structural variables crostructures, improving mechanical properties. Strength
is complex and challenges an extensive array of modern of zirconia and zirconia–alumina refractories can be im-
analytical instrumentation. Diffraction techniques (X-ray, proved another way. Phase transitions which involve
neutron, and electron) are basic to the study of crystal large atomic displacements lead to microcracking during
structures. Improved data analysis techniques make these heating and cooling, which implement fracture. Small-
methods even more powerful for the study of powders. particle-sized zirconia stabilizes a high-temperature phase
Nuclear magnetic resonance (NMR) spectroscopy has be- at lower temperatures. This behavior, called “phase trans-
come a powerful tool for the study of solids with the formation toughening,” has been explained on the basis
advent of magic angle spinning techniques. Neutron in- of higher surface free energies for these systems. Since a
elastic scattering, Raman scattering, and IR vibrational phase transition from this high-temperature phase is elim-
spectroscopic analyses have been traditionally used to inated, the structural properties are improved.
study lattice dynamics and solid-state phase transforma- Research has shown that novel chemical preparation
tions. They can also provide information about dopants methods allow the production of unique materials, demon-
and point-defect structures through studies of local modes strating properties unattainable through more traditional
as well as the extensive crystal structure information. methods. Traditional solid-state synthesis techniques re-
High-resolution electron microscopy lattice imaging has quire high temperatures to increase the kinetics and allow
proven to be a powerful tool for the study of crystal struc- reaction in reasonably short times. It is common to react
tures and extended defects. Electron spin resonance re- solid powders after mixing by grinding or ball-milling.
mains an effective tool for the study of paramagnetic To ensure complete reaction of two powdered reactants
solids, including impurities or low-level dopant structures. it may be necessary to carry out repeated grinding and
A variety of X-ray and electron spectroscopic techniques heating cycles. The grinding is necessary to reduce dif-
have been developed. These are particularly useful for pro- fusion distances and increase product homogeneity. Re-
viding information about elemental composition, surface peated grinding and high-temperature treatments intro-
structures, and cation oxidation states. duce undesirable impurities.
Low-temperature solid preparation methods (meaning
from ∼900◦ C to cryogenic temperatures) can produce
III. PREPARATION TECHNIQUES powders having fewer impurities, high surface areas,
AND PROPERTY VARIATION and other unique characteristics which have useful
applications, such as reactive surfaces for sintering or
The crystal structure of a solid can influence the properties for catalysis. Higher treatment temperatures can actually
of a material, for example, the structure must be noncentric reduce such activity by changing the bulk and/or surface
for a material to demonstrate antiferromagnetic, ferromag- structures.
netic, ferroelectric, or piezoelectric behavior. Rapid cool- Low-temperature syntheses can sometimes allow
ing of a sample from high temperature and/or high pres- unique surface phases to be stable. Tetragonal barium ti-
sure can quench in a structure that is not stable at room tanate, prepared at ∼700◦ C, has hexagonal barium titanate
temperature or atmospheric pressure. High-pressure ox- on the surface, which is stabilized by a higher surface free
ide polymorphs, which are more dense, have been studied energy. Normally this hexagonal phase is not formed be-
to model the earth’s interior. Furthermore, unique crystal low 1460◦ C. This hexagonal surface was also found to
structure characteristics of a material can allow structure– reversibly adsorb CO2 as a surface carbonate.
property variation, for example, insertion compound for- A variety of solution (water or organic solvent) tech-
mation in layered materials. niques have been devised to control composition (e.g.,
Solids can be prepared as single crystals, glasses, thin the Ca:Mn ratio in an oxide such as CaMnO3 ). Control
films, powders, or sintered powder compacts (ceramics). of this ratio is important in terms of the composition-
Powders may be noncrystalline or polycrystalline, exhibit- sensitive properties. This is especially true for transition
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298 Solid-State Chemistry

metal–containing systems because several oxidation states or other metal-containing species to the reaction site, and
are stable and available for most of them. Unusual ox- is used in the production and development of semiconduc-
idation states introduced by variation in cation ratio and tor devices.
oxygen nonstoichiometry can influence catalytic and elec- In some instances materials with potentially useful
tronic properties. The “solid-state precursor” method in- properties have not been exploited until prepared as pure
volves precipitation of a compound or solid solution (e.g., crystals and films. Examples of this include doped polythi-
oxalate or carbonate) with the desired stoichiometry which azyl, (SN)x , and polyacetylene, (CH)x , which have metal-
is then thermally decomposed to form the desired prod- lic properties, including electrical conductivity. The use
uct oxide. Atomic scale mixing of the components pre- of polymer precursors for ceramics (e.g., silicon carbide)
cludes long calcining times at high temperatures. Powders is another interesting solid-state preparation technique.
formed are extremely homogeneous and have high surface An exciting example, demonstrative of every aspect
areas. The composition of the products, however, does de- of solid-state chemistry, is the development of high-
pend on the solution solubilities, and the precision of these temperature superconducting oxides, which has followed
precursor methods is not always high. The so-called “liq- the 1986 discovery of superconducting YBa2 Cu3 O7−x .
uid mix technique” does allow better precision as well This oxide will conduct at temperatures much higher than
as homogeneity because no precipitation occurs; rather, previous superconducting metal alloys, thereby reducing
the solution is heated to a viscous, glasslike form which cooling expense. The synthesis, purification, character-
is then decomposed to the product oxide. No solution– ization, extension to other metal-oxide systems, and the
solid partitioning occurs, giving a composition equal to eventual application of these oxides in devices is certain to
that of the starting mixture. The latter can be weighed become a classic example of solid-state chemical science
to high accuracy (hundreds of ppm or better for major and technology.
components), providing precise control of product cation Control of the structure during preparation and process-
ratios. ing allows one to control the properties and to optimize
The sol–gel technique is a low temperature, solution- material performance for particular applications. Thor-
preparation method which has been applied extensively ough structural characterization is a prerequisite. Based
to produce glasses, fibers, coatings (protective or dielec- on the knowledge of how synthesis and processing influ-
tric), abrasive particles, and controlled-pore-size catalyst– ence structure and of how structure controls properties, the
substrates. This method is used to prepare glasses, for ex- structure can be tailored and materials can be designed for
ample, that cannot be obtained upon quenching from the optimum performance.
melt. Either colloidal or polymeric gels are formed by
gelation of a precursor solution, involving hydrolysis and
condensation of colloidal sols of metal salt or hydroxide SEE ALSO THE FOLLOWING ARTICLES
solutions or of metal alkoxides. Drying, solvent removal,
and firing conditions are then chosen to provide the desired ANALYTICAL CHEMISTRY • BONDING AND STRUCTURE IN
microstructures and properties. SOLIDS • CRYSTALLOGRAPHY • LASERS, SOLID-STATE •
Another important solution technique which should be MICROSCOPY (CHEMISTRY) • PHASE TRANSFORMATIONS,
mentioned is the “homogeneous precipitation technique.” CRYSTALLOGRAPHIC ASPECT • PRECIPITATION REAC-
It favors formation of a more ordered, crystalline prod- TIONS • SOLID-STATE IMAGING DEVICES • SUPERCON-
uct when two solutions are mixed to form an insoluble DUCTORS, HIGH TEMPERATURE • SURFACE CHEMISTRY
compound. The principle is slow precipitation, avoiding
instantaneous formation of a disordered product. The ben-
efits of all of the low-temperature solution techniques in- BIBLIOGRAPHY
clude homogeneity (atomic scale mixing) and minimal
introduction of impurities. Brinker, C. J., and Scherer, G. W. (1990). “Sol–Gel Science,” Academic
Press, Boston.
Other methods of preparation include chemical vapor Corbett, J. K., ed. (1985). Symposium on metal–metal bonding in solid-
deposition (CVD) and electrochemical methods. The lat- state clusters and extended arrays. J. Solid State Chem. 57(1), 1.
ter are used to form thin films and protective coatings as Etourneau, J. (1999). Novel synthesis methods for new materials in solid-
well as battery electrodes. Since this is generally a low- state chemistry. Bull. Mater. Sci. 22(3), 165–174.
temperature method, the structure can differ from that of Fischer, J. E. (1997). Fulleride solid-state chemistry: Gospel, heresies
and mysteries. J. Phys. Chem. Solids 58(11), 1939–1947,
the same material prepared at a higher temperature. It can Grasselli, R. K., and Brazdil, J. F., eds. (1985). “Solid State Chemistry
be disordered or amorphous. Chemical vapor deposition in Catalysis,” Series 279, American Chemical Society, Washington,
involves vapor phase transport of volatile organometallics D.C.
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Solid-State Chemistry 299

Holt, S. L., Milstein, J. B., and Robbins, M., eds. (1980). Snyder, R. L., Condrate, R. A., and Johnson, P. F., eds. (1985). “Advances
“Solid State Chemistry: A Contemporary Overview,” Advances in Materials Characterization II,” Vol. 19, Materials Science Research,
in Chemistry Series No. 186, American Chemical Society, Plenum, New York.
Washington, D.C. Sorensen, O. T., ed. (1981). “Nonstoichiometric Oxides,” Academic
Honig, J. M., and Rao, C. N. R., eds. (1982). “Preparation and Charac- Press, New York.
terization of Materials,” Academic Press, New York. State of the art symposium: Solid state. (1980). J. Chem. Educ. 57, 531–
Nelson, D. L., and George, T. F. (1988). “Chemistry of High-Temperature 590.
Superconductors II,” American Chemical Society, Washington, D.C. West, A. R. (1984). “Solid State Chemistry and its Applications,” Wiley,
Pimentel, G. C., and Coonrod, J. A. (1987). “Opportunities in Chem- New York.
istry, Today and Tomorrow,” National Academy Press, Washington, Zelinski, B. J., and Uhlmann, D. R. (1984). Gel technology in ceramics.
D.C. J. Phys. Chem. Solids 45, 1069.
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Solid-State Electrochemistry
Günter Holzäpfel
Dortmund University

I. Introduction
II. Disorder in Solids
III. Transport Processes—Diffusion, Mobility,
and Partial Conductivity
IV. Solid Electrolytes, Solid Ionic Conductors,
and Solid–Solution Electrodes
V. Galvanic Cells with Solid Electrolytes
VI. Technical Applications of Solid Electrolytes

GLOSSARY Superionic conductor Solid electrolyte with very high

ionic conductivity, comparable to liquid electro-
Disorder Deviations from the regular crystal structure in lytes.
a crystalline compound. Vacancy Missing ion in comparison to the ideal lattice of
Galvanic cell Arrangement for the conversion of chem- a solid.
ical energy to electrical energy using electrodes in
electrolytes.
Interstitial ion Ion in excess compared to the ideal lattice
of a solid. THE FIELD of solid-state electrochemistry deals with re-
Ionic couductivity Electrical conductivity caused by search on physical, chemical or electrochemical problems
ions. using solid electrolytes. Solid electrolytes, also called
Solid electrolyte Solid compound in which the electrical solid ionic conductors, are solid, generally crystalline
current is carried out by ions, associated with mass compounds in which the electrical current is carried by
transfer. ions. Therefore, the passage of current is associated with
Solid solution electrode Solid compounds exhibiting mass transfer. Solid electrolytes enable us to build galvanic
mixed (ionic and electronic) conductivity, where it is cells similar to those in the electrochemistry of liquids.
possible to dissolve or remove additional ions. Such galvanic cells with solid electrolytes play a most im-
Structural disorder Special kind of disorder in a crys- portant role for scientific investigations in the field of ther-
tal in which practically all ions of one kind are mobile modynamics and kinetics as well as for technical appli-
and statistically distributed among their available lat- cations like batteries, sensors, fuel cells, and chemotronic
tice sites. components.

301
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302 Solid-State Electrochemistry

I. INTRODUCTION tities influence the partial conductivity σi . These quantities

are the concentration ci of the particle i and the electrical
The field of solid-state electrochemistry—the electro- mobility u i . The concentration ci corresponds to the disor-
chemistry of solids—has developed rapidly since about der of the solid and the mobility u i to transport processes.
the middle of the twentieth century. This was caused by
the discovery of new solid electrolytes with high ionic
conductivity and some fundamental publications which II. DISORDER IN SOLIDS
pointed out the importance of solid ionic conductors for
the thermodynamic investigations. Under real conditions all ordered compounds exhibit de-
Between the electrochemistry of solids and the elec- viations from a regular crystal structure. These are of
trochemistry in liquids there exist large analogies in the- great importance particularly for the understanding of the
oretical point of view as well as in experimental meth- thermodynamic and kinetic properties of crystalline com-
ods. This is shown in Table I. The theoretical treatment pounds. Such deviations may be:
of the disorder in solids shows extensive analogies to the
theory of electrolytic dissociation. In the case of liquid 1. interstitial ions, which are ions in excess as compared
electrolytes, the dissociated ions enable the conduction to the ideal lattice;
of the electric current. In solid electrolytes the conduc- 2. charged vacancies, which are missing ions compared
tivity is caused by the thermodynamic disorder of the to the ideal lattice;
crystals. This means that there are vacancies or interstitial 3. foreign ions, which may be on either interstitial or
ions in the crystal lattice which enable electrical conduc- regular lattice sites; and
tivity. A further analogy exists regarding galvanic cells. 4. electron disorder, which means the presence of
From a thermodyamic point of view the treatment of gal- quasi-free electrons and electron defects.
vanic cells with solid electrolytes corresponds to that in the
liqud phase. Furthermore, the applied measuring methods These so-called point defects can be described by struc-
largely correspond to those known in the electrochemistry ture elements according to Kröger or by building units ac-
of liquids. cording to Schottky. The symbols used for these descrip-
In spite of these analogies the electrochemistry of solids tions are summarized in Tables II and III. Structure ele-
is more complex than the electrochemistry in aqueous so- ments are defined relative to the empty space, and building
lutions. So it must be noted that apart from ionic conduc- units are defined relative to the ideal lattice. One building
tion, solids often show an electronic conductivity, caused unit according to Schottky corresponds to a combination
by electrons or electron defects, which may be predom- of structure elements (generally two) according to Kröger.
inant in many cases over the ionic conduction. In good This is shown in the third column of Table III.
solid electrolytes the conduction of the electrical current Possible defects are illustrated schematically in Fig. 1
is caused exclusively by the ions—in most cases practi- for an AB crystal using Kröger symbols. The two-dimensi-
cally by only one kind of ion present in a crystal. onal section through the AB lattice shows A and B parti-
To explain the ionic conductivity of the solid the com- cles mainly in their normal positions. These particles have
ponents that influence it must be examined. For the ionic not been assigned any electrical charge because it is only
conductivity σi of an ionic species i to be valid: meaningful to express charge relative to the unperturbed
lattice, and A and B ions in their normal sites are electri-
σi = z i Fu i ci . (1) cally neutral relative to the unperturbed lattice. The figure
Here F is the Faraday constant, z i is the valence, ci is the also shows two A ions at interstitial sites; these ions bear an
concentration, and u i is the electrical mobility of the ions.
From this equation it can be seen that two important quan- TABLE II The Kröger Symbols for Neutral
Structure Elements in an AB Latticea
TABLE I Analogies between the Electrochemistry of Liquids
Foreign
and Solids
Particle Particle Vacancy particle
Liquids Solids Sites A B V C

Electrolytic dissociation Disorder in solid compounds A site AA BA VA CA

Galvanic cells with liquid Galvanic cells with solid B site AB BB VB CB
electrolytes electrolytes Interstitial Ai Bi Vi Ci
Electrochemical kinetics, Reactions in and on solids a The examples chosen are A and B particles, foreign
particularly electrode kinetics
particles C, and vacancies at different sites.
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Solid-State Electrochemistry 303

TABLE III Notation of the Lattice Molecule and Typical De- The concentrations of charged atomic defects—point
fects in an AB Lattice in Terms of Building Units Using the Old defects—follow the law of mass action. The considera-
and New Schottky Symbols Compared to the Corresponding
Structure Elements According to Kröger and Vink
tions of thermodynamic equilibria can be applied to dis-
order equilibria in solid crystalline compounds, the so-
Schottky Schottky called ordered mixtures. Point defects can be regarded as
old new Kröger/Vink
quasi-chemical species with which chemical reactions can
AB lattice molecule AB AB be formulated. This has led to the so-called imperfection
Neutral A particle on AO A Ai − Vi chemistry. As an example, the disorder equilibrium be-
interstitial site tween vacancies and interstitial particles—the so-called
Neutral A vacancy A |A| V A − AA Frenkel equilibrium—will be regarded.
Neutral B particle on A-site B•(A) B|A| BA − AA In this case a particle A moves from an A lattice site to
Neutral C particle on A-site C•(A) C|A| CA − AA an interstitial site whereby, for example, with respect to the
Quasi-free electron  e e unperturbed lattice a single positively charged interstitial
.
Electron hole ⊕ |e· | h particle Ai is formed, a vacancy Vi in the interstitial lattice
is destroyed, and a negatively charged vacancy VA on an
A site is left. This exchange process can be written in the
excess of positive charge denoted with. Two unoccupied form of a chemical reaction, a so-called disorder reaction
.
sites can be seen; these vacancies are negatively charged A + |A| = 0 (2)
relative to the unperturbed lattice and are denoted with  .
Structure elements with the corresponding symbols pro- using the new Schottky notation, we have
.
posed by Kröger and Vink are easy to memorize; this no- AA + Vi = Ai + VA . (3)
tation is now also widely used in the literature. However, it
is very important to know that the numbers of the various Here the reaction is formulated in terms of structure el-
structure elements in a crystalline compound are not inde- ements, which for a thermodynamical treatment must be
pendent of one another. This is due to the fixed ratio of the combined with building units as follows:
.
number of A and B sites in an AB lattice. It is therefore (Ai − Vi ) + (VA − AA ) = 0. (4)
generally impossible to change the concentration of only
one type of structure element in a crystal. Thus, to create a The concentration of the interstitial particles or vacancies
vacancy on an A site we must either remove an A particle as building units is identical with the concentration as
or simultaneously add a B particle to a new B site, so that structure elements.
the ratio of A to B sites remains unchanged. The gener- Symbolizing the concentrations by square brackets the
ation of an interstitial particle leads to the destruction of law of mass action corresponding to Eq. (4) can thus be
a vacancy in the interstitial lattice. Thus, if we increase formulated as follows:
.
the size of a crystal or change the number of defects con- [Ai ][VA ] = const. (5)
tained in it, one must either add or remove combinations
of structure elements, this means that in general building For all crystals there exists at equilibrium a constant prod-
units have to be used. Similarly, the use of structure ele- uct of the concentrations of interstitial particles and the
ments to describe reactions of defects generally involves corresponding vacancies, the so-called Frenkel equilib-
the use of building units. rium which depends on temperature and pressure.
For higher concentrations of defects the equation must
be written in terms of activities instead of concentrations.
Frenkel disorder occurs in the silver halides, for example,
in AgCl.
Another kind of disorder equilibrium exists between A
vacancies and B vacancies in a binary AB crystal—the
so-called Schottky equilibrium. In this case the exchange
of particles between A and B vacancies and the crystal
is considered. This means that either A or B particles are
transferred to the surface of the crystal, which is thus en-
larged, while A or B vacancies are generated, or vice versa.
For example, the A vacancies may be singly negative and
FIGURE 1 Possible defects in an AB crystal using Kröger the B vacancies singly positive. When the particles are
symbols. brought to the surface, two of the particles there will be
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304 Solid-State Electrochemistry

converted to volume particles, that is, the exchange ef-

fectively leads to the generation of a new lattice molecule
and two vacancies. This can be written in terms of the new
Schottky notation as
.
O = |A| + |B| + AB, (6)
or using structure elements:
.
AA + BB = VA + VB + AB. (7)
Here AB denotes the lattice molecule. This equation can
be written in terms of building units:
.
O = (VA − AA ) + (VB − BB ) + AB. (8)
FIGURE 2 Dependence of the concentration of the electrons of
Since the concentration of AB molecules can be regarded ZnO at 900◦ C on the oxygen partial pressure.
as constant at low defect concentration it can be included
into the constant of the law of mass action, and we obtain:
. of ZnO, which is mainly due to the partial conductivity
[VA ][VB ] = const, (9)
of the free electrons, decreases with increasing oxygen
which means the product of A and B vacancies in an AB partial pressures according to Eq. (14).
crystal is constant in this case. At higher concentrations of The concentration of imperfection centers increases
the defects activities must be used again. Schottky disorder with rising temperature. The limiting case is crystals in
is to be found in alkali metal halides such as NaCl and KCl. which the concentrations of vacancies and interstitial par-
Aside from the described kinds of disorder there exist ticles become comparable; there then occurs a statistical
various other types. As an example in which electrons distribution of particles in normal lattice positions and in
and the environment are playing a role in disorder, let us interstitial positions. In this case it is no longer reason-
consider ZnO. able to distinguish between regular and interstitial lattice
At a temperature of 900◦ C the most important disorder positions. The total number of positions a single type of
centers in this compound are single positively charged zinc particle can occupy may be several times higher than the
ions on interstitial sites and free electrons. The following number of such particles in the crystal.
equation representing the incorporation of oxygen, for ex- There exist crystals which have much more equivalent
ample, from the air, into ZnO may therefore be formulated: lattice sites available for one type of ion than ions are
. present in the lattice. At sufficiently high temperatures all
1
O (g) + Zni + e = Vi + ZnO,
2 2
(10)
ions are mobile and may be statistically distributed among
or using building units: these lattice sites. In this case we say a partial lattice of
. the crystal is in a quasi-molten state, the crystal has now a
1
O (g)
2 2
+ (Zni − Vi ) + e = ZnO. (10a)
structural disorder. If such a disorder is present, the natural
Because of electrical neutrality it follows that in ZnO limit of the concentration of the mobile species is reached
. because all ions of one kind are now mobile. The best
[Zni ] ∼
= [e], (11)
electrolytes known have such a disorder. Examples for
that is, the concentration of zinc ions on interstitial sites such types are among others RbAg4 I5 at room temperature
is virtually equal to that of free electrons. The law of and AgI above 149◦ C. At this temperature AgI makes a
mass action corresponding to Eq. (10) is given by transition from the β to the α phase; the partial lattice of Ag
1/2 . becomes quasi-molten, and there exist regions throughout
pO2 [e][Zni ] = const, (12)
which the silver ions virtually perform random motions as
which may be simplified using Eq. (11) to yield shown in Fig. 3.
1/2 The idea that the silver ions in α-AgI are already in a
pO2 [e]2 = const (13)
quasi-molten state is supported by thermodynamic values
or and the diffusion coefficients, which are of the order of
−1/4 10−5 cm2 /s similar to a liquid. The entropy for the tran-
[e] ∼ pO2 . (14)
sition from β-AgI to α-AgI amounts to 14.5 J/K mol, the
According to Eq. (14) the concentration of free electrons entropy of fusion is 11.3 J/K mol.
is proportional to the inverse fourth root of the oxygen It is assumed that silver iodide melts in two stages.
partial pressure; this is shown in Fig. 2. The conductivity In the β–α transition the silver partial lattice passes into
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Solid-State Electrochemistry 305

j = −D dc/d x, (15)
where D is called Fick’s diffusion coefficient. If there is
a concentration coefficient in any direction in space then
we must use the general form of Fick’s first law:
 
dc dc dc
j = −D grad c = −D , , . (16)
d x dy dz
In what follows only gradients in one direction (the x
direction) will be regarded.
The time dependence of the concentration is given by
Fick’s second law:
FIGURE 3 Lattice of silver iodide with regions in which the silver
∂c ∂ 2c
ions can move. = D 2. (17)
∂t ∂x
the quasi-molten state (structural disorder), whereas the These laws are valid in the case of ideal behavior that is,
iodide partial lattice does not become liquid below the when the chemical potential µ of the particles holds:
actual melting point. Comparable crystals that do not c
show the special behavior of structural disorder before µ = µ0 + RT ln 0 , (18)
c
they melt have an entropy of fusion about as large as the
where µ0 is the chemical potential in the standard state, c is
sum of the transition entropy and entropy of fusion in
the concentration of the particles, c0 is their concentration
AgI, that is, about twice as large as the residual entropy
in the standard state, R is the general gas constant, and
of fusion in AgI.
T is the absolute temperature. Using this equation Fick’s
For completeness let us mention that besides the point
first law [Eqs. (15)] can be written as
defects discussed in this chapter there exist still other de-
fects in crystals. These include Dc dµ
jx = − . (19)
RT d x
1. one-dimensional defects such as edge of screw In the case of nonideal behavior, that is, for higher con-
dislocations, centrations of the mobile particles, the more general ex-
2. two-dimensional defects such as surfaces or grain pression
boundaries, and
3. three-dimensional defects such as cavities. µ = µ0 + RT ln a (20)
must be used for the chemical potential of the diffusing
These defects are not discussed here because they are not species, where a is the activity. A component diffusion
properties of the thermodynamic equilibrium. coefficient D K is then defined in such a manner that an
expression analogous to Eq. (19) is obtained:
III. TRANSPORT PROCESSES—DIFFUSION, D K c dµ
MOBILITY, AND PARTIAL j =− . (21)
RT d x
CONDUCTIVITY A relationship between D and D K can be reached in the
following way.
In this section the transport of ions in an electrical field Since dc is equal to c d ln c, Eq. (15) can be expressed as
and their diffusion in a concentration or activity gradient
d ln c
will be treated. The expressions derived are valid for the j = −Dc . (22)
fluxes of each type of ion or electron separately. From dx
these expressions equations for an interconnected trans- From Eqs. (21) and (20) an expression for the particle
port of different types of particles can be derived. In the flux which contains the component diffusion coefficient
following a phenomenological treatment and an outlook D K is obtained:
on the statistical treatment will be given. d ln a
j = −D K c . (23)
dx
A. Transport by Diffusion A comparison of Eqs. (22) and (23) gives the relationship
between D K and Fick’s diffusion coefficient D:
Fick stated an empirical relationship for the diffusion flux
j in a concentration gradient dc/d x in the x direction. d ln a
D = DK . (24)
This is known as Fick’s first law: d ln c
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306 Solid-State Electrochemistry

As can be seen from Eq. (24), D = D K if the activity a is ηi = µi + z i Fϕ (33)

proportional to the concentration c. The factor d ln a/d ln c
is called the thermodynamic factor. the expression in parentheses in Eq. (32) can be summa-
Another diffusion coefficient—the tracer—or self-diff- rized to dηi /d x and we get:
usion coefficient DTr is defined, which can be measured ci D K ,i dηi
at electrochemical equilibrium by using a radioactive iso- ji = − (34)
RT d x
tope. Under certain conditions, for example, for vacancy or
diffusion, the tracer diffusion coefficient DTr is related to
σi dηi
the component diffusion coefficient by: ji = 2 2
(34a)
zi F dx
DTr = f D K , (25)
or using the electrical mobility according to Eq. (1):
where f is the so-called correlation factor. The correlation
factor f is of the order of one for most cases. u i ci dηi
ji = (35)
zi F d x
B. Transport in an Electrical Field From Eqs. (34) and (35) it can be seen that the discussion
of mobility of the particles can be reduced to the discussion
If an electrical field only is present in the crystal and no of the diffusion coefficient D K ,i .
gradient in the concentration or activity of the particles, the
electrical current density i can be related to the electrical
field strength E by Ohm’s law D. Chemical Diffusion
i = σE (26) Under certain conditions the fluxes of ions and electrons
or are related to each other by the conditions of electrical
neutrality. This holds especially in the case when local
i = −σ (dϕ/d x), (27) differences in stoichiometry equilibrate. Here metal ions
where ϕ denotes the electrical potential and σ the electrical and electrons or nonmetal ions and electrons diffuse si-
conductivity. The electrical current density i is connected multaneously. These transient phenomena are described
with the current density j of the particles by the so-called chemical diffusion coefficient D̃. In the
following the result for the relationship between D̃ and the
j = i/z F. (28) component diffusion coefficient will be given for a com-
pound whose partial conductivity σX− of the nonmetal ions
Here F denotes the Faraday constant, and z is the charge
is negligible in comparison with that of metal ions σMe+ ,
of the particles. From Eqs. (27) and (28) it follows that
and at the same time their electron partial conductivity is
σ dϕ much larger than that of metal ions:
j =− . (29)
zF dx
σi  σMe+  σX− . (36)
C. Transport in an Electrical Field and in a In this case we obtain:
Concentration- or Activity-Gradient
d ln aMe
D̃ = D K ,Me , (37)
If besides a gradient of the electrical potential, ϕ, a gradient d ln cMe
of the chemical potential µ or activity a of the particles
where aMe and cMe are the activity of the metal and the
is also present in the compound, we must write the more
concentration, respectively. Examples are the compounds
general equation
FeO and Ag2 S.
D K ,i ci dµi σi dϕ
ji = − − . (30)
RT d x zi F d x
E. Atomistic Interpretation of the Transport
Using Eq. (1) and the Nernst–Einstein equation
of Ions in Solids
D K ,i = (u i /z i F)RT. (31)
To understand the high ionic conductivity of some solid
Eq. (30) may be reduced to give compounds an atomistic interpretation of the transport of
  ions in solids should be regarded.
ci D K ,i dµi z i F dϕ
ji = − + . (32) From the atomistic point of view the movement of ions
RT dx dx in solids can be regarded as successive jumps between
With the definition of the electrochemical potential lattice sites or interstitial sites. For random motion of a
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Solid-State Electrochemistry 307

particle in an isotropic crystal the diffusion coefficient can solid electrolytes reach these values or come near them.
be expressed by They are sometimes called super ionic conductors.
D K ,i = 16 νa 2 (38)
if there is no correlation between the jumps; ν denotes the IV. SOLID ELECTROLYTES, SOLID
jump frequency and a denotes the distance for each jump. IONIC CONDUCTORS, AND
Using Eqs. (38), (31), and (1) we obtain for the partial SOLID–SOLUTION ELECTRODES
conductivity
 Having discussed in Sections II and III concentration and
σi = ci νa 2 z i2 F 2 6RT (39) mobility, which influence the conductivity of solid elec-
and for the electrical mobility: trolytes, a compilation of solid ionic conductors will be
 given in this section. This compilation does not presume to
u i = z i F νa 2 6RT . (40) be complete because new solid electrolytes are discovered
From Eqs. (39) and (40) we can see that the important and developed continuously. In Fig. 4, the conductivities
quantity for the conductivity and the mobility is the prod- of some of the most important ones are shown as a function
uct of the jump frequency of an ion and the square of the of temperaure and reciprocal temperature. The conductiv-
jump distance. The jump distance is of the order of the ity of liquid sulfuric acid is included for comparison. In
lattice parameter. the following, several important solid electrolytes will be
It is possible to estimate an upper limit of the jump treated according to the type of mobile ions that cause the
frequency. The maximum jump frequency νmax , that is, ionic conductivity.
the highest frequency of change of a lattice site, results if
the particles move with thermal speed v between the lattice A. Silver Ion Conductors
sites without performing oscillations on such a site. Thus One of the first solid electrolytes exhibiting a very
νmax = v/a . (41) high ionic conductivity, found in 1914, is α-Agl. This
conducting α-phase is stable above 149◦ C and its high
For a given temperature this natural limit cannot be ex- conductivity is caused by structural disorder. A similar
ceeded. The maximum conductivity denoted as σi (max), disorder exists in RbAg4 I5 . This solid electrolyte exhibits
is then given according to Eqs. (40) and (41) as the highest silver ion conductivity at room temperature
ci vaz i2 F 2 at present. Therefore, it is of great technical interest. A
σi (max) = . (42)
6RT
Herewith we can calculate a maximum possible partial
conductivity for a substance, for example, silver iodide.
Assuming that the silver ions migrate with thermal veloc-
ity v from one lattice site to another without oscillating
at each lattice site, we get a jump frequency ν = v/a =
3.4 × 1012 s−1 at a temperature of 300◦ C, a diffusion co-
efficient of D K ,i = 5.6 × 10−5 cm2 /s, and the maximum
conductivity is σ(max) = 2.8 −1 cm−1 for a jump distance
of 1 Å. The measured conductivity is σ = 1.97 −1 cm−1 ,
which is not much less than the calculated value.
Many efforts have been made to improve this very sim-
ple but already good model. Besides jump and lattice gas
models continuous models have been made. These models
rely on the fact that the diffusion of an ion is not repre-
sented by instantaneous jumps from an equilibrium site to
another one but by a continuous motion in between.
From these considerations it can be seen that there is
a natural upper limit for the value of the ionic conduc-
tivity of solid compounds. This upper limit is between
1 and 10 −1 cm −1 corresponding to a component dif-
fusion coefficient of about 2 to 20 × 10−5 cm2 s. These FIGURE 4 Conductivity of some very common solid electrolytes;
values correspond to those in liquid electrolytes. Good H2 SO4 included for comparison.
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308 Solid-State Electrochemistry

TABLE IV Conductivity of Several Silver Ion TABLE VI Conductivity of Several Sodium Ion
Conductors Conductors

Temperature σ Temperature σ
Compound (◦ C) ×102 /Ω cm)
(× Compound (◦ C) ×102 /Ω cm)
(×

Agl 150–500 130–260 β-NaAl11 O17 20–640 1.5–55

RbAg4 I5 −15–270 14–100 Na5 GdSi4 O12 40–210 0.3–10
Ag3 SI 250–440 84–100 Na3 Zr2 Si2 PO12 40–220 0.3–7.5
Ag3 SBr 20–300 0.1–8.2 NaSbO3 · 16 NaF 40–220 0.001–0.7
Ag2 Hgl4 50–90 0.001–0.4
C5 H5 NHAg5 I6 −20–480 0.1–440
to obtain three-dimensional conductivity. This electrolyte
has become of great interest for building sodium sulfur
number of other silver ion conductors have been devel- batteries, as will be discussed in Section VI.B. The con-
oped. Some of them and their conductivities for the given ductivities of β-Al2 O3 and some other sodium ion con-
temperature ranges are listed in Table IV. ductors are shown in Table VI.

B. Oxygen Ion Conductors D. Copper Ion Conductors

Doped zirconia dioxide and thorium dioxide are impor- The first solid electrolytes with high copper ion conduc-
tant solid electrolytes that owe their conductivity to trans- tivity at room temperature were discovered in 1973. An
port of oxygen ions. They can be used between 600 and example is 7CuBrC6 H12 N4 CH3 Br, whose conductivity at
1600◦ C. They are also an interesting example of how high room temperature is 0.017 −1 cm−1 . Several other cop-
ionic conductivity can arise by processes other than struc- per ion conductors have since been described. One of these
tural disorder. The disorder centers responsible for the conductors represented by the formula Rb4 Cu16 I7 Cl13 has
ionic conductivity of zirconium dioxide are charged oxy- a conductivity of 0.34 −1 cm−1 at 25◦ C. This is the solid
gen ion vacancies. These are produced by dissolution of electrolyte with the highest conductivity at room temper-
CaO, MgO, or Y2 O3 in the zirconium dioxide. The cal- ature known at present. In Table VII the conductivity of
cium is incorporated at zirconium positions, since, how- some copper ion conductors are listed.
ever, only one oxygen ion is introduced with each cal-
cium ion, one oxygen position remains unoccupied for E. Proton Conductors
each calcium atom introduced. The amount of doping is
Solid-state proton conductors with high ionic conduc-
of the order of 10 mol%; in this way it can be seen why
tivity are eagerly sought because they could have im-
doping produces a very large number of vacancies in the
portant practical applications, for example, in fuel cells,
zirconium dioxide. In Table V the conductivities of several
water electrolyzers, and sensors. Substances with an ap-
oxygen conductors in given temperature ranges are listed.
preciable proton conductivity known today are hydrogen
uranyl phosphate tetrahydrate (HUP) HUO2 PO4 ·4H2 O—
C. Sodium Ion Conductors usable above 1◦ C—with an ionic conductivity of σ = 4 ×
The most important Na+ ion conductor is Na2 O 11Al2 O3 , 10−3 −1 cm−1 at 20◦ C and hydrogen uranyl arsenate
the so-called β-Al2 O3 . The mobile sodium ions are incor- tetrahydrate HUO2 AsO4 ·4H2 O—usable above 29◦ C—
porated into planes of the lattice and can therefore move with an ionic conductivity of σ = 6 × 10−3 −1 40◦ C.
only in two dimensions; polycrystalline material is used Another kind of solid proton conductor is the pro-
tonic β-alumina. It can be produced by exchanging the
TABLE V Conductivity of Several Oxygen Ion
Conductors TABLE VII Conductivity of Several Copper Ion
Conductors
Temperature σ
Compound (◦ C) ×102 /Ω cm)
(× Temperature σ
Compound (◦ C) ×102 /Ω cm)
(×
ZrO2 (10 mol% Sc2 O3 ) 600–1400 2–100
ZrO2 (10 mol% Y2 O3 ) 600–1400 0.3–50 Rb4 Cu16 I7 Cl13 10–110 28–62
ZrO2 (13 mol% CaO) 640–1400 0.2–30 7CuBr·C6 H12 N4 CH3 Br 10–130 1.5–14
ThO2 (7.5 mol% Y2 O3 ) 1000–1500 1.3–12 7CuCl·C6 H12 N4 HCl 20–110 0.4–5
Bi2 O3 (20 mol% Er2 O3 ) 270–730 0.001–45 17Cul·3C6 H12 N4 CH3 I 20–140 0.1–2.2
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Solid-State Electrochemistry 309

whole sodium content of the solid sodium ion conductor electrochemistry of solids galvanic cells with solid elec-
Na–β-A12 O3 (see Section IV.C) for H+ , H+ (H2 O)n , or trolytes play a very important role. In analogy to galvanic
NH+ 4 ions. The ionic conductivity of these compounds is cells with liquid electrolytes, those with solid electrolytes
in the region of 10−4 –10−5 −1 cm−1 at room temperature. consist of at least two electrodes separated by an elec-
Various possible mechanisms of the conduction process in trolyte, which in this case is a solid ionic conductor. The
the different proton conductors are being discussed. important properties of such cells will be discussed. For
The longtime stability of these compounds, which is this purpose the following galvanic cell will be considered
especially important for possible technical applications, as an example:
has not been clearly established. There exist still other pO , Pt / ZrO2 (+Y2 O3 ) / Pt, pO
2 2
solid proton conductors but as their conductivity in general ←−−− ←−−−−−−− ←−−−.
is not as high as in the compounds mentioned earlier they 4e− 2O2− 4e−

will not be treated here. I

In addition to the solid electrolytes already described
It consists of doped zirconium dioxide as solid electrolyte
there exist solids in which other ions (e.g., lithium, fluoride
with practically pure ionic conduction for oxygen ions.
or chloride ions) are mobile. These solid ionic conductors
On the two sides there are porous, electronically conduct-
will not be treated here.
ing electrodes (e.g., consisting of porous platinum), sur-
rounded by gaseous oxygen at different partial pressures.
F. Solid–Solution Electrodes
The zirconium dioxide must separate the electrode spaces
Another class of important solids is mixed conducting from one another in gas-tight manner. For example, a tube
solids exhibiting both fast ion transport and electronic con- of zirconium dioxide can be used that carries one elec-
ductivity. If, in addition to these properties a sufficiently trode on the inner side and the second on the outer side,
large range of stoichiometry is present, these mixed con- the outside and the inside being surrounded by gaseous
ducting solids can be used as electrodes, for example, for oxygen at different partial pressures. If in this galvanic
batteries, the so-called solid–solution electrodes. One of cell a positive electrical current flows from the left to the
the most promising solid–solution electrodes is based on right electrode, 1 mol of O2 is transported from the right to
titanium disulfide, in which it is possible to dissolve rel- the left electrode space by the passage of 4 faradays (4f).
atively large amounts of lithium metal in the TiS2 phase. The following cell reaction occurs:
There is a continuous range of nonstoichiometry from
O2 (right electrode) → O2 (left electrode). (43)
TiS2 to LiTiS2 . The structure of TiS2 and other similar
chalcogenides of transition metals can be described as a Considering this cell reaction, we can obtain two proper-
sequence of layers held together by van der Waals forces ties of cell I; the first property is a thermodynamic one
only. The lithium is dissolved between the layers whereby and the second a kinetic one.
the distance between the layers is slightly increased. Other The thermodynamic property is the following. The elec-
changes in the crystal structure do not occur. Compounds trical work that in the reversible case of the galvanic cell
of this kind are sometimes called insertion or intercalation can be performed with the passage of 4 faradays amounts
compounds. to 4EF, where E is the emf of the galvanic cell, defined as
Many other solid–solution electrodes have been inves- the electrical potential of the right electrode minus that of
tigated. Examples of other layer compounds besides TiS2 the left electrode. This work is equal to the negative Gibbs
that are able to dissolve certain alkali metals and in some energy G of cell reaction (43):
cases Cu+ or Ag+ ions include TiSe2 , MoS2 , WS2 , TaS2 ,
G(cel1 reaction) = −4EF. (44)
ZrS2 , NbS2 , VSe2 , MoSe2 , WSe2 , and CrS2 .
In this regard we should also mention a related series of Here G can be related to the chemical potentials µO2
certain transition metal oxides that do not exhibit layered of oxygen, and we then have, for Eq. (44), the following
structures but are able to insert alkali metals or copper or expression:
silver, for example, TiO2 , MnO2 , MoO3 , WO3−y , V2 O5 ,
µO2 (left electrode) − µO2 (right electrode) = −4EF.
and Ta2 O5 .
(45)
The chemical potential µO2 is connected with the oxygen
V. GALVANIC CELLS WITH partial pressure pO2 by the following equation:
SOLID ELECTROLYTES   
µO2 = µ0O2 + RT ln pO2 pO0 2 . (46)
The existence of solid ionic conductors has made possible Here µ0O2 denotes the standard chemical potential of oxy-
the development of the electrochemistry of solids. In the gen, corresponding to a partial pressure pO0 2 of 1 atm; R is
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310 Solid-State Electrochemistry

the gas constant and T is the absolute temperature. Sub- One way to obtain a relation between the Gibbs energy
stitution of Eq. (46) into Eq. (45) gives: and the emf of the cell is to regard the so-called virtual
cell reaction. We assume that a certain amount of charge
RT pO (right electrode) RT pO
E= ln 2 = ln  2 . (47) is passed through the cell as a current. In this example, the
4F pO2 (left electrode) 4F p O2 cell reaction is the formation of 1 mole NiO from solid
This shows a relation existing between E, the emf of the nickel and oxygen by passing a flow of electricity of 2 f
galvanic cell, and the ratio of oxygen partial pressures at through the cell:
the two electrodes. If one oxygen partial pressure is known Ni + 12 O2 = NiO · · · G NiO .
the other one can be determined.
According to Eqs. (45)–(47) the emf of a galvanic cell This reaction does not take place under open-circuit
contains different thermodynamic information. The emf conditions. It would take place under current flow, but
makes it possible to determine the Gibbs energy of the cell then, in general, polarization effects will occur. The maxi-
reaction and the chemical potentials of the electrode com- mum possible electrical energy that we could obtain from
ponents or the partial pressures of gases. It shall be men- the cell for the virtual reaction is the measured emf under
tioned here that reaction enthalpies and reaction entropies open-circuit conditions multiplied by 2 f in this example.
can also be deduced from the temperature dependence of This electrical energy is related to the Gibbs energy G
the emf. More details on thermodynamic investigations of the cell reaction; in this case to the Gibbs energy of
will be given in Section V.A. formation of NiO from solid nickel and oxygen by:
The kinetic properties of galvanic cell I with doped
G 0NiO = −2EF. (49)
zirconia as solid electrolyte arise from the fact that the
flux of current through a cell such as cell I is a measure of Here G 0NiO is written because NiO as well as Ni and O2
the reaction rate by which oxygen is passed from one side are in their standard states. Similar investigations have
of the cell to the other. Only oxygen ions can flow through been carried out on many other systems, for exam-
the electrolyte when the electrical circuit is closed. For the ple, Cu2 O, FeO, PbO, In2 O3 , WO2 , ZnO, SiO2 , MoO2 ,
rate of transport of the O2− particles in moles per unit time NiCl2 O4 , FeCr2 O4 , NiAl2 O4 , MgF2 , ThF4 , UF3 , and AlF3 .
J through the electrolyte we can write: Furthermore, enthalpies and entropies of reaction as well
as partial molar enthalpies and entropies and partial molar
J = I /z F, (48)
volumina can be measured using similar cells.
where I is the electrical current; in the case of oxygen the
valence z is −2.
B. Kinetic Investigations
The transport of mass in the form of ions through the
electrolyte can often be attributed to a chemical reaction According to the electrochemistry of liquids kinetic in-
or a transport process at an electrode. In this way reaction vestigations using solid electrolytes can be carried out in
rates can be measured electrically. It is often possible to different ways.
analyze reaction mechanisms in detail by a combination
of rate measurements by means of the electrical current
with measurements of thermodynamic quantities—in par- 1. Measurements at Zero Current
ticular, chemical potentials—by means of the emf of the In the case of zero-current measurements the electrical
galvanic cell. More details on kinetic investigations using potential difference between the two end phases of the cell
galvanic cells will be given in Section V.B. is measured under open circuit conditions. Information
about thermodynamic quantities of reaction systems, for
example, about chemical potentials, activities, or partial
A. Thermodynamic Investigations
pressures, is obtained from such measurements. This was
As a typical example for thermodynamic investigations already described.
using solid electrolytes the determination of the Gibbs
energy G 0NiO at temperatures of 800–1000◦ C will be con-
sidered. The following cell with doped ZrO2 as solid elec- 2. Measurements under Steady-State Conditions
trolyte for oxygen ions can be used: In this case there is no time dependence of currents and
Pt, Ni, NiO / ZrO2 (+Y2 O3 ) / Pt, pO2 = 1atm
potentials. Therefore, it is experimentally unimportant
2f: ←−−−−− ←−−−−−−− ←−−−−−−−. whether the potentials or the currents are controlled. Here
2e− O2− 2e− the steady-state current that represents a reaction rate may
II be measured as a function of the potential or vice versa.
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Solid-State Electrochemistry 311

3. Measurements under Controlled Potential TABLE VIII Determination of the Diffusion Coefficient
of Oxygen in Various Solid and Liquid Metals
In this case a constant potential difference is applied to the
cell and the resulting current is measured as a function of Solid Temperature Diffusion coefficient
Metal or liquid range (◦ C) (cm2 /s)
time. These investigations are called potentiostatic.
Ag s 760–900 1.5 × 10−5 –2.9 × 10−5
Ag l 970–1200 8.2 × 10−5 –1.7 × 10−4
4. Measurements under Controlled Current
Cu l 990–1220 1.4 × 10−4 –2.2 × 10−4
In this case a constant current is passed through the cell and Cu s 800–1030 9.3 × 10−6 –3.5 × 10−5
the resulting potential difference is measured as a function Sn l 730–930 4.5 × 10−5 –7.4 × 10−5
of time. These investigations are called galvanostatic. If Ni s 1393 1.3 × 10−6
galvanostatic or potentiostatic measurements or investi- Pb l 800–1100 1.0 × 10−5 –1.7 × 10−5
gations under steady-state conditions are carried out it is Fe l 1620 1.5 × 10−4
often preferable to use separate cells of the same type un- Sb l 750–950 1.4 × 10−6 –2.9 × 10−6
der zero current to measure potential differences, so that Bi l 750–950 8.6 × 10−6 –1.4 × 10−5
the reference electrode is not polarized by a current. In the
following, a few examples of kinetic investigations using
solid electrolytes will be discussed. tions. Several systems have been investigated in this way.
Some results are shown in Table VIII.

C. Electrochemical Measurements
D. Measurements of Chemical
of Oxygen Diffusion in Metals
Diffusion Coefficients
The principle of the electrochemical measurement of oxy-
The process of attaining a uniform composition, which
gen diffusion in a metal consists in bringing the metal
occurs in compounds where an existing gradient of sto-
from a well-defined state into another well-defined state
ichiometry is allowed to equalize, can be described by
and following the diffusion-controlled relaxation pro-
the chemical diffusion coefficient D̃ discussed in Sec-
cess electrochemically. For example, the metal sample is
tion III.D.
placed on one side of the solid electrolyte ZrO2 and func-
For such equilibration processes it is necessary, on the
tions as one electrode of a galvanic cell. On the other side
grounds of electrical neutrality, that both ions and elec-
of the electrolyte there is a practically unpolarizable elec-
trons or electron defects must migrate simultaneously
trode such as porous platinum in contact with air, or an
whereby the fluxes of ions and electrons are related to
Fe/FeO electrode, which has a fixed oxygen partial pres-
one another. The electrochemical method for the determi-
sure of about 10−19 atm at 800◦ C. The following cell may
nation of chemical diffusion coefficients D̃ will be shown
be used:
here as an example for the mixed conductor wüstite FeO.
Fe, FeO / ZrO2 (+Y2 O3 ) / Me + O(dissolved)
←−−− ←−−−−−−− ←−−−−−−−−− The basic element for the investigation of wüstite
2e− O2− O Fe1−δ O (δ = deviation from ideal stoichiometry) is the
←−−−−−−−−−. solid-state galvanic cell
2e−
pO 2 , Pt/ZrO2 (+Y2 O3 )/Fe1−δ O)/Pt
III
IV
In cell III there is an Fe/FeO electrode on one side and a
metal containing dissolved oxygen on the other side. The with doped ZrO2 as solid electrolyte, an electrode consist-
emf of the cell before beginning the experiment is a mea- ing of porous platinum in contact with air at one side and
sure of the initial activity or concentration of the dissolved the wüstite being investigated as electrode at the other side.
oxygen. At a certain time an emf is applied to the cell to The experimental setup is shown in Fig. 5. The principle
make the oxygen activity at the metal/electrolyte interface of the measurement is that, starting from a suitable initial
very small. Then oxygen diffuses out of the metal and is state, the potential difference E of cell IV or the current I ,
carried as an electrical current through the electrolyte to respectively, are varied systematically. The other variable
the other side of the cell. In this way the diffusion cur- I or E is measured as a function of time. From the obtained
rent is transformed into an electrical current and can be results the chemical diffusion coefficient D̃ of wüstite can
measured. be calculated. In a potentiostatic experiment a definite
From the time dependence of the current the diffusion value of the chemical potential of oxygen, correspond-
coefficient can be calculated using suitable diffusion equa- ing to a certain deviation δ from the ideal stoichiometry,
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312 Solid-State Electrochemistry

The chemical diffusion coefficients D̃ of Ag2+δ S mea-

sured at 200 and 300◦ C as a function of the deviation from
the ideal stoichiometry are shown in Fig. 6.
Another method for determining chemical diffusion co-
efficients is to use the frequency dependence of the cell
impedance, which is obtained by ac measurements. This
will not be treated here.

E. Electrochemical Investigations of
Formation of Surface Layers on Metals
FIGURE 5 Experimental setup for the measurement of the
chemical-diffusion coefficient of wüstite: W, working electrode; R,
The formation of nickel sulfide on nickel will be discussed
reference electrode; C, counter electrode. as an example. The experimental arrangement is shown
in Fig. 7. Silver iodide was used as the solid electrolyte,
is set up in the wüstite before starting the measurement. being a pure Ag+ ionic conductor under the experimen-
Then a sudden change of the potential of the cell stipulated tal conditions. The negative pole of a power source was
potentiostatically causes a current flow that is measured connected to the left-hand side of the arrangement and
as a function of time. This current is primarily a measure the positive pole to the right-hand side. The electrolytic
of the addition or removal of oxygen at the phase bound- cell itself consisted of tablets pressed together in a glass
ary ZrO2 /wüstite. As a consequence of this, iron diffuses tube furnace flushed with nitrogen. An electrical current
within the wüstite to or from the phase boundary. Thus, passing through the cell is a measure of the rate at which
the current is equivalent to the diffusion current of iron, silver is removed from the silver sulfide, since silver ions
During this process the stoichiometry in the compound migrate through the AgI and electrons through the exter-
changes with time until a new δ value is attained. From nal circuit. In this case, however, the rate of loss of the
the solution of the diffusion equations for this problem the silver corresponds to the rate of the formation of nickel
chemical diffusion coefficient D̃ can be calculated. sulfide on nickel, since in this reaction nickel displaces
The result obtained for wüstite at 1000◦ C and a de- the silver from the Ag2 S. The experiments were carrid out
viation δ = 0.106 from ideal stoichiometry is D̃ = 3.2 × using the galvanostatic and potentiostatic methods. The
10−6 cm2 /s. Similar investigations with an improved ex- important quantities are the current, which is a measure
perimental setup allowed the determination of the chemi- of the reaction rate (here of the formation of nickel sul-
cal diffusion coefficient D̃ of Ag2+δ S over the total range fide), and the cell emf, which is not only a measure of
of stoichiometric composition of this compound. the chemical potential of the silver in silver sulfide, but,

FIGURE 6 Chemical-diffusion coefficients of Ag2+δ S as a function of the deviation δ from stoichiometry at 200 and
300◦ C.
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Solid-State Electrochemistry 313

voltage U . The voltage is proportional to the ratio of mass

to electrical charge of the silver ions and to the length of
the rod. To verify Eq. (52) we should know the acceler-
ation a at every time. In the experiments, however, the
acceleration itself was not measured, rather it was the ve-
locity before striking the ground that was measured. The
FIGURE 7 Galvanic cell for the electrochemical investigation of accleration a and the velocity v are related by
the formation of NiS on nickel.
a = d v/dt , (53)
in view of the Gibbs–Duhem equation, also is a measure
where t is the time. By integration of Eq. (53) over the
of the chemical potential of the sulfur in this compound.
whole time of striking we obtain the negative velocity −v:
Thus, because of the high mobility of the silver in Ag2 S, it
 after strike
is also a measure of the chemical potential of the sulfur at
the Ag2 S/NiS phase boundary. In this way the parabolic a dt = −v (54)
before strike
constant k for the rate of formation of NiS on nickel at
400◦ C could be measured as a function of the chemical because the rod RbAg4 I5 has velocity v = 0 after the
potential of the sulfur on the outside of NiS. The results decleration. Using this we obtain by integration of Eq. (52)
provided information about the disorder in NiS.  after strike
ml
U dt = v. (55)
before strike e
F. Investigations on the Forces of Inertia This equation was used for the interpretation of the exper-
of the Mobile Ions in Solid Ionic Conductors iments. Figure 8 shows a voltage–time curve measured
As an example, a rod of RbAg4 I5 with silver electrodes at 25◦ C with a rod of RbAg4 I5 , which has a length of
at both ends is exposed to an acceleration in the longi- 7.4 cm.
tudinal direction. This acceleration may be produced, for Thevelocity before striking was 1.44 m/s. The voltage
example, by the braking of the rod dropped from different pulse U dt is given by the area below the curve and
heights to a plastic material on the ground. has a value of 1.22 × 10−7 V s. According to Eq. (55) the
Because of the high mobility of the silver ions it may area below the curve depends only on the velocity before
be assumed that in the moment of striking the silver ions striking for a given length of the rod.
will be shifted only a little against the iodide lattice. Thus, Figure 9 shows the measured voltage pulses from drop-
an electrical field having the field strength E is built up ping experiments at 25◦ C using a RbAg4 I5 rod of 7.4-cm
with the result that the silver ions will be decelerated in length as a function of the velocity before striking. The
the same way as the rigid iodide lattice. full line holds for the limiting case of inelastic striking,
The sum of all forces acting on the silver ions must calculated with the help of Eq. (55) where m is the mass of
be zero. In this case the essential forces are the electrical
force and the force of inertia. Quantitatively the electrical
charge e multiplied by the electrical fields strength E is
equal to the mass m of the silver ions multiplied by the
acceleration a:
eE = ma. (50)
Since it can be assumed that the electrical field strength
is constant along the rod of length l, an integration of E
over l delivers the negative volgate −U , which can be
measured between the ends of the rod:
 l
E dl = El = −U . (51)
0

Inserting Eq. (51) in Eq. (50) we obtain:

ml
−U =
a. (52)
e
FIGURE 8 Example of a measured voltage-time curve of a drop-
Equation (52) shows the relationship between the ac- ping experiment (T = 25◦ C; length of the rod = 7.4 cm; velocity
celeration acting on the rod of RbAg4 I5 and the electrical before striking = 1.44 m/s).
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314 Solid-State Electrochemistry

FIGURE 10 Zirconium dioxide sensor for the measurement of

partial pressures of oxygen. The housing and packing are electri-
cally conducting.

The wide range of oxygen partial pressures makes such

FIGURE 9 Voltage pulse as a function of the v before striking at cells an excellent analytical instrument for measurements
25◦ C. (Length of the rod = 7.4 cm; ——, calculated; ×, measured). of gases. It should be mentioned that the measured value
is obtained almost instantaneously. In such measurements
a silver atom. It is seen that the results of the measurements a reference atmosphere, for example, air or a metal–metal
and the calculated voltage pulses are in agreement. oxide mixture, is located on one side of the zirconium
Furthermore, it should be noticed that neither in Eq. (55) dioxide, so that the oxygen partial pressure is already
nor in Eq. (52) is the termperature included as a variable. known at one electrode; the oxygen partial pressure at
That means the values of the voltage pulses should be the other electrode is then measured by the emf in accor-
independent of the temperature. This could be confirmed dance with Eq. (47). In the measurement the gas is passed
by measurements at 25 and 120◦ C and may be of interest to the sensor.
for practical applications, as will be seen. Interesting industrial applications lie in the analysis of
In addition to the investigations described, other ki- exhaust gases from furnaces or combustion engines. It
netic experiments have been carried out with the help of is advisable to arrange the zirconium dioxide probe in
solid-electrolyte galvanic cells. The investigations include the exhaust gas stream near the reaction space. Figure 10
phase-boundary reactions at the solid–gas phase bound- shows such a sensor that can be used for the control
ary (including measurements of evaportion and condensa- and regulation of the combustion process in automobile
tion rates) and phase-boundary reactions at the solid–solid engines. The possibility of very exact control of gasoline–
phase boundary. These investigations will not be discussed air mixtures is of special interest in connection with the
here. control of air pollution.
A similar probe can be used to measure the concentra-
VI. TECHNICAL APPLICATIONS tion or thermodynamic activity of oxygen in liquid metals.
OF SOLID ELECTROLYTES For example, if the probe is dipped in the melt during steel
production, the oxygen activity can be measured directly,
Solid electrolytes are also of great technological impor- which is of appreciable advantage.
tance. Some examples of applications will be described in A further possibility to measure partial pressures of
the following sections. gases is given by the use of galvanic cells, in which another
kind of ions than the corresponding species in the gas is
A. Sensors mobile in the solid electrolyte. As an example, the follow-
ing galvanic cell for measuring chlorine partial pressures
Galvanic cells with solid electrolytes can be used for direct will be regarded
measurement of partial pressures in gases and concentra-  
tions in liquids and melts. An important example is cell Ag/RbAg4 I5 /AgCl, Cl2 pCl2 ,
I, which contains doped zirconium dioxide as solid elec- V
trolyte. By using cells of this type a wide range of oxygen
partial pressures in gases (down to 10−16 atm) can be de- where RbAg4 I5 is used as a silver ion conducting solid
termined. The zirconium dioxide probe for such work is electrolyte. Cell V is in principle a concentration (activity)
used at temperatures between about 500 and 1000◦ C. cell for silver ions analogous to cell I delivering the emf
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Solid-State Electrochemistry 315

RT aAg (AgCl)
E= ln , (56)
F aAg (Ag)
where aAg (AgCl) denotes the activity of silver in the right-
hand AgCl-electrode, and aAg (Ag) denotes the activity of
silver in the left-hand silver electrode, respectively, which
has a value of one in this case because of the pure Ag metal.
The activity of silver in AgCl, which is in equilibrium
with the gas-atmosphere, having a certain chlorine partial
pressure pCl2 , is given by
 −1/2   
aAg (AgCl) = pCl2 /po exp G oAgCl RT , (57)
where p o = 1 atm and G oAgCl is the Standard-Gibbs en-
ergy of formation of AgCl. Inserting Eq. (57) into Eq. (56),
we obtain a relation between the chlorine partial pressure
to be determined and the measured emf E
RT   
E= ln pCl2 /po − G oAgCl F . (58) FIGURE 11 Schematic diagram of a RbAg4 I5 accelerometer.
2F
Also, the partial pressures of other gases, for example,
B. Solid Electrolyte Batteries:
NO2 , O2 , or sulfur, can be measured by such sensors.
The Sodium–Sulfur Cell
Another method of determining the partial pressure of
a gas is given by measuring the current flowing through The principle of a sodium–sulfur cell is shown in Fig. 12.
a suitable galvanic cell with a solid electrolyte. This prin- The solid electrolyte is a Na+ ion conductor, consisting
ciple will be discussed in the following exemplified at an of β-Al2 O3 . It is generally used as a tube closed at one
oxygen sensor. In principle, cell I discussed in Section V end and filled with liquid sodium as the anode. An iron
can be used, where pO 2 is the oxygen partial pressure to sponge, which absorbs the liquid sodium, serves to im-
be measured. In this case, a current is passed through the prove the wetting of the electrolyte and to improve safety.
cell so that oxygen is transported from the right-hand side A metal wire leads out of the anode to carry the current.
of the cell to the left-hand side. For this an outer electri- The cathode consists of liquid sodium polysulfide and sul-
cal voltage has to be applied to the cell. To get a defined fur inserted in porous graphite. The working temperature
correlation between pO 2 and the electrical current flowing of the sodium–sulfur cell is around 300◦ C.
through the cell, a so-called “diffusion-barrier” has to be In the cell reaction sodium ions pass through the elec-
arranged in front of the electrode at the right-hand side. trolyte and electrons through the external circuit, so that
This may, for example, consist of a porous ceramic ma- sodium is dissolved in sodium polysulfide. In this way
terial. The external electrical voltage is chosen in such a electrical energy can be liberated. The energy density of
way that each oxygen molecule reaching the surface of the sodium–sulfur cell is many times greater than that
the right-hand electrode immediately reacts electrochem-
ically to an oxygen ion, which is then transported through
the solid electrolyte. Under these conditions, the flowing
current is proportional to the partial pressure pO 2 and so
can be used to measure pO 2 .
Another type of sensor—an accelerometer—can be
constructed by applying the principles used in the case
of the investigations on the forces of inertia of the mobile
ions in solid ion conductors, described in Section V.F. As
shown in Eq. (52) the voltage U measured at both ends of a
rod of a solid electrolyte is a direct measure of the acceler-
ation acting on this rod at every time; this means that such
an arrangement, consisting of a rod of RbAg4 I5 as solid
electrolyte with silver wires at both ends as electrodes for
measuring the voltage U , can be used as an accelerometer.
This is of interest for practical applications. The principle
of such an accelerometer is shown in Fig. 11. FIGURE 12 Sodium–sulfur cell.
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316 Solid-State Electrochemistry

of the customary lead batteries, and the materials needed high-temperature fuel cell if required. This principle is be-
for the electrolytes and electrodes are available in large ing discussed in connection with large-scale energy stor-
quantities. The cell can be recharged by changing the di- age and transport of energy.
rection of the current. The sodium–sulfur cell is of great
interest for large-scale energy storage and for electrotrac- D. Chemotronic Components
tion for electric vehicles. Prototypes have already been
built. In addition to the sodium–sulfur cell other cell sys- Galvanic cells containing solid electrolytes, which find use
tems have been developed using other solid electrolytes. in electrical circuits, are often called chemotronic com-
ponents. Next we describe as an example coulometers
and time switches. However, there exist more chemotronic
C. Fuel Cells and Electrolyzers building units containing solid electrolytes such as analog
Figure 13 shows schematically a high-temperature fuel memories and capacitors. They will not be described here.
cell incorporating zirconium dioxide as the solid elec- The galvanic cell
trolyte. The zirconium dioxide in a tube or disk form Ag/RbAg4 I5 /Au
separates two electrode compartments, one containing air
or pure oxygen and the other a fuel gas (e.g., hydro- VI
gen). The zirconium oxide carries two porous electrodes: can be used as a coulometer or time switch. Here the
nickel can be used on the fuel side, and on the oxygen electrolyte RbAg4 I5 is a good Ag+ ion conductor even at
side lanthanum–nickel oxide or some other electron- room temperature. By passing a current through this cell
conducting oxide. with the negative pole at the silver side, silver is deposited
In a high-temperature fuel cell the oxygen takes up elec- on the gold electrode. The time switch is then in the loaded
trons at one electrode, then passes through the electrolyte state. The silver can be transported back to the original sil-
as ions and combines at the other electrode with H2 to give ver electrode by a current flowing in the reverse direction.
H2 O, whereby the electrons are given up and flow again In this stripping process the cell potential is determined
to the other electrode in the external current circuit. In this mainly by ohmic losses in the solid electrolyte that lie in
way energy is made available to the user. The advantages the millivolt range. When all the silver has been stripped
of the high-temperature fuel cell are that little or no polar- from the gold electrode the cell shows a sudden rise in po-
ization occurs at the electrodes and high current densities tential, which can be used as a signal. Such electrochemi-
can be achieved. cal switches are suitable for times in the region of seconds
By reversing the direction of the current flow in a high- to months. Cell VI can also be used as a coulometer; the
temperature fuel cell, that is, by supplying the cell with amount of a current flowing through the cell during charg-
electrical energy, steam can be decomposed and the cell ing is then determined by the discharge process.
can thus be used as an electrolyzer. The hydrogen pro-
duced can be stored or conducted by pipelines to remote
sites where it can serve for the production of energy in a SEE ALSO THE FOLLOWING ARTICLES

CRYSTALLOGRAPHY • ELECTROCHEMISTRY • ELEC-

TROLYTE SOLUTIONS, TRANSPORT PROPERTIES • LASERS,
SOLID-STATE • SOLID-STATE CHEMISTRY • SOLID-STATE
IMAGING DEVICES

BIBLIOGRAPHY

Bard, A. J., and Faulkner, L. R. (2001). “Electrochemical Methods:

Fundamentals and Applications,” Wiley, New York.
Bruce, P. G. (1995). “Solid-State Electrochemistry,” Cambridge Univer-
sity Press, Cambridge.
Gellings, P. J., and Boumeester, H. J. M. (eds.) (1997). “The CRC
Handbook of Solid-State Electrochemistry,” CRC Press, Boca Raton,
Florida.
Stimming, U., Singhal, S. C., Tagawa, H., and Lehnert, W. (eds.) (1997).
“Proceedings of the Fifth International symposium on Solid Oxide
Fuel Cells (SOFC-V),” Electrochemical Society, Pennington, New
FIGURE 13 High-temperature fuel cell. Jersey.
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Superacids
George A. Olah
G. K. Surya Prakash
University of Southern California

I. Acid Strength and Acidity Scale

II. Superacid Systems
III. Application of Superacids

GLOSSARY sites. May be of the Brönsted or the Lewis superacid

type.
Brönsted superacids Proton donor acids stronger than Superacids Acid systems that encompass both Brönsted
100% sulfuric acid. and Lewis superacids as well as their conjugate com-
Carbenium ions Compounds containing a trivalent, binations.
tricoordinate carbon bearing a positive charge. Also Superelectrophiles Electrophiles that are further acti-
called “classical cations.” vated by Brönsted or Lewis superacid complexation.
Carbocations Compounds containing carbon bearing a
positive charge which encompass both carbenium and
carbonium ions. CHEMISTS long considered mineral acids such as sul-
Carbonium ions Compounds containing high coordi- furic and nitric acids to be the strongest protic acids to
nate carbon bearing a positive charge with multicenter exist. More recently this view has changed considerably
bonding. Also called “nonclassical” cations. with the discovery of extremely strong acid systems that
Conjugate Brönsted–Lewis superacids Superacidic are hundreds of millions, even billions, of times stronger
proton donor acids comprised of a combination of than 100% sulfuric acid. Such acid systems are termed
Brönsted and Lewis acids. “superacids.” The term “superacids” was first suggested
Hammet’s acidity constant, H 0 A logarithmic thermo- by Conant and Hull in 1927 to describe acids such as
dynamic scale used to relate acidity of proton donor perchloric acid in glacial acetic acid that were capable
acids. of protonating certain weak bases such as aldehydes and
Immobilized superacids Superacids (both Brönsted and ketones.
Lewis types) bound to inert supports such as graphite, Superacids encompass both Brönsted (proton donor)
fluorinated graphite, etc. and Lewis (electron acceptor) acids as well as their con-
Lewis superacids Electron acceptor acids stronger than jugate pairs. The concept of acidity and acid strength
aluminum trichloride. can be defined only in relation to a reference base. Ac-
Solid superacids Solid materials possessing superacid cording to an arbitrary but widely accepted suggestion

175
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176 Superacids

by Gillespie, all Brönsted (protic) acids stronger than A number of methods are available for estimating acid-
100% sulfuric acid are classified as superacids. Vari- ity of protic acids in solution. The best known is the direct
ous methods are available to measure protic superacid measurement of the hydrogen ion activity used in defining
strengths (vide infra). Lewis acids also cover a wide pH [Eq. (1)].
range of acidities extending beyond the strength of the
pH = log aH+ . (1)
most frequently used systems such as AlCl3 and BF3 .
Olah et al. (1985) suggested the use of anhydrous alu- This can be achieved by measuring the potential of a hy-
minum trichloride, the most widely used Friedel–Crafts drogen electrode in equilibrium with a dilute acid solu-
catalyst, as the arbitrary unit to define Lewis superacids. tion. In highly concentrated acid solutions, however, the
Lewis acids stronger than anhydrous aluminum trichloride pH concept is no longer applicable, and the acidity must
are considered Lewis superacids. There remain, however, be related very closely to the degree of transformation
many difficulties in measuring the strength of Lewis acid of a base with its conjugate acid, keeping in mind that
(vide infra). this will depend on the base itself and on medium effects.
The high acidity and the extremely low nucleophilicity The advantage of this method was shown in the 1930s by
of the counterions of superacidic systems are especially Hammett and Deyrup, who investigated the proton donor
useful for the preparation of stable, electron-deficient ability of the H2 O–H2 SO4 system over the whole concen-
cations, including carbocations. Many of these cations, tration range by measuring the extent to which a series of
which were formerly suggested only as fleeting metastable nitroanilines were protonated. This was the first applica-
intermediates and were detectable only in the gas phase tion of the very useful Hammett acidity function [Eq. (2)].
in mass spectrometric studies, can be conveniently stud-
BH+
ied in superacid solutions. New chemical transformations H0 = pKBH+ − log . (2)
and syntheses that are not possible using conventional B
acids can also be achieved with superacids. These include The pKBH+ is the dissociation constant of the conjugate
transformations and syntheses of many industrially im- acid (BH+ ) and BH+ /B is the ionization ratio, which is
portant hydrocarbons. The unique ability of superacids to generally measured by spectroscopic means [ultraviolet,
bring about hydrocarbon transformations, even to activate nuclear magnetic resonance (NMR), and dynamic NMR].
methane (the principal component of natural gas) for elec- Hammett’s “H0 ” scale is a logarithmic scale on which
trophilic reactions, has opened up a fascinating new field 100% sulfuric acid has an H0 value of −12.0.
in chemistry. Various other techniques are also available for acidity
measurements of protic acids. These include electrochem-
ical methods, kinetic rate measurements, and heats of pro-
I. ACID STRENGTH AND ACIDITY SCALE tonation of weak bases. Even with all these techniques it
is still difficult to measure the acidity of extremely acidic
The chemical species that plays the key role in Brönsted superacids, because of the unavailability of suitable weak
acids is the hydrogen ion, that is, the proton: H+ . Since the reference bases.
proton is the hydrogen nucleus with no electron in its 1s In contrast to protic (Brönsted) acids, a common quan-
orbital, it is not prone to electronic repulsion. The proton titative method to determine the strength of Lewis acids
consequently exercises a powerful polarizing effect. Due does not exist. Whereas the Brönsted acid–base interac-
to its extreme electron affinity, proton cannot be found tion always involves a common denominator—the proton
as a free “naked” species in the condensed state. It is al- (H+ ) transfer, which allows direct comparison—no such
ways associated with one or more molecules of acid or the common relationship exists in the Lewis acid–base inter-
solvent (or any other nucleophile present). The strength of action. The result is that the definition of “strength” has
protic acid thus depends on the degree of association of the no real meaning with Lewis acids.
proton in the condensed state. Free protons can exist only The “strength” or “coordinating power” of different
in the gas phase and represent the ultimate acidity. Due Lewis acids can vary widely against different Lewis bases.
to the very small size of a proton (105 times smaller then Despite the apparent difficulties, a number of qualitative
any other cation) and the fact that only 1s orbital is used relationships have been developed to characterize Lewis
in bonding by hydrogen, proton transfer is a very facile acids. Schwarzenbach and Chatt classified Lewis acids
reaction, reaching diffusion-controlled rates, and does not into two types: class a and class b. Class a Lewis acids
necessitate important reorganization of the electronic va- form their most stable complexes with the donors in the
lence shells. Understanding the nature of the proton is first row of the periodic table—N, O, and F. Class b acids,
important when generalizing quantitative relationships in on the other hand, complex best with donors in the sec-
acidity measurements. ond or subsequent row—Cl, Br, I, P, S, etc. Guttmann has
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Superacids 177

introduced a series of donor numbers (DN) and acceptor The complete description of the acidic properties of
numbers (AN) for various solvents in an attempt to quan- a solid requires the determination of the acid strengths
tify complexing tendencies of Lewis acids. Based on a as well as the number of acid sites. The methods that
similar premise, Drago came up with parameter E, which have been used to answer these questions are basically the
measures the covalent bonding potential of each series of same as those used for the liquid acids. Three methods
Lewis acids as well as bases. are generally quoted: (1) rate measurement to relate the
Pearson has proposed a qualitative scheme in which a catalytic activity to the acidity, (2) the spectrophotometric
Lewis acid and base are characterized by two parameters, method to estimate the acidity from the color change of
one of which is referred to as strength and the other as soft- adequate indicators, and (3) titration by a strong enough
ness. Thus, the equilibrium constant for a simple Lewis base for the measurement of the amount of acid. The above
acid–base reaction would be a function of four parameters, experimental techniques vary somewhat, but all the results
two for each partner. Subsequently, Pearson introduced the obtained should be interpreted with caution because of
hard and soft acids and bases (HSAB) principle to ratio- the complexity of the solid acid catalysts. The presence of
nalize behavior and reactivity in a qualitative way. Hard various sites of different activity on the same solid acid,
acids correspond roughly in their behavior to Schwarzen- the change in activity with temperature, and the difficulty
bach and Chatt’s class a acids. They are characterized of knowing the precise structure of the catalyst are some of
by small acceptor atoms that have outer electrons that the major handicaps in the determination of the strength
are not easily excited and that bear a considerable pos- of solid superacids.
itive charge. Soft acids, which correspond to class b acids,
have acceptor atoms of a lower positive charge and a large
size, with easily excited outer electrons. Hard and soft II. SUPERACID SYSTEMS
bases are defined accordingly. Pearson’s HSAB principle
states that hard acids prefer to bind to hard bases and soft Following Conant’s early work, the field of superacids,
acids prefer to bind to soft bases. The principle has proved which had been dormant till the late 1950s, started to un-
useful in rationalizing and classifying a large number of dergo rapid development in the early 1960s, involving the
chemical reactions involving acid–base interactions in a discovery of new systems and an understanding of their
qualitative manner, but it gives no basis for quantitative nature as well as their chemistry. As mentioned, superacids
treatment. encompass both Brönsted and Lewis types and their con-
Many attempts have been made in the literature to jugate combinations.
rate qualitatively the activity of Lewis acid catalysts in
A. Brönsted Superacids
Friedel–Crafts-type reactions. However, such ratings de-
pend largely on the nature of the reaction for which the Using Gillespie’s arbitrary definition, Brönsted superacids
Lewis acid catalyst is employed. are those with an acidity exceeding that of 100% sulfuric
Thus, the classification of Lewis superacids as those acid (H0 , −12). These include perchloric acid (HClO4 ),
stronger than anhydrous aluminum trichloride is only ar- fluorosulfuric acid (FSO3 H), trifluoromethanesulfonic
bitrary. Just as in the case of Gillespie’s classification of acid (CF3 SO3 H), and higher perfluoroalkanesulfonic acid
Brönsted superacids, it is important to recognize that acids (Cn Fn +2 SO3 H). Physical properties of some of the most
stronger than conventional Lewis acid halides exit, with commonly used superacids are listed in Table I.
increasingly unique properties. Studies by Gillespie have shown that truly anhydrous
Another area of difficulty is measuring the acid strength hydrogen fluoride (HF), which is extremely difficult to
of solid superacids. Since solid superacid catalysts are obtain in the pure form, has a Hammett acidity constant
used extensively in the chemical industry, particularly in (H0 ) of −15.1 rather than the −11.0 found for the usual
the petroleum field, a reliable method for measuring the anhydrous acid. However, traces of water impurity drop
acidity of solids would be extremely useful. The main the acidity to the generally observed value. Thus for prac-
difficulty to start with is that the activity coefficients for tical purposes, hydrogen fluoride, which always contains
solid species are unknown and thus no thermodynamic some water impurity, is not discussed here, as its acidity
acidity function can be properly defined. On the other of H0 = −11.0 is lower than that of H2 SO4 .
hand, because the solid by definition is heterogeneous, Teflic acid (TeF5 OH) has been suggested to have
acidic and basic sites can coexist with variable strength. an acidity comparable to that of fluorosulfuric acid.
The surface area available for colorimetric determinations However, no concrete acidity measurements are available
may have acidic properties widely different from those of to support such a claim. A number of carbocationic
the bulk material; this is especially true for well-structured salts bearing carborane anions [CB11 H6 Cl− 6 , etc.] have
solids such as zeolites. been studied. However, their parent Bronsted acids,
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178 Superacids

TABLE I Physical Properties of Brönsted Superacids

Property HClO4 ClSO3 H HSO3 F CF3 SO3 H

Melting point (◦ C) −112 −81 −89 −34

Boiling point (◦ C) 110 151–152 162.7 162
(Explosive) (Decomposing)
Density (25◦ C), g/cm3 1.767a 1.753 1.726 1.698
Viscosity (25◦ C), cP — 3.0b 1.56 2.87
Dielectric constant — 60 ± 10 120
Specific conductance — 0.2–0.3 × 10−3 1.1 × 10−4 2.0 × 10−4
(20◦ C), −1 · cm−1
−H0 (neat) ≈13.0 13.8 15.1 14.1
a At 20◦ C.
b At 15◦ C.

which can be considered as potential superacids, are still bond. It is prepared by the direct combination of sulfur tri-
unknown. oxide and dry hydrogen chloride gas. The reaction is very
exothermic and reversible, making it difficult to obtain
1. Perchloric Acid (HClO4 ) chlorosulfuric acid free of SO3 and HCl. On distillation,
Commercially, perchloric acid is manufactured by either even in a good vacuum, some dissociation is inevitable.
reaction of alkali perchlorates with hydrochloric acid or The acid is a powerful sulfating and sulfonating agent as
direct electrolytic oxidation of 0.5 N hydrochloric acid. well as a strong dehydrating agent and a specialized chlo-
Another commercially attractive method is the direct elec- rinating agent. Because of these properties, chlorosulfuric
trolysis of chlorine gas (Cl2 ) dissolved in cold, dilute per- acid is rarely used for its protonating superacid properties.
chloric acid. Perchloric acid is commercially available in a Gillespie and co-workers have measured systematically
concentration of 70% (by weight) in water, although 90% the acid strength of the H2 SO4 –ClSO3 H system using aro-
perchloric acid also had limited availability (due to its ex- matic nitro compounds as indicators. They found an H0
plosive hazard, it is no longer provided at this strength); value of −13.8 for 100% ClSO3 H.
for 70–72% HClO4 , an azeotrope of 28.4% H2 O, 71.6%
HClO4 , boiling at 203◦ C is safe for usual applications. It 3. Fluorosulfuric Acid (HSO3 F)
is a strong oxidizing agent, however, and must be handled Fluorosulfuric acid, HSO3 F, is a mobile colorless liquid
with care. Anhydrous acid (100% HClO4 ) is prepared by that fumes in moist air and has a sharp odor. It may be
vacuum distillation of the concentrated acid solution with regarded as a mixed anhydride of sulfuric and hydroflu-
a dehydrating agent such as Mg(ClO4 )2 . It is stable only oric acid. It has been known since 1892 and is prepared
at low temperatures for a few days, decomposing to give commercially from SO3 and HF in a stream of HSO3 F. It
HClO4 · H2 O (84.6% acid) and ClO2 . is readily purified by distillation, although the last traces
Perchloric acid is extremely hygroscopic and a very of SO3 are difficult to remove. When water is excluded,
powerful oxidizer. Contact of organic materials with an- it may be handled and stored in glass containers, but for
hydrous or concentrated perchloric acid can lead to violent safety reasons the container should always be cooled be-
explosions. For this reason, the application of perchloric fore opening because gas pressure may have developed
acid has serious limitations. The acid strength, although from hydrolysis.
not reported, can be estimated to be around H0 = −13 for
the anhydrous acid. HSO3 F + H2 O 
 H2 SO4 + HF
Although various cation salts can be prepared with per- Fluorosulfuric acid generally also contains hydrogen
chlorate gegen ions, the ionic salts tend to be unstable (ex- fluoride as an impurity, but according to Gillespie the
plosive) due to their equilibria with covalent perchlorates. hydrogen fluoride can be removed by repeated distillation
The main use of perchloric acid is in the preparation of under anhydrous conditions. The equilibrium HSO3 F  
its salts, such as NH+ −
4 ClO4 , a powerful oxidant in rocket SO3 + HF always produces traces of SO3 and HF in stored
fuels and pyrotechniques. HSO3 F samples. When kept in glass for a long time, SiF4
and H2 SiF6 are also formed (secondary reactions due
2. Chlorosulfuric Acid (ClSO3 H)
to HF).
Chlorosulfuric acid, the monochloride of sulfuric acid, is Fluorosulfuric acid is employed as a catalyst and
a strong acid containing a relatively weak sulfur–chlorine chemical reagent in various chemical processes including
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Superacids 179

alkylation, acylation, polymerization, sulfonation, isome- TABLE II Characteristics of Perfluoroalkanesulfonic Acids

rization, and production of organic fluorosulfates. It is bp (◦ C) Density H0
insoluble in carbon disulfide, carbon tetrachloride, chloro- Compound (760 mm Hg) (25◦ C) (22◦ C)
form, and tetrachloroethane, but it dissolves most organic
compounds that are potential proton acceptors. The acid CF3 SO3 H 161 1.70 −14.1
can be dehydrated to give S2 O5 F2 . Electrolysis of fluoro- C2 F5 SO3 H 170 1.75 −14.0
sulfuric acid gives S2 O6 F2 or SO2 F2 + F2 O, depending C4 F9 SO3 H 198 1.82 −13.2
on the conditions employed. C5 F11 SO3 H 212
HSO3 F has a wide liquid range (mp = −89◦ C, bp = C6 F13 SO3 H 222 −12.3
+162.7◦ C), making it advantageous as a superacid solvent C8 F17 SO3 H 249
241
for the protonation of a large variety of weak bases.

4. Trifluoromethanesulfonic Acid (CF3 SO3 H)

257
Trifluoromethanesulfonic acid (CF3 SO3 H, triflic acid), the
first member in the perfluoroalkanesulfonic acid series,
has been studied extensively. Besides its preparation by
electrochemical fluorination of methanesulfonyl halides,
triflic acid may also be prepared from trifluoromethane- heptane, carbon tetrachloride, and perfluorinated liquids.
sulfenyl chloride. Many of the perfluoroalkanesulfonic acids have been pre-
Cl2 Cl2 pared by the electrochemical fluorination reaction of the
CF3 SSCF3 −→ CF3 SCl −→ CF3 SO2 Cl corresponding alkanesulfonic acids (or conversion of the
H2 O
corresponding perfluoroalkane iodides to their sulfonyl
aq. KOH
−−−→ CF3 SO3 H halides). α,ω-Perfluoroalkanedisulfonic acids have been
prepared by aqueous alkaline permanganate oxidation of
CF3 SO3 H is a stable, hygroscopic liquid that fumes in the compounds, Rf SO2 (CF2 CF2 )n –SO2 F. C8 F17 SO3 H and
moist air and readily forms the stable monohydrate (hy- higher perfluoroalkanesulfonic acids are surface-active
dronium triflate), which is a solid at room temperature agents and form the basis for a number of commercial
(mp, 34◦ C; bp, 96◦ C/1 mm Hg). The acidity of the neat fluorochemical surfactants.
acid as measured by UV spectroscopy with a Hammett
indicator indeed shows an H0 value of −14.1. It is mis-
cible with water in all proportions and soluble in many B. Lewis Superacids
polar organic compounds, such as dimethylformamide, Lewis superacids are arbitrarily defined as those stronger
dimethylsulfoxide, and acetonitrile. It is generally a very than anhydrous aluminum trichloride, the most commonly
good solvent for organic compounds that are capable of used Friedel–Crafts catalyst. Some of the physical prop-
acting as proton acceptors in the medium. The exceptional erties of the commonly used Lewis superacids are given
leaving-group properties of the triflate anion, CF3 SO− 3, in Table III.
make triflate esters excellent alkylating agents. The acid
and its conjugate base do not provide a source of fluoride 1. Antimony Pentafluoride (SbF5 )
ion even in the presence of strong nucleophiles. Further-
more, as it lacks the sulfonating properties of oleums an Antimony pentafluoride is a colorless, highly viscous liq-
HSO3 F, it has gained a wide range of application as a uid at room temperature. Its viscosity is 460 cP at 20◦ C,
catalyst in Friedel–Crafts alkylation, polymerization, and which is close to that of glycerol. The pure liquid can be
organometallic chemistry. handled and distilled in glass if moisture is excluded.

5. Higher Homologous TABLE III Physical Properties of Some Lewis Superacids

Perfluoroalkanesulfonic Acids
Property SbF5 AsF5 TaF5 NbF5 B(OSO2 CF3 )3
Higher homologous perfluoroalkanesulfonic acids (see
mp (◦ C) 7.0 −79.8 97 72–73 43–45
Table II) are hygroscopic oily liquids or waxy solids. They
bp (◦ C) 142.7 −52.8 229 236 68–83 (0.5 Torr)
are prepared by the distillation of their salts from H2 SO4 ,
Specific gravity 3.145 2.33a 3.9 2.7 —
giving stable hydrates that are difficult to dehydrate. The
at 15◦ C (g/cc)
acids show the same polar solvent solubilities as trifluo-
romethanesulfonic acid but are quite insoluble in benzene, a At the bp.
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180 Superacids

The polymeric structure of the liquid SbF5 has been es- ciation, but it is a monomeric covalent compound with
tablished by 19 F NMR spectroscopy and is shown to have a high degree of coordinating ability. It is prepared by
the following frameworks: a cis-fluorine bridged structure reacting fluorine with arsenic metal or arsenic trifluo-
is found in which each antimony atom is surrounded by ride. As a strong Lewis acid fluoride, it is used in the
six fluorine atoms in an octahedral arrangement. preparation of ionic complexes and, in conjunction with
Brönsted acids, forms conjugate superacids. It also forms,
with graphite, stable intercalation compounds that show an
electrical conductivity comparable to that of silver. Great
care should be exercised in handling any arsenic com-
pound because of its potential high toxicity.

3. Tantalum and Niobium Pentafluoride

The close similarity of the atomic and ionic radii of nio-
Antimony pentafluoride is a powerful oxidizing and a bium and tantalum are reflected by the similar properties of
moderate fluorinating agent. It readily forms stable inter- tantalum and niobium pentafluorides. They are thermally
calation compounds with graphite, and it spontaneously stable white solids that may be prepared either by the di-
inflames phosphorus and sodium. It reacts with water rect fluorination of the corresponding metals or by reacting
to form SbF5 · 2H2 O, an unusually stable solid hydrate the metal pentachlorides with HF. Surprisingly, even re-
(probably a hydronium salt, H3 O+ SbF5 OH) that reacts acting metals with HF gives the corresponding pentaflu-
violently with excess water to form a clear solution. orides.They both are strong Lewis acids, complexing a
Slow hydrolysis can be achieved in the presence of dilute wide variety of donors such ethers, sulfides, amines, and
NaOH and forms Sb(OH)− 6 . Sulfur dioxide and nitrogen halides. They both coordinate with fluoride ions to form
dioxide form 1:1 adducts, SbF5 :SO2 and SbF5 :NO2 , as anions of the type (MF6 )− . TaF5 is a somewhat stronger
do practically all nonbonded electron-pair donor com- acid than NbF5 , as shown by acidity measurements in HF.
pounds. The exceptional ability of SbF5 to complex and The solubility of TaF5 and NbF5 in HF and HSO3 F is much
subsequently ionize nonbonded electron-pair donors more limited than that of SbF5 or other Lewis acid fluo-
(such as halides, alcohols, ethers, sulfides, and amines) to rides, restricting their use to some extent. At the same time,
carbocations, first recognized by Olah in the early 1960s, their high redox potentials and more limited volatility
has made in one of the most widely used Lewis halides in make them catalysts of choice in certain hydrocarbon con-
the study of cationic intermediates and catalytic reactions. versions, particularly in combination with solid catalysts.
Vapor density measurements suggest a molecular asso-
ciation corresponding to (SbF5 )3 at 150◦ C and (SbF5 )2 at 4. Boron tris(Trifluoromethanesulfonate)
250◦ C. On cooling, SbF5 gives a nonionic solid composed [B(OSO2 CF3 )3 ]
of trigonal bipyramidal molecules. Antimony pentafluo-
Boron tris (trifluoromethanesulfonate) was first prepared
ride is prepared by the direct fluorination of antimony
by Engelbrecht and Tschager in trifluoromethanesulfonic
metal or antimony trifluoride (SbF3 ). It can also be pre-
acid solution (vide infra) as a conjugate acid system. Olah
pared by the reaction of SbCl5 with anhydrous HF, but the
and co-workers have isolated B(OSO2 CF3 )3 in pure form
exchange of the fifth chloride is difficult, and the product
by treating boron trihalides (chlorides, bromides) with 3
is generally SbF4 Cl.
equiv of triflic acid in Freon 113 or SO2 ClF solution.
As shown by conductometric, cryoscopic, and related
acidity measurements, it appears that antimony pentaflu- BX3 + 3CF3 SO3 H → B(OSO2 CF3 )3 + 3HX
oride is by far one of the strongest Lewis acids known.
Boron tris(trifluoromethanesulfonate) is a colorless
Antimony pentafluoride is also a strong oxidizing agent,
low-melting compound [mp, 43–45◦ C; bp, 68–73◦ C
allowing, for example, preparation of arene dications. At
(0.5 Torr)] which decomposes on heating above 100◦ C at
the same time, its easy reducibility to antimony trifluoride
atmospheric pressure. It is extremely hygroscopic
represents a limitation in many applications, although it
and is readily soluble in methylene chloride, 1,1,2-
can be easily refluorinated.
trifluorotrichloroethane (Freon 113), SO2 , and SO2 ClF.
Boron tris(trifluoromethanesulfonate) is a strong nonoxi-
2. Arsenic Pentafluoride (AsF5 )
dizing Lewis acid and an efficient Friedel–Crafts catalyst.
Arsenic pentafluoride (AsF5 ) is a colorless gas at room Apart from the discussed Lewis acids, other highly
temperature, condensing to a yellow liquid at −53◦ C. Va- acidic systems such as Au(OSO2 F)3 , Ta(OSO2 F)5 ,
por density measurements indicate some degree of asso- Pt(OSO2 F)4 , and Nb(OSO2 F)5 have been reported as
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Superacids 181

+ −
their conjugate acids in HSO3 F solution. All the above HB(HSO4 )4 + H2 SO4 
 H3 SO4 + B(HSO4 )4
conjugate superacids were found to be highly conducting
and strongly ionizing over the entire conecentration range. The increase in acidity is, however, limited to H0 = −13.6
as a result of insoluble complexes that precipitate when
C. Conjugate Brönsted–Lewis Superacids the concentration of the boric acid approaches 30 mol%.

1. Oleums: Polysulfuric Acids

3. Fluorosulfuric Acid–Antimony
SO3 -containing sulfuric acid (oleum) has long been con- Pentafluoride (Magic Acid)
sidered the strongest mineral acid and one of the earliest
Of all superacids, “Magic Acid,” a mixture of fluorosulfu-
superacid systems to be recognized. The concentration of
ric acid and antimony pentafluoride, is probably the most
SO3 in sulfuric acid can be determined by weight or by
widely used medium for the spectroscopic observation
electrical conductivity measurement. The most accurate
of stable carbocations. The fluorosulfuric acid–antimony
H0 values for oleums so far have been published by
pentafluoride system was developed in the early 1960s by
Gillespie and co-workers (Table IV).
Olah for the study of stable carbocations and was studied
The increase in acidity on the addition of SO3 to sulfuric
by Gillespie for electron-deficient inorganic cations. The
acid is substantial, and an H0 value of −14.5 is reached
name Magic Acid originated in Olah’s laboratory at Case
with 50 mol% SO3 . The main component up to this SO3
Western Reserve University in the winter of 1966. The
concentration is pyrosulfuric (or disulfuric) acid H2 S2 O7 .
HSO3 F:SbF5 mixture was used extensively by his group
On heating or in the presence of water, it decomposes and
to generate stable carbocations. J. Lukas, a German post-
behaves like a mixture of sulfuric acid and sulfur trioxide.
doctoral fellow, put a small piece of Christmas candle left
In sulfuric acid, it ionizes as a stronger acid:
over from a lab party into the acid system and found that it
+ −
H2 S2 O7 + H2 SO4 
 H3 SO4 + HS2 O7 dissolved readily. He then ran a 1 H NMR spectrum of the
(K = 1.4 × 10−2 ) solution. To everybody’s amazement, he obtained a sharp
spectrum of the t-butyl cation. The long-chain paraffin,
At higher SO3 concentrations, a series of higher polysul- of which the candle was made, had obviously undergone
furic acids such as H2 S3 O10 and H2 S4 O13 is formed and a extensive cleavage and isomerization to the more stable
corresponding increase in acidity occurs. However, as can tertiary ion. It impressed Lukas and others in the labora-
be seen from Table IV, the acidity increase is very small tory so much that they started to nickname the acid system
after reaching 50 mol% of SO3 , and no data are available Magic Acid. The name stuck, and soon others started to
beyond 75%. use it too. It is now a registered trade name and has found
Despite its high acidity, oleum has found little applica- its way into the chemical literature.
tion as a superacid catalyst, mainly because of its strong The acidity of the Magic Acid system as a function
oxidizing power. Also, its high melting point and viscos- of the SbF5 content has been measured successively by
ity have considerably hampered its use for spectroscopic Gillespie, Sommer, Gold, and their co-workers. The in-
study of ionic intermediates and in synthesis, except as an crease in acidity is very sharp at a low SbF5 concentra-
oxidizing or sulfonating agent. tion (≈10%) and continues up to the estimated value of
H0 = −26.5 for a 90% SbF5 content.
2. Tetra(hydrogensulfato)Boric
The initial ionization of HSO3 F:SbF5 is as follows.
Acid–Sulfuric Acid
HB(HSO4 )4 prepared by treating boric acid [B(OH)3 ] with  H2 SO3 F+ + SbF5 (SO3 F)−
2HSO3 F + SbF5 
sulfuric acid ionizes in sulfuric acid as shown by acidity At higher concentrations of SbF5 , complex polyantimony
measurements. fluorosulfate ions are formed.

TABLE IV H0 Values for the H2 SO4 –SO3 System SbF5 + SbF5 (SO3 F)− 
 Sb2 F10 (SO3 F)−
Mol% SO3 H0 Mol% SO3 H0 Mol% SO3 H0 Due to these equilibria, the composition of the HSO3 F:
SbF5 system is very complex and depends on the SbF5 con-
1.00 −12.24 25.00 −13.58 55.00 −14.50
tent. Aubke and co-workers have investigated the struc-
2.00 −12.42 30.00 −13.76 60.00 −14.74
tures of complex anions in the Magic Acid system by
5.00 −12.73 35.00 −13.94 65.00 −14.84
modern 19 F NMR studies.
10.00 −13.03 40.00 −14.11 70.00 −14.92
The major reason for the wide application of the Magic
15.00 −13.23 45.00 −14.28 75.00 −14.90
Acid system compared with others (besides its very high
20.00 −13.41 50.00 −14.44
acidity) is probably the large temperature range in which
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182 Superacids

it can be used. In the liquid state, NMR spectra have been is the H3 F+ +
2 ions. The H2 F ion is observed only in highly
recorded from temperatures as low as −160◦ C (acid di- concentrated solutions (40–100 mol% SbF5 ), contrary to
luted with SO2 F2 and SO2 ClF) and up to +80◦ C (neat the widespread belief that it is the only proton-solvated
acid in a sealed NMR glass tube). Glass is attacked by the species in HF:SbF5 solutions.
acid very slowly when moisture is excluded. The Magic Ionization in dilute HF solutions of SbF5 (1–20% SbF5 )
Acid system can also be an oxidizing agent that results in is thus
reduction to antimony trifluoride and sulfur dioxide. On
− +
occasion this represents a limitation. SbF5 + 3HF 
 SbF6 + H3 F2

The structure of the hexafluoroantimonate and of its

4. Fluorosulfuric Acid–Sulfur Trioxide higher homologous anions Sb2 F− −
11 and Sb3 F16 , which are
Freezing-point and conductivity measurements have formed when the SbF5 content is increased, have been
shown that SO3 behaves as a nonelectrolyte in HSO3 F. determined by 19 F NMR studies.
Acidity measurements show a small increase in acidity
that is attributed to the formation of polysulfuric acids
HS2 O6 F and HS3 O9 F up to HS7 O21 F. The acidity of these 7. HSO3 F:HF:SbF5
solutions reaches a maximum of −15.5 on the H0 scale When Magic Acid is prepared from fluorosulfuric acid not
for 4 mol% SO3 and does not increase any further. carefully purified (which always contains HF), on addition
of SbF5 the ternary superacid system HSO3 F:HF:SbF5 is
5. Fluorosulfuric Acid–Arsenic Pentafluoride formed. Because HF is a weaker Brönsted acid, it ionizes
fluorosulfuric acid, which, on addition of SbF5 , results in
AsF5 ionizes in FSO3 H, and the AsF5 FSO− 3 anion has an a high-acidity superacid system at low SbF5 concentra-
octahedral structure. The H0 acidity function increases up tions. 19 F NMR studies on the system have indicated the
to 5 mol% AsF5 , with a value of −16.6. presence of SbF− −
6 and Sb2 F11 anions, although these can
result from the disproportionality of SbF5 (FSO3 )− and
6. Hydrogen Fluoride–Antimony Pentafluoride Sb2 F10 (FSO3 )− anions.
(Fluoroantimonic Acid)
The HF:SbF5 (fluoroantimonic acid) system is considered 8. HSO3 F:SbF5 :SO3
the strongest liquid superacid and also the one that has the
widest acidity range. Due to the excellent solvent proper- When sulfur trioxide is added to a solution of SbF5
ties of hydrogen fluoride, HF:SbF5 is used advantageously in HSO3 F, there is a marked increase in conductivity
for a variety of catalytic and synthetic applications. An- that continues until approximately 3 mol of SO3 has
hydrous hydrogen fluoride is an excellent solvent for or- been added per mol of SbF5 . This increase in conduc-
ganic compounds with a wide liquid range. The acidity tivity has been attributed to an increase in H2 SO3 F+
of HF, initially estimated as H0 ≈ −11, has now been re- concentration arising from the formation of a much
vised to an H0 of −15.1 for highly purified anhydrous HF. stronger acid than Magic Acid. Acidity measurements
A dramatic increase in acidity (H0 ≈ −20.5) is observed have confirmed the increase in acidity with SO3 :SbF5
when 1 mol% SbF5 is added to anhydrous HF. The initial in the HSO3 F system. This has been attributed to the
sharp increase in acidity is apparently due to the removal presence of a series of acids of the type H[SbF4 (SO3 F)2 ],
of residual moisture impurity. For more concentrated so- H[SbF3 (SO3 F)3 ], H[SbF2 (SO3 F)4 ] of increasing acidity.
lutions, only kinetic data are available, mainly from the Of all the fluorosulfuric acid-based superacid systems,
work of Brouwer and co-workers, who estimated the rel- sulfur trioxide-containing acid mixtures are, however,
ative acidity ratio of 1:1 HF:SbF5 and 5:1 HSO3 F:SbF5 to difficult to handle and cause extensive oxidative side
be 5 × 108 :1. This means an H0 value in excess of −30 reactions on contact with organic compounds.
on the Hammett scale for the 1:1 composition. The acidity
may increase still further for higher SbF5 concentrations.
9. HSO3 F–Nb(SO3 F)5 and HSO3 H–Ta(SO3 F)5
It has been shown by infrared measurements that an 80%
SbF5 solution has the maximum concentration of H2 F+ . The in situ oxidation of niobium and tantalum metals in
In any case, even for the composition range of 1–50% HSO3 F by bis(fluorosulfuryl)peroxide, S2 O6 F2 , gives the
SbF5 , this is the largest range of acidity known. The solvated Lewis acids M(SO3 F)5 , M = Nb or Ta. These acid
same infrared study has also shown that the predominant systems have been shown to be highly acidic by conduc-
cationic species (i.e., solvated proton) in 0–40 mol% SbF5 tivity studies.
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Superacids 183

10. HSO3 F–Au(SO3 F)3 and HSO3 F–Pt(SO3 F)4 tion studies indicate that the HF:TaF5 system is a weaker
superacid than HF:SbF5 .
These superacids based on gold and platinum have been
developed. They show a high acidity and good thermal
stability. However, the high cost of the metals involved 13. Hydrogen Fluoride–Boron Trifluoride
precludes their widespread use. (Tetrafluoroboric Acid)
Boron trifluoride ionizes anhydrous HF as follows:
−
11. Perfluoroalkanesulfonic Acid-Based Systems  BF4 + H2 F+
BF3 + 2HF 
a. CF3 SO3 H:SbF5 . CF3 SO3 H:SbF5 (n = 1) was in- The stoichiometric compound exists only in an excess
troduced by Olah as an effective superacid catalyst for iso- of HF or in the presence of suitable proton acceptors. The
merizations and alkylations. The composition and acidity HF:BF3 (fluoroboric acid)-catalyzed reactions cover many
of systems where n = 1, 2, 4 have been studied by Com- of the Friedel–Crafts type reactions. One of the main ad-
meyras and co-workers. The change in composition of the vantages of this system is the high stability of HF and BF3
triflic acid–antimony pentafluoride system depending on and their nonoxidizing nature. Both are gases at room
the SbF5 content has been studied. For the 1:1 composi- temperature and are easily recovered from the reaction
tion, the main counteranion is [CF3 SO3 SbF5 ]− , and for mixtures. Acidity measurements of the HF:BF3 system
the 1:2 composition [CF3 SO3 (Sb2 F11 )]− is predominant. have been limited to electrochemical determinations, and
With increasing SbF5 concentration, the anionic species a 7 mol% BF3 solution was found to have an acidity of
grow larger and anions containing up to 5 SbF5 units H0 = −16.6. This indicates that BF3 is a much weaker
have been found. In no circumstances could free SbF5 be Lewis acid compared with either SbF5 or TaF5 . Never-
detected. theless, the HF:BF3 system is strong enough to proto-
nate many weak bases and is an efficient and widely used
b. CF3 SO3 H:B(SO3 CF3 )3 . The acidity of triflic acid catalyst.
can also be substantially increased by the addition of boron
triflate B(OSO2 CF3 )3 as indicated by Engelbrecht and 14. Conjugate Friedel–Crafts Acids
Tschager. The increase in acidity is explained by the ion- (HBr:AIBr3 , HCl:AICl3 , Etc.)
ization equilibrium:
The most widely used Friedel–Crafts catalyst systems are
B(OSO2 CF3 )3 + 2HSO3 CF3 HCl:AlCl3 and HBr:AlBr3 . These systems are indeed su-
+
 2HSO3 CF3 + − B(SO3 CF3 )4
 peracids by Gillespie’s definition. However, experiments
directed toward preparation from aluminium halides and
The measurements were limited due to the lack of a hydrogen halides of the composition HAlX4 were unsuc-
suitable indicator base, and even 1,3,5-trinitrobenzene the cessful in providing evidence that such conjugate acids
weakest base used, was fully protonated (H0 ≈ −18.5) in are formed in the absence of proton acceptor bases.
a 22 mol% solution of boron triflate. The acid system
has found many synthetic applications, due mainly to the
efforts of Olah and co-workers. D. Solid Superacids
The acidic sites of solid acids may be of either the Brönsted
(proton donor, often OH group) or the Lewis type (electron
12. Hydrogen Fluoride–Tantalum Pentafluoride
acceptor). Both types have been identified by IR studies of
HF:TaF5 is a catalyst for various hydrocarbon conversions solid surfaces absorbed with pyridine. Various solids dis-
of practical importance. In contrast to antimony pentaflu- playing acidic properties, whose acidities can be enhanced
oride, tantalum pentafluoride is stable in a reducing en- to the superacidity range, are listed in Table V.
vironment. The HF:TaF5 superacid system has attracted
attention mainly through the studies concerning alkane
1. Immobilized Superacids
alkylation and aromatic protonation. Generally, heteroge-
(Bound to Inert Supports)
neous mixtures such as 10:1 and 30:1 HF:TaF5 have been
used because of the low solubility of TaF5 in HF (0.9% Ways have been found to immobilize and/or to bind su-
at 19◦ C and 0.6% at 0◦ C). For this reason, acidity mea- peracidic catalysts to an otherwise inert solid support.
surements have been limited to very dilute solutions, and These include graphite intercalated superacids. Graphite
an H0 value of −18.85 has been found for the 0.6% solu- possessing a layered structure can form intercalation com-
tion. Both electrochemical studies and aromatic protona- pounds with Lewis acids such as AsF5 and SbF5 . These
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184 Superacids

TABLE V Solid Acids III. APPLICATION OF SUPERACIDS

1. Natural clay minerals: kaolinite, bentonite, attapulgite,
montmorillonite, clarit, Fuller’s earth, zeolites, synthetic clays or A. Preparation of Stable
zeolites Trivalent Carbocations
2. Metal oxides and sulfides: ZnO, CdO, Al2 O3 , CeO2 , ThO2 , TiO2 ,
ZrO2 , SnO2 , PbO, As2 O3 , Bi2 O3 , Sb2 O5 , V2 O5 , Cr2 O3 , MoO3 , Superacids such as Magic Acid and fluoroantimonic acid
WO3 , CdS, ZnS have made it possible to prepare stable, long-lived carbo-
3. Metal salts: MgSO4 , CaSO4 , SrSO4 , BaSO4 , CuSO4 , ZnSO4 , cations, which are too reactive to exist as stable species in
CdSO4 , Al2 (SO4 )3 , FeSO4 , Fe2 (SO4 )3 , CoSO4 , NiSO4 , Cr2 (SO4 )3 , more basic solvents. Stable superacidic solutions of a large
KHSO4 , (NH4 )2 SO4 , Zn(NO3 )2 , Ca(NO3 )2 , K2 SO4 , Bi(NO3 )3 ,
variety of carbocations, including trivalent cations (also
Fe(NO3 )3 , CaCO3 , BPO4 , AlPO4 , CrPO4 , FePO4 , Cu3 (PO4 )2 ,
Zn3 (PO4 )2 , Mg3 (PO4 )2 , Ti3 (PO4 )4 , Zr3 (PO4 )4 , Ni3 (PO4 )2 , AgCl, called carbenium ions) such as t-butyl cation 1 (trimethyl-
CuCl, CaCl2 , AlCl3 ,TiCl3 , SnCl2 , CaF2 , BaF2 , AgClO4 , Mg(ClO4 )2 carbenium ion) and isopropyl cation 2 (dimethylcarbe-
4. Mixed oxides: SiO2 :Al2 O3 , SiO2 :TiO2 , SiO2 :SnO2 , SiO2 :ZrO2 , nium ion), have been obtained. Some of the carbocations,
SiO2 :BeO, SiO2 :MgO, SiO2 :CaO, SiO2 :SrO, SiO2 :ZnO, as well as related acyl cations and acidic carboxonium ions
SiO2 :Ga2 O3 , SiO2 :Y2 O3 , SiO2 :La2 O3 , SiO2 :MoO3 , SiO2 :WO3 , and other heteroatom stabilized carbocations, that have
SiO2 :V2 O5 , SiO2 :ThO2 , Al2 O3 :MgO, Al2 O3 :ZnO, Al2 O3 :CdO,
been prepared in superacidic solutions or even isolated
Al2 O3 :B2 O3 , Al2 O3 :ThO2 , Al2 O3 :TiO2 , Al2 O3 :ZrO2 , Al2 O3 :V2 O5 ,
Al2 O3 :MoO3 , Al2 O3 :WO3 , Al2 O3 :Cr2 O3 , Al2 O3 :Mn2 O3 , from them as stable salts are shown in Fig. 1.
Al2 O3 :Fe2 O3 , Al2 O3 :Co3 O4 , Al2 O3 :NiO, TiO2 :CuO, TiO2 :MgO, CH3 H
TiO2 :ZnO, TiO2 :CdO, TiO2 :ZrO2 , TiO2 :SnO2 , TiO2 :Bi2 O3 ,
TiO2 :Sb2 O5 , TiO2 :V2 O5 , TiO2 :Cr2 O3 , TiO2 :MoO3 , TiO2 :WO3 ,  
C C
TiO2 :Mn2 O3 , TiO2 :Fe2 O3 , TiO2 :Co3 O4 , TiO2 :NiO, ZrO2 :CdO,
ZnO:MgO, ZnO:Fe2 O3 , MoO3 :CoO:Al2 O3 , MoO3 :NiO:Al2 O3 , H3C CH3 H3C CH3
TiO2 :SiO2 :MgO, MoO3 :Al2 O3 :MgO 1 2
5. Cation-exchange resins, polymeric perfluorinated resinsulfonic acids
6. Heteropolyacids (Keggin type) Spectroscopic techniques such as 1 H and 13 C NMR, in-
7. Bis(perfluorosulfonyl)imides, bis- and tris(trifluoromethylsulfonyl) frared, ultraviolet, and X-ray photoelectron spectroscopy
methanes have been employed to characterize carbocations. In many
cases cation salts can be isolated with the superacid gegen
ion, and some of them are structurally characterized by
intercalates are not very stable, however, as the Lewis acid X-ray crystallography.
tends to leach out. Similar intercalates have been obtained
with other Lewis acids such as AlCl3 , AlBr3 , NbF5 , and
B. Aromatic and Homoaromatic
TaF5 and conjugate acid systems such as HF:SbF5 .
Cations and Carbodications
Flourine-complexed acids such as SbF5 -fluorinated
graphite and SbF− 5 -fluorinated alumina have been used According to Hückel’s (4n + 2) electron rule, if a carboca-
for hydrocarbon isomerizations. tion has an aromatic character, it is stabilized by resonance.

 
 RHX ROH2 
RH2 R2OH
 
ArH2 RCHCH3
RX ROH
RH R2O
ArH RCHCH2
 R2CO RSH 
R2C OH RSH2
HSO3F-SbF5
 RCHO R2S 
RCH OH or HF-SbF5 R2SH
(RO)2CO RCOOH
X 
R RCOOH2
RCONR2 RCOOR′ R2CX2 X∆
 
(RO)2C OH  R RCOH2O
RCONR2   X 

H RCOOR′ R2CX R
H
R
FIGURE 1 Some ways of generating carbocations generated in superacids.
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Superacids 185

FIGURE 2 Aromatically stabilized cations and dications and

some bridgehead dications.
FIGURE 3 Degenerate classical (carbenbium) and nonclassical
(carbonium) carbocations.
Some aromatically stabilized Hückeloid systems gener-
ated in superacid media along with some carbodications as ethers, amines, and sulfides) but also weak σ -electron
are shown in Fig. 2. donors such as saturated hydrocarbons including the
parent alkane and methane are protonated. The ability of
C. Static-Bridged or Equilibrating Carbocations superacids to protonated saturated hydrocarbons (alkanes)
rests on the ability of the two-electron, two-center cova-
Some carbocations tend to undergo fast degenerated re- lent bond to share its bonded electron pair with empty
arrangements through intramolecular hydrogen or alkyl orbitals ( p or s) of a strongly electron-deficient reagent
shifts to the related identical (degenerate) structures. The such as a protic acid:
question arises whether these processes involve equilibra-
tions between limiting “classical” ion intermediates (triva- H
lent carbenium ions), whose structures can be adequately R–H  H R
H
described by using only Lewis-type two-electron, two-
center bonds separated by low-energy transition states, or Superacids are suitable reagents for chemical transforma-
whether intermediate “nonclassical” hydrogen- or alkyl- tion, particularly of hydrocarbons.
bridged carbonium ions (higher coordinate carbonium
ions) are involved, which also require the presence of two- E. Isomerization
electron bonds between three or more centers for their de-
The isomerization of hydrocarbons is of practical impor-
scription. It is difficult to answer this question by NMR
tance. Isomeric dialkylbenzenes, such as xylenes, are start-
spectroscopy because of its slow time scale; however,
ing materials for plastics and other products. Generally, the
NMR has been used to delineate structures where degen-
need is for only one of the possible isomers, and thus there
erate rearrangements lead to averaged shifts and coupling
is a potential for intraconversion (isomerization). Straight-
constants.
chain alkanes with five to eight carbon atoms have con-
Solid-state 13 C NMR (using cross-polarization magic-
siderably lower octane numbers than their branched iso-
angle spinning techniques), isotopic substitution, and
mers, and hence there is a need for higher-octane branched
faster methods such as infrared, Raman, and, especially,
isomers. Isomerizations are generally carried out under
X-ray photoelectron spectroscopy (ESCA) are particularly
thermodynamically controlled conditions and lead to equi-
useful in investigating these systems. Some typical
libria. The ionic equilibria in superacid systems generally
examples are depicted in Fig. 3.
favor increasing amounts of the higher-octane branched
isomers at lower temperatures.
D. Hydrocarbon Transformations
Lewis-acid-catalyzed isomerization of alkanes can
The astonishing acidity of Magic Acid and related be effected with various systems. Superacid-catalyzed
superacids allows protonation of exceedingly weak bases. reactions can be carried out at much lower temperatures,
Not only all conceivable π -electron donors (such as even at or below room temperature, and thus provide
olefins, acetylenes, and aromatics) and n-donors (such more of the branched isomers. This is of particular
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186 Superacids

importance in preparing lead-free gasoline. Increasing the

octane number by this means is preferable to the addition
of higher-octane aromatics or olefins, which may pose
environmental or health-hazard problems.
Of the many important superacid-catalyzed isomeriza-
tions, the isomerization tricyclo [5.2.1.02,6 ] decane to FIGURE 4 Mechanism of oxidative methane oligocondensation.
adamantane is unique, a reaction discovered by Schleyer.

Because of the high reactivity of primary and sec-

ondary ions under these conditions, the alkylation reaction
is complicated by hydride transfer and related competing
reactions. However, in this mechanism it is implicit
Isomerization of alkylaromatics can also be effectively
that an energetic primary cation will react directly
carried out with superacids.
with methane or ethane. This opens the door to new
chemistry through activation of these traditionally passive
F. Alkylation molecules.
Alkylation of aromatics is carried out industrially on a A convenient way to prepare an energetic primary cation
large scale; an example is the reaction of ethylene with is to react ethylene with superacid. This has been used with
benzene to produce ethylbenzene, which is then dehy- HF–TaF5 catalyst to achieve ethylation of methane in a
drogenated to styrene, the monomer used in producing flow system at 50◦ C. With a methane–ethylene mixture
polystyrene. Traditionally, these alkylations have been (85:14), propane is the major product.
carried out in solution with a Friedel–Crafts acid catalyst
such as AlCl3 . However, these processes are quite energy G. Polymerization
consuming and form a complex mixture of products re-
The key initiation step in cationic polymerization of
quiring large amounts of catalyst, most of which is tied
alkenes is the formation of a carbocationic intermediate,
up as complexes and can be difficult or impossible to re-
which can then interact with excess monomer to start
cover. The use of solid superacidic catalyst permits clean,
propagation. The mechanism of the initiation of cationic
efficient heterogeneous alkylations with no concomitant
polymerization and polycondensation has been exten-
complex formation.
sively studied. Trivalent carbenium ions play the key role,
CH2CH3 not only in acid-catalyzed polymerization of alkenes, but
AlCl3–HCl also in polycondensation of arenes (π -bonded monomers),
 CH2 CH2
as well as in cationic polymerization of ethers, sulfides,
and nitrogen compounds (nonbonded electron-pair donor
Aliphatic alkylation is widely used to produce high- monomers). Pentacoordinated carbonium ions, on the
octane gasolines and other hydrocarbon products. Con- other hand, play the key role in the electrophilic reactions
ventional paraffin (alkane)–olefin (alkene) alkylation is of σ -bonds (single bonds), including the oligocondensa-
an acid-catalyzed reaction; it involves the addition of a tion of alkanes and the cocondensation of alkanes and
tertiary alkyl cation, generated from an isoalkane (via alkenes.
hydride abstraction) to an olefin. An example of such a Alkylation and oligocondensation reactions of alka-
reaction is the isobutane–ethylene alkylation, yielding nes giving higher molecular weight alkanes have been
2,3-dimethylbutane. achieved under superacid conditions.
The great interest in strong-acid chemistry is further
exemplified by the discovery that lower alkanes such as
H. Superacids in Organic Syntheses
methane and ethane can be polycondensed in Magic Acid
and Superelectrophilic Activation
at 50◦ C, yielding mainly C4 to C10 hydrocarbons of the
gasoline range. The proposed mechanism (Fig. 4) necessi- Since the discovery of stable carbocations, they were
tates the intermediacy of protonated alkanes (pentacoordi- known to be readily quenched by various nucleophiles.
nate carbonium ions), at least as high-lying intermediates These reactions, which were first used to confirm the
or transition states. Hydrogen must be oxidatively re- structure of the ions, proved to be very useful in organic
moved (by either the excess superacid or added oxidants) synthesis. The selectivity of the reactions is based on the
to make the condensation of methane thermodynamically fact that generally only thermodynamically more stable
feasible. ions are formed under the reaction conditions, resulting in
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Superacids 187

a high selectivity. The new functional group created in a su- H

peracid medium will itself undergo protonation and, thus, HF-SbF5
be protected against any further electrophilic attack. In this COOCH3
CO/CH3OH
way, a number of new selective reactions were achieved O O
H
in a high yield, as shown by the examples below. Fur-
thermore, electrophiles that contain nonbonded electron Olah et al. have developed direct carbonylation of isoalka-
pairs, π -bonds, or even σ -bonds can be further activated nes that lead to ketones in high conversion and high selec-
by protonation or Lewis acid complexation leading to su- tivity under HF:BF3 catalysis. The chemistry is unlike the
perelectrophiles. Such activated species react with many Koch reaction and involves activated formyl cation insert-
deactivated aromatic as well as aliphatic compounds. ing directly into the C–H σ -bond of isoalkanes, followed
by strong acid-catalyzed rearrangement.
1. Phenol–Dienone Rearrangement
This isomerization is of substantial importance in natural O
product syntheses, usually catalyzed by a strong base. The H3C HF:BF3 H3C
reaction occurs with good yields in polycyclic systems H3C H CO CH3
under superacidic conditions, as shown by Gesson and H3C CH3
Jacquesay.
CH3 O CH3 O
4. Oxidation

HF-SbF5 Novel oxidations of hydrocarbons in superacids with

H H H ozone or hydrogen peroxide have been investigated. Proto-
HO O nated ozone (O+ +
3 H) or hydrogen peroxide (H3 O2 ) attacks
the single σ -bond, resulting in oxygen insertion. These
can be followed by protolytic transformation, such as the
2. Reduction conversion of isobutane into acetone and methyl alcohol.

Hydride ion transfer to carbocations is a well-known O3
H
(CH3)3C H2O2
reaction in hydrocarbon chemistry. This reaction has been Magic acid
O3H 

used successfully in superacid to reduce α,β-unsaturated (CH3)3CH

H
 [(CH3)3C O]
H2O2 H2O
ketones with methylcyclopentane as the hydride Magic acid
(CH3)3C
OOH 1,2CH3
donor. Superacid-catalyzed reduction of aromatics, as shift
shown by Wristers, requires both a hydride donor and H2O 
(CH3)2C O  CH3OH (CH3)2C O
hydrogen. CH3

H
By similar procedures aromatics are also hydroxylated in
HF-SbF5 high yields at low temperatures.

O O
H H2O2
HSO3F/SO2ClF

HF-TaF5
isopentane CH
H2
5. Superelectrophilic Activation
Electrophiles such as NO+ + +
2 , CH3 CO , and H3 O can be
3. Carbonylation
further activated in strong protic acids to their respective
The reaction between carbocations and carbon monoxide dications: NO2 H2+ , CH3 COH2+ , and H4 O2+ . Such su-
affording oxocarbenium ions (acyl cations) is a key step perelectrophiles are responsible for the high electrophilic
in the well-known Koch–Haaf reaction for preparing car- reactivity in superacids. For example, acetyl cation is a
boxylic acids from alkenes. This reaction has been exten- poor acetylating agent for chlorobenzene in trifluoroacetic
sively studied under superacidic conditions. An example acid. However, in superacidic trifluoromethanesulfonic
is indicate below. acid medium, acetylation takes place with ease.
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188 Superacids

Cl Cl Olah and co-workers have shown hydrogen–deuterium

exchange of molecular H2 and D2 , respectively, with
1:1 HF:SbF5 and HSO3 F:SbF5 at room temperature. The
 CH3COSbF6 facile formation of HD does indicate that protonation or
deuteration occurs involving 3 at least as a transition state
COCH3 in the kinetic exchange process. The H3 ion, 3, is the sim-
plest two-electron, three-center bonded entity.
in CF3COOH at 60°C, 24 hr, 1%
H
in CF3SO3H at 60°C, 30 min, 81%
H H
Similar activations have been proposed for Lewis acid
3
complexations.

I. Miscellaneous Reactions 3. Cations of Other Nonmetallic Elements

Many acid-catalyzed reactions can be advantageously car- Elemental sulfur, selenium, and tellurium give colored so-
ried out using solid superacids instead of conventional lutions when dissolved in a number of strongly acidic me-
acid systems. The reactions can be carried out in ei- dia. It has been shown that S2+ 2+ 2+ 2+ 2+
16 , S8 , S4 , Se8 , Te4 ,
2+
ther the gaseous or the liquid phase. Using the example and Te6 are present in such solutions. These cations
Nafion-H (a perfluoroalkane resin sulfonic acid, devel- are formed by the oxidation of elements by H2 S2 O7 or
oped by DuPont) solid acid, several simple procedures S2 O6 F2 ; for example,
−
were reported to carry out alkylation, transbromination, 4S + 6H2 S2 O7 → S2+
4 + 2HS3 O10 + 5H2 SO4 + SO2
nitration, acetalization, hydration, and so on.
Like the halogen cations, the sulfur, selenium, and
tellurium cations are highly electrophilic and undergo
J. Superacids in Inorganic Chemistry disproportionation in media with any appreciable basic
properties, although, as would be anticipated, the ease
1. Halogen Cations
of disproportionation increases in series tellurium <
It has often been postulated that the monoatomic ions I+ , selenium < sulfur.
Br+ , and Cl+ are the reactive intermediates in halogena-
tion reactions of aromatics and alkenes. The search for
4. Noble Gas Cations
the existence of such species has led to the discovery of I+
2
and other related halogen cations, which are stable in su- Noble gas cationic salts of xenon and krypton have also
peracids. The I+
2 cation may be generated by the oxidation been isolated from superacid medium. The examples
of I2 with S2 O6 F2 in HSO3 F solution, include XeF+ , Xe2 F+ + + +
3 , HCNXeF , XeOF3 , KrF , and
+
Kr2 F3 .
2I2 + S2 O6 F2 → 2I+
2 + 2SO3 F
−

and a stable blue solution of this cation can also be ob-

tained by oxidizing iodine with 65% oleum. In a less acidic
SEE ALSO THE FOLLOWING ARTICLES
medium, the I+2 cation disproportionates to more stable ox-
NOBLE-GAS CHEMISTRY • ORGANOMETALLIC CHEM-
idation states. The electrophilic Br+
2 cation is obtainable
ISTRY • PHYSICAL ORGANIC CHEMISTRY
only in the very strong superacid Magic Acid or fluoroan-
timonic acid, and it disproportionates in HSO3 F. The Cl+2
cation, which is much more electrophilic, has not yet been BIBLIOGRAPHY
observed in solution. Monoatomic halogen cations seem
to be too unstable for direct observation. Gillespie, R. J., and Peel, T. E. (1971). Adv. Phys. Org. Chem. 9, 1.
Jost, R., and Sommer, J. (1988). Rev. Chem. Int. 9, 171.
Olah, G. A. (1993). Angew. Chem. Int. Ed. Engl. 32, 767.
2. The Trihydrogen Cation, H+
3 Olah, G. A., Prakash, G. K. S., and Sommer, J. (1985). “Superacids,”
Wiley, New York.
The H3 ion, 3, was first discovered by Thompson in Tanabe, K. (1970). “Solid Acids and Bases; Their Catalytic Properties,”
1912 in hydrogen discharge studies. Actually, it was the Academic Press, New York.
first observed gaseous ion–molecule reaction product. Vogel, P. (1985). “Carbocation Chemistry,” Elsevier, Amsterdam.
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Surface Chemistry
Simon R. Bare
G. A. Somorjai
University of California, Berkeley, and
Lawrence Berkeley Laboratory

I. Surface Structure of Clean Surfaces

II. Surface Structure of Adsorbates
on Solid Surfaces
III. Thermodynamics of Surfaces
IV. Electrical Properties of Surfaces
V. Surface Dynamics

GLOSSARY Surface relaxation Equilibration of surface atoms to new

positions that changes the interlayer distance between
Adsorbate Adsorbed atom or molecule. the first and second layers of atoms.
Adsorption Process by which molecules are taken up on Surface state Electronic state localized at the surface.
the surface by chemical or physical action. Surface unit cell Two-dimensional repeating unit that
Chemisorption Binding of molecules to surfaces by fully describes the surface structure.
strong chemical forces. Work function Minimum energy required to remove an
Desorption Process by which molecules are removed electron from the surface into the vacuum outside the
from the surface. solid.
Heat of adsorption Binding energy of the adsorbed
species.
Physisorption Binding of molecules to surfaces by weak SURFACES constitute the boundaries of condensed mat-
chemical forces. ter, solids, and liquids. Surface chemistry explores the
Sticking probability Ratio of the rate of adsorption to structure and composition of surfaces and the bonding and
the rate of collision of the gaseous molecule with the reactions of atoms and molecules on them. There are many
surface. macroscopic physical phenomena that occur on surfaces
Surface free energy Energy necessary to create a unit or are controlled by the electronic and physical properties
area of surface. of surfaces. These include heterogeneous catalysis, cor-
Surface reconstruction Equilibration of surface atoms rosion, crystal growth, evaporation, lubrication, adhesion,
to new positions that changes the bond angles and and integrated circuitry. Surface chemistry examines the
rotational symmetry of the surface atoms. science of these phenomena as well.

. 373
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374 Surface Chemistry

I. SURFACE STRUCTURE vented by Müller in 1936. The basic microscope can

OF CLEAN SURFACES be very simple. In an ultrahigh vacuum cell, a poten-
tial of about 10,000 V is applied between a hemispher-
A. Introduction ical tip of refractory metal of radius ∼10−4 cm and a
fluorescent screen. The tip is charged positively, and a
To the naked eye the surface of a single crystal of a metal gas (usually helium) is allowed to impinge on the sur-
looks perfectly planar with no imperfections. If this crys- face. Under the influence of the very strong electric field
tal is now examined with an optical microscope features helium atoms that are incident on the tip are ionized.
of the surfaces down to the wavelength of visible light The positive ions thus created are repelled radially from
(∼5000 Å) can be resolved. The surface will look gran- the surface and accelerated onto the fluorescent screen,
ular with distinct regions of crystallinity separated from where a greatly magnified image of the crystal tip is dis-
each other by boundaries or dislocations. These disloca- played. The ionization probability depends strongly on
tions indicate areas on the surface where there is a mis- the local field variations induced by the atomic struc-
match of the crystalline lattice, and they can take several ture of the surface—protruding atoms generate stronger
forms, for example, edge dislocations or screw disloca- ionization than atoms embedded in close-packed planes,
tions. The presence of these dislocations or defects can thereby producing individual bright spots on the screen.
dominate certain physical properties of the material. Dis- The small radius of the tip is needed to produce the
location densities of the order of 106 –108 cm−2 are com- large fields necessary for ionization, but it also permits
monly found on metal single crystals, whereas the number the immense magnification of the microscope. The tip
is lower (104 –106 cm−2 ) on semiconductor surfaces due surface is directly imaged with magnification of about
to the different nature of the bonding. These defect den- 107 . Figure 1 depicts the image of a tungsten field-ion
sities must be compared with the total concentration of tip. Well-defined atomic planes of the crystal tip can
surface atoms (about 1015 cm−2 ). On further magnifica- be readily identified, indicating that there is order of
tion, for example, using a scanning electron microscope, the atomic scale, i.e., most of the surface atoms in any
features can be resolved down to about 1000 Å, and our crystal face are situated in ordered rows separated by
view of the surface changes further. The surface will look well-defined interatomic distances. The technique is lim-
pitted, with distinct planar areas (terraces) bounded by ited to the refractory metals (W, Ta, Ir, and Re) which
walls many atomic layers in height. Thus, on the micro- can withstand the strong electric field at the tip with-
scopic and submicroscopic scale the surface morphology out desorption or evaporation from the surface. However,
appears to be heterogeneous, with many different surface its great advantage is that individual atoms can be im-
sites that differ by the number of neighboring atoms sur- aged on the screen, which also allows studies of surface
rounding them. What about the nature of the surface on diffusion.
an atomic scale?
In order to be able to discuss and understand the struc-
ture of surfaces it is necessary to understand the techniques
that are capable of viewing the surface on an atomic scale.
We briefly describe such techniques, illustrating their ca-
pabilities with pertinent examples. The techniques more
commonly used are field-ion microscopy (FIM), low-
energy electron diffraction (LEED), helium atom diffrac-
tion, and high-energy ion scattering. In addition, the rel-
atively new technique of scanning tunneling microscopy
(STM) is proving to be a very promising tool. Only brief
descriptions are given here and the reader is referred to
some of the excellent books on the subject given in the
bibliography.

B. Techniques Sensitive to Surface Structure

1. Field-Ion Microscopy
Field-ion microscopy is one of the oldest techniques FIGURE 1 Field-ion micrograph of a tungsten tip. Various crystal
used for surface structure determination, having been in- planes are labeled. (Courtesy of Lawrence Berkeley Laboratory.)
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Surface Chemistry 375

2. Low-Energy Electron Diffraction If the crystal surface is well-ordered, a diffraction pat-

tern consisting of bright, well-defined spots will be dis-
Another method which has demonstrated that crystal sur-
played on the screen. The sharpness and overall inten-
faces are ordered on an atomic scale is low-energy electron
sity of the spots are related to the degree of order of the
diffraction (LEED). This method is the most frequently
surface. When the surface is less ordered, the diffraction
used technique, such that virtually all modern surface
beams broaden and become less intense, while some dif-
science laboratories now rely on it for surface structural
fuse intensity appears between the beams. A typical set of
information.
diffraction patterns from a well-ordered surface is shown
In order to obtain diffraction from surfaces, the inci-
in Fig. 4. The presence of the sharp diffraction spots clearly
dent wave must satisfy the condition λ ≤ d, where λ is
indicates that the surface is ordered on an atomic scale.
the wavelength of the incident beam and d the interatomic
Similar LEED patterns have been obtained from solid
distance. In addition, the incident beam should not pene-
single-crystal surfaces of many types including metals,
trate much below the surface plane but should backdiffract
semiconductors, alloys, oxides, and intermetallics.
predominantly from the surface so that the scattered beam
Due to the importance of LEED in surface chemistry we
reflects the properties of the surface atoms and not those of
briefly discuss other aspects of the technique which make
the bulk. The deBroglie
√ wavelength λ of electrons is given
it one of the most powerful surface sensitive tools. It is con-
by λ (in Å) = 150/E, where E is in electron volts. Thus,
venient to subdivide the technique into two-dimensional
in the energy range 10–500 eV, the wavelength varies from
LEED and three-dimensional LEED. In two-dimensional
3.9 to 0.64 Å, which is smaller or equal to most interatomic
LEED we observe only the symmetry of the diffraction
distances, and the escape depth of the backscattered elec-
pattern on the fluorescent screen. The bright spots which
trons in this energy range is 5–10 Å, thereby providing
correspond to the two-dimensional reciprocal lattice be-
surface sensitivity. These elastically scattered low-energy
longing to the repetitive crystalline surface structure yield
electrons yield surface structural information. The tech-
immediate information about the size and orientation of
nique of LEED is depicted schematically in Fig. 2, while
the surface unit cell, i.e., the geometry of the surface
a schematic of the LEED apparatus is shown in Fig. 3. A
layer. This is important information since reconstruction-
collimated primary beam of electrons with a diameter of
induced and adsorbate-induced new periodicities are im-
0.1–1 mm at energies of 15–350 eV is impinged on a sur-
mediately visible. The diffuse background intensity also
face and the elastically backscattered electrons, after trav-
contains information about the nature of any disorder
eling through a field-free region, are spatially analyzed.
present on the surface. In three-dimensional LEED the in-
This is achieved most commonly (see Fig. 3) by passing
formation gained from the two-dimensional pattern is sup-
the scattered electrons through four hemispherical grids.
plemented by the intensities of the diffraction spots which
The first grid is at the crystal potential while the second
are measured as a function of incident electron energy.
and third are at a retarding voltage to eliminate inelas-
By comparing these intensity-versus-voltage curves [I (V )
tic electrons, and the fourth is at ground. After passing
curves] with those simulated numerically with the help of a
through these grids the diffracted beams are accelerated
suitable theory, the precise location of atoms or molecules
onto a hemispherical phosphor screen.
in the surface with respect to their neighbors is determined.
Thus, the bond length and bond angles in the surface layer
are calculated. It should be mentioned, however, that the
analysis of the LEED beam intensities requires a theory
of the diffraction process which is a nontrivial point due
to multiple scattering of LEED electrons by the surface,
and this is not simple to represent in a theory.

3. Atomic-Beam Diffraction
Another technique that utilizes the principle of diffraction
is atomic- or molecular-beam diffraction. The deBroglie
wavelength λ associated with helium atoms is given by
the following:
h 0.14
FIGURE 2 Scheme of the low-energy electron diffraction experi- λ(Å) = 1/2
= , (1)
ment. (Courtesy of Lawrence Berkeley Laboratory.) (2ME) E(eV)1/2
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376 Surface Chemistry

FIGURE 3 Scheme of the low-energy electron diffraction apparatus employing the postacceleration technique.

FIGURE 4 LEED pattern from a Pt(111) crystal surface at (a) 51 eV, (b) 63.5 eV, (c) 160 eV, and (d) 181 eV incident
electron energy. (Courtesy of Lawrence Berkeley Laboratory.)
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Surface Chemistry 377

where h is Planck’s constant and M and E are the mass

and energy, respectively, of the helium atom. Atoms with
a thermal energy of ∼20 meV have λ = 1 Å and can read-
ily diffract from surfaces. The information obtained from
atomic-beam diffraction is similar to that from LEED, but
there are differences between the two techniques. In LEED
the relatively high-energy (20–200 eV) electrons used pen-
etrate the crystal, multiple scattering events are important,
and the LEED electrons are scattered primarily from the
ion cores of the crystal lattice. In atom diffraction, there is
virtually no penetration of the low-energy (10–200 meV)
atomic beam, making it much more surface sensitive than
the electron beam. The atomic beam is primarily scat-
tered from the valence electrons of the surface atoms. In
fact, their scattering is usually simulated by a “hard wall”
around the atoms in the top layer of the surface so that
diffraction is from a “corrugated hard wall” with the pe- FIGURE 5 Helium diffraction traces for Au(110)-(1 × 2) at a sur-
riodicity of the surface mesh. As in LEED the location face temperature of 100 K with incident angle i = 48◦ . The wave-
of the diffracted beams indicates the surface periodicity. length λHe is (a) 1.09 Å and (b) 0.57 Å.
Their intensities are related to the structure of the scatter-
ing potential within a unit mesh, in this case to the relative
scale on single-crystal surfaces. It images surface topogra-
amplitude and positions of corrugations around the surface
phies in real space with a lateral resolution of ∼2 Å and
atoms.
vertical resolution of ∼0.05 Å. The technique utilizes the
The essential elements of the apparatus necessary to
tunnel effect. Due to the wave nature of electrons, they are
perform atomic-beam diffraction are an atomic beam of
not strictly confined to the interior bounded by the surface
gas and a detector. The atomic beam is usually gener-
atoms. Therefore, the electron density does not drop to
ated from a nozzle source incorporating several skimmers.
zero at the surface but decays exponentially on the outside
The energy (wavelength) of the beam is varied by either
with a decay length of a few angstroms. If two metals are
heating or cooling the nozzle. The detector usually em-
approached to within a few angstroms, the overlap of their
ployed is a mass spectrometer, mounted on a rotatable
surrounding electron clouds becomes substantial, and a
device to enable it to be movable over a large range of
measurable current can be induced by applying a small
scattering angles. The atomic beam is chopped with a
voltage between them. This tunnel current is a measure of
variable-frequency chopper before it impinges on the sur-
the wave-function overlap, and depends very strongly on
face. In this way, an alternating intensity of the beam is
the distance between the two metals. This is the physical
generated at the mass spectrometer detector, which is read-
basis of the scanning tunneling microscope. Experimen-
ily separated from the noise due to helium atoms in the
tally one of the electrodes is sharpened to a pointed tip
background.
which is scanned over the surface to be investigated (the
To illustrate the type of data that is obtained, Fig. 5
other electrode) at constant tunnel current. The tip thus
shows the He diffraction traces from a Au(110)-(1 × 2)
traces contours of constant wave-function overlap, and in
surface at two different wavelengths.
the case of constant decay length, the trace is an almost
Helium diffraction is especially sensitive to surface or-
true image of the surface atomic positions, i.e., the surface
der on an atomic scale. On scattering from a well-ordered
topography. An example is shown in Fig. 6.
single crystal surface nearly 15% of the scattered helium
atoms appear in the specular helium beam whereas this
fraction can drop to 1% when the surface is disordered.
5. Ion Scattering
Measurements of the fraction of specularly scattered he-
lium can therefore provide information on the degree of Ion scattering from surfaces is usually subdivided into two
atomic disorder in the solid surface. scattering regions: low-energy ion scattering (LEIS), ener-
gies typically ∼1 keV, and high-energy scattering (HEIS),
energies 0.1–1 MeV. High-energy ion scattering is a probe
4. Scanning Tunneling Microscopy
that tests the local position of surface atoms relative to their
The relatively new technique of scanning tunneling mi- bulklike sites. In HEIS the velocity of the ion is such that
croscopy also clearly demonstrates order on an atomic it is moving fast compared to the thermal motions of the
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378 Surface Chemistry

FIGURE 6 Scanning tunneling microscope picture of a clean (1 × 5) reconstructed Au(100) surface with monatomic
steps. Divisions on the crystal axes are 5 Å, with approximately 1.5 Å from scan to scan. The inset shows the LEED
pattern of the predominant (1 × 5) corrugation. (Courtesy of Lawrence Berkeley Laboratory.)

atoms in the solid, thus the beam senses a frozen lattice. If proximation, can be written analytically which leads to an
the target is amorphous each atom would sense a uniform estimate of the two-atom surface peak intensity I :
distribution of impact parameters of the ions and diffuse    
scattering results. However, the scattering spectrum from a R2 −R
I =1+ 1+ 2 exp , (3)
single crystal aligned with a major symmetry axis parallel 2ρ 2ρ 2
to the beam is drastically modified from that of the amor-
phous target. The impact parameter distribution is also where ρ is the two-dimensional root mean square thermal
uniform at the first monolayer, but the first atom shad- vibrational amplitude. The first term represents the unit
ows the second from the beam, and small angle scattering contribution from the first atom in the string, the second
events determine the impact parameter distribution at the term represents the variable contribution from the second
second atom. This results in a unique (nonuniform) flux
distribution at the second atom. Figure 7 illustrates the ef-
fect of small-angle scattering in a two-atom model. Ions
incident at the smallest impact parameter undergo large-
angle scattering, those at large impact parameter suffer
small deflections which determine the flux distribution of
ions near the second atom. The closest approach of the
ion to the second atom, R, can be approximated assuming
Coulomb scattering as follows:
  1/2
R = 2 Z 1 Z 2 e2 d E , (2)

where Z 1 and Z 2 are the masses of the incident and tar-

get atoms, respectively; d is the atomic spacing; and E is
FIGURE 7 Schematic showing the interactions at the surface of
the incident ion energy. This gives rise to a shadow cone an aligned single crystal and the formation of the shadow cone.
beneath the surface atom as illustrated in Fig. 7. The flux The energy spectra for the aligned and nonaligned case are also
distribution at the second atom, within the Coulomb ap- shown.
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Surface Chemistry 379

atom. While the two-atom Coulomb approximation is not

adequate enough to compare to experiment, it illustrates
that the surface peak intensity is a function of one param-
eter, ρ/R.
The intensity of the surface peak is thus sensitive to the
atomic arrangement on the surface, i.e., the positions of
the surface atoms with respect to their bulklike positions.
The effect on the surface peak of different surface struc- FIGURE 9 Model of a heterogeneous solid surface, depicting
tures is depicted in Fig. 8. The nature of reconstructed, different surface sites. These sites are distinguishable by their
relaxed, and adsorbate-covered surfaces are discussed in number of nearest neighbors.
the sections below.
High-energy ion scattering is also a sensitive tool for
answering other important questions in surface chemistry, Fig. 9. The surface may have atoms in any of the positions
namely what type of atoms are present on the surface and shown in the figure. There are atoms in the surface at kink
how many are present. positions and in ledge positions, and there are adatoms ad-
All of the techniques discussed so far indicate that the sorbed on the surface at various sites. Atomic movement
solid surface is ordered on an atomic scale. Most of the from one position to another proceeds by surface diffu-
surface atoms occupy equilibrium atomic positions that sion. To the first approximation, the binding energy of the
are located in well-defined rows separated by equal in- surface atoms is proportional to the number of nearest and
teratomic positions. This atomic order is predominant de- next-nearest neighbors. Therefore, for example, atoms at
spite the fact that there are large numbers of atomic posi- a ledge are bound more strongly than are adatoms. In equi-
tions on the surface where atoms have different numbers librium there is a certain concentration of all these surface
of neighbors. A pictorial representation of the topology species, with those species predominating whose bind-
of a monatomic crystal on an atomic scale is shown in ing energies are greatest. Thus, the adatom concentration
on clean well-equilibrated surfaces should be very small
indeed. However, while these surfaces are ordered on an
atomic scale their structure is not always one of simple ter-
mination of the bulk unit cell, relaxation or reconstruction
being common.

C. Surface Relaxation
Generally, the surface unit cells of clean metal surfaces
have been found to be those expected from the projection
of the bulk X-ray unit cell onto the surface, referred to
as a (1 × 1) structure (in Miller index notation), and the
uppermost layer z spacing (spacing in the direction nor-
mal to the surface plane) is equal to the bulk value within
about 5%. Such surfaces include the (111) crystal faces
of face centered cubic aluminum, platinum, nickel, and
rhodium, and the (0001) crystal faces of hexagonal close
packed cadmium and beryllium. This information has al-
most exclusively been determined by a detailed intensity
analysis of the diffraction beams in LEED as a function
of incident electron energy, and the interatomic positions
in the surface layer are calculated to within 0.1 Å. The
Al (110) surface shows a 5–15% contraction, the Mo(100)
surface a 11–12% contraction, and the W(100) surface a
FIGURE 8 Schematic of the dependence of the intensity of the 6% contraction of the top-layer z spacing with respect
surface peak (SP) on different crystal surface structures. (a) The
to the bulk, while retaining the (1 × 1) surface unit cell.
ideal crystal SP from “bulklike” surface, (b) enhanced SP observed
in normal incidence for a reconstructed surface, (c) enhanced SP Generally, crystal planes whose atoms are less densely
observed in nonnormal incidence for a relaxed surface, and (d) re- packed [for example, bcc (100) and fcc (110) planes] will
duced SP observed in normal incidence for a registered overlayer. be more likely to show relaxation than the more densely
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380 Surface Chemistry

packed planes. In forming a surface of the less densely gold, platinum, and iridium. The ideal unreconstructed
packed planes it is necessary to remove a larger num- surfaces have a square net of atoms. Surface reconstruction
ber of nearest-neighbor atoms. Thus, to minimize the sur- produces a superlattice that is basically five times larger
face free energy a relocation of the surface atoms from in one direction than for the ideal surface. For Ir(100)
their bulk positions is quite likely. There are several ex- the superlattice is denoted (5 × 1), for Pt(100) by the ma-
planations as to why surface relaxation is prevalent on trix notation ( −15 14
1
), and for Au(100) by the superlattice
the more open surfaces. First, it can be imagined that the (5 × 20). From LEED I (V ) analyses, evidence indicates
electron cloud attempts to smooth its surface, thereby pro- that the nature of the reconstruction is similar on all three
ducing electrostatic forces that draw the surface atoms metals and consists of a close-packed hexagonal top layer
toward the substrate, the effect being stronger the less that is positioned in slightly different ways on the square
closely packed the surface. Second, with fewer neigh- net substrate. These reconstructions are consistent with
bors the two-body repulsion energy is smaller, allowing the knowledge that the (111) face of fcc metals is ener-
greater atomic overlap and therefore more favorable bond- getically the most favorable. It is worth noting here that
ing at shorter bond lengths. Third, for surface atoms the the adsorption of gases such as oxygen, carbon monox-
bonding electrons are partly redistributed from the bro- ide, or hydrogen, or the presence of impurities can inhibit
ken bonds to the remaining unbroken bonds, thereby the these surface reconstructions. On the other hand, the pres-
charge content of the latter is increased, reducing the bond ence of such adsorbates can also induce different surface
length. reconstructions.
The nature and cause of these surface phase transfor-
mations are not well established at present. The case of
D. Surface Reconstruction
structural change from metastable to stable on adsorption
Surface atoms in any crystal are in an anisotropic envi- or removal of adsorbates indicates the likelihood of elec-
ronment which is very different from that around bulk tronic transitions that accompany reconstruction. At the
atoms. The crystal symmetry that is experienced by each surface there are fewer nearest neighbors as compared to
surface atom is markedly lower than when the atom is in atoms in the bulk. The electronic structure that is the most
the bulk. This symmetry change and lack of neighbors in stable in this reduced-symmetry environment may be sub-
the direction perpendicular to the surface allows displace- stantially different from that of the bulk metal. Since the
ment of surface atoms in ways which are not allowed in surface atoms are surrounded by atoms only on one side
the bulk. Surface relaxation is one consequence of this, and there is vacuum on the other, they may change their co-
the other major consequence being surface reconstruc- ordination number by slight relocation with simultaneous
tion. Here the two-dimensional surface unit cell is differ- changes in the electronic structure. It is indeed surprising
ent from that given by the termination of the bulk structure that more surfaces do not show reconstruction.
on the plane of interest. Surface reconstruction can give
rise to a multitude of different structures depending on the
E. Stepped and Kinked Surfaces
electronic structure of a given substance. The phenomenon
is more frequent on semiconductor surfaces than on metal The close-packed faces of solids (low-Miller-index faces)
surfaces. While the geometry is readily observed in the have the lowest surface free energy, and therefore they
LEED pattern, the actual elucidation of the real-space re- are the most stable with respect to rearrangement on
constructed surface structure is often extremely difficult, disordering up to or near the melting point. However,
and in some cases even after years of study and many stepped and/or kinked surfaces (high-Miller-index
proposals of the structure, the true structure is still not faces), although of higher surface free energy, are very
known. Such a system is the Si(111) surface. Upon cleav- important. They are known to play important roles during
ing in UHV at room temperature, the surface exhibits a evaporation, condensation, and melting. Steps and kinks
(2 × 1) surface structure. On heating to about 700 K the are sites where atoms break away as an initial process
surface structure changes to one with (7 × 7) periodicity. leading to desorption, or where atoms migrate during
This (7 × 7) structure is then the stable structure of the condensation to be incorporated into the crystal lattice.
(111) face. While this surface has been studied by a mul- Theories of crystal growth, evaporation, and the kinetics
titude of techniques, including LEED, STM, and He atom of melting have identified the significance of these lower
diffraction there is still no generally accepted structure of coordination-number sites in controlling the rate processes
either the (2 × 1) or (7 × 7) reconstructions. associated with phase changes. In addition, studies of
One of the best known examples of reconstruction of chemisorption and catalysis using single-crystal surfaces
metallic surfaces is that for the (100) faces of three 5d have revealed different binding energies and enhanced
transition metals that are neighbors on the periodic table: chemical activity at steps and kinks on high-Miller-index
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Surface Chemistry 381

FIGURE 10 LEED patterns (left) and surface structures (right) of (a) flat, (b) stepped, and (c) kinked platinum surfaces.
(Courtesy of Lawrence Berkeley Laboratory.)

transition metal surfaces as compared to low-Miller- ognizable in LEED. Upon removing the impurities from
index surfaces. Adsorption of diatomic or polyatomic the surface, the original one-atom-height step ordered ter-
molecules frequently leads to dissociation with greater race surface structure is usually regenerated.
probability of steps and kinks than on flat atomic
terraces.
II. SURFACE STRUCTURE OF
The presence of steps on a single crystal surface is read-
ADSORBATES ON SOLID SURFACES
ily discernible by LEED. The LEED patterns differ from
those expected from crystals with low-index faces in that
A. Introduction
the diffraction beams are split into doublets. This splitting
(Fig. 10) is a function of ordered steps on the surface. The While the knowledge of the structure of clean solid sur-
distance between the split beams is inversely related to the faces is important in its own right for determining var-
distance between the steps, i.e., the terrace width. From ious properties of those surfaces, many phenomena are
the variation of the intensity maximum of the doublet associated with the presence of adsorbates on the sur-
spots with electron energy the step height can be faces. In fact, in the natural environment of our planet,
determined. surfaces are never truly free of adsorbates. On approach-
Many stepped surfaces exhibit high thermal stability. ing a surface each atom or molecule encounters a net at-
In particular the one-atom-height step periodic terrace tractive potential. This results in a finite probability that
configuration appears to be the stable surface structure it will be trapped on the surface. This trapping, adsorp-
of many high-Miller-index surfaces. While most of the tion, is always an exothermic process. At the low pressure
stepped surfaces are stable when clean in their one-atom- of 1 × 10−6 torr, approximately 1 × 1015 gas molecules
height step ordered terrace configuration, in the presence collide with each square centimeter of surface per sec-
of a monolayer of carbon or oxygen many stepped surfaces ond. Since the surface concentration of atoms is about
undergo structural rearrangement. The step height and ter- 1015 cm−2 , at this pressure the surface may be covered
race width may double, or faceting may occur. Faceting with a monolayer of gas within seconds; this is the ma-
occurs when the step orientation becomes as prominent as jor reason why surface studies are performed under ultra-
that of the terrace and new diffraction features become rec- high vacuum conditions (P < 1 × 10−8 torr). The very low
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382 Surface Chemistry

pressure is needed to maintain clean surface conditions B. The Ordering of Adsorbed Monolayers
for a time long enough to perform experimental measure-
ments. At atmospheric pressure the surface will be covered The ordering process in the adlayer is due to an interplay
within a fraction of a second. The constant presence of of the bonding with the substrate and the bonding between
the adsorbate layer influences the chemical, mechanical, the adatoms or admolecules. Once a molecule adsorbs it
and surface electronic properties. Adhesion, lubrication, may diffuse on the surface or remain bound at a specific
and resistance to mechanical or chemical attack or photo- site during most of its residence time. Thermal equilibra-
conductivity are just a few of the many macroscopic sur- tion among the adsorbate and between the adsorbate and
face processes that are controlled by various properties of substrate atoms (i.e., adsorption) is assured if Hads and
∗
monolayers. E D(bulk) , the activation energy for bulk diffusion, are high
Two macroscopic experimentally determinable param- enough as compared to kT (≥10kT ). However, ordering
eters characterize the adsorbed monolayer: the coverage primarily depends on the depth of the potential energy
and the heat of adsorption. The coverage  is defined as barrier that keeps an atom or molecule from hopping to
the ratio of the number of adsorbed atoms or molecules a neighboring site along the surface. The activation en-
∗
to the total number of adsorption sites (usually taken as ergy for surface diffusion, E D(surface) , is an experimen-
the number of atoms in the surface plane). The heat of tal parameter that is of the magnitude of this potential
adsorption Hads , is implicitly linked to the strength of energy barrier. E D∗ can be experimentally determined
the adsorbate–substrate bond. Knowledge of both param- on well-characterized surfaces by field-ion microscopy,
eters often reveals the nature of bonding in the adsorbed for example, and for Ar and W adatoms and O atoms on
layer. tungsten surfaces has the value 2, 15, and 10 kcal mol−1 ,
∗
Atoms or molecules that impinge on the solid surface respectively. For small values of E D(surface) ordering is
from the gas phase will have a residence time τ on the sur- restricted to low temperatures, since as the temperature is
face. If the impinging molecules achieve thermal equilib- increased the adsorbate becomes very mobile. As the value
∗
rium with the surface atoms τ = τ0 exp Hads /RT , where of E D(surface) increases, ordering cannot commence at
τ0 is related to the average vibrational frequency associ- low temperature since the adsorbate atoms need to have
ated with the adsorbate. The heat of adsorption is always a considerable mean free path along the surface to find
positive and is defined as the binding energy of the ad- their equilibrium position once they land on the surface
sorbed species. A larger Hads and lower temperature in- at a different location. Naturally, if the temperature is too
crease the residence time. For a given incident flux, larger high, the adsorbate will desorb or vaporize.
Hads and lower temperature yield higher coverages. The binding forces of adsorbates on substrates have
It is conventional to divide adsorption into two cate- components perpendicular and parallel to the surface. The
gories: physisorption and chemisorption. Physisorption perpendicular component is primarily responsible for the
(or physical adsorption) systems are characterized by binding energy ( Hads ), while the parallel component of-
weak interactions ( Hads < 15 kcal mol−1 , accompanied ten determines the binding site on the surface. The binding
by short residence times) and require adsorption studies site may also be affected by adsorbate–adsorbate interac-
to be performed at low temperature and relatively high tions, which produce ordering within an overlayer. These
pressure (high flux). Adsorbates that are characterized by interactions may be subdivided into direct adsorbate–
stronger chemical interactions ( Hads ≥ 15 kcal mol−1 ), adsorbate interactions (not involving the substrate at all)
where near-monolayer adsorption commences even at and substrate mediated interactions. The latter are compli-
room temperature and at low pressures (≤10−6 torr), cated many-atom interactions, for example dipole–dipole
are called chemisorption systems. While the two names interactions.
imply two distinct types of adsorption, there is a grad- The adsorbate–adsorbate interactions may be repulsive;
ual change from the physisorption to the chemisorption they always are repulsive at sufficiently small adsorbate–
regime. adsorbate separations. At larger separations they may be
One of the most fascinating facts about the structure attractive, giving rise to the possibility of island formation.
of these physisorbed and chemisorbed overlayers in the They may also be oscillatory, moving back and forth be-
submonolayer to few monolayer regime is the preponder- tween attractive and repulsive as a function of adsorbate–
ance of the formation of long-range ordered structures. adsorbate separation, with a period of several angstroms
Well over 1000 two-dimensional unit cells have been doc- giving rise, for example, to non-close-packed islands.
umented in the literature. While only the shape, size, and Except for the strong repulsion at close separations, the
orientation of the cells are known for most of them, the adsorbate–adsorbate interactions are usually weak com-
adsorption site and bond lengths have been determined for pared to the adsorbate–substrate interactions, even when
about 500 of them. we consider only the components of the forces parallel
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Surface Chemistry 383

to the surface. In the case of chemisorption, where the

adsorbate–substrate interaction dominates, the adsorbates
usually choose an adsorption site that is independent of
the coverage and of the overlayer arrangement (the posi-
tions the other adsorbates choose). This adsorption site is
usually that location which provides the largest number of
nearest substrate neighbors, which is independent of the
position of other adsorbates. Adsorbates with these prop-
erties normally do not accept close packing; the substrate
controls the overlayer geometry and imposes a unique ad-
sorption site. Close packing of an adsorbate layer is also
observed. In this case the overlayer chooses its own lattice
(normally a hexagonal close-packed arrangement) with its
own lattice constant independent of the substrate lattice
and results in the formation of incommensurate lattices. In
this case no unique adsorption site exists: each adsorbate
is differently situated with respect to the substrate. This
situation is especially common in the physisorption of rare
gases. Their relatively weak adsorbate–substrate interac-
tions allow the adsorbate–adsorbate interactions to play
the dominant role in determining the overlayer geometry. FIGURE 11 Monolayer and multilayer phases of the n-paraffins
The chemisorption case is exemplified by oxygen and C3 to C8 on Pt(111) and the temperatures at which they are ob-
sulfur on metals; the physisorption case by krypton and served at 10−7 torr.
xenon on metals and graphite. Intermediate cases exist.
Although undissociated CO on metals is not physisorbed the adsorbed monolayer. Although changing the pressure
but chemisorbed, it sometimes produces incommensurate at a given temperature may be used to vary the coverage by
close-packed hexagonal overlayers. small amounts and thereby change the surface structures
in some cases, the variation of temperature has a much
more drastic effect on ordering.
1. The Effect of Temperature on Ordering
Temperature also markedly influences chemical bond-
Temperature has a major effect on the ordering of adsorbed ing to surfaces. There are adsorption states that can only
monolayers: all of the important ordering parameters (the be populated if the molecule overcomes a small poten-
rates of desorption and surface and bulk diffusion) are tial energy barrier. The various bond-breaking processes
exponential functions of the temperature. are similarly activated. The adsorption of most reactive
The influence of temperature on the ordering of C3 –C8 molecules on chemically active solid surfaces takes place
saturated hydrocarbons on the Pt(111) crystal face is without bond breaking at sufficiently low temperatures.
shown in Fig. 11. At the highest temperatures, adsorp- As the temperature is increased, bond breaking occurs se-
tion may not take place, since under the exposure condi- quentially until the molecule is atomized. Thus, the chem-
tions the rate of desorption is greater than the rate of con- ical nature of the molecular fragments will be different at
densation of the vapor molecules. As the temperature is various temperatures. There is almost always a tempera-
decreased, the surface coverage increases and ordering be- ture range for the ordering of intact molecules in chemi-
comes possible. First, one-dimensional lines of molecules cally reactive adsorbate–substrate systems. It appears that
form; then at lower temperatures ordered two-dimensional for these systems ordering is restricted to low tempera-
surface structures form. Not surprisingly, the temperatures tures below 150 K, and consideration of surface mobility
at which these ordering transitions occur depend on the becomes, perhaps, secondary.
molecular weights of the hydrocarbons, which also con-
trol their vapor pressure, heats of adsorption, and activa-
2. The Effect of Surface Irregularities on Ordering
tion energies for surface diffusion. As the temperature is
further decreased, multilayer adsorption may occur and A solid surface exhibits a large degree of roughness on
epitaxial growth of crystalline thin films of hydrocarbon a macroscopic scale. Therefore, it is to be expected that
commences. if nucleation is an important part of the ordering process,
Figure 11 clearly demonstrates the controlling effect of surface roughness is likely to play an important role in
temperature on the ordering and the nature of ordering of preparing ordered surface structures. The transformation
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384 Surface Chemistry

temperature or pressure at which one adsorbate surface ing a molecule such as CO, which has interactions strong
structure converts into another can also be affected by the enough to induce ordering in the overlayer. Similar phe-
presence of uncontrolled surface irregularities (surface de- nomena have been observed on Pt(111), and it is thought
fects). Other causes that could influence ordering are the that this coadsorbate-induced ordering may prove to be a
presence of small amounts of surface impurities that block very general phenomenon.
nucleation sites or interfere with the kinetics of ordering,
or impurities below the surface that are pulled to the sur-
C. Ordered Adsorbate Structures
face during adsorption and ordering.
The effect of surface irregularities on ordering can be As mentioned in the introduction to this section, well over
investigated in a more controlled way using stepped crys- 1000 ordered adsorbate structures have been observed
tal surfaces. In general, the smaller the ordered terrace with LEED. A full listing and discussion of these struc-
between the steps, the stronger the effect of steps on or- tures is outside the scope of this article. Instead, one ex-
dering. For instance, the ordering of small molecular ad- ample of each of the three following categories of ad-
sorbates on a high-Miller-index Rh(S)-[6(111) × (100)] is sorption are presented to give an illustrative indication of
largely unaffected by the presence of steps whereas on the the types of structures found: (i) an ordered monolayer of
Rh(S)[3(111) × (111)] the ordering is influenced by the atoms, (ii) an ordered organic monolayer, and (iii) an or-
higher step density. Steps can also affect the nucleation of dered molecular monolayer. First, a few generalities of the
ordered domains. It is frequently observed on W and Pt ordered adsorbate structures are discussed, based on the
stepped surfaces that when two or three equivalent ordered large number of LEED observations: the so-called “rules
domains may form in the absence of steps, only one of the of ordering”:
ordered domains grows in the presence of steps.
1. The rule of close-packing. Adsorbed atoms or
molecules tend to form surface structures characterized
3. The Effect of Coadsorbates on Ordering by the smallest unit cell permitted by the molecular dimen-
It has been found that although certain molecules may not sions and adsorbate–adsorbate and adsorbate–substrate
order when present on their own on a surface they can be interactions. They prefer close-packing arrangements.
induced to order by coadsorption of either carbon monox- Large reciprocal unit meshes are uncommon and the
ide or nitric oxide. For example Table I summarizes the most frequently observed meshes are the same size as the
ordered structures that have been observed by the coad- substrate mesh, i.e., (1 × 1) or are approximately
√ √ twice as
sorption of alkylidynes, acetylene, aromatics, and alkalis large, e.g., (2 × 2), c(2 × 2), (2 × 1), ( 3 × 3).
with CO on Rh(111). 2. The rule of rotational symmetry. Adsorbed atoms
At low temperature both Na and ethylidyne form (2 × 2) or molecules form ordered structures that have the same
overlayers on Rh(111) but with increasing temperature rotational symmetry as the substrate surface. If the surface
begin to disorder. If CO is coadsorbed then the adsorbates unit mesh has a lower symmetry than the substrate, then
can be reordered into a c(4 × 2) unit cell. domains of the various possible mesh orientations are to be
It is thought that the nature of this type of order- expected on different areas of the surface with a resulting
ing process is due to adsorbate–adsorbate interactions: increase in symmetry.
A molecule that might not otherwise order due to weak 3. The rule of similar unit cell vectors. Adsorbed atoms
adsorbate–adsorbate interactions is ordered by coadsorb- as molecules in monolayer thickness tend to form ordered
surface structures characterized by unit cell vectors closely
TABLE I Ordered Structures Induced by CO on Rh(111)
related to the substrate unit cell vectors. The surface struc-
ture bears a closer resemblance to the substrate structure
Type of molecule LEED pattern System than to the structure of the bulk condensate.
Alkylidynes c(4 × 2) CCH3 + CO
√ √ These are not hard-and-fast rules but rather are gener-
(2 3 × 2 3)R30◦ 3CCH2 CH3 + CO
Acetylene c(4 × 2) C2 H2 + CO
alizations of a great many systems.
(3 × 3) C6 H5 F + 2CO
Aromatics (3 × 3) C6 H6 + 2CO 1. Ordered Atomic Monolayers
√
c(2 3 × 4)Rect C6 H6 F + CO
√ Some important conclusions can be drawn from the known
c(2 3 × 4)Rect C6 H6 + CO
√ structures of atomic adsorbates on single-crystal surfaces.
Alkalis ( 3 × 7)Rect Na + 7CO
First, the adsorbed atoms tend to occupy sites where they
c(4 × 2) Na + CO
are surrounded by the largest number of substrate atoms
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Surface Chemistry 385

(largest coordination number). This site is usually the one

that the bulk atoms would occupy in order to continue the
bulk lattice into the overlayer. The tendency toward occu-
pying the site with the largest coordination number during
adsorption on metals holds independently of the crystal-
lographic face of a given metal, the metal for a given crys-
tallographic face, and the adsorbate for a given substrate.
Second, the adsorbed atom–substrate atom bond lengths
are similar to the bond lengths in organometallic com-
FIGURE 13 Structure of the p (2 × 2) and c (2 × 2) sulphur over-
pounds that contain the atom pairs under consideration.
layers on Ni(100).
The most common adsorption geometries are displayed
in Fig. 12. The threefold hollow sites on the fcc(111) and
hcp(0001) and bcc(110) are shown both in top and side actions there may be a rearrangement of the substrate
views. Similarly, the fourfold hollow sites on the fcc(100) layer (an adsorbate-induced reconstruction). One exam-
and bcc(100) crystal faces are shown. Finally, the center, ple is oxygen on the Fe(100) crystal face.
long-bridge, and short-bridge sites on the fcc(100) crystal As an example of ordered atomic adsorption Fig. 13 por-
face and the location of atoms in an underlayer in the trays the two structures of sulfur on Ni(100). At a coverage
hcp(0001) crystal face are also displayed. of one-quarter of a monolayer of S, a p(2 × 2) overlayer is
In addition to the situations discussed, there exist some formed, and at one-half of a monolayer a c(2 × 2) structure
unique atomic adsorbate geometries. For example, small is observed. In both cases the S sits in the fourfold hollow
atoms such as nitrogen and hydrogen often prefer to sit site (highest coordination). A LEED intensity analysis has
below the surface, as in the case of titanium single-crystal been performed for both structures, and within experimen-
surfaces. Also in the presence of strong chemical inter- tal error the bond lengths are the same for both structures.

FIGURE 12 Top and side views (in top and bottom sketches of each panel) of adsorption geometries on various
metal surfaces. Adsorbates are drawn shaded. Dotted lines represent clean surface atomic positions; arrows show
atomic displacements due to adsorption.
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386 Surface Chemistry

2. Ordered Molecular Monolayers LEED pattern. A LEED structural analysis has not been
performed for this structure, but supporting evidence us-
Molecules adsorbed on surfaces may retain their ba-
ing infrared spectroscopy indicates that the CO molecules
sic molecular identity, bonding as a whole to the sub-
sit in the threefold hollow sites. As the coverage  is in-
strate. They may dissociate into their constituent atoms,
creased to one-half of a monolayer the LEED pattern trans-
which bond individually to the substrate. Alternatively,
forms to a c(4 × 2). In this structure the CO molecules all
molecules may break up into smaller fragments which
sit in twofold bridge sites. If the adsorption takes place at
become largely independent or recombine into other con-
low temperature (90 K), incrcasing the CO coverage be-
figurations. There are also cases of intermediate character
yond  = 0.5 leads to the appearance of a series of LEED
where relatively strong bonding distorts the molecule.
patterns arising from hexagonal superstructures, which by
One example of ordered molecular monolayers is CO
a continuous compression and rotation of the c(4 × 2) unit
on Pd(111). The (111) surface of fcc metals is the close-
cell lead to a (2 × 2) coincidence pattern at a coverage of
packed plane and shows similar ordering for adsorbed
√ √CO  = 0.75. These transformations are also shown schemat-
for a variety of transition metals. That is the ( 3 × 3)-
ically in Fig. 14.
R30◦ structure, formed at a coverage of one-third of a
monolayer on the (111) faces of Pd, Ni, Pt, Ir, Cu, and
Rh. This similarity in ordering is probably due to their
3. Ordered Organic Monolayers
surfaces being rather smooth with respect to variations in
the CO adsorption energy. Smaller diffusion barriers be- The adsorption characteristics of organic molecules on
tween different adsorption sites are to be expected, and solid surfaces are important in several areas of surface
for large coverages repulsive interactions will be mainly science. The nature of the chemical bonds between the
responsible for the arrangement of the adlayer.
√ √Figure 14 substrate and the adsorbate and the ordering and orien-
shows a schematic representation of this ( 3 × 3)-R30◦ tation of the adsorbed organic molecules play important
CO structure on Pd(111) and the corresponding observed roles in adhesion, lubrication, and hydrocarbon catalysis.

FIGURE 14 Schematic representation of the CO on Pd(111) system. Structure models and observed LEED structures
for the various CO coverages  are shown.
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Surface Chemistry 387

There are many examples in the literature of ordered D. Vibrational Spectroscopy

structures observed by LEED, but only a few of these
structures have been calculated from the diffraction beam Vibrational frequencies have been used for many years by
intensities. However, the ordering characteristics and size chemists to identify bonding arrangements in molecules.
and orientation of the unit cells have been determined from Each bond has its own frequency, so the vibrational
the geometry of the LEED patterns. By studying the sys- spectrum yields information on the molecular structure.
tematic variation of their shape and bonding characteris- This same information can now be obtained when
tics correlations can be made between these properties and molecules are adsorbed on single-crystal surfaces and,
their interactions with the metal surfaces. when combined with another surface-structure-sensitive
Examples of ordered organic monolayers are normal technique (e.g., LEED), gives a very powerful combi-
paraffins on platinum and silver (111) surfaces. If straight- nation of surface-structure determination. Vibrational
chain saturated hydrocarbon molecules from propane spectroscopy also provides significant information on the
(C3 H8 ) to octane (C8 H18 ) are deposited from the vapor identity of the surface species; its geometric orientation;
phase onto Pt or Ag (111) between 100 and 200 K ordered the adsorption site; the adsorption symmetry; the nature
monolayers are produced. As the temperature is decreased of the bonding involved; and, in some cases, bond lengths,
a thick crystalline film can condense. The paraffins adsorb bond angles, and bond energies. For example, if CO is
with their chain axis parallel to the platinum substrate, and adsorbed and we observe the C O stretching mode the
their surface unit cell increases smoothly with increasing adsorption is molecular, whereas if the individual modes
chain length as shown in Fig. 15. of metal-C and metal-O are observed then dissociation has
Multilayers condensed on top of the ordered monolay- taken place. In addition, each of these vibrational modes
ers maintain the same orientation and packing found in (C, O, and CO) has a different frequency for each bonding
the monolayers. The monolayer structure determines the site. The intensities also relate to the concentration of
growth orientation and the surface structure of the grow- each species on the surface.
ing organic crystal. This phenomenon is called pseudo- Electrons scattering off surfaces can lose energy in var-
morphism, and as a result, the surface structures of the ious ways. One of these ways involves excitation of the
growing organic crystals do not correspond to planes in vibrational modes of atoms and molecules on the sur-
their reported bulk crystal structures. face. The technique to detect vibrational excitation from
surfaces by incident electrons is called high-resolution
electron energy loss spectroscopy (EELS). This is the
most common type of vibrational spectroscopy used for
studying surface–absorbate complexes on single-crystal
surfaces.
Experimentally, a highly monoenergetic beam of elec-
trons is directed toward the surface, and the energy spec-
trum and angular distribution of electrons backscattered
from the surface is measured. In a typical experiment the
kinetic energy of the incident electron beam is in the range
of 1–10 eV. Under these conditions the electrons penetrate
only the outermost few layers of the crystal, and the back-
scattered electrons contain only surface information. The
incident electrons, monochromatized typically between
3 and 10 meV (∼25–80 cm−1 , 1 meV = 8.065 cm−1 ) and
with energy E i , can lose energy hω upon exciting a quan-
tized vibrational mode. These backscattered electrons of
energy E i − hω produce the vibrational spectrum. There
are several designs of electron monochromator and elec-
tron energy analyzers for performing EELS, and one of the
most common designs, that of a single-pass 127◦ cylindri-
cal electrostatic deflector, is shown in Fig. 16. A typical
EELS spectrum, that of CO on Rh(111) is shown in Fig. 17.
The sensitivity of EELS in detecting submonolayer
FIGURE 15 Observed surface unit cells for n-paraffins on quantities of adsorbates on the sample depends on the par-
Pt(111). ticular parameters of the spectrometer, the sample, and the
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388 Surface Chemistry

adsorbate. However, typical sensitivity is quite high due in

part to the high inelastic electron cross section. A detection
limit of ∼10−4 monolayers can be achieved for a strong
dipole scatterer such as CO. In addition, unlike many other
surface spectroscopies, EELS is also capable of detecting
adsorbed hydrogen, although at a lower sensitivity (typi-
cally 10−1 –10−2 monolayers). It is a nondestructive tech-
nique and can be used to explore the vibrational modes
of weakly adsorbed species and those susceptible to beam
damage, such as hydrocarbon overlayers.
The spectral range accessible with high-resolution
EELS is quite large. Typical experiments examine
between 200 and 4000 cm−1 , but much larger regions can
be analyzed. Vibrational modes as far out as 16,000 cm−1
have been examined. Besides fundamentals, energy losses
due to overtones, combination bands, and multiple losses
are distinguishable.
A distinct advantage of EELS is that electrons can ex-
cite the vibrational modes of the surface by three different
mechanisms: dipole scattering, impact scattering, and res-
onance scattering. By analyzing the angular dependence
FIGURE 16 Schematic diagram of an EELS spectrometer of the of the inelastically scattered electrons a complete symme-
single-pass 127◦ cylindrical electrostatic deflector type.
try assignment of the surface–adsorbate complex can be
made.
The restrictions on the adsorption system are minimal:
ordered or disordered overlayers can be examined, as can
either well-structured single crystal samples or optically
rough surfaces. Hence, chemisorption on evaporated
films can be studied, as can the nature of metal overlayer–
semiconductor interactions. In addition, coadsorbed
atoms and molecules can be studied without difficulty.
The major disadvantage of EELS, especially compared
to optical techniques, is the relatively poor instrumental
resolution, which usually varies between 3 and 10 meV
(25–80 cm−1 ). The spectral resolution hinders assignment
of vibrations due to individual modes, although peak as-
signments can be made to within 10 cm−1 . The high sen-
sitivity of EELS coupled with the advantages discussed
above has encouraged rapid development and use of this
technique, despite resolution limitations, such that it has
now been used to study hundreds of adsorptions systems.
As an example of the type of surface chemistry that can
be followed using EELS, Fig. 18 shows a series of EELS
spectra of the adsorption and thermal decomposition of
ethylene on Rh(111).

III. THERMODYNAMICS OF SURFACES

FIGURE 17 Electron energy loss spectrum of CO adsorbed on A. Introduction

Rh(111). The loss peak at 468 cm−1 is due to the Rh–CO sym-
metric stretch, and that at 2036 cm−1 is due to the C–O symmetric The environment of atoms in a surface is substantially dif-
stretch. The spectrum was recorded at a resolution of 30 cm−1 . ferent to that of atoms in the bulk of the solid. Surface
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Surface Chemistry 389

Therefore, E S is the excess of total energy that the solid

has over E 0 , which is the energy that the system would
have if the surface were in the same thermodynamic state
as the interior.
The other surface thermodynamic functions are defined
similarly, for example, the specific surface free energy G S
is given by the following:
G S = H S − T SS, (5)
S S
where H and S are the specific surface enthalpy and
entropy, respectively.

B. Surface Tension in a
One-Component System
Creating a surface involves breaking chemical bonds and
removing neighboring atoms, and this requires work.
Under conditions of constant temperature and pressure
at equilibrium, the surface work δW S is given by the
following:
δWT,P
S
= d(G S A), (6)
where A is the increase in the surface area. If G S is
independent of the surface area, surface work is as follows:
δWT,P
S
= G S d A. (7)
In a one-component system the specific surface free en-
ergy, G S , is frequently called the surface tension or surface
pressure and is denoted by γ . Here γ may be viewed as
a pressure along the surface opposing the creation of new
surface. It has dimensions of force per unit length (dynes
per centimeter, ergs per square centimeter, or newtons
per meter). The surface tension γ for an unstrained phase
is also equal to the increase of the total free energy of the
system per unit increase of the surface area as follows:
 
∂G
γ =G = S
. (8)
∂ A T,P
FIGURE 18 EELS spectra of the adsorption and decomposition
of ethylene (C2 H4 ) on Rh(111) at (a) 77 K, (b) 220 K, and (c) The free energy of formation of a surface is always
450 K. positive, since work is required in creating a new surface,
which increases the total free energy of the system. In or-
atoms are surrounded by fewer nearest neighbors than der to minimize their free energy solids or liquids assume
bulk atoms, and these neighbors are not distributed evenly shapes in equilibrium with the minimum exposed surface
around the surface atoms. An atom in the interior experi- area as possible. For example, liquids tend to form a spher-
ences no net forces, but these forces become unbalanced ical shape and crystal faces which exhibit the closest pack-
at the surface. Consequently the thermodynamic parame- ing of atoms tend to be the surfaces of lowest free energy
ters used to describe surfaces are defined separately from of formation and thus the most stable. Surface tension
those that characterize the bulk phase. The specific surface is one of the most important thermodynamic parameters
energy E S , the energy per surface area, is related to the characterizing the condensed phase. Table II lists selected
total energy E by the following equation: experimentally determined values of surface tensions of
liquids and solids that were measured in equilibrium with
E = NE 0 + AE S , (4)
their vapor.
where A is the surface area of a solid composed of N Comparing the surface tension values of metals and ox-
atoms, and E 0 is the energy of the bulk phase per atom. ides in Table II it can be seen that oxides have in general
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390 Surface Chemistry

TABLE II Selected Values of Surface Tension of related to the heat of vaporization, which is related to the
Solids and Liquids energy input necessary to break all the bonds of atoms in
Material γ (ergs cm−2 ) T (◦ C) the condensed phase. In fact, it has been found experimen-
tally that the molar surface free energy of a liquid metal
He (1) 0.308 −270.5 can be estimated by the following:
N2 (1) 9.71 −195
Ethanol (1) 22.75 20 γlm = 0.15 Hvap , (9)
Water 72.75 20 where Hvap is the heat of vaporization of the liquid, and
Benzene 28.88 20 the molar surface free energy of a solid metal is given by
n-Octane 21.80 20 the following:
Carbon tetrachloride 26.95 20
Bromine 41.5 20 γsm = 0.16 Hsub , (10)
W (s) 2900 1727
where Hsub is the heat of sublimation of the solid.
Nb (s) 2100 2250
For other materials, oxides, or organic molecules, such
Au (s) 1410 1027
a simple relationship does not work due to the complexity
Ag (s) 1140 907
of bonding and the rearrangement or relaxation of surface
Ag (l) 879 1100
atoms at the freshly created surfaces.
Fe (s) 2150 1400
Fe (l) 1880 1535
Pt (s) 2340 1311 C. Surface Tension of Multicomponent Systems
Cu (s) 1670 1047
In many important surface phenomena, such as heteroge-
Ni (s) 1850 1250
neous catalysis or passivation of the surface by suitable
Hg (l) 487 16.5
protective coatings, the chemical composition of the top-
NaCl (s) 227 25
most layer controls the surface properties and not the com-
KCl (s) 110 25
position in the bulk. Thus, investigations of the physical–
CaF2 (s) 450 −195
chemical parameters that control the surface composition
MgO (s) 1200 25
are of great importance. One of the major driving forces
SiO2 (s) 307 1300
for the surface segregation of impurities from the bulk and
Al2 O3 (s) 690 2323
for the change of composition of alloys and other multi-
Polytetrafluoroethylene 18.5 20
component systems is the need to minimize the surface
Polyethylene 31 20
free energy of the condensed phase system.
Polystyrene 33 20
The change of the total free energy of a multicomponent
Poly(vinyl chloride) 39 20
system can be expressed with the inclusion of the surface
term as follows:

a low surface tension. Therefore, a reduction in the total dG = S dT + V d P + γ d A + µi dn i , (11)
i
free energy of the system can be achieved by oxidation of
the surface and a uniform oxide layer covering the surface where µi is the chemical potential of the ith compo-
is expected under conditions near thermodynamic equilib- nent and dn i is the change in the number of moles of
rium. Similarly, deposition and growth of a metal film on a the ith component. At constant temperature and pressure,
metallic substrate of higher surface tension should yield a Eq. (11) can be rewritten as follows:

uniform layer that is evenly spread to completely cover the dG T,P = γ d A − µi dn i , (12)
substrate surface. Likewise, a very poor spreading of the i
film is expected on deposition of a metal of high surface
where the minus sign indicates the decrease of the bulk
tension on a low-surface-tension substrate. This latter con-
concentration of the ith component. Comparing this equa-
dition results in “island growth” and the deposited high-
tion with Eq. (8), the surface tension γ is no longer equal
surface-tension metal will grow as whiskers to expose
to the specific surface free energy per unit area for a mul-
as much of the low-surface-tension substrate during the
ticomponent system. Using simple arguments in which
growth as possible. These, of course, are surface thermo-
number of moles of the condensed phase are transferred
dynamic predictions and may be overidden by the presence
to the freshly created surface, the Gibbs equation can be
of impurities at the surface or difficulties of nucleation.
derived as follows:
Since atomic bonds must be broken to create surfaces, 
it is expected that the specific surface free energy will be dγ = −S S dT = i dµi , (13)
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Surface Chemistry 391


where i is the excess number of moles of compound i X 2S X 2b (γ1 − γ2 )a (l + m)
at the surface. Just like the free energy relations for bulk = exp exp
X 1S X 1b RT RT
phases, the Gibbs equation predicts changes in surface ten-
sion as a function of experimental variables such as tem-  2  2 l  S 2  S 2
× X 1b − X 2b + X2 − X1 ,
perature and surface concentration of various components. RT
As a result of the Gibbs equation, the surface composition (17)
in equilibrium with the bulk for a multicomponent system
can be very different from the bulk composition. where  is the regular solution parameter and is directly
As an example we discuss the surface composition of related to the heat of mixing Hm by the following:
an ideal binary solution. For such a solution at a con- Hm
stant temperature the Gibbs equation can be expressed as =  .
X 1b l − X 1b
follows:
Here l is the fraction of nearest neighbors to an atom in
dγT = −1 dµ1 − 2 dµ2 (14) the plane and m is the fraction of nearest neighbors below
and it has been shown that the surface tension of the plane containing the atom. In this approximation the
component 1 in an idea dilute solution is given by the surface composition becomes a fairly strong function of
following: the heat of mixing, its sign, and its magnitude in addition
   to the surface tension difference and temperature.
γ = γ1 + (RT /a) ln X 1S X 1b , (15)
Auger electron spectroscopy (AES) and ion scattering
where γ1 is the surface tension of the pure component spectroscopy (ISS) are two experimental techniques which
and a the surface area occupied by one mole of com- are most frequently used for quantitative determination of
ponent 1. Perfect behavior is assumed, i.e., the surface the surface composition. Figure 19 shows the surface atom
areas occupied by the molecules in the two different com- fraction of gold, determined by AES and ISS, plotted as a
ponents are the same (a1 = a2 = a); X 1S and X 1b are the function of the bulk atom fraction for the Ag–Au system.
atom fractions of component 1 in the surface and in The solid line gives the calculated surface composition
the bulk, respectively. It is also assumed that the sur- using the regular solution model and the dashed line indi-
face consists of only the topmost atomic layer. For a cates the curve that would be obtained in the absence of
two-component system, Eq. (15) can be rewritten in the surface enrichment. The regular solution model appears
following form: to overestimate somewhat the surface segregation in this
 case, although the surface is clearly enriched in silver.
X 1S X 1b (γ2 − γ1 )a
S
= b exp , (16) Table III lists several binary alloy systems that have
X2 X2 RT been investigated experimentally by AES or ISS and
where X 1S , X 2S , X 1b , X 2b have their meaning defined above;
γ1 and γ2 are the surface tensions of the pure compo-
nents; and the other symbols have their usual meaning.
From Eq. (16), it can be seen that the component that
has the smaller surface tension will accumulate on the
surface.
Equation (16) also predicts that the surface composi-
tion of ideal solutions should be an exponential function
of temperature. While the bulk composition of a multicom-
ponent system is little affected by temperature, the surface
concentration of the constituents may change markedly.
The surface segregation of one of the constituents be-
comes more pronounced the larger the difference in sur-
face tensions between the components that make up the
solution. Surface segregation is expected to be prevalent
for metal solutions, since metals have the highest surface
tensions.
In reality, however, metallic alloys are not ideal solu-
tions since they have some finite heat of mixing. In such a
case the surface composition can be approximated in the
regular solution monolayer approximation FIGURE 19 Surface phase diagram of Au–Ag alloy.
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392 Surface Chemistry

TABLE III Surface Composition of Alloys: system. As a result, the surface composition may markedly
Experimental Results and Predictions of the change with changing ambient conditions.
Regular Solution Model
The mechanical properties of solids, embrittlement,
Segregating constituent and crack propagation, among others, depend markedly
on the surface composition. These studies indicate that
Alloy Predicted
system regular solution Experimental
the surface composition and the mechanical properties of
structural steels may change drastically when the ambi-
Ag–Pd Ag Ag ent conditions are changed from reducing to oxidizing
Ag–Au Ag Ag environments.
Au–Pd Au Au
Ni–Pd Pd Pd
D. Equilibrium Shape of a Crystal
Fe–Cr Cr Cr
or a Liquid Droplet
Au–Cu Cu Au, none, or Cu
depending on In equilibrium the crystal will take up a shape that corre-
composition
sponds to a minimum value of the total surface free energy.

Cu–Ni Cu Cu
In order to have the equilibrium shape, the integral γ d A
Au–Ni Au Au
over all surfaces of the crystal must be a minimum. Crystal
Au–Pt Au Au
faces that have high atomic density have the lowest sur-
Pb–In Pb Pb
face free energy and are therefore most stable. The plot of
Au–In In In
the surface free energy as a function of crystal orientation
Al–Cu Al Al
is called the γ plot.
Pt–Sn Sn Sn
Solids and liquids will always tend to minimize their
Fe–Sn Sn Sn
surface area in order to decrease the excess surface free
Au–Sn Sn Sn
energy. For liquids, therefore, the equilibrium surface be-
comes curved where the radius of curvature will depend
on the pressure difference on the two sides of the interface
the segregating components that were experimentally and on the surface tension as follows:
observed and also predicted by the regular solution
(Pin − Pext ) = 2γ /r, (18)
model. The agreement is certainly satisfactory. It appears
that for binary metal alloy systems that exhibit regular where Pin and Pext are the internal and external pressures,
solution behavior there are reliable methods to predict respectively, and r is the radius of curvature. In equi-
surface composition. librium a pressure difference can be maintained across
So far we have discussed the surface composition of a curved surface. The pressure inside the liquid drop or
multicomponent systems that are in equilibrium with their gas bubble is higher than the external pressure, because
vapor or in which clean surface–bulk equilibrium is ob- of the surface tension. The smaller the droplet or larger
tained in ultrahigh vacuum. In most circumstances, how- the surface tension, the larger is the pressure difference
ever, the surface is covered with a monolayer of adsor- that can be maintained. For a flat surface r = ∞, and the
bates that frequently form strong chemical bonds with the pressure difference normal to the interface vanishes.
surface atoms. This solid–gas interaction can markedly Let us now consider how the vapor pressure of a
change the surface composition in some cases. For exam- droplet depends on its radius of curvature r . We obtain
ple, carbon monoxide, when adsorbed on the surface of a the following:
Ag–Pd alloy, forms much stronger bonds with Pd. While
ln (P/P0 ) = 2γ Vin /RT r, (19)
the clean surface is enriched with Ag, in the presence of
CO, Pd is attracted to the surface to form strong carbonyl where Vin is the internal volume. This is the well-known
bonds. When the adsorbed CO is removed, the composi- Kelvin equation for describing the dependence of the va-
tion returns to its original Ag-enriched state. Nonvolatile por pressure of any spherical particle on its size. Small
adsorbates, such as carbon or sulfur, may have a simi- particles have higher vapor pressures than larger ones.
lar influence on the surface composition as long as their Similarly, very small particles of solids have greater solu-
bonding to the various constituents of the multicomponent bility than large particles. If we have a distribution of parti-
system is different. cles of different sizes, we will find that the larger particles
Adsorbates should therefore be viewed as an additional will grow at the expense of the smaller ones. Nature’s way
component of the multicomponent system. A strongly in- to avoid the sintering of small particles that would occur
teracting adsorbate converts a binary system to a ternary according to the Kelvin equation is to produce a system
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Surface Chemistry 393

with particles of equal size. This is the world of colloids ting ability of the liquid at the solid interface is so im-
where particles are of equal size and therefore stabilized portant in practical problems of adhesion or lubrication,
and are usually charged either all negative or all positive there is a great deal of work being carried out to deter-
or to repel each other by long-range electrostatic forces. mine the interfacial tensions for different combinations of
Milk and our blood are only two examples of systems that interfaces.
contain colloids. The usefulness of a lubricant is determined by the extent
to which it wets the solid surface and maintains complete
E. Adhesion and the Contact Angle coverage of the surface under various conditions of use.
The strength of an adhesive is determined by the extent to
Let us turn our attention to the interfacial tension, that which it lowers the surface free energy by adsorption on
is, the surface tension that exists at the interface of two the surface. The work of adhesion is defined as follows:
condensed phases. Let us place a liquid droplet on a solid
surface. The droplet either retains its shape and forms a WAs = γ1,0 + γs,0 − γsl , (21)
curved surface or it is spread evenly over the solid. These where γ1,0 and γs,0 are the surface tensions in vacuum of
two conditions indicate the lack of wetting or wetting of the liquid and solid, respectively. In general, solids and liq-
the solid by the liquid phase, respectively. The contact uids that have large surface tension form strong adhesive
angle between the solid and the liquid, to a large extent, bonds, i.e., have large work of adhesion. The work of ad-
permits us to determine the interfacial tension between hesion is in the range of 40–150 ergs/cm2 for solid–liquid
the solid and the liquid. The contact angle is defined by pairs of various types. Organic polymers often make ex-
Fig. 20. If the contact angle is large ( approaching 90◦ ), cellent adhesives because of the large surface area covered
the liquid does not readily wet the solid surface. If  ap- by each organic molecule. The adhesive energy per mole
proaches zero, complete wetting of the solid surface takes is much larger than that for adhesion between two metal
place. For  larger than 90◦ the liquid tends to form spher- surfaces or between a liquid and a solid metal because of
ical droplets on the solid surface that may easily run off, the many chemical bonds that may be formed between the
i.e., the liquid does not wet the solid surface at all. Re- substrate and the adsorbed organic molecule.
membering that the surface tension always exerts a pres-
sure tangentially along a surface, the surface free energy
F. Nucleation
balance between the surface forces acting in opposite di-
rections at the point where the three phases solid, liquid, Another important phenomenon that owes its existence to
and gas meet is given by the following: positive surface free energy is nucleation. In the absence
cos  = (γsg − γsl )/γlg . (20) of a condensed phase, it is very difficult to nucleate one
from vapor atoms because the small particles that would
Here γlg is the interfacial tension at the liquid–gas inter- form have a very high surface area and dispersion and, as
face and γsg and γsl are the interfacial tensions between a result, a very large surface free energy. The total energy
the solid–gas and the solid–liquid interfaces, respectively. of a small spherical particle has two major components:
Knowing γlg and the contact angle in equilibrium at the its positive surface free energy, which is proportional to
solid–liquid–gas interface, we can determine the differ- πr 2 γ , where r is the radius of the particle, and its neg-
ence γsg − γsl but not their absolute values. Since the wet- ative free energy of formation of the particle with vol-
ume V . The volumetric energy term is proportional to
−r 3 ln (P/Peq ), where P is the pressure over the system
and Peq is the equilibrium vapor pressure:
   
4πr 3 P
G(total) = − RT ln + 4πr 2 γ , (22)
3Vm Peq
where Vm is the molar volume of the forming particle. Ini-
tially, the atomic aggregate is very small and the surface
free energy term is the larger of the two terms. In this cir-
cumstance a condensate particle cannot form from the va-
por even at relatively high saturation (P > Peq ). Similarly,
a liquid may be cooled below its freezing point without
FIGURE 20 Definition of the contact angle between a liquid and solidification occurring.
solid and the balance of surface forces at the contact point among Above a critical size of the spherical particles the
the three phases (solid, vapor, and liquid). volumetric term becomes larger and dominates since it
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394 Surface Chemistry

FIGURE 22 One-dimensional potential energy of an adatom in a

physisorbed state on a planar surface as a function of its distance
z from the surface.

An incoming molecule with kinetic energy E k must lose

at least this amount of energy in order to stay on the
surface. It loses energy by exciting lattice phonons in
the substrate, for example, and the molecule comes to
equilibrium in a state of oscillation in the potential well
FIGURE 21 Free energy of homogeneous nucleation as a func- of depth equal to the binding energy or adsorption energy
tion of particle size. E a = Hads . In order to leave the surface (desorb) the
molecule must acquire enough energy to surmount the
potential-energy barrier E a . The desorption energy is
decreases as ∼r 3 , while the surface free energy term in- equal to the adsorption energy. The binding energies of
creases only as ∼r 2 . Therefore, a particle that is larger than physisorbed molecules are typically ≤15 kcal mol−1 .
this critical size grows spontaneously at P > Peq . This is Chemisorption involves chemical bonding; it is similar
shown in Fig. 21. Because of the difficulty of obtaining to a chemical reaction and involves transfer of electronic
this critical size, which involves as many a 30–100 atoms charge between adsorbent and adsorbate. The most ex-
or molecules, homogeneous nucleation is very difficult treme form of chemisorption occurs when integral num-
indeed. To avoid this problem we add to the system parti- bers of electrons are transferred, forming a pure ionic
cles of larger than critical size that “seed” the condensation bond. More usually there is an admixture of the wave
or solidification. The use of small particles to precipitate functions of the valence electrons of the molecule with the
water vapor in clouds to start rain and the use of small valence electrons of the substrate into a new wave func-
crystallites as seeds in crystal growth are two examples of tion. The electrons responsible for the bonding can then
the application of heterogeneous nucleation. be thought of as moving in orbitals between substrate and
adatoms and a covalent bond has been formed. Two exam-
ples of the potential energy diagrams for chemisorption are
G. Physical and Chemical Adsorption
shown in Fig. 23. Some of the impinging molecules are ac-
The concepts of physical adsorption (physisorption) and commodated by the surface and become weakly bound in a
chemical adsorption (chemisorption) were introduced physisorbed state (also called a precursor state) with bind-
above. The nature of the two classifications is linked ing energy E p . During their stay time in this state, elec-
to the heat of adsorption, Hads , which is defined as tronic or vibrational processes can occur which allow them
the binding energy of the adsorbed species. Physical to surmount the energy barrier, and electron exchange oc-
adsorption is caused by secondary attractive forces (van curs between the adsorbate and substrate. The molecule,
der Waals) such as dipole–dipole interaction and induced or adatom in the case of dissociative chemisorption, now
dipoles and is similar in character to the condensation of finds itself in a much deeper well; it is chemisorbed.
vapor molecules onto a liquid of the same composition. Figure 23a shows the case in which the energy barrier
The interaction can be described by the one- for chemisorption is less than E p , so there is no overall
dimensional potential energy diagram shown in Fig. 22. activation energy to chemisorption. Figure 23b illustrates
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Surface Chemistry 395

the case of adsorption isotherms for physical adsorption,

to determine the surface area of the adsorbing solid.
Consider a uniform surface with a number n 0 of equiva-
lent adsorption sites. The ratio of the number of adsorbed
atoms or molecules n to n 0 is defined as the coverage,
 = n/n 0 . Atoms or molecules impinge on the surface
from the gas phase, where they establish a surface con-
centration [n a ]s (molecules per square centimeter). As-
suming that only one type of species of concentration [n a ]g
(molecules per cubic centimeter) exists in the gas phase
the adsorption process can be written as follows:
k
FIGURE 23 One-dimensional potential energy curves for disso- Agas 
 Asurface
k
ciative adsorption through a precursor or physisorbed state: (a)
adsorption into the stable state with no activation energy and (b) and the net rate of adsorption as
adsorption into the chemisorption well with activation energy E ∗ .
F (molecules cm−2 sec−1 ) = k[n a ]g − k  [n a ]s , (23)

where k and k are the rate constants for adsorption and
the case in which there is an overall activation energy E ∗ desorption, respectively. Starting with a nearly clean sur-
to chemisorption. In the former case the activation energy face far from equilibrium, the rate of desorption may be
for desorption E d is equal to the heat of adsorption, while taken as zero and Eq. (23) becomes the following:
in the latter case the heat of adsorption is given by the
difference between the heat of desorption and the acti- F (molecules cm−2 sec−1 ) = k[n a ]g , (24)
vation energy. The occurrence of an activation energy to where k, derived from the kinetic theory of gases, equals
chemisorption is by far the exception rather than the rule. α(RT /2π M)1/2 cm sec−1 , α is the adsorption coefficient,
From these considerations it is expected that to a first and M the molecular weight of the impinging molecules.
approximation physisorption will be nonspecific, any gas The surface concentration [n a ]s under these conditions is
will adsorb on any solid under suitable circumstances. the product of the incident flux F and the surface residence
However, chemisorption will show a high degree of speci- time τ :
ficity. Not only will there be variations from metal surface
to metal surface, as would be expected from the differ- [n a ]s = Fτ. (25)
ences in chemistries between the metals, but also different Here τ is the surface residence time, given by:
surface planes of the same metal may show considerable
differences in reactivity toward a particular gas. τ = τ0 exp( Hads /RT ). (26)
Replacing [n a ]g by the pressure using the ideal gas law,
H. Adsorption Isotherms Eq. (25) can be rewritten as follows:
 
An adsorption isotherm is the relationship at constant tem- αPN A Hads
[n a ]s = τ0 exp . (27)
perature between the partial pressure of the adsorbate and (2π MRT)1/2 RT
the amount adsorbed at equilibrium. Similarly an adsorp- The simplest adsorption isotherm is obtained from
tion isobar expresses the functional relationship between Eq. (27), which can be rewritten as
the amount adsorbed and the temperature at constant pres-
sure, and an adsorption isostere relates the equilibrium  = k  P (28)
pressure of the gaseous adsorbate to the temperature of where
the system for a constant amount of adsorbed phase. Usu-  
1 αNA Hads
ally it is easiest from an experimental viewpoint to deter- k  = τ0 exp . (29)
mine isotherms. The coordinates of pressure at the differ- n 0 (2π MRT )1/2 RT
ent temperatures for a fixed amount adsorbed can then be The coverage is proportional to the first power of the pres-
interpolated to construct a set of isosteres, and similarly sure at a given temperature provided that there are an un-
to obtain an isobaric series. limited number of adsorption sites available and Hads
Adsorption isotherms can be used to determine thermo- does not change with coverage.
dynamic parameters that characterize the adsorbed layer The isotherm of Eq. (28) is unlikely to be suitable to
(heats of adsorption and the entropy and heat capacity describe the overall adsorption process, but the Langmuir
changes associated with the adsorption process), and in isotherm is a simple modification which represents a more
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396 Surface Chemistry

 2
real situation. The Langmuir isotherm assumes that ad- 1 
sorption is terminated on completion of one molecular P= 
k 1−
adsorbed gas layer (monolayer) by asserting that any
or
gas molecule that strikes an adsorbed atom must reflect
from the surface. All the other assumptions used to de- (k  P)1/2
= . (33)
rive Eq. (28) are maintained (i.e., homogeneous surface 1 + (k  P)1/2
and noninteracting adsorbed species). If [n 0 ] is the sur- A clear weakness of the Langmuir model is the assumption
face concentration of a completely covered surface, the that the heat of adsorption is independent of coverage.
number of surface sites available for adsorption, after ad- Several other isotherms have been developed which are
sorbing [n a ]s molecules is [n 0 ] − [n a ]s . Of the total flux all modifications of the Langmuir model. For example, the
incident on the surface, a fraction ([n a ]s /[n 0 ])F will strike Temkin isotherm can be derived if a linearly declining heat
molecules already adsorbed and, therefore, be reflected. of adsorption is assumed, i.e., H = H0 (1−β), where
Thus, a fraction (1 − [n a ]s /[n 0 ])F of the total incident H0 is the initial enthalpy of adsorption. The isotherm is
flux will be available for adsorption. Equation (25) should
RT
then be modified as follows: = ln A P, (34)
  β H0
[n a ]s
[n a ]s = 1 − Fτ, (30) where A is a constant related to the enthalpy of adsorption.
[n 0 ]
The possibility of multilayer adsorption is envisaged
which can be rearranged to give
in the Brunauer–Emmett–Teller (BET) isotherm. The as-
[n 0 ]Fτ [n 0 ]k P sumption is made that the first layer is adsorbed with a
[n a ]s = = (31)
[n 0 ] + Fτ [n 0 ] + k P heat of adsorption H1 and the second and subsequent lay-
from which ers are all characterized by heats of adsorption equal to
the latent heat of evaporation, HL . By considering the dy-
k P
= , (32) namic equilibrium between each layer and the gas phase
1 + k P the BET isotherm is obtained,
where k  = k/[n 0 ]. p 1 c−1 p
Equation (32) is the Langmuir isotherm. The adsorp- = + . (35)
V ( p0 − p) Vm c Vm c p0
tion of CO on Pd(111) obeys the Langmuir isotherm, and
typical isotherms from this system are shown in Fig. 24. In this equation V is the volume of gas adsorbed, p
It can readily be shown that in the case of dissociative the pressure of gas, p0 the saturated vapor pressure of the
adsorption the Langmuir isotherm becomes liquid at the temperature of the experiment, and Vm the

FIGURE 24 Adsorption isotherms for CO on Pt(111) single-crystal surfaces.

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Surface Chemistry 397

volume equivalent to an adsorbed monolayer. The BET The last, and most common, method of determining
constant c is given by the following: the heat of adsorption is a kinetic method called tem-
perature programmed desorption (TPD). The method is
c = exp(H1 − HL )/RT. (36)
as follows. The sample is cleaned in ultrahigh vacuum
The BET equation owes its importance to its wide use and a gas is allowed to adsorb on the surface at known
in measuring surface areas, especially of films and pow- pressures while the surface is kept at a fixed temperature.
ders. The method followed is to record the uptake of an The sample is then heated at a controlled rate, and the
inert gas (Kr) or nitrogen at liquid nitrogen temperature pressure changes during the desorption of the molecules
(−195.8◦ C). A plot of p/V ( p0 − p) versus p/ p0 , usually are recorded as a function of time and temperature. The
for p/ p0 up to about 0.3, yields Vm , the monolayer up- pressure–temperature profile is usually referred to as the
take. This value is expressed as an area by assuming that desorption spectrum. The desorption rate F(t) is com-
the area per molecule for nitrogen is 16.2 Å and 25.6 Å for monly expressed as follows:
krypton.  
E des
In general, the BET isotherm is most useful for de- F(t) = v f (σ ) exp − , (39)
scribing physisorption for which H1 and HL are of the RT
same order of magnitude while the preceding isotherms where v is the preexponential factor and f (σ ) an adsor-
are more useful for chemisorption. It is worth noting that bate concentration-dependent function. The various pro-
the BET isotherm reduces to the Langmuir isotherm when cedures for determining these parameters are well de-
H1  HL . scribed in the literature.
Assuming that v and E des are independent of the ad-
sorbate concentration σ and t, E des can be obtained for
I. Heat of Adsorption
zeroth-, first-, and second-order desorption, respectively,
An important physical–chemical property that character- as follows:
izes the interaction of solid surfaces with gases is the bond  
E0 ν0 E
energy of the adsorbed species. The determination of bond = exp − (40)
R σa RTp
energy is usually made indirectly by measuring the heat
 
of adsorption (or heat of desorption) of the gas. The heat E1 v1 E1
of adsorption can be determined readily in equilibrium by = exp − (41)
RTp2 α RTp
measuring several adsorption isotherms. The Clausius–
Clapeyron equation  
E2 v2 σ E2
  = exp − , (42)
∂(ln P) Hads RTp2 α RTp
= (37)
∂T  RT 2 where Tp is the temperature at which a desorption peak
can be integrated to give is at a maximum and σ is the initial adsorbate concentra-
    tion. The subscripts 0, 1, and 2 denote the zeroth-, first-,
P1 − Hads 1 1
ln = − . or second-order desorption processes; α is a constant of
P2  R T1 T2
proportionality for the temperature rise with time, usu-
Measuring the adsorption isotherm at two different tem- ally T = T0 + αt; that is, the temperature of the sample
peratures, provided that proper equilibrium is established is raised linearly with time. As seen from the equations,
between the adsorbed and gas phase, yields the heat of Tp is independent of σ for the first-order desorption pro-
adsorption. cess. Alternatively, Tp is increased or is decreased with
The heat of adsorption can also be obtained by direct σ0 for the zeroth- and second-order process, respectively.
calorimetry. The method most commonly used consists of Equations (40)–(42) allow us to determine the activation
measuring the temperature rise caused by the addition of energy and the preexponential factor and also to distin-
a known amount of gas to a film of the metal prepared guish between zeroth-, first-, and second-order desorption
by evaporation in vacuo. This measurement will yield the processes from the measurements of the dependence of
differential heat of adsorption qd at the particular value the peak temperatures on initial adsorbate concentrations
of . The differential heat of adsorption is related to the and heating rate α. A typical TPD spectrum is shown in
isosteric heat of adsorption by the following: Fig. 25.
The bond energy Hbond is readily extracted from the
q = qd + RT ; (38)
heat of adsorption. In the case of the chemisorption of
the difference is only RT, which is within experimental a diatomic molecule X2 onto a site on a uniform solid
error. surface M the molecule may adsorb without dissociation
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398 Surface Chemistry

FIGURE 26 Isoteric heat of adsorption for CO on Pd(111) crystal

face as a function of coverage.

with increasing adsorbate coverage are commonly ob-

served due to repulsive adsorbate–adsorbate interactions.
Second, the surface is heterogeneous by nature. There
are many sites where the adsorbed species have different
binding energies. Perhaps the most striking effect is that
for adsorption on stepped and kinked platinum and nickel
single crystal surfaces where molecules dissociate in the
presence of these surface irregularities while they remain
intact on the smooth low-Miller-index surfaces. If a poly-
crystalline surface is utilized for chemisorption studies
FIGURE 25 Typical thermal desorption spectra of CO from a instead of a structurally well-characterized single-crystal
Pt(553) stepped crystal face as a function of coverage. The two
peaks are indicative of CO bonding at step and terrace sites. The
surface the measured Hads will be an average of adsorp-
higher temperature peak corresponds to CO bound at step sites. tion at the various binding sites. In fact, even on the same
crystal surface molecules may occupy several different ad-
sorption sites with different coordination numbers and ro-
to form MX2 . In this case, the heat of adsorption, Hads tational symmetries, and each site may exhibit a different
is defined as the energy needed to break the M X2 bond binding energy and therefore a different heat of chemisorp-
tion. For example, on the (111) face of fcc metals the
Hads
MX2(ads) −−→ M + X2(gas) adsorbates may occupy a three-fold site, a twofold bridge
site, or an on-top site. Figure 27 shows the measured heats
If the molecule adsorbs dissociatively, the heat of adsorp- of adsorption of CO or single-crystal surfaces for many
tion is defined as follows: different transition metals while Fig. 28 shows the heats of
Hads adsorption of CO on polycrystalline transition metal sur-
2MX(ads) −−→ 2M + X2(gas) faces. The heats of chemisorption on single-crystal planes
The energy of the surface chemical bond is then given by indicate the presence of binding sites on a given surface
which differ by ∼20 kcal mol−1 . It is not possible to iden-
Hbond (MX2 ) = Hads tify one value of the heat of chemisorption of an adsorbate
on a given transition metal unless the binding state is spec-
for associative adsorption or ified or it is certain that only one binding state exists. A
  polycrystalline surface however exhibits all the adsorp-
Hads + DX2
Hbond (M X ) = tion sites of the faces from which it is composed. Since
2
these sites are present simultaneously heats of chemisorp-
for dissociative adsorption, where DX2 is the dissociation tion for these surfaces represent an average of the binding
energy of the X2 gas molecule. energies of the different surface sites. As a result the mea-
The heat of adsorption is not a constant, quantity for sured heats of adsorption of Fig. 28 do not show the large
a particular adsorbate–substrate system; there are several structural variations that can be seen in Fig. 27.
factors which affect the value of Hads . First, the heat of The adsorbate may also change bonding as a function
adsorption can change markedly with the coverage  of of temperature as well as the adsorbate concentration. For
the adsorbed pahse. An example of this is shown in Fig. 26 example, oxygen may be molecularly adsorbed at low tem-
for CO on a Pd(111) surface. Decreasing values of Hads peratures while it dissociates at higher temperatures.
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Surface Chemistry 399

for materials of different types. Metals, which are good

conductors of electricity with resistivities in the 10−4  m
range, have large free electron concentrations; almost ev-
ery atom contributes one electron to the lattice as a whole.
For insulators, with a resistivity of 109  m, and semicon-
ductors with intermediate values, often less than 1 of every
106 atoms may contribute a free electron. The temperature
dependence of the carrier concentration and the conduc-
tivity may be different for different materials depending on
the mechanism of excitation by which the mobile charge
carriers are created.
Under incident radiation or bombardment by an elec-
tron beam surfaces emit photons, electrons, or both. The
emission properties of solid surfaces differ widely, just as
their mechanisms or relaxation after excitation by high-
energy radiation differ. Many surface-sensitive experi-
mental techniques providing information related to the
electronic properties of surfaces are based on these pro-
cesses, for example, Auger electron spectroscopy (AES),
X-ray photoelectron spectroscopy (XPS), and ultraviolet
photoelectron spectroscopy (UPS). These are discussed
below.
The underlying reason for the differences of the con-
FIGURE 27 Heats of adsorption of CO on single-crystal surfaces ductivity mechanisms and emission properties on the sur-
of transition metals. faces of the different materials lies in the differences in
their electronic band structure. The band structure model
of solids has been successful in explaining many solid-
IV. ELECTRICAL PROPERTIES state properties, and we may apply it with confidence in
OF SURFACES studies of solid surfaces. There are many excellent text-
books on the subject of solid-state physics giving detailed
A. Introduction
descriptions of the band theory of solids, and a descrip-
Many of the physical and chemical properties of solid tion is not presented here. In the following section a basic
surfaces are directly influenced by the concentration of understanding of electron bands is assumed.
mobile charge carriers (electrons and diffusing ions). The
concentration of these free charge carrier varies widely
B. The Energy Level Diagram
For many purposes, in analyzing the electrical properties
of metals or semiconductors, we are not concerned with
the detailed shape of the electronic bands. We may con-
veniently represent schematically the electronic bands by
straight lines where the potential energy of the electron
near the top of the valence band and at the bottom of the
conduction band is plotted against distance x through the
crystal starting from the surface (x = 0). The energy gap
represents the minimum potential energy difference be-
tween the two bands. In this type of diagram the electron
energy increases upward and the energy of the positive
hole increases downward, as indicated in Fig. 29. For a ho-
mogeneous crystal the bands may be horizontal, as shown
in this figure. At the surface the bands may vary in energy
with respect to their value in the bulk of the solid since the
FIGURE 28 Heats of adsorption of CO on polycrystal-line free carrier concentrations at the surface may be different
transition-metal surfaces. from those in the bulk of the crystal.
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400 Surface Chemistry

of charge carriers in the surface with respect to the bulk

carrier concentration. Such a space charge may also be
induced by the application of an external electric field or
by the presence of a charged layer on the surface such
as adsorbed ions or electronic surface states which act as
a source or sink of electrons. The height of the surface
potential barrier Vs and its distance of penetration into
the bulk, d, depend on the concentration of mobile charge
carriers in the surface region.
It can be shown that
 
FIGURE 29 Energy-level diagram as a function of distance x from 2εε0 Vs 1/2
the surface (x = 0). d≈ , (43)
en e (bulk)
where ε is the dielectric constant in the solid, ε0 the per-
C. Surface Dipole and Surface Space Charge mittivity of free space, and n e (bulk) the bulk carrier con-
centration. The higher the free carrier concentration in the
The anisotropic environment of surface atoms not only material, the smaller is the penetration depth of the applied
gives rise to such processes as surface relaxation and sur- field into the medium. Using a typical value of ε = 16, for
face reconstruction but also to a redistribution of charge electron concentrations of 1017 cm−3 or larger, the space
density. For a metal this redistribution can be explained charge is restricted to distances on the order of one atomic
as follows. In the bulk of a metal each electron lowers layer or less. This is due to the large free carrier density
its energy by “pushing” the other electrons aside to form screening the solid from the penetration of the electrostatic
an “exchange correlation hole.” This attractive interaction field caused by the charge imbalance. In most metals al-
Vexch is lost when the electron leaves the solid, so there is a most every atom contributes one free valence electron and
sharp potential barrier Vs at the surface. In a quantum me- since the typical atomic density is of the order of 1022 cm−3
chanical description, the electrons are not totally trapped the free carrier concentration in metals is in the range of
at the surface and there is a finite probability for them to 1020 –1022 cm−3 . Thus, Vs and d are so small that they
spread out into the vacuum. This is depicted in Fig. 30. can usually be neglected. For semiconductors, or insula-
This charge redistribution induces a surface dipole Vdip tors on the other hand, typical free carrier concentrations
that modifies the barrier potential. The work function φ at room temperature are in the range of 1010 –1016 cm−3 .
(which will be discussed in detail below) is the minimum Therefore, at the surfaces of these materials, there is a
energy necessary to remove an electron at the Fermi energy space-charge barrier of appreciable height (several elec-
E F from the metal into the vacuum. The magnitude of this tron volts) and penetration depth that could extend over
induced surface dipole is different at various sites on the thousands of atomic layers (≈104 Å) into the bulk. This
heterogeneous metal surface. For example, a step site on is the reason for the sensitivity of semiconductor devices
a tungsten surface has dipole of 0.37 Debye (D) per edge to ambient changes that affect the space-charge barrier
atom as measured by work function studies. At a tungsten height. There is an induced electric field at the surface
adatom on the surface there is a dipole moment of 1 D. under most experimental conditions due to the adsorption
At semiconductor and insulator surfaces the separation of gases or because of the presence of electronic surface
of negative and positive charges leads to the formation states. The electronic and many other physicochemical
of a space-charge region. This space-charge region near properties of semiconductor and insulator surfaces depend
the surface is formed by the accumulation or depletion very strongly on the properties of the space charge. For
example, the conduction of free carriers across the solid
or along its surface could become space-charge-limited.
The rate of charge transfer from the solid to the adsorbed
gas, which results in chemisorption or chemical reaction,
can become limited by the transfer rate of electrons over
the space-charge barrier.
When the energy level diagram was introduced, it was
assumed that the electron energy levels remained un-
changed right to the surface (x = 0). However, the pres-
FIGURE 30 Charge density oscillation and redistribution at a ence of the space charge (and also surface states) leads
metal–vacuum interface. to a bending of the bands. If the surface region becomes
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Surface Chemistry 401

FIGURE 31 Energy-level diagram (a) in the absence of any FIGURE 32 Potential energy diagram illustrating the work func-
space charge and (b) with a surface space charge due to de- tion. EF is the Fermi energy, φ is the work function, and W is
pletion of electrons in the surface region. the potential well bonding the conduction band electrons into the
solid.

depleted of electrons it would require more energy to trans- insulators it can be regarded as the difference in energy
fer an electron to the conduction band from, for example, between an electron at rest in the vacuum just outside
the reference state E F , due to the space charge potential the solid (i.e., at the level of zero kinetic energy) and the
barrier. This is depicted schematically in Fig. 31. Con- most loosely bound electrons in the solid. Thus, the work
versely, it is now easier to transfer a hole to the surface function is evidently an important parameter in situations
since the difference between E F and E V becomes smaller. where electrons are removed from the solid.
It is very likely that there is accumulation or depletion A schematic energy level diagram assuming the free-
of charges at semiconductor or insulator surfaces under electron model of a metal showing the work function is
all ambient conditions. For surfaces under atmospheric depicted in Fig. 32.
conditions, adsorbed gases or liquid layers at the interface From the figure it can be seen that the value of φ de-
provide trapping of charges or become the source of free pends on W , the depth of the potential well bonding the
carriers. For clean surfaces in ultrahigh vacuum, there conduction electrons into the solid. Here W is a bulk prop-
are electronic surface states that act as traps or sources of erty determined by the attraction for its electrons of the
electrons and produce a space-charge layer of appreciable lattice of positive ions as a whole; it has an energy of the
height. Thus, the mobile carriers from the surface layer are order of a few electron volts.
swept into the interior or are trapped at the surface as the The origin of the work function itself can be considered
space-charge layer consists dominantly of static charges, as being due to the image potential of the escaping elec-
the one most frequently encountered in experimental tron. Electrostatic theory shows that a charge −e outside
situations. a conductor is attracted by an image charge +e placed at
We have so far considered the space-charge layer prop- the position of the optical image of −e in the conducting
erties only in the insulating solid, assuming that the surface plane. If −e is a distance x from the plane the image force
layer that acts as a donor or the electron trap is of mono- is e2 /16π ε0 x 2 . This force is experienced by the electron
layer thickness. However, considering the properties of escaping into the vacuum and is negligible beyond 10−6 –
solid–liquid interfaces or semiconductor–insulator con- 10−5 cm away from the surface.
tacts, it should be recognized that the space-charge layer The image potential is a specific surface contribution to
may extend to effective Debye lengths on both sides of the W , and a second surface contribution is the existence of a
interface. This is a most important consideration when we surface double layer or dipole layer. Surface atoms are in
investigate the surface properties of colloid systems or of an unbalanced environment, they have other atoms on one
semiconductor–electrolyte interfaces. side of them but not on the other; thus, the electron dis-
tribution around them will be unsymmetrical with respect
to the positive ion cores. This leads to the formation of
D. Work Function and Contact Potential
a double layer. Two important effects emanate from this;
The work function of a solid is a fundamental physical the work function is sensitive to both the crystallographic
property of the solid which is related to its electronic plane exposed and to the presence of adsorbates.
structure. It is defined as the potential that an electron The orientation of the exposed crystal face affects φ
at the Fermi level must overcome to reach the level of because the strength of the electric double layer depends
zero kinetic energy in the vacuum. In semiconductors and on the density of positive ion cores which in turn will vary
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402 Surface Chemistry

TABLE IV Work Functions Measured from a tungsten tip. The changes in φ produced by adsorbed
Different Crystal Faces of Tungsten and atoms or molecules can be followed in the FEM.
Molybdenum
The work function of a solid is also sensitive to the pres-
Work function (eV) ence of adsorbates. In fact, in virtually all cases of adsorp-
Crystal
tion the work function of the substrate either increases or
face Tungsten Molybdenum
decreases; the change being due to a modification of the
(110) 4.68 5.00 surface dipole layer. The formation of a chemisorption
(112) 4.69 4.55 bond is associated with a partial electron transfer between
(111) 4.39 4.10 substrate and adsorbate and the work function will change.
(001) 4.56 4.40 Two extreme cases are (i) the adsorbate may only be po-
(116) 4.39 — larized by the attractive interaction with the surface giving
rise to the build up of a dipole layer, as in the physisorption
of rare gases on metal surfaces; and (ii) the adsorbate may
from one face to another. The work function of various be ionized by the substrate, as in the case of alkali metal
crystal planes of tungsten and molybdenum are listed in adsorption on transition metal surfaces. If the adsorbate
Table IV. It can be seen that there is more than 0.3 eV is polarized with the negative pole toward the vacuum the
difference in work function values. This variation of work consequent electric fields will cause an increase in work
function from one crystal face to another can clearly be function. Conversely, if the positive pole is toward the vac-
demonstrated using a field emission microscope (FEM). uum then the work function of the substrate will decrease.
This microscope is identical in construction to the FIM The work function is a rather complicated (and not fully
described earlier. However, instead of having helium or understood) function of the surface composition and ge-
another imaging gas in the vacuum, no gas is admitted. ometry. Nevertheless, general systematic observations of
The potential on the sample tip is reversed so that electrons φ are quite helpful. For example, the sign of φ for
are accelerated out of it by a very high local electric field atomic adsorption is mostly that implied by the magni-
(∼ 4 × 107 V cm−1 ). The current emitted from the tip sur- tude of the ionization potential, electron affinity, or dipole
face where the work function is φ is approximately propor- moment of the adsorbates as one would expect. The most
tional to exp(−Aφ 3/2 ) and is a very fast function of φ. The common usage of work function changes in surface chem-
brightness observed on the fluorescent screen is a function istry is in the monitoring of the various stages of adsorp-
of the value of φ at that place on the tip, and the FEM image tion as a function of coverage. Often the work function
will consist of darker and brighter areas, the brightness de- change will go through a maximum or minimum at par-
pending on the work function of each crystal face exposed. ticular coverages corresponding to the completion of an
An image is shown in Fig. 33 which is the FEM image of ordered atomic arrangement.
Experimentally, the most accurate way of measuring
changes in work function is by the Kelvin method, which
uses a vibrating probe as a variable capacitor. A contact
potential difference is set up between two conductors con-
nected externally and the sample and a reference electrode
form a parallel plate condenser. The distance between the
two is periodically varied, thus generating an alternating
current in the connecting wire. If a voltage source is placed
in the connecting circuit just balancing out the contact po-
tential difference, no current will flow. Once this situation
has been achieved for the clean surface, a change in work
function due to adsorption is simply the additional voltage
which needs to be applied to compensate the change and
keep the current zero. Accuracies of φ to within ±1 meV
are obtainable.
Intimately linked to the concept of work function is the
process of thermionic emission. Thermionic emission is,
as the name suggests, the phenomenon whereby electrons
FIGURE 33 Field emission pattern of a tungsten tip. The are ejected from a metal when it is heated in vacuum.
(011) plane is in the center. (Courtesy of Lawrence Berkeley The electrons that require the least amount of thermal en-
Laboratory.) ergy to overcome their binding energy in the solid and
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Surface Chemistry 403

escape are those in the high-energy tail of their equilibrium

distribution in the metal. Thermionic emission is the most
frequently used method to produce electron beams, for
instance, in oscilloscope tubes and electron microscopes.
Refractory metals (e.g., W) have traditionally been used
as filaments in electron guns, mainly due to the fact that
they can be heated to high temperatures and thus produce
a relatively intense thermionic current. Since the work
function of W is relatively high W filaments are often
coated with a metal for lower work function, for example, FIGURE 34 Energy-level diagrams for an intrinsic semiconductor
Th (φ = 2.7 eV) to enable them to be operated at lower in the presence of (a) electron–donor or (b) electron–acceptor
temperature for the same current thereby extending their surface states.
lifetime.
due to relaxation, reconstruction, structural imperfections,
or adsorbed impurities. If the charge associated with any
E. Surface States
of these surface states is different from the bulk charge
In a bulk solid the infinite array of ion cores in crys- distribution then band bending will occur.
tallographic sites leads to a potential that varies in a Surface states can be observed, for example, using ul-
three-dimensionally periodic manner. The solutions to traviolet photoelectron spectroscopy, which is discussed
Schrödinger’s equation for such a potential lead to allowed below.
energy bands, which are occupied by the electrons in the
solid, and to particular values of the wave vector k of the
F. Electron Emission from Surfaces
electron where no traveling-wave solutions exist. The ab-
sence of eigenstates for these values of k leads to the band The most important methods of analyzing the surface elec-
gaps in the electronic structure of the solid. The solid, tronic and chemical composition involve energy analysis
however, is not infinite but is bounded by surfaces. In of electrons emitted from a surface during its bombard-
turn, surface atoms have fewer nearest neighbors and are ment with electrons, ultraviolet photons, or X-ray photons.
in an asymmetric environment. The introduction of such a For example, part of the experimental verification of the
discontinuity at the surface perturbs the periodic potential band theory of metals comes from the measured intensity
and gives rise to solutions of the wave equation that would and energy distribution of electrons emitted under exci-
not have existed for the infinite crystal. These are derived tation by photons. It should be remembered that we have
by using appropriate boundary conditions to terminate the already mentioned two ways in which electrons can be
crystal and are called surface-state wave functions. These emitted from surfaces; (i) by applying a very high electric
special solutions are waves which can travel parallel to field (∼107 V cm−1 ) which pulls electrons from the sur-
the surface but not into the solid. They are localized at face, as used in FEM, and (ii) by heating the solid as in
the surface and can have energies within the band gap of thermionic emissions.
the bulk band structure. These states can trap electrons Before discussing the two major electron emission tech-
or release them into the conduction band. The concentra- niques from surfaces, photoelectron spectroscopy and
tion of electronic surface states in clean surfaces can be Auger electron spectroscopy (AES), it is pertinent to
equal to the concentration of surface atoms (∼1015 cm−2 ). briefly discuss the surface sensitivity of the interaction
Impurities or adsorbed gases can reduce the surface state of electrons with solids. Figure 35 shows the mean free
density. path of electrons in metallic solids as a function of the
One important consequence of the presence of elec- electron energy. This curve is often called the “universal
tronic surface states is that the electron bands are modi- curve,” and shows a broad minimum in the energy range
fied at the surface even in the absence of a space charge between 10 and 500 eV with the corresponding mean free
or electron acceptor or donor species (such as adsorbed path on the order of 4–20 Å. Electron emission from solids
gases). The shape of the conduction band at the surface with energy in this range must originate from the top few
of an intrinsic semiconductor in the presence of electron- atomic layers. Therefore, all experimental techniques in-
donor and electron-acceptor surface states is shown in the volving the incidence and/or convergence from surfaces
energy level diagrams in Figs. 34a and 34b. of electrons having energy between 10 and 500 eV are
Surface states can be associated not only with the termi- surface sensitive. For incident electrons of higher energy
nation of a three-dimensional potential at a perfect clean (1–5 kV) the surface sensitivity can be enhanced by hav-
bulk exposed plane but also with changes in the potential ing the electron beam impinging on the surface at grazing
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404 Surface Chemistry

FIGURE 35 Universal curve for the electron mean free path as a function of electron kinetic energy. Dots indicate
individual measurements.

incidence. Photons have a much larger penetration depth 5000 eV) strikes the atoms of a material, electrons that
into the solid due to the much smaller scattering cross have binding energies less than the incident beam energy
section. However, electrons created by excitation below may be ejected from the inner atomic level. By this process
a few atomic layers from the surface cannot escape due a singly ionized, excited atom is created. The electron
to inelastic scattering within the solid. If a monoenergetic
beam of electrons of energy E p strikes a metal surface
then a typical plot of the number of scattered electrons
N (E) as a function of their kinetic energy E is shown in
Fig. 36. The curve is dominated by a strong peak at low
energies due to secondary electrons created as a result
of inelastic collisions between the incident electrons and
electrons bound to the solid. Other features in the spec-
trum include (i) the elastic peak at E p that is utilized in
LEED, (ii) inelastic peaks at loss energies of 10–500 meV
which provide information about the vibrational structure
of the surface–adsorbate complex utilized in EELS, (iii)
inelastic peaks at greater loss energies (plasmon losses)
which provide information about the electronic struc-
ture of surface atoms, and (iv) small peaks on the large
secondary electron peak due to Auger electrons which
provide information on the chemical composition of the
surface.

Auger Electron Spectroscopy

Auger electron spectroscopy is the most common tech-
nique for determining the composition of solid and liquid
surfaces. Its sensitivity is about 1% of a monolayer, and it
is a relatively simple technique to perform experimentally. FIGURE 36 Experimental number of scattered electrons N(E) of
Auger electron emission occurs in the following manner. energy E versus electron energy E curve. (Courtesy of Lawrence
When an energetic beam of electrons or X-rays (1000– Berkeley Laboratory.)
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Surface Chemistry 405

FIGURE 37 Scheme of the Auger electron emission process.

vacancy formed is filled by deexcitation of electrons from

other electron energy states. The energy released in the
resulting electronic transition can, by electrostatic inter-
action be transferred to still another electron in the same
FIGURE 38 Typical Auger spectra from (a) a clean Mo(100)
atom or in a different atom. If this electron has a binding
single-crystal and (b) a Mo(100) surface contaminated with sulfur.
energy that is less than the energy transferred to it from
the deexcitation of the previous process that involves the
filling of the deep-lying electron vacancy, it will be ejected cal analysis in addition to elemental compositional anal-
into vacuum, leaving behind a doubly ionized atom. The ysis of the surface. It is possible to separate the sur-
electron that is ejected as a result of the deexcitation pro- face composition from the composition of layers below
cess is called an Auger electron, and its energy is primar- the surface by appropriate analysis of the Auger spec-
ily a function of the energy-level separations in the atom. tral intensities. In this way the surface composition as
These processes are schematically displayed in Fig. 37. well as the composition in the near-surface region can be
To a first approximation the energy of the Auger electron obtained.
depicted in Fig. 37 is given by When chemical analysis is desired in the near-surface
region, AES may be combined with ion sputtering to
E Auger = E K − E LI − E LIII (44)
obtain a depth-profile analysis of the composition. Us-
and is independent of the energy of the incident beam. ing high-energy ions, the surface is sputtered away layer
This is an important difference between AES and photo- by layer while, simultaneously, AES analysis detects the
electron spectroscopy and means that it is not necessary composition in depth. Sputtering rates of 100 Å/min are
to monochromatize the electron beam which adds to the usually possible and the depth resolution of the compo-
experimental convenience. sition is about 10 Å, which is mainly determined by the
There are two major experimental designs for AES. statistical nature of the sputtering process.
One is using the retarding grid analyzer which uses the A different aspect of AES concerns shifts in the ob-
same electron optics as LEED, thus LEED and AES can served peak energies that are due to chemical shifts of
be performed using the same apparatus. The second is the atomic core levels (in a way analogous to X-ray photo-
cylindrical mirror analyzer (CMA) which has an inher- electron spectroscopy). For example, studies of different
ently better signal-to-noise ratio. Scanning Auger micro- oxidation states of oxygen at metal surfaces have shown
probes are now in widespread use in the microelectronics chemical shifts that grow with the formation of higher
industry for spatial chemical analysis of surfaces. With the oxidation states.
exception of hydrogen and helium, all other elements are
detectable by Auger electron spectroscopy.
G. Photoelectron Spectroscopy
The Auger spectrum is usually presented as the second
derivative of intensity, d 2 I /d V 2 , as a function of elec- Photoelectron spectroscopy is a technique whereby
tron energy (eV). This way the Auger peaks are read- electrons directly ejected from the surface region of a
ily separated from the background, due to other electron solid by incident photons are energy analyzed and the
loss processes that occur simultaneously. A typical Auger spectrum is then related to the electron energy levels
spectrum of molybdenum is shown in Fig. 38. of the system. The field is usually arbitrarily divided
By suitable analysis of the experimental data, as well as into two classes: ultraviolet photoelectron spectroscopy
by the use of suitable reference surfaces, the Auger elec- (UPS) and X-ray photoelectron spectroscopy (XPS). The
tron spectroscopy study can provide quantitative chemi- names derive from the energies of the photons used in the
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406 Surface Chemistry

particular spectroscopy. Ultraviolet photoelectron spec-

troscopy studies the properties of valence electrons
that are in the outermost shell of the atom and utilizes
photons in the vacuum ultraviolet region of the electro-
magnetic spectrum [He I (21.22 eV), He II (40.8 eV),
and Ne I (16.85 eV) resonance lamps are the most
commonly used photon sources]. X-ray photoelectron
spectroscopy investigates the properties in the inside
shells of atoms and uses photons in the X-ray region
[Mg Kα (1253.6 eV) and Al Kα (1486.6 eV) being
the most common]. With the advent of synchrotron
radiation, a polarized, tunable light source covering the
entire useful energy range, the division is now somewhat
redundant.
In both types of spectroscopy, if the incident photon
has enough energy hν it is able to ionize an electronic
shell and an electron which was bound to the solid with
energy E B is ejected into vacuum with kinetic energy E k .
By conservation of energy:
E k = hν − E B . (45)
If the incident radiation is monochromatic and of known FIGURE 39 Is electronic binding energy shifts in nitrogen, indi-
energy, and if E k can be measured using a high-resolution cating the different photoelectron energies observed in various
energy analyzer (such as either a concentric hemispherical chemical environments.
or cylindrical mirror analyzer), then the binding energy E B
can be deduced. is in general accompanied by an increase in the binding
Equation (45) gives a highly simplified relationship be- energy E B of the core electrons.
tween the kinetic energy, E k , of the emitted photoelectrons Relative surface coverages can also be obtained with
and their binding energy; E k is modified by the work func- XPS by monitoring the intensities of the core level peaks.
tion of the energy analyzer and by several atomic param- Absolute coverages can be obtained from the core level
eters that are associated with the electron emission pro- intensities, but it is usual to calibrate against another
cess. The ejection of one electron leaves behind an excited technique.
molecular ion. The electrons in the outermost and in other As mentioned above UPS probes the valence electrons
orbitals experience a change in the effective nuclear charge of the solid. It is these electrons which form a chemisorp-
due to an alteration of screening by other electrons. This tion bond and a knowledge of electronic density of states
gives rise to satellite peaks near the main photoelectron at a surface is of vital importance in attempts to under-
peaks. Several other effects, including spin-orbit splitting, stand the formation of chemical bonds between solid sur-
Jahn–Teller effect, and resonant absorption of the incident faces and adsorbed atoms or molecules; UPS can provide
photon by the atom, influence the detected photoelectron even more information about the system if the emitted
spectra. electrons are both energy and spatially analyzed. This is
One of the most important applications of XPS is the known as angle-resolved UPS (ARUPS). Using ARUPS
determination of the oxidation state of elements at the the band structures of clean and adsorbate-covered sur-
surface. The electronic binding energies for inner-shell faces have been determined, mapping out the dispersion
electrons shift as a result of changes in the chemical en- of electronic states; ARUPS also reveals directional ef-
vironment. An example of these shifts can be seen in ni- fects due to the spatial distribution of electronic orbitals
trogen, indicating the photoelectron energy for various of atoms and molecules at the surface. By changing the
chemical environments (Fig. 39). These energy shifts are angle of incidence and the angle of detection, the elec-
closely related to charge transfer in the outer electronic tronic orbitals from which the photoelectrons are ejected
level. The charge redistribution of valence electrons in- can be identified. In addition, ARUPS provides detailed
duces changes in the binding energy of the core electrons, information about the surface chemical bond including the
so that information on the valence state of the element is direction of the bonding orbitals and the orientation of the
readily obtainable. A loss of negative charge (oxidation) molecular orbitals of adsorbed species on the surface.
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Surface Chemistry 407

V. SURFACE DYNAMICS mass, k is Boltzmann’s constant, T is the temperature, and

D is the Debye temperature. (The Debye temperature is
A. Atomic Vibrations associated with the energy ωmax of the highest frequency
phonon mode possible in the Debye model of vibrations
Until now it has been convenient to discuss both the prop- in the solid, hωmax = kD .)
erties and methods in terms of rigid lattices of atoms or Equation (47) implies that a plot of the logarithm of
molecules. In reality, the atoms are in motion and this mo- the intensity at a given energy (wavelength) as a func-
tion should be included in a complete treatment of any tion of temperature is a straight line, the slope of which
properties it may affect. yields D , a measure of the surface vibrational amplitude
In X-ray diffraction experiments it is well known that perpendicular to the surface.
the intensity of the scattered rays decreases as the tem- In reality, the electron-beam penetration varies as a
perature is increased. Simultaneously, the intensity of the function of energy, so that Eq. (47) provides, at any given
diffuse background of the diffraction pattern increases. energy, an effective Debye temperature, which is some
The simplest explanation for this observation is that the average of the surface and bulk layers. In empirical fash-
atoms are not rigid, but are vibrating about their equilib- ion, however, we may arrive at a surface Debye temper-
rium positions, and as a result, the exact Bragg condition ature from the low-energy limit of this effective Debye
is not met. Scattered waves from the rigid lattice that were temperature.
adding up in phase now have a phase difference fluctuat- Adsorbates should have a marked influence on surface-
ing with time due to the atomic motion. The effect of this atom vibrations, since they change the bonding environ-
motion on the intensity of the elastically diffracted beams ment with respect to that on the clean surface. The adsorp-
is described in most good solid-state physics texts. Briefly, tion of oxygen on tungsten increases the surface Debye
if I0 is the intensity elastically diffracted by a rigid lattice temperature with respect to the bulk value due to the
then the intensity I due to scattering by the vibrating lat- stronger W O bond as compared to the W W bond.
tice in the direction determined by Bragg scattering due Studies of surface-atom vibrations in the presence of ad-
to a reciprocal-lattice vector ḡ is given by the following: sorbates provide information on the nature of the surface
I = I0 exp(−αu 2 |g|), (46) bond.
assuming that the atoms are in simple harmonic motion. B. Surface Diffusion
u 2  is the mean-square amplitude of vibration in the di-
rection ḡ and α is a constant related to the number of As discussed above, at any finite temperature the atoms
dimensions in which the atoms are allowed to vibrate. In at the surface of a crystal are vibrating at some fre-
one dimension α = 1; in three dimensions α = 13 . The ex- quency ν0 . Thus, ν0 times every second each atom strikes
ponential factor in Eq. (46) is called the Debye–Waller the potential-energy barrier separating it from its near-
factor and is often denoted as exp(−2M). est neighbors (Fig. 40). The thermal energy causing the
The same kind of effect is observed in LEED only be- atoms to oscillate with increasing amplitude as the tem-
cause LEED intensities arise from the just few atomic perature is increased is not sufficient to dislodge most of
layer of a crystal the value of u 2  is that for the surface them from their equilibrium positions. The thermal energy
atoms. Because of the absence of nearest neighbors on (3RT ≈ 1.8 kcal mol−1 at 300 K) tied up in lattice vibra-
the vacuum side we expect that u 2  at the surface will be tions is only a small fraction of the total energy necessary
greater than in the bulk.
By using the Debye model of the solid it is possible
to relate the observed intensity of the elastically scattered
electrons in LEED to measurable quantities. We obtain
the following:
 
 12h 2  cos φ 2 T 
 
I00 (T ) = I00 (0) exp −  , (47)
 mk λ 2D 
where I00 (T ) is the temperature-dependent intensity of the
(0, 0) beam resulting from a beam of electrons of wave-
length λ incident on the surface at an angle  relative to the
surface normal. I00 (0) is the specularly reflected intensity FIGURE 40 One-dimensional potential energy diagram parallel
from a rigid lattice, h is Planck’s constant, m is the atomic to the surface plane.
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408 Surface Chemistry

to break an atom from its neighbors and to move along square centimeters per second. If D is determined experi-
the surface. This bond breaking energy is of the order 15– mentally as a function of temperature, then a plot of ln D
50 kcal mol−1 for many metal surfaces. As the temperature versus 1/T will yield us the activation energy of the diffu-
of the surface is increased, more and more surface atoms sion process, provided that the diffusion occurs by a single
may acquire enough activation energy to break bonds with mechanism.
their neighbors and move along the surface. Such surface The rms distance X 2 1/2 can be expressed in terms of
diffusion plays an important role in many surface phe- the diffusion coefficient by substitution of Eq. (50) into
nomena involving atomic transport, e.g., crystal growth, Eq. (49) to give for b = 6 as follows:
vaporization, and adsorption. The migration of atoms or
X 2 1/2 = (4Dt)1/2 . (52)
molecules along the surface is one of the most important
steps in surface reactions and has proved to be the rate- From measurements of the mean travel distance of dif-
limiting step for many reactions that have been studied at fusing atoms the diffusion coefficient can be evaluated.
low pressures. Conversely, knowledge of the diffusion coefficient allows
A surface contains many defects on an atomic scale. us to estimate the rms distance or the time necessary to
Atoms in different surface sites have different binding en- carry out the diffusion. For example, the diffusion coef-
ergies. Surface diffusion can be considered as a multistep ficients of silver ions on the surface of silver bromide
process whereby atoms break away from their lattice po- can be estimated to be 10−19 and 10−13 cm2 /sec at 300
sition (e.g., a kink site at a ledge) and migrate along the and 100 K, respectively. Assuming that a rms distance of
surface until they find a new equilibrium site. 10−4 cm is required for silver particle aggregation (print-
The frequency f with which an atom will escape from out) to commence, of what duration are the light-exposure
a site will depend upon the height, E D∗ , of the potential times required? Using Eq. (52) we have t = 5 sec and
energy barrier it has to climb in order to escape as follows: t = 5 × 104 sec at 300 and 100 K, respectively. The ex-
  ponential temperature dependence of D is, of course, the
E D∗
f = zν0 exp − , (48) reason that silver bromide photography cannot be carried
kB T out at low temperatures (much below 300 K) but is eas-
where z is the number of equivalent neighboring sites. For ily utilized at about room temperature. We can also see
a (111) face of an fcc metal, z = 6, the vibration frequency that at slightly elevated temperature (∼450 K) the ther-
is of the order of 1012 sec−1 . Assuming that E D is 20 kcal mal diffusion of silver particles should be rapid enough
mol−1 , at 300 K the atom makes one jump in every 50 sec, (D ≈ 3 × 10−7 cm2 sec−1 ) so that their aggregation will
while at 1000 K one in 10−8 sec. Thus, the rate of surface take place rapidly even in the dark (t ≈ 10−2 sec) in the
diffusion varies rapidly with temperature. This is the case absence of any photoreaction.
for a single jump to a neighboring equilibrium surface site. Surface diffusion has so far been discussed in terms of
What is of great importance is the long-distance motion a single surface atom. However, on a real surface many
of a surface atom. The result is derived from considering atoms diffuse simultaneously and in most diffusion ex-
a mathematical treatment of an atom executing a random periments the measured diffusion distance after a given
walk for a time t over a mean-square distance X 2 . diffusion time is an average of the diffusion lengths of a
For a sixfold symmetrical surface, we obtain the large, statistical number of surface atoms. A thermody-
following: namic treatment in terms of macroscopic parameters can
be followed to yield the following:
X 2  = f td 2 /3. (49)
D = D0 exp(−Q/RT ), (53)
The value of f d 2 is a property of the material that char-
acterizes its atomic transport. Its value provides informa- where Q is the total activation energy for the overall
tion about the mechanism of atomic transport, and it is diffusion process and only one diffusion mechanism is
customary to define the diffusion coefficient D as follows: involved.
Experimentally, the diffusion coefficient D is obtained
D = f d 2 /2b, (50) by using a relationship between the diffusion rate and cov-
where b is the number of coordinate directions in which erage gradient, namely Fick’s second law of diffusion in
diffusion jumps may occur with equal probability. one dimension:
Equation (50) can therefore be rewritten as ∂c/∂t = D(∂ 2 c/∂ x 2 ), (54)
  
D = D0 exp − E D∗ kB T , (51)
where c is the concentration of adatoms, t the time, and x
where D0 = (v0 d 2 /6), (v0 d 2 /4), for sixfold or fourfold the distance along the surface. In most surface diffusion
symmetry, respectively; D is usually given in units of studies the surface concentration of diffusing atoms, c, is
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Surface Chemistry 409

measured as a function of distance x along the surface, plane at 327 K. The field ion images are taken at 1-min
and Eq. (54) is solved by the use of boundary conditions intervals and the Rh atom can clearly be seen to have
that approximate the experimental geometry. These ex- diffused across the surface. Unfortunately because of the
periments are by no means trivial, and many novel ex- high field strengths employed, adsorbates such as O or N
perimental techniques have been applied to study surface tend to be stripped from the surface as ions, so their mi-
diffusion on single crystals. croscopic diffusion cannot be studied by this method. An
A technique which has been used to measure surface interesting result from FIM studies of metal adatoms on
diffusion rates is scanning Auger electron spectroscopy, metals is the recognition of clusters as important contri-
which can follow adsorbate diffusion. A particular Auger butions to material transport. It has been found that rhe-
transition of the adsorbate under investigation is used as a nium dimers diffuse more rapidly than single Rh atoms on
monitor of relative concentration versus distance scanned the W(112) plane, and Rh trimers diffuse at roughly the
across the surface. Profiles are recorded after heating pe- same rate as dimers. This is not a general trend, how-
riods to observe the change in concentration profile as a ever, as iridium dimers move much more slowly than
function of time and temperature. singles.
While this technique monitors mass transport, and val- While the single adatom diffusion technique gives us
ues of D and Q are averaged values, field ion microscopy detailed microscopic information, the mass transport tech-
can be used to follow the diffusion of individual atoms niques are of use as they help to give understanding of the
across a surface. To study diffusion, the metal is vapor technologically important processes such as sintering and
deposited onto the tip. The tip is then heated to remove creep.
evaporated adatoms until only one or two remain on the
surface plane of interest. The diffusion is then examined
C. Surface Reactions
by photographically recording the position of the adatom
at low temperatures, removing the applied field, and heat- Heterogeneous catalysis, corrosion, photosynthesis, and
ing to the desired temperature for a given time. The tip is adhesion are examples of chemical processes that are par-
then cooled, the field reapplied, and the field ion image tially or fully controlled by reactions at surfaces. For the
examined to see if the atom has moved to a neighboring case of gas–solid reactions the surface reactions can be
site. This process is then repeated many times to obtain divided into two major categories: (i) stoichiometric sur-
useful values of diffusion rates, and by examining the dif- face reactions where the solid surface participates directly
fusion over a temperature range, the activation barrier to in the reaction by compound formation and (ii) catalytic
surface diffusion can be determined. Figure 41 shows a surface reactions where the reaction occurs at the solid
series of field ion images of a Rh atom on the W(112) surface but the surface does not undergo any net chemical
change. In both cases gaseous molecules impinge on the
surface, adsorb, react, and form various intermediates of
varying stability, and then the products desorb into the gas
phase if they are volatile.
All surface reactions involve a sequence of elementary
steps that begins with the collision of the incident atoms or
molecules with the surface. As the gas species approaches
the surface it experiences an attractive potential whose
range depends upon the electronic and atomic structures of
the gas and surface atoms. A certain fraction of the incident
gas molecules is trapped in this attractive potential well
with a sticking probability given by the following:
S(, T ) = S0 (1 − ) exp(−E a /RT ), (55)
where S0 is the initial (zero coverage) sticking coeffi-
cient,  the surface coverage (0 <  < 1), and E a the
activation energy for adsorption. If this force attraction
is due to a van der Waals interaction, the trapping is due
to physical adsorption. If the attraction is much stronger,
FIGURE 41 Diffusion of rhenium atoms on W(211) at 327 K. Field having the character of chemical bonding then we have
ion images are taken after 60 sec diffusion intervals. (Courtesy of chemisorption and the process is known as sticking. The
Lawrence Berkeley Laboratory.) boundary between the two types of bonding is usually
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410 Surface Chemistry

set at a binding energy of 15 kcal mol−1 . Sticking by adsorbed species is given in terms of the gas pressure P
chemisorption is often preceded by trapping into a physi- by the Langmuir isotherms:
sorbed state, in which case the physisorbed state is known
 = KP/(1 + KP), (56)
as a precursor state for chemisorption. The presence of a
precursor state is indicated by a sticking coefficient that where K is an equilibrium constant. Catalyzed surface
remains almost constant as surface coverage increases un- reactions usually take place between two or more coad-
til a saturation coverage is reached, when it rapidly falls to sorbed species which compete for adsorption sites on the
zero. This behavior arises because molecules in the rela- surface. When j gases adsorb competitively and associa-
tively mobile precursor state diffuse to parts of the surface tively, the surface coverage by species i is given by the
which are not covered by chemisorbed molecules. In di- following:
 
rect chemisorption the sticking coefficient varies strongely 
with coverage and with ordering of the chemisorbed  = K i Pi 1+ K j Pj . (57)
layer. j
The adsorbed species may also desorb from the surface Many catalyzed surface reactions can be treated as
if its energy overcomes the attractive surface forces. When a two-step process with an adsorption equilibrium fol-
a surface reaction occurs a certain proportion of the ad- lowed by one rate-determining step (diffusion, surface re-
sorbed species either decomposes (unimolecular reaction) action, or desorption). The surface reaction kinetics are
or reacts with a second adsorbed species (bimolecular re- usually discussed in terms of two limiting mechanisms,
action) before the product desorbs. the Langmuir–Hinshelwood (LH) and Eley–Rideal (ER)
During the initial interaction of the gas molecule with mechanisms. In the LH mechanism, reaction takes place
the surface as the incoming molecule falls into a potential directly between species which are chemically bonded
well the kinetic energy normal to the surface increases. (chemisorbed) on the surface. For a bimolecular LH sur-
Unless this energy is transferred to some other degree of face reaction. Aads + Bads → products, with competitive
freedom the molecule will simply bounce off; there will chemisorption of the reactants, the rate of reaction is given
be no trapping or sticking. In the case of physisorption en- by the following expression:
ergy transfer via phonons is usually most important while
Rate = kR A B
for chemisorption electronic excitation via electron–hole
pairs is thought to be important. = kR K A K B PA PB /(1 + K A PA + K B PB )2 . (58)
The exchange of translational energy T with the pho-
nons Vs is called T − Vs energy exchange. The gas mole- The reaction rate is proportional to the surface coverages
cule may also exchange internal energy, rotation R or vib- A and B and to the reaction rate constant kR . For non-
ration V with the vibrating surface atoms. In this case there competitive adsorption, the rate expression becomes the
are also R − Vs and V − Vs energy transfer processes. following:
In order to understand the dynamics of gas–surface in- kR K A K B PA PB
Rate = kR A B = . (59)
teraction, it is necessary to determine how much energy is (1 + K A PA )(1 + K B PB )
exchanged between the gas and surface atoms through the General rate expressions of the form given in equa-
various energy-transfer channels. In addition the kinetic tions and have been experimentally verified for many
parameters (rate constants, activation energies, and pre- types of LH reactions. Similar but more complicated
exponential factors) for each elementary surface step of rate expressions are easily derived assuming different
adsorption, diffusion, and desorption are required in order (non-Langmuir) isotherms, higher-order reaction steps,
to obtain a complete description of the gas–surface energy or dissociative chemisorption of the reactants. In the
transfer process. ER mechanism, surface reaction takes place between a
Most surface reactions take place at high pressures (1– chemisorbed species and a nonchemisorbed species, e.g.,
100 atm) either because of the chemical environment of Aads + Bg → products. The nonchemisorbed species may
our planet or to establish optimum reaction rates in chem- be physisorbed or weakly held in a molecular precursor
ical processing. Under these conditions, surfaces are usu- state. In this case, the rate expression for the surface
ally covered by at least one monolayer of adsorbed species. reaction becomes
Since activation energies for adsorption and surface dif-
fusion are generally small (a few kT ), equilibrium among Rate = kR A PB = kR K A PA PB /(1 + K A PA ). (60)
the different surface species, reactants, reaction interme- Presently no proven examples exist in which surface re-
diates, and products, is readily established. In the simplest action occurs by the ER mechanism.
(but not general and important) case of localized, associa- Surface reaction kinetics determined experimentally are
tive adsorption into a single state, the surface coverage by often expressed in the form of a power rate law as follows:
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Surface Chemistry 411


Rate = kR Piαi , (61) molecules, together with their angular and velocity distri-
i butions provide detailed information about the T –Vs en-
ergy transfer processes that occur during the gas–surface
where kR is the apparent rate constant and αi is the exper-
interaction. A complete dynamical description for this in-
imental order of the reaction (positive, negative, integer,
teraction (T –Vs plus R–Vs and V –Vs ) can be determined
or fraction) with respect to the reactants and products.
if the distribution of internal energy states for the product
The apparent rate constant in Eq. (61) is not that of an
molecules is determined simultaneously with their veloc-
elementary reaction step (it contains adsorption equilib-
ity distributions. This type of detection is known as state
rium constants), but it can usually be represented by an
selective detection.
Arrhenius equation as follows:
The angular distribution of scattered molecules is
kR = A exp(−E R /RT ), (62) usually displayed by plotting the intensity of detected
molecules per unit solid angle versus the angle of
where A is an apparent preexponential factor and E R is scattering r that is measured with respect to the surface
the apparent activation energy for the surface reaction. normal. Angular distributions in the two limiting cases of
The magnitude of A and E A can provide important gas–surface interaction, cosine and specular scattering,
information about the rate-determining step of a sur- are shown in Fig. 42. The scattered intensity for the cosine
face reaction, and very frequently kR and A display a distribution decreases as cos  with respect to the surface
compensation effect. A related quantity is the reaction normal. Cosine scattering is expected when the adsorbed
probability, λi = (2π m K T )1/2 νR /Pi = rate/flux; that is, species have long residence times or are strongly coupled
the probability that an incident reactant molecule will to the vibrational states of the surface atoms. It is a
undergo reaction. necessary criterion for complete thermal accommodation,
The simplified isotherms and rate expressions devel- a situation in which the molecules desorb with a kinetic
oped in this section are extremely useful despite the im- temperature or velocity distribution that is the same as
plicit assumption that a single state exists for the adsorbed the temperature of the solid surface. Specular scattering
species. Real surfaces are heterogeneous on an atomic occurs when the scattered intensity is sharply peaked at
scale with a variety of distinguishable adsorption sites. the angle of incidence (specular angle). In this case the
Gas molecules adsorbed at each type of site may display interaction is elastic or quasielastic and little or no energy
a wide distribution of excited rotational, vibrational, and transfer takes place between the incident gas molecules
electronic states. Experimentally, we can measure mean- and the surface. Sharply peaked angular distributions
ingful rate and adsorption equilibrium constants provided for surface reaction products (I () ∼ cosm , m > 1)
that adsorption and desorption are fast compared with indicate that a repulsive barrier exists in the exit channel.
surface reactions so that an adsorption equilibrium ex- Measurements of velocity distributions provide more
ists. In this circumstance the kinetic parameters are an
ensemble average over all surface sites and states of the
system.

1. Molecular-Beam Scattering
The most powerful experimental technique for investigat-
ing the dynamics of the gas–solid interaction is molecular-
beam surface scattering (MBS). The experimental ar-
rangement is similar to that already described for helium
atom diffraction. Instead of using an atomic beam of a
light molecular weight gas and observing diffraction ef-
fects, a well-collimated beam of molecules strikes the ori-
ented, preferably single-crystal, surface, and the species
that are scattered at a specific solid angle are detected by
a mass spectrometer. The angular distribution of the scat-
tered molecules can be obtained by rotation of the mass
spectrometer about the sample. The velocity distribution
of the molecules after scattering is deduced by chopping FIGURE 42 Rectilinear plot displaying the (a) specular scattering
the scattered molecules and thereby measuring their time and (b) cosine angular distribution of scattered beams. The arrow
of flight to the detector. The surface residence times of the indicates the angle of incidence.
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412 Surface Chemistry

direct information on inelastic scattering than angular dis- Exchange of hydrogen and deuterium to form HD is one
tributions alone. Although considerable information can of the simplest reactions that can be catalyzed on clean
be gained from such studies it has been impossible to get metal surfaces at temperatures as low as 100 K. The same
state specific information and indeed it is often unclear reaction is immeasurably slow in the gas phase due to the
whether internal states present more efficient energy very high dissociation energies of the reacting molecules
transfer channels than phonons or vice versa. The diffi- (103 kcal mol−1 ). the H2 –D2 exchange reaction has
culties in studying internal energy transfer in molecular been studied over flat (111) and stepped (332) single
collisions with surfaces can be resolved by the applica- crystal surfaces of platinum. The Pt(332) surface contains
tion of state-specific detection techniques. Laser-induced high concentrations of periodic surface irregularities
fluorescence, multiphonon ionization, IR excitation with (steps) that are one atom in height. Reaction probabilities
bolometric detection, and IR emission techniques have averaged over the cosine HD angular distributions were
all been used to obtain state-resolved measurements of 0.07 on the (111) surface and 0.35 on the (332) surface
the internal energy distributions of molecules scattering under identical experimental conditions (Ts = 1100 K,
from surfaces. It has also been possible to separate exp- Tg = 300 K). The reaction probability on the stepped
erimentally direct inelastic and trapping-desorption scat- surface varied markedly with the angle of incidence
tering. In the direct inelastic scattering of diatomics, co- of the mixed H2 –D2 molecular beam. This is shown
upling to rotational energy has been found to be very in Fig. 43. The reaction probability was highest when
important and to exhibit several interesting phenomena: the beam was incident on the open edge of the step
rotational rainbows and the production of rotationally and lowest when the bottom of the step was shadowed
aligned molecules in scattering.

2. Molecular-Beam Reactive Scattering

While molecular-beam scattering has made great advances
in our understanding of the energy exchange processes
during the gas–surface collision, molecular-beam tech-
niques have also made important contributions to the un-
derstanding of the mechanisms of chemical reactions oc-
curring at surfaces in the form of molecular-beam reactive
scattering (MBRS). The use of time-of-flight techniques
permits measurement of product velocity distributions and
the detailed time resolution of fast transient reactions. Also
of great value is the use of state-specific detection meth-
ods to determine product vibrational and rotational states.
Although MBRS can only be utilized at low pressures
(≤10−4 torr) its pressure range permits wide variations
of surface coverages. The reaction probabilities on a sin-
gle scattering can be determined together with the surface
residence times of adsorbates. The surface kinetic infor-
mation is obtained by measurements of the intensity and
the phase shift of the product molecules with respect to
the reactant flux. Residence times in the range 10−6 –1 sec
can be monitored with relative ease, and activation en-
ergy is determined from the temperature dependences of
the intensities and the phase shifts. The phase shift of the
product molecules is usually measured at different chop-
ping frequencies of the incident beam. At a given chopping
frequency, only those product molecules are detected that
are formed in the surface process and desorbed in less time
FIGURE 43 HD production as a function of angle of incidence 
than the chopping period.
of the molecular beam, normalized to the incident D2 intensity. (a)
As an example of an investigation of the dynamics Pt(332) surface with the step edges perpendicular to the incident
of a catalyzed surface reaction studied by MBRS we beam (φ = 90◦ ); (b) Pt(332) where the projection of the beam on
will consider the isotope exchange reaction, H2 –D2 . the surface is parallel to the step edges (φ = 0◦ ); and (c) Pt(111).
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Surface Chemistry 413

(curve a). When the H2 –D2 beam was incident parallel metals display heats of adsorption for oxygen that are com-
to the steps, the rate of HD production was independent parable to the heats of formation of the stable metal oxides.
of the angle of incident at all angles of crystal rotation Metals such as Ti, Zr, Mn, Al, Cu, and Fe dissolve oxy-
(curve b). These results indicate that the atomic step sites gen more readily and form stable oxide films even at room
are about seven times more active than the (111) terrace temperature. At low oxygen pressures these films often as-
sites for the dissociative chemisorption of hydrogen and sume a crystalline structure, whereas at higher pressures
deuterium molecules. Detailed analysis of the scattering (>10−3 atm) the films tend to be amorphous. At higher
data revealed a barrier height of 4–8 kJ mol−1 for temperatures (400–1000 K), oxide formation occurs read-
dissociative H2 chemisorption on the (111) surface. On ily on the surfaces of nearly all metals.
the other hand, this barrier did not exist (E a = 0) on the Growth of surface oxide films takes place only if
stepped surface. This difference in activation energy cations, anions, and electrons can diffuse through the
alone accounts for the different reaction probabilities of oxide layer. The growth kinetics of very thin films
the step and terrace sites. While the dissociation proba- (∼10–50 Å) often follow the Mott or Cabrera–Mott
bility of hydrogen molecules was higher on the stepped mechanisms in which electrons tunnel through the film
surface than on Pt(111), the kinetics and mechanism and associate with oxygen atoms to produce oxide ions
of HD recombination appear to be identical over both at the surface. A large local electric field (106 –107 V/cm)
surfaces once dissociation takes place. On both surfaces, results at the surface which facilitates cation diffusion
HD formation follows a parallel LH mechanism with from the metal–oxide interface to an interstitial site of the
one of the reaction branches operative over the entire oxide. The film thickness Z at time t is given by
temperature range of 300–1075 K. This branch has an
Z = α1 ln (α2 t + 1) (63)
activation energy and pseudo-first-order preexponential
factor of E a = 54 kJ mol−1 and A1 = 8 × 104 sec−1 or inverse logarithmic
for the stepped surface and E a = 65 kJ mol−1 and
1/Z = α3 − α4 ln t (64)
A1 = 3 × 105 sec−1 for the Pt(111) surface. A second
branch is observed for temperatures above 575 K, but the law of growth depending on whether electron tunneling
kinetic parameters for this pathway could not be accurately or cation diffusion is rate limiting. The constants α1 –α4
determined. are determined by the material, its structure, and the re-
action conditions. The electron field strength and rate of
growth decrease exponentially as the film thickens, result-
D. Stoichiometric Surface Reactions
ing in an effective limiting thickness for the surface oxide
Stoichiometric surface reactions are those in which the layer.
surface participates directly in the reaction by compound In addition to surface oxides, a vast array of surface
formation. Oxidation and corrosion are the two most im- compounds can be produced from the reactions of halo-
portant classes of such reactions. gens, chalcogenides, and carbon-containing molecules
Surface oxidation of metals encompasses a series of with metal surfaces. Chemisorption of chlorine near 300 K
at least three reaction steps that include (1) dissociative on Cu, Ti, W, Mo, Ta, Ni, Pd, and Au, for example, re-
chemisorption of oxygen on the metal surface, (2) rear- sults in the formation of stable surface compounds which
rangement of the surface atoms with dissolution of oxygen often evaporate as molecular chlorides upon heating at el-
into the near surface region, and (3) nucleation of oxide evated temperatures. Chemisorption of chlorine at 300 K
islands which grow laterally and eventually condense to on Ag(100) and Ag(111) produces chemisorbed chlorine
produce continuous oxide films. The oxide islands appear overlayers which react irreversibly at about 425 K to pro-
to precipitate suddenly once a critical oxygen concentra- duce AgCl with an activation energy of 56 kJ mol−1 . Upon
tion is reached in the near surface region. Nucleation takes heating, AgCl desorbs at about 830 K with a desorption
place most readily at surface irregularities such as atomic activation energy of 192 kJ mol−1 .
steps, dislocations, and stacking faults. At room tempera- MBRS has been used to investigate the dynamics of
ture, noble metals such as Rh, Ir, Pd, and Pt display little several surface corrosion reactions at low reactant pres-
tendency for oxygen incorporation or surface rearrange- sures. Systems studied include the oxidation Si, Ge, Mo,
ment. Initial heats of oxygen chemisorption on these met- and graphite, and the halogenation of Si, Ge, Ta, and Ni.
als are much greater than the heats of formation of the With the exception of silicon and germanium oxidation,
corresponding bulk oxides. Other metals such as Cr, Nb, where dissociative chemisorption of oxygen is apparently
Ta, Mo, W, Re, Ru, Co, and Ni, dissolve surface oxygen rate limiting, the kinetics of these surface reactions gen-
by a place exchange mechanism in which oxygen atoms erally appear to be controlled by surface or bulk diffusion
interchange positions with underlying metal atoms. These of the reacting species.
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414 Surface Chemistry

E. Catalytic Surface Reactions the sequence of elementary reactions that include ad-
sorption, surface migration, chemical rearrangements, and
A major goal of basic surface chemistry is in trying to
reactions in the adsorbed state, and desorption of the
understand heterogeneous catalysis on an atomic scale.
products, the rate of each step must be of steady state.
Virtually all chemical technologies and many technolo-
The rate of the overall catalytic reaction per unit area
gies in other fields use catalysis as an essential part of the
catalyst surface can be expressed as (moles of prod-
process. The most important catalytic processes are sum-
uct/catalyst area × time). Another expression for catalytic
marized in Table V. These processes are listed together
rate is the turnover number or turnover frequency. This
with the pertinent chemical reactions, widely used cata-
is the (number of molecules of product/number of cata-
lysts, and typical reaction conditions. There are several
lyst sites × time). For most heterogeneous catalyzed small
definitions of a catalyst, one general definition being that
molecule reactions the turnover number varies between
it is a substance that accelerates a chemical reaction with-
10−2 and 102 sec−1 . The calculation of the turnover num-
out visibly undergoing chemical change. Indeed, a major
ber is limited by the difficulty of determining the true
role of a catalyst is in accelerating the rate of approach to
number of active sites.
chemical equilibrium. However, a catalyst cannot change
The reaction probability reveals the overall efficiency
the ultimate equilibrium determined by thermodynamics.
of a catalyst. It is defined as follows:
Another major function of a catalyst is to provide reac-
tion selectivity. Under the conditions in which the reaction reaction probability
is to be carried out, there may be many reaction channels, rate of formation of product molecules
each thermodynamically feasible, that lead to the forma- =
rate of incidence of reactant molecules.
tion of different products. The selective catalyst will accel-
The determination of the rates of the net catalytic re-
erate the rate of only one of these reactions so that only the
actions and how the rates change with temperature and
desired product molecules form with near-theoretical or
pressure is of great practical importance. Although there
100% efficiency. One example is the dehydrocyclization
are many excellent catalysts that permit the achievement
of n-heptane to toluene:
of chemical equilibria (for example, Pt for oxidation of
CH3 CO and hydrocarbons to CO2 and H2 O), most catalyzed
reactions are still controlled by the kinetics of one of the
CH3 (CH2)5 CH3  4H2 surface processes. From the knowledge of the activation
energy and the pressure dependencies of the overall reac-
tion, the catalytic process can be modeled and the optimum
This is a highly desirable reaction that converts aliphatic reaction conditions can be calculated. Such kinetic anal-
molecules to aromatic compounds. The larger concentra- ysis, based on the macroscopic rate parameters, is vital
tion aromatic component in gasoline, for example, greatly for developing chemical technologies based on catalytic
improves its octane number. However, n-heptane may par- reactions.
ticipate in several competing simpler reactions. These in- The rates of reactions are extremely sensitive to small
clude hydrogenolysis, which involves C C bond scission changes of chemical bonding of the surface species
to form smaller molecular weight fragments (methane, that participate in the surface reaction. Since the energy
ethane, and propane); partial dehydrogenation, which pro- necessary to form or break the surface bonds appears
duces various olefins; and isomerization, which yields in the exponent of the Arrhenius expression for the
branched chains. All of these reactions are thermody- rate constant for the overall reaction, it can increase or
namically feasible, and since they appear to be less com- decrease the rate exponentially. For example, a change
plex than dehydrocyclization, they compete effectively. of 3 kcal in the activation energy alters the reaction rate
A properly prepared platinum catalyst surface catalyzes by over an order of magnitude at 500 K. Small variations
the selective conversion of n-heptane to toluene without of chemical bonding at different surface irregularities,
permitting the formation of other products. The catalyst steps, and kinks, as compared to atomic terraces, can give
selectivity is equally important for the reactions of small rise to a very strong structure sensitivity of the reaction
molecules (such as the hydrogenation of CO to produce rates and the product distribution. Rate measurements
a desired hydrocarbon) or very large molecules of bio- exponentially magnify the energetic alterations that
logical importance, where enzyme catalysts provide the occur on the surface and could provide a very sensitive
desired selectivity. probe of structural and electronic changes at the sur-
Catalysis is a kinetic phenomenon; we would like to face and changes of surface bonding on the molecular
carry out the same reaction at an optimum rate over and scale.
over again using the same catalyst. In most cases such One of the most important considerations in catalysis
a steady-state operation is desirable and aimed for. In is the need to provide a large contact area between the
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Surface Chemistry 415

TABLE V Chemical Processes Based on Heterogeneous Catalysis

Processes Typical reactions Catalyst Reaction conditions

Ammonia synthesis N2 + 3H2 → 2NH3 Triply promoted iron

(Fe K2 O Al2 O3 CaO); 720–800 K
40–100 atm
Dehydrogenation Fe2 O3 Cr2 O3 K2 O 800–900 K
H2  mixed metal oxides 10–50 atm

Epoxidation C2 H4 + 12 O2 → C2 H4 O AgCl K2 O/Al2 O3 520–600 K

Fischer–Tropsch synthesis CO + H2 → alkanes olefins aromatics Fe3 O4 K2 O/Al2 O3 500–700 K
of hydrocarbons supported Co, Ru, Ni, Rh 10–50 atm
Fischer–Tropsch synthesis CO + H2 → aldehydes acids alcohols Rh2 O3 ·H2 O K2 O 500–700 K
of oxygenates LaRhO4 supported Pd, Pt 10–50 atm
Hydrotreating (desulfurization R S R + H2 → 2RH + H2 S Co Mo, Ni Mo, 570–770 K
and denitrification) R N—R + 32 H2 → 2RHH + NH3 Ni Co Mo/Al2 O3 30–200 atm
Ni W/Al2 O3 , MoS2 , WS2
Isomerization
Olefins Solid acids, zeolites 270–470 K
Group VIII metals 1–5 atm
Xylenes ZSM-5-zeolites 480–580 K
2–5 atm

Alkanes Zeolites, Pt/Al2 O3 570–770 K

5–50 atm
Methanol synthesis CO + 2H2 → CH3 OH ZnCrO3 570–670 K
ZnO Cu2 O Cr2 O3
ZnO Cu2 O Al2 O3 100–600 atm
Methanol to gasoline CH3 OH → aromatics olefins, H2 O ZSM-5-zeolites 480–540 K
2–15 atm
NOx Reduction NO + 52 H2 → NH3 + H2 O Ru, Rh, Pd, Pt/SiO2 370–520 K
2NO + 2H2 → N2 + 2H2 O Ru, Rh, metal oxides 1–10 atm
2CO + 2NO → 2CO2 + N2 450–650 K
1–10 atm
Olefins +
Oxidation + O2 → CO2 + H2 O Group VIII metals 370–670 K
Alkanes
2NH3 + 5
2 O2 → NO + 3H2 O
CO + 1
2 O2 → CO2
Partial oxidations
Alcohols CH3 OH + 12 O2 → H2 CO + H2 O Ag, Fe2 (MoO4 )3 550–570 K
o-Xylene O V2 O5 1–10 atm

 3O2 O  3H2O

O
Olefins C2 H4 + 12 O2 → CH3 CHO V2 O5

1
O2 O SnO2 ·MoO3
2

 O2 Bi2 O3 ·MoO3
O
 H2O
Reforming
Dehydrogenation R R Pt, Pt–Re, Pt–Ge 700–800 K
 3H2

continues
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416 Surface Chemistry

TABLE V (Continued )
Processes Typical reactions Catalyst Reaction conditions

Dehydrocyclization Pt Au, Pt Re Cu 5–50 atm

 3H2

Dehydroisomerization Ir Au/Al2 O3
 3H2

Isomerization

Hydrogenolysis  H2 2C3H8
Hydrogenation
 H2

Selective
Hydrogenation H2  NiS 420–500 K
Olefins 1–10 atm
Alkynes R C CH + H2 → RHC CH2 Pt/Al2 O3 220–250 K
1–10 atm
Steam reforming CH4 + H2 O → CO + 3H2 Ni K2 O/Al2 O3 850–1100 K
30–100 atm
Water gas CO + H2 O → CO2 + H2 Fe2 O3 ·Cr2 O3 ZnO Cu2 O 650–800 J
20–50 atm

reactants and the surface. The total rate (moles of product square meters per gram of catalyst, is available in these
per time) is proportional to the surface area. As a conse- catalyst systems. Transition-metal catalysts are generally
quence, a lot of effort is expended to prepare large surfaces employed in a small, 10- to 100-Å-diameter particle form
area catalysts and to measure the surface area accurately. dispersed on large-surface-area supports. The support can
One example of high-surface-area catalysts is the group be a specially prepared alumina or silica framework (or
of catalysts known as zeolites, which are aluminosilicates a zeolite) that can be produced with surface areas in the
used for the cracking of hydrocarbons. They have crystal 102 -m2 /g range. These supported metal catalysts are of-
structures full of pores 8–20 Å in size. The structure of one ten available with near-unity dispersion (dispersion is de-
of the many zeolites used for catalysis, faujasite, is shown fined as the number of surface atoms per total number
in Fig. 44. Since the catalytic reactions occur inside the of atoms in the particle) of the metal particles and are
pores, an enormous inner surface area, of several hundred usually very stable in this configuration during the cat-
alytic reaction. The metal is frequently deposited from
solution as a salt and then reduced under controlled con-
ditions. Alloy catalysts and other multicomponent catalyst
systems can also be prepared in such a way that small al-
loy clusters are formed on the large-surface-area oxide
supports.
Most catalytic reactions take place via the formation of
intermediate compounds between the reactants or prod-
ucts and the surface. The surface atoms of the catalyst
form strong chemical bonds with the incident molecules,
and it is this strong chemical surface–adsorbate interac-
tion which provides the driving force for breaking high-
binding-energy chemical bonds (C C, C H, H H, N N,
and C O bonds), which are often an important part of the
catalytic reaction.
A good catalyst will also permit rapid bond breaking
FIGURE 44 Line drawing of the structure of the zeolite faujasite. between the adsorbed intermediates and the surface and
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Surface Chemistry 417

the speedy release or desorption of the products. If the TABLE VI Structure-Sensitive and Structure-
surface bonds are too strong, the reaction intermediates Insensitive Catalytic Reactions
block the adsorption of new reactant molecules, and the Structure sensitive Structure insensitive
reaction stops. For too-weak adsorbate-catalyst bonds, the
necessary bond-scission processes may be absent. Hence, Hydrogenolysis Ring opening
the catalytic reaction will not occur. A good catalyst is Ethane: Ni Cyclopropane: Pt
thought to be able to form chemical bonds of intermediate Methylcyclopentane: Pt
strength. These bonds should be strong enough to induce Hydrogenation Hydrogenation
bond scission in the reactant molecules. However, the bond Benzene: Ni Benzene: Pt
should not be too strong to ensure only short residence Isomerization Dehydrogenation
times for the surface intermediates and rapid desorption Isobutane: Pt Cyclohexane: Pt
of the product molecules, so that the reaction can proceed Hexane: Pt
with a large turnover number. Cyclization
Of course, activity is only one of many parameters that Hexane: Pt
are important in catalysis. The selectivity of the catalyst, its Heptane: Pt
thermal and chemical stability, and dispersion, are among
the other factors that govern our choices. While macro-
scopic chemical-bonding arguments can explain catalytic viewed as modified acid–base reactions. It is common to
activity in some cases, atomic-scale scrutiny of the surface refer to an oxide catalyst as acidic or basic according to
intermediates, catalyst structure, and composition, and an its ability to donate or accept electrons or protons.
understanding of the elementary rate processes are nec- The electron transfer capability of a catalyst is ex-
essary to develop the optimum selective catalyst for any pressed according to the Lewis definition. A Lewis acid
chemical reaction. is a surface site capable of receiving a pair of electrons
One of the important directions of research in catalysis from the adsorbate. A Lewis base is a site having a free
is the identification of the reaction intermediates. The sur- pair of electrons that can be transferred to the adsorbate.
face residence times of many of these species are longer The proton-transfer capability of a catalyst is expressed
than 10−5 sec under most catalytic reaction conditions (as according to the Brønsted definition. A Brønsted acid is
inferred from the turnover frequency). They may be de- a surface site capable of losing a proton to the adsorbate
tected by suitable spectroscopic techniques either during while a Brønsted base is a site that can accept a proton
the steady-state reaction or when isolated by interrupting from the adsorbed species.
the catalytic process. Perhaps the most widely used catalysts, the zeolites,
The concept of active sites is an important one in catal- best represent the group of oxides that exhibit acid–base
ysis. A surface generally possesses active sites in numbers catalysis. Zeolites are alumina silicates, some of which
that are smaller than the total number of surface atoms. The are among the more common minerals in nature. Modern
presence of unique atomic sites of low coordination and synthesis techniques permit the preparation of families of
different valency that are very active in chemical reactions zeolite compounds with different Si/Al ratios. Since the
has been clearly demonstrated by atomic-scale studies of Al3+ ions lack one positive charge in the tetrahedrally
metal and oxide surfaces. A catalytic reaction is defined to coordinated silica, Si4+ , framework, they are sites of pro-
be structure sensitive if the rate changes markedly as the ton or alkali–metal affinity. Variation of the Si/Al ratio
particle size of the catalyst is changed. Conversely, the re- gives rise to a series of substances of controlled but dif-
action is structure insensitive on a given catalyst if its rate ferent acidity. By using various organic molecules dur-
is not influenced appreciably by changing the dispersion ing the preparation of these compunds that build into the
of the particles under the usual experimental conditions. structure, subsequent decomposition leaves an open pore
In Table VI we list several reactions that belong to these structure, where the pore size is controlled by the skeletal
two classes. Clearly, variations of particle size give rise to structure of the organic deposit. Very high internal sur-
changes of atomic surface structure. The relative concen- face area catalysts (102 m2 /g) can be obtained this way
trations of atoms in steps, kinks, and terraces are altered. with controlled pore sizes of 8–20 Å and controlled acidity
Nevertheless, no clear correlation has been made to date [(Si/Al) ratio]. These catalysts are utilized in the cracking
between variations of macroscopic particle size and the and isomerization of hydrocarbons that occur in a shape
atomic surface structure. selective manner as a result of the uniform pore structure
Most surface reactions and the formation of surface and are the largest volume catalysts in petroleum refining.
intermediates involve charge transfer, either an electron They are also the first of the high-technology catalysts in
transfer or a proton transfer. These processes are often which the chemical activity is tailored by atomic-scale
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418 Surface Chemistry

study and control of the internal surface structure and prevent side reactions, and alter the reaction paths in a
composition. variety of ways.
A catalyst used in industry is very rarely a pure ele- While industrial catalytic systems are complex and are
ment or compound. Most catalysts contain a complex mix- not readily suited to basic science studies to understand
ture of chemical additives or modifiers that are essential how they work on an atomic scale, one approach to their
ingredients for high activity and selectivity. Promoters are understanding is the synthetic approach. In this approach
beneficial additives that increase activity, selectivity, or we begin with a very simple system then synthesize com-
useful catalyst lifetime (stability). Structural promoters plexity from this. The catalyst particle is viewed as com-
inhibit sintering of the active catalyst phase or present posed of single crystal surfaces, as shown in Fig. 45. Each
compound formation between the active component and surface has different reactivity and the product distribu-
the support. The most frequently used chemical promoters tion reflects the chemistry of the different surface sites.
are electron donors such as the alkali metals or electron We may start with the simplest single crystal surface [for
acceptors such as oxygen and chlorine. For example, in the example, the (111) crystal face of platinum] and examine
petroleum industry, chlorine and oxygen are often added its reactivity. It is expected that much of the chemistry
to commercial platinum catalysts used for reforming reac- of the dispersed catalyst system would be absent on such
tions by which aliphatic straight-chain hydrocarbons are a homogeneous crystal surface. Then high-Miller-index
converted to aromatic molecules (dehydrocyclization) and crystal faces are prepared to expose surface irregularities,
branched isomers (isomerization). steps, and kinks of known structure and concentration,
These additives accomplish several tasks during the re- and their catalytic behavior is tested and compared with
action. By changing the chemical bonding of some of the the activity of the dispersed supported catalyst under iden-
surface intermediates, the steady-state concentration of tical experimental conditions. If there are still differences,
these intermediates may be altered, and thus a somewhat the surface composition is changed systematically or other
higher concentration of the catalytically active species is variables are introduced until the chemistries of the model
obtained. In this way the rate of the reaction is increased system and the working catalyst become identical. This
and the selectivity may be improved. approach is described by the following sequence:
Often multicomponent catalyst systems are utilized to
carry out reactions consisting of two or more active metal
components or both oxide and metal constituents. For ex-
ample, a Pt–Rh catalyst facilitates the removal of pol-
lutants from car exhausts. Platinum is very effective for
oxidizing unburned hydrocarbons and CO to H2 O and
CO2 , and rhodium is very efficient in reducing NO to
N2 , even in the same oxidizing environment. Dual func-
tional or multifunctional catalysts are frequently used to
carry out complex chemical reactions. In this circumstance
the various catalyst components should not be thought
of as additives, since they are independently responsible
for different catalytic activity. Often there are synergistic
effects, however, whereby the various components ben-
eficially influence each other’s catalytic activity to pro-
vide a combined additive and multifunctional catalytic
effects.
It should be clear from this discussion that the working,
active, and selective catalyst is a complex, multicompo-
nent chemical system. This system is finely tuned and
buffered to carry out desirable chemical reactions with
high turnover frequency and to block the reaction paths for
other thermodynamically equally feasible but unwanted
reactions. Thus, an iron catalyst or a platinum catalyst
is composed not only of iron or platinum but of several
other constituents as well to ensure the necessary surface FIGURE 45 Catalyst particle viewed as a crystallite, composed
structure and oxidation state of surface atoms for optimum of well-defined atomic planes. (Courtesy of Lawrence Berkeley
catalytic behavior. Additives are often used to block sites, Laboratory.)
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Surface Chemistry 419

structure of crystal surfaces and adsorbed gases lower part of the high-pressure isolation cell is then lifted
↓↑ to enclose the sample in a 30-cm3 volume. The isolation
surface reactions on crystals at low pressures chamber can be pressurized to 100 atm if desired and is
(≤10−4 torr) connected to a gas chromatograph that detects the product
↓↑ distribution as a function of time and surface temperature.
surface reactions on crystals at high pressures The sample may be heated resistively both at high pres-
(10+3 −10+5 torr) sure or in ultrahigh vacuum. After the reaction study the
↓↑ isolation chamber is evacuated, opened, and the catalytic
reactions on dispersed catalysts surface is again analyzed by the various surface-diagnostic
techniques. Ion bombardment cleaning of the surface or
Investigations in the first step define the surface struc- means to introduce controlled amounts of surface addi-
ture and composition on the atomic scale and the chemical tives by vaporization are also available. The reaction at
bonding of adsorbates. Studies in the second step, which high pressures may be studied in the batch or the flow
are carried out at low pressures, reveal many of the ele- mode.
mentary surface reaction steps and the dynamics of surface Typical catalytic reactions that have been investigated,
reactions. Studies in the third and fourth steps establish the in some detail, using this approach include hydrocarbon
similarities and differences between the model system and conversion on platinum and modified platinum surfaces
the dispersed catalyst under practical reaction conditions. (isomerization, hydrogenolysis, hydrogenation, dehydro-
The advantage of using small-area catalyst samples is genation and cyclization), dehydrosulfurization on molyb-
that their surface structure and composition can be pre- denum, ammonia synthesis on iron, and carbon monoxide
pared with uniformity and can be characterized by the hydrogenation on iron.
many available surface diagnostic techniques.
In this approach to catalytic reaction studies the sur-
face composition and structure are determined in the same F. Photochemical Surface Reactions
chamber where the reactions are performed, without ex- Photochemical surface reactions form their own class
posing the crystal surface to the ambient atmosphere. This due to the fact that a thermodynamically uphill reaction
necessitates the combined use of an ultrahigh vacuum en- ( G > 0) may be carried out with the aid of an external
closure, where the surface characterization is carried out, source of energy, light. In fact, one of the most important
and a high-pressure isolation cell, where the catalytic stud- chemical reactions of our planet, photosynthesis, requires
ies are performed. Such an apparatus is shown in Fig. 46. the input of 720 kcal/mol of energy to convert carbon
The small-surface-area (approximately 1-cm2 ) catalyst is dioxide and water to one mole of sugar:
placed in the middle of the chamber, which can be evac-
uated to 10−9 torr. The surface is characterized by LEED light
6CO2 → 6H2 O−−−−−−→6H12 O6 + 6O2 (65)
and AES and by other surface diagnostic techniques. The chlorophyll

FIGURE 46 Schematic representation of the experimental apparatus to carry out catalytic reaction-rate studies on
single-crystal surfaces of low surface area at low and high pressures in the range 10−7 to 104 torr.
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420 Surface Chemistry

It is useful to consider light as one of the reactants in ically allowed photon-assisted reactions. The latter reac-
photosynthesis. By adding the light energy to Eq. (65), the tions are thermodynamically feasible without any external
reaction becomes athermic or even exothermic if excess energy input, but light is used to obtain certain product
light energy is utilized, selectively. Excitation of selected vibrations, rotations, or
electronic states of the incident or adsorbed molecules by
hv + H2 O + CO2 = CH2 + 32 O2
light permits us to change the reaction path or increase the
We may consider photon-assisted or photochemical reac- reaction rate. For example, the hydrogenation of acetylene
tions of many types that lead to the formation of lower or the oxidation of ammonia can be photon-assisted,
molecular weight hydrocarbons and of other products. leading to different reaction rates than in the absence of
One of the simplest of these important new classes of light.
reactions leads to the dissociation of water: As an example of a photocatalyzed surface reaction
we discuss the photoelectrochemical dissociation of wa-
hv + H2 O = H2 + 12 O2 (66)
ter. It was shown in 1972 that upon illumination of re-
Another leads to the formation of methane: duced titanium oxide (TiO2 ), which served as the anode
in basic electrolyte solution, oxygen evolution was de-
hv + CO2 + 2H2 O = CH4 + 32 O2 (67)
tectable at the anode, and hydrogen evolved at a metal
or to the fixation of nitrogen: (platinum) cathode. This reaction requires an energy of
1.23 V/electron (a two-electron process per dissociated
hv + 3H2 O + N2 = 2NH3 + 32 O2 (68)
water molecule). In the presence of light of energy equal
Light as a reactant may be employed in two ways. The to or greater than the band-gap energy of titanium oxide
adsorbed molecules can be excited directly by photons (3.1 eV), an external voltage as low as 0.2 V was suf-
of suitable energy to a higher vibrational or electronic ficient to dissociate water. The process stopped as soon
states. The excited species then may undergo chemical re- as the light was turned off, and started again upon reil-
arrangements or interactions that are different from those lumination. Shortly after, several other systems showed
in the ground vibrational or electronic states. Alterna- the ability to carry out photon-assisted dissociation of
tively, the solid can be excited by light in the near-surface water. When p-type gallium phosphide, GaP, was used
region. Photons of band-gap or greater energy may ex- as a cathode instead of platinum upon illumination of
cite electron–hole pairs at the surface. As long as these the TiO2 anode, O2 and H2 could be generated at the
charge carriers have a relatively long lifetime (i.e., they are semiconductor anode and cathode, respectively, without
trapped at the surface, so that their recombination is not an the need of applying any external potential. When stron-
efficient process), there is a high probability of their cap- tium titanate, SrTiO3 , was substituted for TiO2 as the an-
ture by the adsorbed reactants. These, in turn, can undergo ode, H2 O photodissociation was found to take place with-
reduction or oxidation processes using the photogenerated out external potential even when a platinum cathode was
electrons and holes, respectively. The photographic pro- employed.
cess is one example of this type of surface photochemical
reaction. However, we would like the photogenerated elec-
trons and holes to be captured by the adsorbed molecules
in order to carry out photochemical surface reactions of
the adsorbates instead of the photodecomposition of the
solid at the surface. The cross sections for adsorption of
band-gap or higher-than-band-gap energy photons are so
large that the photogeneration of electron–hole pairs is
a most efficient process. At present, this cannot be read-
ily matched by the efficiency of direct photoexcitation
of vibrational or electronic energy states of the adsorbed
molecules.
Many solid surfaces efficiently convert light to long-
lived electron–hole pairs that can induce the chemical
changes leading to the reactions in Eqs. (66)–(68). In fact,
FIGURE 47 Energy conditions needed to reduce B+ to B and
inorganic photoreaction is one of the exciting new fields
oxidize A− to A at a semiconductor surface. Electrons that are
of surface science and heterogeneous catalysis. excited by photons into the conduction band ECB must be able to
It is important to distinguish between thermodynami- reduce B+ , and electron vacancies (holes) in the valence band
cally uphill photochemical reactions and thermodynam- E VB must be able to oxidize A− .
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Surface Chemistry 421

Figure 47 shows a schematic energy diagram to indicate flat-band potential, may become photochemically active
the conditions necessary to carry out photoelectrochemi- as a result of strong band bending at the surface.
cal reactions efficiently. If the band-gap energy is greater Often the oxidation or reduction photoreactions lead
than the free energies for the reduction and oxidation reac- to the decomposition of the semiconductor electrode ma-
tions, the photoelectron that is excited into the conduction terial. Instead of the photoreactions of adsorbate ions or
band by light could reduce B+ to B by electron transfer molecules, a solid-state photoreaction occurs. This is par-
from the surface to the molecule. The photogenerated elec- ticularly noticeable at the surfaces of illuminated CdS, Si,
tron vacancies (holes) could also oxidize the A− anions and GaP. Much of the research is therefore directed toward
to A by capturing the electron. For the photodissociation stabilizing these photoelectrode materials by suitable ad-
of water, the conduction band must be above the H+ /H2 sorbates that could prevent the occurrence of photodecom-
potential and the valence band below the O2 /OH− po- position by providing an alternative chemical route for the
tential to be able to carry out the photoreaction without photoreduction or photooxidation.
an external potential. The band gap must be greater than
1.23 V and the flat-band potential of the conduction and
valence bands energetically well placed with respect to the ACKNOWLEDGMENT
(H+ /H2 ) and O2 /OH− couples. The flat-band potentials
can be obtained by capacitance measurements as a func- This work was supported by the Assistant Secretary for Energy Research,
Office of Basic Energy Sciences, Materials Sciences Division of the U.S.
tion of external potential.
Department of Energy under Contract No. DE-AC03-76SF00098.
There is, of course, considerable band bending of the
conduction and valence bands of any semiconductor at the
surface. This is due to the presence of localized electronic
surface states and to charge transfer between the adsor-
SEE ALSO THE FOLLOWING ARTICLES
bates and semiconductor. Potential-energy diagrams that
ADHESION AND ADHESIVES • ADSORPTION • AUGER
show the band positions schematically at an n-type or p-
ELECTRON SPECTROSCOPY • BONDING AND STRUCTURE
type semiconductor liquid interface are shown in Fig. 48.
IN SOLIDS • CATALYSIS, INDUSTRIAL • CATALYST
The band bending provides an efficient means of sepa-
CHARACTERIZATION • CHEMICAL THERMODYNAMICS •
rating electron–hole pairs, since the potential gradient as
CRYSTALLOGRAPHY • PHOTOCHEMISTRY, MOLECULAR •
shown for the n-type semiconductor drives the electrons
PHOTOELECTRON SPECTROSCOPY • SOLID-STATE ELEC-
away from the semiconductor surface while it attracts the
TROCHEMISTRY • TRIBOLOGY
holes in the valence band toward the semiconductor elec-
trolyte interface. As a result, the oxidation reaction takes
place at the oxide anode while the reduction reaction takes
place at the cathode to which the photoelectron migrates BIBLIOGRAPHY
along the external circuit. The magnitude of the band bend-
ing at the surface depends primarily on the carrier concen- Adamson, A. W. (1982). “Physical Chemistry of Surfaces,” 4th ed.,
Wiley, New York.
tration in the semiconductor and on the electron-donating Anderson, J. R., and Boudart, M. (1981). “Catalysis Science and Tech-
or -accepting abilities of the adsorbates at the surface. nology,” Vols. 1–7, Springer-Verlag, Berlin/New York.
Semiconductors that are not likely to carry out the pho- Ertl, G., and Gomer, R., eds. (1983). “Springer Series in Surface Sci-
todissociation of water, according to the location of their ences,” Vols. 1–4, Springer-Verlag, Berlin/New York.
Ertl, G., and Kuppers, J. (1979). “Low Energy Electrons and Surface
Chemistry,” Verlag Chemie, Weinheim.
Feuerbacher, B., Fitton, B., and Willis, R. F. (1979). “Photoemission and
the Electronic Properties of Surfaces,” Wiley, New York.
King, D. A., and Woodruff, W. P., eds. (1983). “The Chemical Physics
of Solid Surfaces and Heterogeneous Catalysis,” Vols. 1–4, Elsevier,
New York.
Morrison, S. R. (1977). “The Chemical Physics of Surfaces,” Plenum,
New York.
Roberts, M. W., and McKee, C. S. (1978). “Chemistry of the Metal-Gas
Interface,” Oxford Univ. Press, London.
Somorjai, G. A. (1981). “Chemistry in Two Dimensions: Surfaces,”
Cornell Univ. Press, Ithaca, NY.
Tompkins, F. C. (1978). “Chemisorption of Gases on Metals,” Academic
Press, NY.
FIGURE 48 Band bending at the n-type and p-type semiconduc- Vanselow, R., and Howe, R., eds. (1979). “Chemistry and Physics of
tor interfaces. Solid Surfaces,” Vols. 1–6, Springer-Verlag, Berlin/New York.
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Ligand Field Concept

Gunter Gliemann Yu Wang
University of Regensburg National Taiwan University

I. Basic Experimental Findings

II. Model and Theory
III. Optical Properties of Complexes
IV. Magnetic Properties of Complexes
V. Stabilization of Complexes

GLOSSARY tude depends on the orbit diameter and the mass and
velocity of the particle.
Charge transfer transition Change of the electronic Spin crossover complex Complex undergoes a spin tran-
state of a complex ion by the transfer of an electron sition induced by certain external factor such as tem-
from mainly the central ion state to mainly the ligand perature, pressure, light, etc.
system state or vice versa. Tanabe-Sugano diagram Term splitting as a function of
Coordination number Number of ligands bound at the ligand field strength for 3d-transition metal ions in oc-
central ion. tahedral field, originated by Tanabe and Sugano.
Electron spin Intrinsic angular momentum vector of the Term Entity of states of equal energy.
electron. It is a quantum phenomenon, which has no Transition metals Elements with incompletely filled d
analog in classical mechanics. orbitals: scandium, titanium, through copper (3d se-
Jahn-Teller effect For a nonlinear molecule in an elec- ries); yttrium, zirconium through silver (4d series); lan-
tronically degenerate ground state, distortion must oc- thanum, hafnium through gold (5d series).
cur to lower the symmetry and to lower the energy to a
more stable nondegenerate ground state.
Ligand Atomic ion, molecular ion, or molecule coordi- THE LIGAND FIELD CONCEPT is the basis of a quan-
nated at the central ion of a complex. tum theoretical model developed in the 1950s for describ-
Magnetic moment A property associated with a mag- ing the electron systems of transition metal complexes. A
netic domain. It is an experimental measure of the mag- transition metal complex is composed of a transition metal
netism of a compound, generally measured in units of ion (central ion) surrounded by a system of ligands (atomic
magnetons. ions, molecular ions, or molecules). The ligands produce
Orbital angular momentum Mechanical vector quan- the electrical field (the ligand field) acting on the electron
tity perpendicular to the orbit of a particle. Its magni- system of the central ion. As the ligand field theory shows,

523
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524 Ligand Field Concept

the optical, magnetic, and stability properties of transition

metal complexes strongly depend on the symmetry and
strength of the ligand field.

I. BASIC EXPERIMENTAL FINDINGS

Crystallized salts of metal complexes have an amazing

variety of brilliant colors, which are expressed by such
prefixes as violeo-, praseo-, luteo-, purpureo-, and roseo-
(Table I). Investigations of the underlying chemical struc-
tures reveal a close relationship between color and com-
position, an immediate challenge for the spectroscopist.
Therefore, after the foundation of coordination theory by
A. Werner (1907) extended studies on the absorption spec-
tra of complexes were investigated. The aim of these stud-
ies was to derive relations between the number and the
position of absorption bands and the nature of the central
ion and the ligands. Because the techniques and apparatus FIGURE 1 A schematic absorption spectrum of a transition metal
complex ion in the UV-VIS region. The central ion bands corre-
for measuring absorption spectra were still rather unde- spond to d →d transitions; the ligand bands correspond to charge
veloped, endeavors to interpret the spectra according to transfer transitions and/or to intraligand transitions.
the theory of electrons remained unsatisfactory until the
1940s. But it was soon recognized that the existence of d Stimulated by Linhard’s work, in 1946 F. E. Ilse and
electrons is significant for the color of transition metal ion H. Hartmann formulated the ligand field concept, based
complexes. on the classical ionic model of transition metal complexes
The outstanding work of M. Linhard and coworkers, (W. Kossel and A. Magnus) and on appropriate group the-
starting in 1944 with the investigation of Co3+ and Cr3+ oretical methods (H. Bethe).
complexes, set the standard for the precision of absorption
spectroscopy of dissolved complexes. One of the main
results of Linhard’s work is indicated schematically in
Fig. 1. The absorption spectra of transition metal com-
plexes can be divided into two spectral regions. In the long-
wavelength region (λ ≥ 350–400 nm) one finds one or
more weak bands (extinction coefficient ε = 1–102 liters
mol−1 cm−1 ). These bands do not appear when the central
ion is not a transition metal ion (e.g., Al3+ instead of Cr3+ ;
see Fig. 2). Therefore, these weak bands were assigned to
transitions involving d electrons of the central ion (cen-
tral ion bands, d-d bands). In the short-wavelength re-
gion (λ ≤ 350–400 nm) strong absorption bands (ε ∼ 103 –
106 liters mol−1 cm−1 ) are observed. These strong bands
(ligand bands) are usually charge transfer bands, due to
electron transfer between the central ion and the ligand
system, or intraligand bands, caused by excitation of the
electron system of the ligands.

TABLE I Nomenclature Describing the Colors

of Some Transition Metal Complexes
TM complexes Color Prefix

cis-[Co(NH3 )4 Cl2 ]+ Violet Violeo-

trans-[Co(NH3 )4 Cl2 ]+ Green Praseo-
[Cr(NH3 )6 ]3+ Yellow Luteo-
[Co(NH3 )5 H2 O]3+ Rose Roseo- FIGURE 2 Absorption spectra of [Cr(C2 O4 )3 ]3− (full line) and
[Al(C2 O4 )3 ]3− (dotted line). [From Schläfer, H. L. (1957). Z. Phys.
[Co(NH3 )5 Cl]2+ Purple red Purpureo-
Chem. 11, 65.]
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Ligand Field Concept 525

tron pairs. Neither the ionic model nor the covalent model
provided a satisfactory interpretation of several optical
properties, since these models were concerned primarily
with the electronic ground state of the complex ions.
For a large number of complexes certain spectral re-
gions of the absorption spectra can be assigned alterna-
tively to the different components of the complex (central
ion, ligand system). On this account a model that starts
with the assumption of separated electron systems for the
central ion and for the ligands will be appropriate for a
theoretical treatment.
If one is interested primarily in the electronic states
of the central ion bound in the complex, one has to con-
sider the electric field generated by the ligand system, so-
FIGURE 3 L-edge absorption spectra of Fe2+ in Fe(phen)2
called the ligand field. The effect of this ligand field on the
(NCS)2 at 298 K (solid line) and at 15 K (dotted line). [From Lee,
J. J., Sheu, H. S., Lee, C. R., Chen, J. M., Liu, R. G., Lee, J. F., electronic states of the central ion is then taken into con-
Wang, C. C., Huang, C. H., and Wang, Y. (2000). J. Am. Chem. sideration. The theory treating this concept of the ligand
Soc. 122, 5742.] field is the ligand field theory, where the electronic struc-
ture of the ligand system is taken explicitly into account.
In other words, the complete molecular orbital treatment
In addition to the absorption spectra at UV-VIS range,
of the complex is undertaken. To a first approximation
the absorption in the much higher energy range has also
the charge distribution of the ligands is represented by
been observed in recent years. Here the electron transition
point charges and/or point dipoles in their centers, the lig-
is between the inner core orbitals and the valence orbitals
and field treatment can be reduced to an atomic orbital
of the central ions. An example of Fe L-edge absorption is
treatment of the central ion, this extended ionic model is
given in Fig. 3 to display the electron transition between
designated as crystal field theory.
2 p and 3d orbitals. The magnetic properties of the transi-
The starting point of the crystal field theory is the
tion metal complexes are known to exhibit quite a variety
description of the electronic states of the free, isolated
even with the same metal ion, for example, diamagnetic,
transition metal ion (the central ion) in a complex. Infor-
and paramagnetic are found in Fe2+ , Co3+ complexes of
mation on the electronic ground state and the excited states
various ligands (low-spin, high-spin complexes). The un-
even distribution of electron density around the metal ion
in a complex is demonstrated by the deformation density
at the metal center shown in Fig. 4, where the spherical
electron density is subtracted from the observed molecu-
lar electron density. Since the spherical density means that
even populations are among five degenerated d-orbitals,
the deformation density may give the direct observation
on the difference among d-orbital population. All these
recent experimental findings can be rationalized by the
ligand field concept.

II. MODEL AND THEORY

In the 1920s and 1930s two apparently contrary models,

the ionic model and the covalent model, were developed
to explain the binding between the central ion and the lig-
ands, which were both represented by point charges and
point dipoles. In the ionic model of Kossel and Magnus, the
binding between the central ion and the ligands is due to the
FIGURE 4 Deformation density of Ni(disn)2 plane around Ni,
electrostatic forces between the components. In the cova- solid line positive, dotted line negative, contour interval is
lent model of Sidgwick and Pauling, the binding between 0.1 eÅ−3 . [From Lee, C. S., Hwang, T. S., Wang, Y., Peng, S. M.,
the central ion and the ligands is accomplished by elec- and Hwang, C. S. (1996). J. Phys. Chem. 100, 2934–2941.]
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526 Ligand Field Concept

of the free ions is available from the analysis of the cor-

responding absorption or emission spectra and/or from
quantum mechanical calculations.

A. Electronic States of a Free Ion

The electronic states of a free ion can be characterized
by their energy and by their angular momentum, which
includes the orbital angular momenta and the spins of the
electrons involved. For atoms with atomic number Z ≤ 30,
the Russell-Saunders coupling is a good approximation. In
this approximation the orbital angular momenta of elec-
trons are added vectorically to the total orbital angular
momentum L and the spins of the electrons are coupled
to the total spin S:
 
Ij = L; sj = S
j j

where lj and sj are the orbital and the spin angular mo-
mentum of the jth electron, respectively. As shown by
quantum mechanics the absolute values of the vectors L
and S are restricted to certain discrete amounts FIGURE 5 Spatial orientations of a spin vector S with S = 32 .

|L| = h L(L + 1), L = 0, 1, 2, 3, . . . There are 2S + 12 = 4 different allowed values of projection on the
 z axis.
|S| = h S(S + 1),
 ration with the two electron spins antiparallel, ↑↓) and
0, 1, 2, 3, . . . for even number of electrons 3 (triplet, ↑↑). There are, in total, two triplet terms and
S=
1/2, 3/2, 5/2, 7/2, . . . for odd number of electrons three singlet terms: 3 P, 3 F, 1 S, 1 D, and 1 G. The 3 F [com-
where h is h/2π (h is Planck’s constant); L and S is the posed of (2 × 3 + 1)(2 × 1 + 1) = 21 states] is the ground-
quantum number of the total orbital angular momentum state term. The five Russell-Saunders term of a d 2 ion are
and the total spin of the system of electrons, respectively. shown in the energy-level diagram of Fig. 6. The com-
For the numerical values L = 0, 1, 2, 3, . . . it is conven- plete sets of Russell-Saunders terms for the d N ions with
tional to use the letters S, P, D, F, . . . By quantum mechani- N = 1, 2, . . . , 9 are given in Table II.
cal rules spin S with quantum number S can take 2S + 1 to
different special orientations with respect to a given direc- TABLE II Russell-Saunders Terms for Free dN Ionsa
tion shown in Fig. 5. The 2S + 1 is denoted as multiplicity
Occupation
M. Correspondingly, an orbital angular momentum L with of the d shell Russell-saunders term
quantum number L can assume 2L + 1 different spatial
orientations. Therefore, a given set of quantum numbers d1, d9 2D

L and S can assume a total of (2L + 1)(2S + 1) states d2, d8 3 F, 3 P

1 G, 1 D, 1 S
with different orientations of orbital and/or spin angular
momentum. These states form a Russell-Saunders term, d3, d7 4 F, 4 P

symbolized by 2S+1 L. All (2L + 1)(2S + 1) states of the 2 H, 2 G, 2 F, a2 D, 2 P

same term have equal energies, if the coupling between d4, d6 5D

3 H, 3 G, a3 F, b3 F, 3 D, a3 P, b3 P
L and S is ignored. They are energetically “degenerate.”
1 I, a1 G, b1 G, 1 F, a1 D, b1 D, a1 S, b1 S
Usually, different terms have different energies. By Hund’s
rule the term with the highest multiplicity M and the high- d5 6S
4 G, 4 F, 4 D, 4 P
est L value is the ground-state term (energetically most
2 I, 2 H, a2 G, b2 G, a2 F, b2 F, a2 D, b2 D, c2 D, 2 P, 2 S
stable term). The energy difference between the terms is
expressed in terms of B, an energy parameter of electron- a If for a d N ion (N = 1, . . . , 9) several terms with the same L
electron repulsion. value and the same S value exist, they are distinguished by prefixes
For example, a d 2 ion (two d electrons) will result in a, b, c. Terms with underlined L symbols are the ground terms for the
various states with multiplicity 1 (singlet; spin configu- first d N configuration.
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Ligand Field Concept 527

FIGURE 6 Russell-Saunders terms of a d 2 free ion with and without spin-orbital coupling.

If the coupling between the total orbital angular mo- B. Crystal-Field Theory
mentum, L, and the total spin angular momentum, S, has
In the course of forming a complex, the central ion is bound
to be taken into account, the total angular momentum J
to be affected by the ligand field (electrical field of the lig-
should be used. Where J is the vector sum of L and S.
ands), and thereby the motion modes of the electrons of
The quantum number of the vector J is again restricted to
the central ion will be perturbed. Accordingly, the term
certain discrete amounts.
system of the central ion will be changed. Some terms of
the free ion are energetically merely shifted, while others
J = L + S, J = |L + S|, |L + S − 1|, . . . . . . . |L − S|
are split into progeny terms 2S+1 i , i = 1, 2, . . . with dif-

|J| = h J (J + 1) ferent energies (intracomplex Stark effect). The symbol
i describes the orbital state of the ith progeny term.
The number of the progeny terms 2S+1 i can be exactly
The energy term is symbolized as 2S+1 L J , for example, the determined by the methods of group theory. It depends on
ground state of d 2 (3 F) is split into 3 F4 , 3 F3 , and 3 F2 , where the L value of the (parent) term 2S+1 L and on the symmetry
the order of energy is such that 3 F4 > 3 F3 > 3 F2 as shown of the ligand system: Number of progeny terms 2S+1 i = f
in Fig. 6. Each term is in 2J + 1 degeneracy and can be (L, symmetry)
separated by applying magnetic field, i.e., the Zeemann
effect. However, the splitting due to the L − S coupling is 1. Term Splitting Under Oh Symmetry
much smaller than the splitting due to the electron-electron
repulsion designated the energy difference between the The general group theoretical result can be illustrated by
Russell-Saunders terms. a simple model system. First we consider a system of six
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528 Ligand Field Concept

states will be shifted by the same amount when the ligand

field is acting on the central ion. No splitting will be ob-
served. For a d electron (2L + 1 = 5), however, there are
distributions that are obviously not equivalent with regard
to the ligands (Fig. 8). The maxima of the distributions
dx y , dx z , and d yz are directed equivalently into the angular
bisectors between the bonds. Therefore, these three states
will have the same energy. The distribution dz 2 and dx 2 −y 2
have maxima along the bonds to the ligands located on
the x, y, and z axis. It follows that the dx 2 −y 2 and dz 2 states
will have higher energy than the dx y , dx z , and d yz states
because of the stronger repulsion between the electron of
FIGURE 7 Schematic probability distributions and energy states central ion and the point charges of the ligands. Quanti-
of a p electron (L = 1) in an octahedral and square-planar ligand tative calculations show that the dz 2 state is energetically
field induced by negative point charges. degenerate with the dx 2 −y 2 state. Therefore, the fivefold
D term of a d 1 ion is split into a threefold state t2 and a
ligands (represented by electrical negative point charges) twofold state e (Fig. 8). From these two examples we see
at the corners of a regular octahedron. That is, the central that for the same symmetry of the ligand field the num-
ion is subjected to an octahedral environment, Oh sym- ber of progeny terms depends on the quantum number L
metry. The central ion within this system is to be varied of the orbital angular momentum of the electron system.
with regard to its orbital angular momentum (quantum Under the influence of an octahedral symmetry of the lig-
number L). To simplify the problem the central ion may and field, P terms (L = 1) are merely shifted, whereas D
contain only one electron, either a p electron (L = 1) or terms (L = 2) are split into a twofold (e) and a threefold
a d electron (L = 2). The corresponding probability dis- ( t2 ) degenerate term. Table III summarizes the resulting
tributions of the electron charge known from the theory term-splitting under the octahedral field for L values up
of atoms are shown in Fig. 7 and Fig. 8. The p electron to 4. The numbers in parentheses give the orbital degen-
can occupy three different orbital states (2L + 1 = 3). All eracy of the terms. A, B, E, and T symbolize different
three distributions are in equivalent positions with regard orbital symmetries of the terms, i.e., the progeny term
to the ligands (Fig. 7). Therefore, the energies of the three 2S+1
i mentioned above, where A and B represent non-
degenerate, E represents twofold degenerate, and T repre-
sents threefold degenerate terms. The term-splitting of the
ground states of d N complexes with N = 1 to 5 in an octa-
hedral ligand field are shown schematically in Fig. 9. The
d N and d 10−N ions exhibit equivalent splitting diagrams,
for example, the ground state of d 8 (3 F) exhibit the same
splitting diagram as that of d 2 (T1 + T2 + A1 ) but the or-
der of energy is inverted. Thereby the order of energy is
T1 < T2 < A1 for d 2 , but is A2 < T2 < T1 for d 8 . This is a
consequence of the so-called electron-hole correlation.

2. Term-Splitting Under D4h Symmetry

For the same quantum number L of the orbital angular
momentum, the number of progeny terms depends on the
symmetry of the ligand system. When the octahedral sym-
metry of the ligand system is reduced to a square-planar
(D4h ) symmetry by canceling the ligands on the z axis,
the pz distribution is subjected to a weaker field than the
px and p y distributions. Thus lowering of the symmetry
from Oh to D4h yields a term-splitting of T1 to A1 + E. In
FIGURE 8 Schematic probability distributions and energy states the same way, the D terms (L = 2) are split further into
of a d electron (L = 2) in an octahedral and square-planar ligand A1 + B1 + B2 + E terms (Fig. 8). Such splitting is demon-
field induced by negative point charges. strated by the uneven population of B1 (dx 2 −y 2 ) and B2
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Ligand Field Concept 529

TABLE III Splitting of Orbital States with L = 0, 1, 2, 3, 4 in an Octahedral (Oh ) and a Square-Planar (D4h ) Ligand
Field
Orbital state of the free ion
Quantum State Orbital states in an
number L symbola Oh ligand field Orbital states in a D4h ligand field

0 S(1) →A1 (1) →A1 (1)

1 P(3) →T1 (3) →A2 (1) + E(2)
2 D(5) →E(2) + T2 (3) →A1 (1) + B1 (1) + B2 (1) + E(2)
3 F(7) →A2 (1) + T1 (3) + T2 (3) →A2 (1) + B1 (1) + B2 (1) + 2E(2)
4 G(9) →A1 (1) + E(2) + T1 (3) + T2 (3) →2A1 (1) + A2 (1) + B1 (1) + B2 (1) + 2E(2)
a The numbers in parentheses give the orbital degeneracy of the states.

(dx y ) terms of Ni2+ in roughly D4h symmetry as shown as parameters in the calculation and are fit to experimental
in Fig. 4. As for the splitting of the other terms, they are data. Normally a value in Dq is represented.
listed in Table III. It is worth noticing that the lower the Since both the electron-electron interaction and the in-
symmetry is, the more splitting of the terms occurs. In fluence of the ligand field have to be treated, there are two
D4h , the highest degeneracy is E, whereas in Oh , it is T. methods for finding the term system of a transition metal
complex when the central ion contains two or more d elec-
3. Weak- and Strong-Field Methods, trons. Both methods start with the free d N ion of which
Term Diagrams the electron-electron repulsion is not yet taken into ac-
The amount of the energetic splitting or shifting can be (ap- count. They differ only in the order of which one is treated
proximately) determined by the methods of quantum me- first. According to the expected relative amounts of these
chanical perturbation theory. Since the perturbation comes energetic quantities, the weak-field method is employed
from the electrical interaction between the electrons of when the effect of electron-electron interaction dominates,
the central ion and the charge distribution within the lig- whereas the strong-field method is appropriate when the
and system, the magnitude of energetic splitting or shift- influence of the ligand field is dominant. Complete treat-
ing will depend on the central ion-ligand distance R and ments of a complex ion by both methods will ultimately
on the charges q and electrical dipole moments µ of the yield the same results. The weak-field method is described
ligands: by the following scheme:
Magnitude of energetic splitting and/or shifting d N −−−−−−→ 2S+1 L −−−−−→ 2S+1
electr on−electr on ligand
= F(R, q, µ) interaction f ield

The first step considers the electron-electron interaction.

Since the charge distributions within the ligands are not
This step gives result in the Russell-Saunders terms 2S+1 L
known exactly, an absolute calculation of these energetic
of the free ion following the procedure described in
effects is very tedious and time-consuming. In practice
section II.A. In the second step the splitting of these terms
these magnitudes (as functions of R, q, and µ) are taken
by the ligand field is determined, following the procedure
given in Section II.B.1 or B.2.
The two steps of the strong-field method have the op-
posite order:
d N −−−−−→ t2n e N −n −−−−−→ 2S+1
ligand electr on
f ield(Oh ) interaction

In the first step the splitting of one-electron states of the d

shell in the ligand field is considered. Under the octahedral
ligand field, the five orbitals of the d shell are split into a
family of two degenerate states e(dx 2 −y 2 , dz 2 ) and a family
of three degenerate states t2 (dx y , dx z , d yz ) shown in Fig. 8.
By quantum mechanical perturbation theory the energy
FIGURE 9 Term-splitting of the ground states of d 1 to d 5 and d 8
in an octahedral ligand field. Term-splitting of the ground states of difference between e and t2 is calculated as ≡ 10 Dq.
d N , N > 5 is the same as that in d 10−N , but with the energy order The N d electrons can occupy the levels e and t2 following
inverted, see d 8 versus d 2 . Pauli’s principle, such as t2n e N −n . In the second step of the
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530 Ligand Field Concept

increasing Dq value the terms are either shifted (L ≤ 1)

or split (L > 1). This Tanabe-Sugano diagram will provide
nice interpretation to the optical properties of Cr3+ in ruby
(Section III).
However, when central ion is d N with N = 4 ∼ 7, not
only the shifting and splitting of the terms occurred as
indicated in d 3 ion. There also appears to be an apparent
change at certain Dq/B value (VT ). An example of Fe2+
complex in an Oh environment, a Tanabe-Sugano diagram
of d 6 , is shown in Fig. 12. The ground state of the strong-
field (Dq/B > VT ) is 1 A1 , a low-spin state, but that of
weak-field (Dq/B < VT ) is 5 T2 , a high-spin state. When
the Dq/B value is very close to VT , the spin crossover
phenomenon occurs, where the spin state of the central
ion can be fine tuned by varying temperature or pressure.
The light-induced excitation of the spin state was also
observed.

FIGURE 10 Term correlation diagram of d 2 in weak- and strong

ligand fields.

strong-field method, the electron-electron interaction is

taken into account. Take d 2 as an example. The weak- and
strong-field methods are illustrated on the left and right
side of Fig. 10, respectively. The solid and dotted lines in
the middle indicate the correlation between two methods.
This means the two methods will ultimately yield exactly
the same result in term splitting.
The influence of the ligand field can be conveniently
presented in the form of diagrams showing the term ener-
gies as functions of the strength of the ligand field. For
systems with octahedral symmetry the energies of the
terms 2S +1 depend on the single parameter 10 Dq de-
fined above. An example of the term diagram for Cr3+
FIGURE 11 Term diagram of a Cr 3+ ion in an octahedral ligand
(d 3 ) in an octahedral environment is shown in Fig. 11, the field. Term energies as functions of the ligand field strength Dq,
Tanabe-Sugano diagram of d 3 . When Dq = 0, the term- Tanabe-Sugano diagram of d 3 . [From Tanabe, Y., and Sugano, S.
splitting of the free Cr3+ ion are as in Table III. With (1954). J. Phys. Soc. Jpn. 9, 753.]
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Ligand Field Concept 531

tor is a characteristic of the central ion. The influences

of the central ion and of the ligands on Dq value are as
follows:

1. Influence of the central ion on Dq.

For the same ligand system,
(a) The Dq values are very similar for transition
metals of the same series and the same charge.
For example, the Dq value of the complexes
[Mn(H2 O)6 ]2+ , [Fe(H2 O)6 ]2+ , and [Ni(H2 O)6 ]2+
is 8500, 10,400 and 8500 cm−1 , respectively.
This indicates that divalent 3d transition metal
ions have roughly the same Dq value.
(b) The Dq values increase when going from the first
to the second and to third series of transition
metal ions, i.e., for the analogous complexes, the
trend being 3d < 4d < 5d. As an example, for
[M(NH3 )6 ]3+ complexes, the Dq value is 2287,
3400 and 4120 cm−1 for M = Co3+ , Rh3+ , and
Ir3+ , respectively.

TABLE IV Dq Values of Six-Coordinate Transi-

tion Metal Complexes

f g (cm−1 )a (cm−1 )b

[CrF6 ]3− 0.9 17,400 15,060

[Cr(H2 O)6 ]3+ 1 17,400 17,400
[Cr(en)3 ]3+ 1.28 17,400 22,300
[Cr(CN)6 ]3− 1.7 17,400 26,600
[Mo(H2 O)6 ]3+ 1 24,600 26,000
[MnF6 ]2− 0.9 23,000 21,800
[TcF6 ]2− 0.9 30,000 28,400
[Fe(H2 O)6 ]3+ 1 14,000 14,000
[Fe(ox)3 ]3− 0.99 14,000 14,140
FIGURE 12 Tanabe-Sugano diagram of d 6 . [From Tanabe, Y., [Fe(CN)6 ]3− 1.7 14,000 35,000
and Sugano, S. (1954). J. Phys. Soc. Jpn. 9, 753.]
[Ru(H2 O)6 ]2+ 1 20,000 19,800
[Ru(CN)6 ]4− 1.7 20,000 33,800
4. Dq Values and Spectrochemical Series
[CoF6 ]3− 0.9 18,200 13,100
For a given central ion the field strength parameter Dq [Co(H2 O)6 ]3+ 1 18,200 20,760
depends on the central ion-ligand distance (R) and on the [Co(NH3 )6 ]3+ 1.25 18,200 22,870
charge distribution within the ligands (q, µ). The value of [Co(en)3 ]3+ 1.28 18,200 23,160
Dq is determined from experimental data. [Co(H2 O)6 ]2+ 1 9,000 92,00
By comparison of the optical absorption data of octa- [Co(NH3 )6 ]2+ 1.25 9,000 10,200
hedral complex ions with the Tanabe-Sugano term dia- [Rh(H2 O)6 ]3+ 1 27,000 27,200
gram, the 10 Dq (or ) values for several transition metal [Rh(NH3 )6 ]3+ 1.25 27,000 34,100
complexes are given in Table IV. Jørgensen developed a [Ir(NH3 )6 ]3+ 1.25 32,000 41,200
means of estimating the value of 10 Dq for an octahedral
complex by treating it as the product of two independent Note: ox = oxalate = C2 O2− 4 ; en = ethylenedia-mine
= HN2 CH2 CH2 NH2 .
factors. a Jørgensen, C. K. (1971). “Modern Aspects of Ligand

10 Dq ≈ f (ligand) × g(central ion) Field Theory,” Chap. 26, Elsevier, New York.
b Experimentaln data from Lever, A. B. P. (1986).
Where the factor f describes the field strength of ligand “Inorganic Electronic Spectroscopy,” 2nd ed., Chaps. 6
relative to water, which is assigned to 1.0. The g fac- and 9, Elservier, New York.
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532 Ligand Field Concept

(c) The Dq values increase with increasing ionic

charge on the central ion, for example, the Dq
value of [CrF6 ]3− and [CrF6 ]2− is 1506 and
2200 cm−1 , respectively.
2. Influence of the ligands on Dq.
For the same central ion,
(a) The Dq values increase with the number of the
ligands, for example, the Dq value of
[Co(NH3 )4 ]2+ and [Co(NH3 )6 ]2+ is 590 and
1020 cm−1 , respectively.
(b) The Dq value increases in the order of the
spectrochemical series:
I− < Br− < C1− ∼ SCN− ∼ N− 3 < (C2 H5 O)2 PS2
−
− − −
< F < (C2 H5 )2 NCS2 < (NH2 )2 CO < OH
− −
< (COO)2−2 ∼ H2 O < NCS < NH2 CH2 COO
+
< NCSHg ∼ NH3 ∼ C5 H5 N < NH2 CH2 CH2 NH2
− − − −
∼ SO2−3 < NH2 OH < NO2 < H ∼ CH3 < CN

An underlined atomic symbol indicates that the

ligand is coordinated with that atom.

FIGURE 13 Combinations of a central ion d : (a) dx2 −y2 (b) dxy or-
C. Ligand-Field theory bital, and (c) the σ group orbitals of the ligand σx + σ−x − σ y − σ−y .

In the crystal-field model, it is assumed that the electrons

of central ion are perturbed by the crystal field in the form
of point charges located at the coordinated atoms of the 1. The combination orbitals must have the same
ligand. Basically the crystal-field approach is still limited symmetry. For example, in Fig. 13 the dx 2 −y 2 orbital
at the atomic orbital level, nevertheless, it did interpret (Fig. 13a) of the central ion has the same symmetry as
successfully on many properties of the transition metal the σ group orbitals of the ligand system shown in
complex (see the following sections). However, purely Fig. 13c, therefore a combination between these two
based on the point charge model, it is hard to rationalize can be made. But the dx y orbital (Fig. 13b) has
why in the spectrochemical series CN− is such a strong different symmetry from the σ group orbitals; thus no
field, but F− is such a weak field. Apparently there is combination can be formed between the dx y orbital
a need of improving the crystal-field model in order to and the σ group orbitals.
reason the order of spectrochemical series. To improve 2. The energies of the combination orbitals must be of
the model of the crystal-field theory, the electrons are al- comparable magnitude for significant interaction to
lowed to move over the whole complex ion in molecular occur.
orbitals. In other words, we have to consider the com- 3. The combining orbitals must overlap.
plex at a molecular orbital level. In a common approxi-
mation, the molecular orbitals are described by suitable Every pair of orbitals suitable of forming linear com-
linear combination of atomic orbitals (LCAO approxima- bination yields a stabilized (bonding) and destabilized
tion). In this approach, in addition to d, p, and s orbitals (anti-bonding) states shown in Fig. 14. The anti-bonding
of the central ion, the orbitals of the ligand system will state is usually labeled by an asterisk. When the energy
also be included. In recent years, due to the great im- difference between the combining orbitals is small, the
provement of both hardware and software in computa- energy splitting becomes large and the interaction be-
tion, an ab initio quantum calculation of such complexity tween two orbitals is strong (Fig. 14a). The energy-level
becomes feasible. However, in this content we will keep diagram of the molecular orbitals of an octahedral com-
it as conceptual as possible. Namely, the group orbitals plex is presented in Fig. 15a, where only σ bonds between
of the ligand will be included only in the form of σ and the central ion and the ligand are considered. According
π bond. to the group theoretical treatment, the group orbitals of
As shown by quantum mechanics and group theory only the ligand in the form of σ bond consist of a1 + e + t1
certain linear combinations yield energetic effects: orbitals. The corresponding orbitals of the central ion
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Ligand Field Concept 533

FIGURE 14 Two atomic orbitals form a bonding and an antibond- FIGURE 16 Comparison of the ligand field strength, value of
ing state: (a) with small difference in energy of A and B and (b) ligands with σ -donor, π -donor, and π-acceptor character.
with large difference in energy of A and B.

longer nonbonding orbitals, they can combine with πL or

include a1 (s), t1(u) ( px , p y , pz ) and e(dx 2 −y 2 , dz 2 ), i.e.,
πL∗ group orbitals of the ligand shown in Fig. 15b. This
an sp 3 d 2 hybrid. These orbitals combine with the group
π -interaction can either increase or decrease the 10 Dq
orbitals of ligand and yield six σ bonding and six σ ∗
value (of which only σ -bond is considered) depending on
anti-bonding states, each contains a1 , e, t1 , and a1∗ , e∗ , t1∗ ,
whether the ligand is a π -acceptor or a π -donor. When
respectively. The central ion orbitals t2(g) (dx y , d yz , dzx ) are
the ligand is served as a π -acceptor, for example CN− ,
“nonbonding” since there are no σ orbitals of the ligands
where a low-lying empty πL∗ is available, the t2(g) orbitals
with suitable symmetry as indicated in Fig. 13. Each
of the central ion are stabilized by the π -interaction, there-
coordinated ligand atom contributes two σ -electrons
fore increasing the 10 Dq value. On the other hand, when
(σ -donor) to fill up the σ -bonding orbitals a1 , t1 , e.
the ligand is served as a π -donor, for example, fluoride
Therefore, the d electrons of the central ion will occupy
F− ion, the t2(g) orbitals of the central ion are destabilized
the t2(g) and e∗ orbitals. The energy gap between t2(g) and
and thus decrease the 10 Dq value. The effect of this π-
e∗ corresponds to the crystal field parameter 10 Dq.
interaction on the 10 Dq value is illustrated in Fig. 16.
If a π -bond interaction between the central ion and the
With this π -interaction in mind, it is not too hard to un-
ligand is taken into account, the group orbitals of the ligand
derstand the order of ligand field strength in the spectro-
in the form of π , π ∗ consist of t1(g) , t2(g) , t1(u) , t2(u) orbitals.
chemical series given above.
The t2(g) orbitals of the central ion (dx y , d yz , dzx ) are no
The energetic order within the system of progeny terms
2S+1
i (A1 , T1 , E, etc.) determines the important proper-
ties of the complex ions:

1. Optical properties. The energetic differences between

the ground state and the few lowest excited states,
mainly d-d transition, correspond to the absorption
bands in the spectral region with λ ≥ 300–700 nm,
with extinction coefficient of 100 –102 . There are also
bands with much higher extinction coefficient
(102 –106 ) which normally correspond to charge
transfer band or intraligand transition. These bands
are responsible for the color of the compound
(Section III).
2. Magnetism. The spin multiplicity M = 2S + 1 of the
ground term determines roughly the magnetic
FIGURE 15 Molecular orbital diagram of an octahedral complex behavior of the complex ion (Section IV).
considering. (a) σ -bonding only. (b) σ - and π-bonding between 3. Stability. The stabilization of the ground term by the
the central ion and the ligand. ligand field stabilization energy represents an
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534 Ligand Field Concept

increase in the binding energy of the complex ion, in

addition to that obtained by the ionic model of Kossel
and Magnus (Section V).

III. OPTICAL PROPERTIES

OF COMPLEXES

The main features of the optical absorption and emission

spectra of transition metal complexes can be interpreted on
the basis of crystal-field or ligand-field theory. Generally,
the energies of the absorption and the emission bands cor-
respond to energetic differences between electronic states.
Therefore, an interpretation of the optical spectra will start
with a comparison between the experimental spectra and
the term diagram of the complex ion, according to the
crystal-field theory. This procedure will be demonstrated FIGURE 18 Absorption (a) and emission (b) spectra of Cr3+ ion
in ruby.
by two informative examples.
The absorption spectrum of the [Ti(H2 O)6 ]3+ ion con-
sisting of one d-d band with its maximum at 492 nm is strong increase in absorption below ∼ 350 nm belongs to
shown in Fig. 17. The ground state of this Ti3+ (d 1 ) free ion the charge transfer band, possibly from t2 to empty ligand
is 2 D (Table III). In an octahedral ligand field the 2 D term excited states of suitable symmetry and spin states.
is split into the low-lying 2 T2 ground state and a 2 E state at The second example is the absorption spectrum of Cr3+
higher energies (Fig. 9). By the absorption of a photon with in ruby shown in Fig. 18. Two relatively strong bands I
energy of E(2 E−2 T2 ), the complex ion will be excited and II and three very weak absorption J1 , J2 , and J3 can be
from its ground state 2 T2 into the state 2 E. The excitation seen. At wavelengths below 300 nm a very strong increase
energy in an octahedral d 1 ion is by definition equal to in the absorption due to charge transfer transitions is
10 Dq. From the wavelength of the absorption maximum observed (not shown in Fig. 18). Ruby is an Al2 O3 crystal
at 492 nm, it follows that Dq has a value of ∼ 2030 cm−1 . wherein some Al3+ ions are substituted by Cr3+ ions. The
In the molecular orbital theory the 492-nm band corre- absorption spectrum (Fig. 18) is due to the Cr3+ ions (d 3
sponds to the electron transition between the nonbonding ions) since Al3+ does not have any d electrons. This can
t2 state and the anti-bonding e∗ state (see Fig. 15). The be confirmed by the absorption spectra of Cr(ox)3− 3 and
Al(ox)3−3 shown in Fig. 2. Every Cr 3+
ion is surrounded
by six oxygen ions forming an octahedron. The three
lowest terms of the free Cr3+ ions are 4 F (ground state),
4
P, and 2 G (Table II). In the presence of the Oh ligand field,
the terms 4 F and 2 G are split into three (4 A2 , 4 T2 , 4 T1 )
and four (2 E1 , 2 T1 , 2 T2 , 2 A1 ) progeny terms, respectively.
A comparison between this term diagram (Fig. 11) of
Cr3+ in ruby and the absorption spectrum yields the
following assignment. The relatively intense bands I and
II belong to the spin-allowed transitions 4 A2 → 4 T2 and
4
A2 → 4 T1 , respectively, whereas J1 , J2 , and J3 are due
to quartet-doublet spin-forbidden transitions (4 A2 → 2 E,
4
A2 → 2 T1 , 4 A2 →2 A1 ). On the basis of this assign-
ment and the corresponding Tanabe-Sugano diagram
(Fig. 11), one can determine the Dq and B values of the
complex.
The significant intensity difference between the high-
energy charge transfer bands (λ < 300 nm), the bands I
FIGURE 17 Absorption spectrum of [Ti(H2 O)6 ]3+ . [From and II, and the weak bands J1 , J2 , and J3 originates in
Hartman, H., Schlafer, H. L., and Hansen, K. H. (1957). Z. Anorg. the different nature of the corresponding transitions. As
Chem. 40, 289.] shown by quantum theory, the absorption of photons by
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Ligand Field Concept 535

molecules is regulated by some general rules or the so-

called spectra-selection rules:

1. The total spin of the electron system remains constant

(spin-allowed).
2. The direct product of the symmetries corresponding
to ground state, excited state, and the optical
transition moment should be totally symmetric
(symmetry allowed or LaPorte allowed)

These two criteria are fulfilled by most of charge trans-

fer bands. The d → d transitions, however, are distinctly
weaker than the charge transfer transitions, since they are
LaPorte forbidden. Among the d → d transitions the spin-
allowed transitions show a significantly stronger absorp-
tion (bands I and II) than the spin-forbidden transitions
(bands J1 , J2 , and J3 ).
Ruby was the first crystalline compound to exhibit op-
tical laser properties. The ruby laser works as follows.
The excited quartet terms 4 T2 and 4 T1 (ref. to Fig. 11)
are populated by irradiation (optical pumping) using the
broad absorption bands at I and II from the ground term
4
A2 . Then radiationless transitions into the 2 E state take
place within a period of <10−10 sec. The electron at 2 E
state is stable for a relatively long time ( ∼5 × 10−3 sec)
before the photon emission occurs. Therefore, the 2 E state
is populated more and more by optical pumping, and fi-
nally the number of Cr3+ ions in 2 E excited state is larger
FIGURE 19 The observed (top) and calculated (buttom)
than the number in the 4 A2 ground state (population in- LIII,II -edge absorption spectra of Fe2+ in low-spin state. [From Lee,
version). When this “laser condition” is fulfilled, the ac- J. J., Sheu, H. S., Lee, C. R., Chen, J. M., Liu, R. G., Lee, J. F.,
cumulated energy can be emitted as an intense beam of Wang, C. C., Huang, C. H., and Wang, Y. (2000). J. Am. Chem.
photons with energy ∼14000 cm−1 ( E(2 E−4 A2 )), the Soc. 122, 5742.]
brilliant red beam of the ruby laser.
The X-ray absorption spectra can probe the atom-
specific transition between inner core orbitals and valence IV. MAGNETIC PROPERTIES
orbitals. Take L-edge absorption as an example, it is the OF COMPLEXES
transition between 2s, 2 p orbitals and 3 p, 3d orbitals:
LI -edge absorption is assigned to the transition between Every electron has a permanent magnetic moment of
2s and 3 p. LII -, LIII -edge absorption spectra are assigned amount µB = 9.27 × 10−24 J T−1 (Bohr’s magneton, BM),
to the transition between 2P1/2 , 2P3/2 , and 3d transition. which is parallel to its spin s. For an electron system with
The LII -, LIII -edge absorption spectra of Fe2+ in high-spin total angular momentum quantum number J , the magnetic
(solid line) and in low-spin state (dotted line) are displayed moment is µ = g[J (J + 1)]1/2 BM where g is the Landé
in Fig. 3. It clearly demonstrates that the difference in d or- splitting factor, and g = 1 + {[J (J + 1) + S(S + 1) −
bital populations is distinctively reflected by these L-edge L(L + 1)]/2J (J + 1)}. For complexes in which the L-S
absorption spectra. The multiplet calculation according to coupling
√ is negligible, the magnetic moment becomes
the crystal-field theory, including the L-S coupling, can µ = 4S(S + 1) + L(L + 1) BM. However, in most 3d
be utilized to reproduce the experimental measurement transition metal complexes, the orbital contribution is
and estimate the Dq value. The observed and calculated insignificant,
√ so the effective
√ magnetic moment becomes
LII -, LIII -edge absorption spectra of the low-spin Fe2+ in µef f = 4S(S + 1) = n(n + 2) BM, where n designates
Fe(phen)2 (NCS)2 complex, are shown in Fig. 19. The cor- the number of unpaired electrons. This is a spin-only
responding 10 Dq values are 7420 and 17,750 cm−1 for model. The magnetic properties of some 3d transition
high- and low-spin complex, respectively. metal complexes are listed in Table V, the calculated
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536 Ligand Field Concept

TABLE V Magnetic Properties of Some Complexes of the First-Row Transition Metalsa

High-spin complexes Low-spin complexes
No. of No. of
Central No. of d unpaired µ(calc)b unpaired µ(calc)b
metal electrons electrons µ(expt) BM BM electrons µ(expt) BM BM

Ti3+ 1 1 1.73 1.73 — — —

V4+ 1 1 1.68–1.78 1.73 — — —
V3+ 2 2 2.75–2.85 2.83 — — —
V2+ 3 3 3.80–3.90 3.88 — — —
Cr3+ 3 3 3.70–3.90 3.88 — — —
Mn4+ 3 3 3.80–4.00 3.88 — — —
Cr2+ 4 4 4.75–4.90 4.90 2 3.20–3.30 2.83
Mn3+ 4 4 4.90–5.00 4.90 2 3.18 2.83
Mn2+ 5 5 5.65–6.10 5.92 1 1.80–2.10 1.73
Fe3+ 5 5 5.70–6.00 5.92 1 2.00–2.50 1.73
Fe2+ 6 4 5.10–5.70 4.90 — — —
Co3+ 6 4 — 4.90 — — —
Co2+ 7 3 4.30–5.20 3.88 1 1.8 1.73
Ni3+ 7 3 — 3.88 1 1.80–2.00 1.73
Ni2+ 8 2 2.80–3.50 2.83 — — —
Cu2+ 9 1 1.70–2.20 1.73 — — —
a Burger, K. (1973). “Coordination Chemistry: Experimental Methods,” Butterworth, London.
b µ is spin-only value.

µef f values based on the spin-only model are in adequate V. STABILIZATION OF COMPLEXES
agreement with the corresponding experimental ones. As
mentioned above, the magnetic properties are directly In the ionic model, the formation of a complex ion from
related to the spin multiplicity of the ground state, or the the free central ion and the ligands is combined with a
number of unpaired electrons at the ground state. In the stabilization by the electrostatic binding energy Eclass . The
case of d 1 ∼ d 3 and d 8 ∼ d 10 of octahedral complexes, resulting state corresponds to the electronic ground state
the spin multiplicity of the ground state keeps the same of the complex. From the crystal-field theory, however,
(high-spin state) even at very strong ligand field. But in
the case of d 4 ∼ d 7 system in Oh , the spin multiplicity
of the ground state drops beyond certain Dq value (VT )
called a low-spin state, therefore an apparent change TABLE VI Ligand Field Stabilization Energy for Octahedral
of magnetic moment is observed. For example, the Transition Metal Complexesa
µef f of high-spin state of Fe2+ (d 6 ) complex is ∼ 5.0 High-spin Low-spin
BM, whereas that of low spin is ∼ 0 BM. For the spin configuration configuration
crossover system, two different spin multiplicities can be Number of Ground LFSE Ground LFSE
detected on the same complex at different temperatures. d electrons term (Dq) term (Dq)
For example, the magnetic moment of Fe(phen)2 (NCS)2 1 t12 [2 T2 ] −4
measured at various temperatures is displayed in Fig. 20. 2 t22 [3 T1 ] −8
The spin multiplicity below 176 K is a singlet, but the spin 3 t32 [4 A2 ] −12
multiplicity above 176 K becomes a quintet. The corre- 4 t32 e1 [5 E] −6 t42 [3 T1 ] −16
sponding effective magnetic moment is 0.5 and 4.9 BM, 5 t32 e2 [6 T1 ] 0 t52 [2 T2 ] −20
respectively. 6 t42 e2 [5 T2 ] −4 t62 [1 A1 ] −24
The deviations between the theoretical (spin only) and 7 t52 e2 [4 T1 ] −8 t62 e1 [2 E] −18
experimental values of the magnetic moment in Table V 8 t62 e2 [3 A2 ] −12
are mainly due to the fact that besides the spins the orbital
9 t62 e3 [2 E] −6
angular momentum can also contribute to the effective
magnetic moments. a Calculated in the strong-field approximation.
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Ligand Field Concept 537

A. Relative Stability of Low-Spin Complexes

As shown in the preceding section octahedral complexes
with d 4 , d 5 , d 6 , and d 7 electron systems in principle can
form high- or low-spin configurations. Why some of these
transition metal ions form low-spin complexes and not the
high-spin modification can be understood by comparison
of the CFSEs of both spin configurations. From Table VI
the gain of CFSE for the transition from the high- to the
low-spin complexes amounts to 10 Dq for d 4 and d 7 com-
plexes and 20 Dq for d 5 and d 6 complexes. Therefore, in
strong ligand fields the low-spin complex is more stable
than the high-spin complex. However, in low-spin com-
plexes the CFSE is partly compensated by an increase in
electron-electron repulsion, since two electrons are mov-
ing in the same orbital space.

B. Heats of Hydration
m+
By the dissolving of gaseous metal ions Mgas in water, the
m+
corresponding hexa-aquo ions [M(H2 O)6 ]aq are formed
and the heat of hydration, H H , is generated:
2O
m
Mgas −−−→[M(H2 O)6 ]aq
m+
+ HH
The variation of the experimental values of − H H with
the atomic number of the bivalent and trivalent metal ions
FIGURE 20 Effective magnetic moment, µeff , of Fe(phen)2 of the first transition series is plotted in Fig. 21. The solid
(NCS)2 as a function of temperature. [From Lee, J. J., Sheu, H. S.,
Lee, C. R., Chen, J. M., Liu, R. G., Lee, J. F., Wang, C. C., Huang,
C. H., and Wang, Y. (2000). J. Am. Chem. Soc. 122, 5742.]

it is known that the ground-state term of the central ion

can be split into several progeny terms, depending on
its orbital angular momentum and the symmetry of the
ligand field. The lowest energy term after the splitting be-
comes the ground state. It is stabilized by the crystal-field
stabilization energy (CFSE) in addition to the electrostatic
binding energy.
For central ions with an octahedral ligand system the
five d states are split into t2 and e states. According to
crystal-field theory, the t2 state is stabilized by −4 Dq,
whereas the e state is destabilized by +6 Dq. Therefore,
in the strong-field approximation for an octahedral
complex ion with t2n e N −n electron system, the CFSE
amounts to CFSE(Oh ) = −[4n − 6(N − n)]Dq, where N
is the total number of d electrons, n is the number of t2
electrons, and N − n is the number of e electrons. The
CFSE (Oh ) values for high- and low-spin complexes for
N = 1, . . . , 9 are summarized in Table VI. They yield
FIGURE 21 Heats of hydration of transition metal ions as a func-
important information about the relative stability and tion of atomic number, (•) experimental data with standard deriva-
several thermodynamic properties of transition metal tion, (×) corrected from LFSE. [From George, P., and McClure,
complexes. D. S. (1959). Prog. Inorg. Chem. 1, 418.]
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538 Ligand Field Concept

     
lines connecting the data points are not monotonic. On the High-spin d 3 : 4 A2 t23 ; d 5 : 6 A1 t23 e2 ; d 8 : 3 A2 t26 e2
basis of the ionic theory it is expected that with increasing
 
atomic number (within a series) the ionic radii decrease Low-spin d 6 : 1 A1 t26
monotonically because the electron cloud contracts under
the influence of the increasing nuclear charge. Therefore, All the other octahedral complexes are Jahn-Teller unsta-
for electrostatic reasons the heat of hydration should also ble. In some of these complexes stability can be achieved
increase monotonically with increasing atomic number, as by elongation or compression of the coordination octa-
indicated by the dashed lines in Fig. 21. hedron along one of its axes. Often the distortions are
The discrepancy between this expected behavior and expressed in the physical and chemical properties of the
the experimental data is due to the fact that the hexa- complexes. For example, the asymmetry of the absorption
aquo complexes have nonspherical symmetry. The octa- band of [Ti(H2 O)6 ]3+ (Fig. 17) is due to the Jahn-Teller ef-
hedral ligand field splits the ground-state terms, yielding fect. The distortion splits the degenerate ground state 2 T2
the CFSEs given in Table VI. Therefore, the total heat of into a low-lying nondegenerate level and other progeny
hydration H H will be composed of two parts, namely, terms. The distortion may also split the excited level 2 E,
the “classical” part Hclass , resulting from the ionic thus more absorption bands would be observed. Since the
theory, and the “ligand field” part HL F ≡ CFSE: energies of these bands are very close, only one band with
asymmetric shape appears.
HH = Hclass + HL F

The Hclass values can be obtained by subtraction of the SEE ALSO THE FOLLOWING ARTICLES
CFSEs from the experimental H H values. If the CFSEs
are calculated with Dq values obtained from absorption ELECTROMAGNETICS • ELECTRON TRANSFER REAC-
spectra, the resulting Hclass values are very close to the TIONS • GROUP THEORY • MICROWAVE MOLECULAR
dashed lines as shown in Fig. 21. SPECTROSCOPY
By corresponding considerations, apparent irregular-
ities in the lattice energies of metallic halogenides in
the heats of formation and heats of reactions and in the
kinetic stability of transition metal complexes can be BIBLIOGRAPHY
rationalized.
The structural stability of transition metal complexes is Burger, K. (1973). “Coordination Chemistry: Experimental Methods,”
Butterworth, London.
largely influenced by the Jahn-Teller effect. As Jahn and Cotton, F. A. (1990). “Chemical Applications of Group Theory,” 3rd ed.,
Teller have proved, the nuclear configuration of a nonlin- Wiley, New York.
ear polyatomic molecule is unstable when its electronic Douglas, B. E., McDaniel, D. H., and Alexander, J. J. (1994). “Concepts
ground state is orbitally degenerate. A molecule in such and Models of Inorganic Chemistry,” 3rd ed., Wiley, New York.
a situation will undergo a structural distortion such that Drago, R. S. (1992). “Physical Methods for Chemistry,” 2nd ed.,
Saunders College, Orlando.
the resulting ground state is orbitally nondegenerate. The Huheey, J. E., Keiter, E. A., and Keiter, R. L. (1993). “Inorganic Chem-
character of the distortion can be static, yielding a per- istry: Principles of Structure and Reactivity,” 4th ed., Harper Collins
manent deformation in geometry, or dynamic by oscillat- College, New York.
ing between several structures with nondegenerate ground Jørgensen, C. K. (1971). “Modern Aspects of Ligand Field Theory,”
states. North-Holland, Amsterdam.
Lever, A. B. P. (1984). “Inorganic Electronic Spectroscopy,” Elsevier,
Only the following octahedral transition metal com- Amsterdam.
plexes have an orbitally nondegenerate ground state (see Schläfer, H. L., and Gliemann, G. (1969). “Basic Principles of Ligand
Tables V and VI): Field Theory,” Wiley, New York.
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Valence Bond Theory

Richard P. Muller
William A. Goddard III
California Institute of Technology

I. Introduction
II. Bonding in H+2
III. Bonding in H2
IV. Bonding of Hydrogen to Carbon

GLOSSARY to molecules, ground to excited states, reactants to prod-

ucts, etc.
Orbital Function that describes the distribution of one
electron; used in approximate wave functions.
Schrödinger equation Fundamental equation of quan- I. INTRODUCTION
tum mechanics; wave functions are solutions of the
Schrödinger equation. The orbital description of atoms and molecules is probably
Wave function Function defined in quantum mechanics, the most powerful unifying concept to provide an under-
which contains all the information about a system. standing of chemistry. At the foundation is the Aufbau
principle for atoms, which serves as a semiuniversal or-
dering of hydrogen-like orbitals that explains the peri-
THE DEVELOPMENT of quantum mechanics (QM) odic changes in the ground-state character of the atoms
placed a, theoretical foundation under the experimental and their excited states. Similarly, our most powerful con-
science of chemistry. One could argue—as did Physics cepts of molecular structures and properties are based on
Nobelist Paul Dirac in a famous quote—that understand- combining these atomic orbitals in ways appropriate for
ing chemistry is no more than solving these equations. molecules. There are two major paradigms for doing this:
In fact, this is not correct. Doing chemistry requires a
qualitative understanding of how a reaction would change 1. Molecular orbital (MO) theory. In MO theory, one
if the solvent, temperature, or pressure is changed or if starts with a molecular framework and considers combi-
the concentrations or ingredients are changed. Solving the nations of the atomic orbitals optimum for the molecule.
Schrödinger equation for any specified conditions would These one-electron orbitals are ordered by energy, and
not necessarily provide any understanding of the chem- the electrons are used to populate the lowest ones (re-
istry. To gain an understanding would require concepts taining the Pauli principle—no more than two elec-
based on QM that allow us to make comparisons: atoms trons per orbital). This approach is particularly useful

. 411
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412 Valence Bond Theory

for predicting excited states and is quite popular in spec- χl = N exp(−Ra ) (1)
troscopy. Also, it is the framework used in rigorous QM
and
calculations identified by names such as Hartree–Fock
(HF), self-consistent field (SCF) and density functional χr = N exp(−Rb ), (2)
theory (DFT). Thus, to describe N2 , we would take the
respectively, where χl and χr denote hydrogen 1s or-
five occupied atomic orbitals (denoted 1s, 2s, 2 px , 2 p y ,
bitals centered on the left and right protons, respectively,
and 2 pz ) of each N atom and form 10 molecular orbitals
and N is a normalization factor—a scalar factor included
(denoted σg 1s, σu 1s, etc.) and occupy the lowest 7 with
to guarantee that the wave function contains only one
two electrons each (one with up spin and one with down
electron.
spin).
For finite R, the exact wave functions no longer have
2. Valence bond (VB) theory. In VB theory one starts
the atomic form, but useful approximate wave functions
with the occupied atomic orbitals of the atoms and con-
are obtained by combining the atomic orbitals to form the
structs a many-electron wave function to describe bonding
wave function
directly in terms of these atomic orbitals. Although sim-
ilar to MO, the differences will become transparent (be- ϕ = Cl χl + Cr χr . (3)
low). VB theory is most useful for describing reactions
and bond dissociations because the many-electron states This simple wave function is often referred to as linear
of the atoms are built into VB. However, VB is computa- combination of atomic orbitals (LCAO). The optimum
tionally much more complicated than MO, and it is much linear combination of atomic orbital wave functions is the
less obvious how to describe excited states in terms of VB. symmetric combination
Important chemical concepts such as resonance are based ϕ g = χl + χ r , (4)
on VB concepts.
where for simplicity we now ignore the normalization fac-
In this article, we will illustrate the use of VB and MO tor. The other combination of the orbitals is the antisym-
concepts for the simplest molecules and then apply these metric combination,
ideas to two simple problems that detail how to use them. ϕu = χl − χr , (5)
where again we ignore normalization.
II. BONDING IN H+ The g and u labels denote the symmetry of the wave
2 functions with respect to inversion, and stand respectively
Consider first the smallest possible molecule, H+ for the German words gerade (even) and ungerade (un-
2 , consist-
ing of one electron and two protons that are separated by even). Although symmetry arguments can be very power-
a distance R. This system is sketched in Fig. 1, where the ful, we eschew them here, and the reader may assume that
two protons are denoted as a and b. The most important these labels represent good and ungood, respectively.
question is whether this system forms a bond (i.e., is the The energies for the wave functions ϕg and ϕu in Eqs. (4)
lowest energy for a finite value of R). and (5) are shown as a function of R in Fig. 2. Here
we see that the g state is strongly bonding (the energy

A. Description Based upon Linear

Combination of Atomic Orbitals
In the case of R = ∞, the two protons are infinitely far
apart, and the ground state is obtained by placing the elec-
tron in the 1s orbital of one or the other of the two protons.
This leads to the two states H H+ and H+ H, which are
described by the wave functions

FIGURE 1 Coordinate system for H+

2. FIGURE 2 Bonding of the g and u states for H+
2.
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Valence Bond Theory 413

drops as the nuclei are brought together), Whereas the

u state is strongly antibonding (the energy increases as
the nuclei are brought together). Thus, starting with two
atoms at R = 2 Å (4 bohr), the g state would experience
forces pushing it toward smaller R, whereas the u state
would have a force pushing the atoms apart to R = ∞. The
objective of this section is to understand both the the ϕg
and ϕu state bonding and antibonding character. FIGURE 4 Potential energy for H+ 2 . The potential is −∞ at the
nuclei a and b and is negative and finite at the midpoint.

B. Contragradience and the Origin

of Chemical Bonding where ∇ is the gradient (derivative) of the wave function.
Thus, in CM the lowest T is for p = 0 (electron standing
Starting with the atomic orbitals and combining them to still), whereas in QM it is lowest for a very smooth wave
form MOs, we find that g is bonding and u is antibonding. function (∇ = 0).
Now we want to understand the physics that underlies the Indeed, as is shown in Fig. 5, adding the two atomic
bonding and antibonding character. One common idea is orbitals to get g dramatically decreases the gradient in the
that the g coherent superposition of atomic orbitals causes bond region; for u the subtraction dramatically increases
the electron density to increase in the bond region and the gradient. These changes in T are much larger than
that this increased charge attracts the two positive nuclei, the changes in V . The result is that bonding is dominated
leading to stabilization. The resulting change in the elec- by the decrease in the kinetic energy resulting from the
trostatic energy (denoted Vg ) is shown in Fig. 3, where symmetric combination of atomic orbitals. The amount
we see that it increases as the atoms are brought together. of the bonding depends on how much the gradient de-
The problem is that the increase in the density in the bond creases. Thus, for the best bonding, we want the case in
region comes at the expense of a decrease in the nuclear which both atomic orbitals have large gradients in op-
region. As indicated in Fig. 4, the potential is most nega- posite directions so that adding them leads to a big de-
tive near the nucleus, so that the increase of the density in crease in gradient. From Figure 3, we see that Tg has a
the bond region is antibonding in nature. minimum at 1 Å. The reason is clarified in Fig. 6. For
The only energy term in addition to electrostatics is ki- large distances, the orbitals in the bond midpoint region
netic energy. In QM, kinetic energy (denoted as T ) has a have small slopes and hence do not change much in form-
dramatically different form than that of classical mechan- ing ϕu . For R near zero, the atomic orbitals have large
ics (CM): gradients but the decrease is only for the very small re-
p2 gion between the atoms, which is too small to be signifi-
TCM = , (6) cant. Thus, the optimum bonding is created at a distance
2M
where both atomic orbitals are significant at the bond mid-
(∇)2 point. This is approximately the sum of the atomic radii
TQM = , (7)
2M (2 × 0.53 Å = 1.06 Å).

FIGURE 3 Kinetic, T, and potential, V, energies of the bonding

g and antibonding u orbitals for H+
2 . Note that even though Vg is FIGURE 5 Bonding with g orbitals reduces the electron density
unstable, the Tg effect compensates to create a bonding state. at the nuclei.
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414 Valence Bond Theory

left and electron 2 on the right. The wave function for this
configuration is
a (r1 , r2 ) = χl (r1 )χr (r2 ). (9)
This wave function a says that the probability of elec-
tron 1 being at a particular position is independent of where
electron 2 is, and vice versa. Since the atoms are infinitely
far apart, the electrons are not influenced by each other.
A second wave function that is just as good, or as bad,
as Eq. (9), is
b (r1 , r2 ) = χr (r1 )χl (r2 ), (10)
where the electrons have been interchanged. This wave
function b is different from a since electron 1 is now
FIGURE 6 Overlap of 1s orbitals at (a) bonding and (b) too-close on the opposite side of the universe. However, the energies
distances, and overlap of 2 p orbitals at (c) bonding and (d) too- of b and a must be the same since electrons 1 and 2 have
close distances. Note that in both of the too-close examples, the
contragradient region extends over a smaller region of space than
the same properties (they are indistinguishable particles).
in the bonding examples, leading to less stabilization. It will be useful to combine a and b into two new
wave functions,

C. The Nodal Theorem VB

g (1, 2) = a (1, 2) + b (1, 2)

We saw in Section II.B that kinetic energy dominates = χl (1)χr (2) + χr (1)χl (2), (11)
bonding in H+2 . An analysis of kinetic energy allows us to VB
u (1, 2) = a (1, 2) − b (1, 2)
make some general predictions about the shape of wave
functions. = χl (1)χr (2) − χr (1)χl (2), (12)
Consider a one-dimensional potential V (x) and con-
without normalization, because at finite R these are the
sider the set of all eigenfunctions (all solutions of the
optimum wave functions. Before examining the energies,
Schrödinger Equation)
we need to understand how to think about the relative
Hφj = Eφj . (8) locations of the electrons in these wave functions.
In Fig. 7, we plot the four wave functions a , b , VBg ,
We can show quite generally that, except for very diaboli-
and VB u . We see that  VB
u has a nodal plane corresponding
cal V (x), the ground state is nodeless. It is always positive
to z 1 = z 2 , whereas g does not. Indeed, along the line be-
except at the boundaries, where it goes to zero. A simple
tween the two peaks in Fig. 7c, we notice that the gradient
example is seen with H+ 2 , where we found two orbitals g of the VBg wave function is smaller than that of a or b ,
and u. The nodal theorem indicates that the lowest state is
g-like, i.e., nodeless. We will use this below to work out whereas the gradient of the VB u wave function is larger.
the bonding in H2 . This decrease in the gradient of VB g and increase for u
VB

are inversely related to R. Thus, based on kinetic energy,

we would expect that VB g is bonding and u is antibond-
VB

ing, and indeed this is the case: Figure 8 shows the energies
III. BONDING IN H2
E g and E u for the valence bond wave functions of H2 .
With this understanding of the fundamental of chemical
bonding in H+
2 , we move our attention to H2 . B. The Molecular Orbital Description of H2
The simplest wave function for H2 is found by starting
A. The Valence Bond Description of H2 with an electron in the best molecular orbital of H+ 2 and
In the VB description of a molecule, we start with the full to place a second electron in this ϕg orbital. This leads to
wave function for each atom at R = ∞ and combine the the molecular orbital wave function for H2 ,
wave functions to form the wave function of the molecule, MO
gg (r1 , r2 ) = ϕg (r1 )ϕg (r2 ). (13)
and then bring the atoms together to obtain optimal bond-
ing. For H2 at R = ∞, this configuration consists of two The first step is to examine the meaning of the wave
hydrogen atoms infinitely far apart, say electron 1 on the function (13). The total probability for electron 1 to be
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Valence Bond Theory 415

dice are independent so that the probabilities multiply. To

summarize: a product wave function, as in Eq. (13), im-
plies that the electrons move independently of each other,
i.e., there is no correlation of their motions.
In addition to using the ϕg molecular orbital, we may
construct wave functions of H2 using the ϕu molecular
orbital, leading to wave functions of the form
MO
ug (1, 2) = ϕu (1)ϕg (2), (15)
MO
gu (1, 2) = ϕg (1)ϕu (2), (16)
and
MO
uu (1, 2) = ϕu (1)ϕu (2), (17)
Since the ϕu orbital is antibonding, the above wave func-
tions for H2 lead to much higher energies than Eq. (13),
except at large R; we expect an energy level diagram as
in Fig. 9.
So far we have discussed the molecular orbital wave
FIGURE 7 (a) a (1, 2) = χl (1)χr (2); (b) b (1, 2) = χr (1)χl (2); (c)
function assuming that the bonding orbital ϕg is much bet-
g = a + b = χl χr + χr χl ; (d) u = a + b = χl χr − χr χl .
ter than the antibonding orbital ϕu . This is true for shorter
internuclear distance R, but does not remain true as the
at some position r1 when electron 2 is simultaneously at
bond is stretched and broken. In general, molecular orbital
some position r2 is
wave functions lead to a good value for the bond length but
 2
P(r1 , r2 ) = MO (r1 , r2 ) a very poor description of the processes of dissociation.
The origin of this problem can be seen by substituting
= |ϕg (r1 )|2 |ϕg (r2 )|2 the atomic orbital description of the molecular orbital (4)
= Pg (r1 )Pg (r2 ). (14) into the molecular orbital wave function (13), leading to

This expression is just the product of the independent prob- χgg

MO
(1, 2) = χl χl + χr χr + χl χr + χr χl
abilities for electron 1 to be at position r1 and electron 2 to = VB
g + g ,
ION
(18)
be at position r2 . Thus, the probability distribution for elec-
tron 1 is independent of electron 2. Consider the analogous (again ignoring normalization) where
case of a red die (electron 1) and a green die (electron 2).
VB
g = χl χr + χr χl , (19)
The probability of rolling a red 3 is 1/6 and the probability
of rolling a green 5 is 1/6, so that the total probability of ION
g = χl χl + χr χr . (20)
getting both a red 3 and a green 5 is 1/6 × 1/6 = 1/36. The
At very large R, the exact wave function will have one
electron near the left proton and one near the right, as in
Eq. (19), which we will refer to as the covalent part of the
wave function. The other terms of (18) have both electrons
near one proton and none near the other, thus creating an
ionic wave function. At R = ∞, these ionic terms lead

FIGURE 8 Energies of the g and u states of the VB wave FIGURE 9 Simple energy diagram for molecular orbital wave
function. functions of H2 .
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416 Valence Bond Theory

to the energy of H− and H+ 2 rather than the energy of

two hydrogen atoms. Since the molecular orbital wave
function must have equal covalent and ionic contributions,
it yields unfavorable energies for large R.
The basic problem with the molecular orbital wave
function is that both electrons are in the same ϕg orbital,
and hence each electron has an equal probability of being
on either center, regardless of the instantaneous location of
the other electron. In the exact wave function, the motions
of the electrons tend to be correlated so that if one elec- FIGURE 11 (a) MO
gu = φg (1) φg (2), (b) g = χl χr + χr χl .
VB

tron is on the left, the other tends to be on the right. This

correlation is necessarily ignored in the molecular orbital
wave function, and the resulting error is often referred to The wave functions are compared in Fig. 11, show-
as the correlation error. For small R, the two centers are ing graphically how the valence bond wave function has
close to each other, and this neglect of correlation is not smaller probability of having z 1 = z 2 , leading to lower
particularly important. At R = ∞, however, the correla- electron repulsion energies. However, the molecular or-
tion of electrons is of paramount importance and neglect bital wave function is smoother, leading to smaller ki-
of correlation leads to ludicrously poor wave functions. netic energies. For normal bond distances, the electron
In the next section, we will discuss a simple wave func- repulsion effects dominate, so that the valence bond wave
tion, the valence bond wave function, that eliminates this function is better, but for very short R, the kinetic en-
problem of describing large R. ergy becomes dominant, so the molecular orbital and va-
lence bond wave functions lead to nearly identical total
C. Comparison of VB and MO Wave Functions energies.
Expanding the molecular orbital description of the
The molecular orbital wave function, ignoring normaliza- excited states in terms of atomic orbitals, ignoring nor-
tion, is malization, leads to
MO
gg (1, 2) = ϕg (1)ϕg (2) MO
gu = (χl + χr ) (χl − χr )
= [χl χr + χr χl ] + [χl χl + χr χr ], (21)
= χl χl + χr χl − χl χr − χr χr (23)
whereas the valence bond wave function is
and
VB
g (1, 2) = [χl χr + χr χl ]. (22)
MO
ug = (χl − χr ) (χl + χr )
The energies for these wave functions are compared in
Fig. 10, where we see that the valence bond is always = χl χl − χr χl + χl χr − χr χr (24)
better, but that the difference becomes negligible for small We may rewrite these equations as
R. Figure 10 illustrates the energy of the molecular orbital
wave function for the ground state of H2 with comparison MO
gu = u + u
VB ION
(25)
to the valence bond and exact energies.
MO
ug = u − u
VB ION
(26)
(again ignoring normalization), where
VB
u = χr χl − χl χr (27)
ION
u = χl χl − χr χr (28)
That is, the first excited state of the molecular orbital de-
scription is identical to the first excited state in the valence
bond description. Both describe a covalent repulsive state
that separates to two free H atoms.
The molecular orbital description of the other excited
state is
MO
uu = (χl − χr ) (χl − χr )

FIGURE 10 Energies of MO and VB wave functions. = χl χl + χr χr − χl χr + χr χl (29)

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Valence Bond Theory 417

FIGURE 12 The ground state of the C atom. −

FIGURE 14 Bonding an H to a C lobe orbital, resulting in the 4
state.

Recalling Eq. (21), we see that combining the gg and uu

MO wave functions forms the VB description of the bond: We now consider binding an H atom to the ground state
of C.
VB
g = gg − λuu ,
MO MO
(30)
where λ is a scalar factor, and we again ignore normal- B. Low-Lying States of CHn
ization. Thus, we can fix up the molecular orbital wave
The lowest states of CH arise from bonding an H to either
function so that it behaves like the valence bond wave
a carbon p orbital, forming the 2 ground state, as in
function by mixing the MO
gg and uu wave functions.
MO
Fig. 13, or to a lobe orbital forming the 4 − state, shown
in Fig. 14.
The major difference between the two states is that in
IV. BONDING OF HYDROGEN TO CARBON order to bond to a lobe orbital, the two lobe orbitals must
undo the spin pairing; such rearrangement costs energy
The principles of bonding discussed in simple examples and weakens the overall bond. Thus, bonding to the p
above apply also to chemical bonding in general. In this orbital, forming the 2 state, is more favorable.
section, we will apply these simple valence bond ideas Now we take the 2 state of CH and bond another H
about chemical bonding to simple hydrocarbon examples. to it to form CH2 . The lowest states of CH2 are obtained
by bonding an H either to a p orbital, leading to a singlet
A. Ground State of Carbon Atom state (1 A1 ), shown in Fig. 15, or a lobe orbital, leading to
a triplet state (3 B1 ), shown in Fig. 16.
The ground state (3 P) of carbon has the electronic config- For CH2 , the 3 B1 state is favored by 9 kcal/mole. Inter-
uration (1s)2 (2s)2 (2 p)2 . Here the 1s electrons are core estingly, for SiH2 , the 1A1 is more favorable, lying 18 kcal
electrons and stay very close to the nucleus, and thus do lower than the triplet state. Comparing CH2 with SiH2 ,
not participate in chemical bonding. Thus, when we con- we find two important factors favoring the 3 B1 state rel-
sider the chemical bonding of the C atom, we normally ative to the 1A1 . First, the bonds of the 1A1 state involve
consider only the behavior of the other, valence electrons. perpendicular p orbitals, and hence will favor small bond
Schematically, we represent the wave function for C angles, approximately 90◦ . The bonds in the 3 B1 state favor
atom in Fig. 12. The ovals above and below the atom larger angles, approximately 128◦ (see above). For first-
indicate a lobe orbital: the 2s the pair of electrons that row compounds, the importance of bond–bond repulsions,
have hybridized with the 2 px orbitals; the line connecting which are largest at small bond angles, leads to a
the lobe orbitals indicates singlet pairing of the electrons
in the orbitals. The dots without lines connected to them
indicate electrons that are not spin paired.

FIGURE 13 Bonding an H to a C p orbital, resulting in the 2

state. FIGURE 15 The 1 A1 state of CH2 .

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418 Valence Bond Theory

FIGURE 18 Two methylene 3 B 1 molecules forming a σ and a π

bond in ethylene.
FIGURE 16 The 3 B 1 state of CH2 .

leading to the planar molecule ethylene molecule shown

significant increase in the energy of states involving small in Fig. 18.
bond angles relative to those with larger angles. This ef- In the triplet state of CH2 , the HCH bond angle is 132.3◦ ,
fect increases the energy of the 1A1 state relative to the 3 B1 but forming a bond to the carbon should decrease this angle
state. The second factor that account for the favoring of because of Pauli repulsion from the new bond pair. Thus,
the 3 B1 state is that the lobe orbitals of first-row atoms are in CH3 the bond angle is decreased to 120◦ , and in ethylene
closer in energy to p orbitals than in atoms in the Si row. the HCH bond angle is decreased further to 117.6◦ .
The 1A1 state involves two bonds to p orbitals, whereas the Consider now the case where the plane of one methylene
group is rotated about the CC axis by an angle of 90◦ with
3
B1 state involves one p bond and one lobe bond. Thus,
this second effect also lowers the energy of the 3 B1 state respect to the other. The structure of the resulting molecule
relative to the 1 A1 state for CH2 . The net result is that is shown in Fig. 19. Here only a sigma bond is formed. The
the ordering of the first two states of CH2 is inverted with nonbonding orbitals πl and πr can be combined into singlet
respect to the energies of SiH2 . and triplet states. The singlet state is usually referred to
Starting with the 3 B1 ground state of CH2 , there are two as N , for normal or ground state, and the triplet state is
possibilities for bonding a third hydrogen, the unpaired referred to as T . Based solely on Hund’s rule, we would
lobe orbital or the p π orbital. These two options are shown expect the T state to be slightly lower than the N state for
as B and C, respectively, in Fig. 17. the twisted geometry. However, since these orbitals are
Again, due to the importance of bond–bond interac- localized on different centers, the energy splitting is quite
tions, the lower configuration will be the one with larger small, approximately 1–2 kcal. In fact, other small effects
bond angles. Bonding to the lobe leads to planar CH3 , lead to the N state at 90◦ being about 1 kcal below the T
with 120◦ bond angles, whereas bonding to the p π orbital state.
leads to two 90◦ bond angles. Thus, the lowest energy Comparison of the energies of twisted and planar ethy-
configuration of CH3 is planar, whereas SiH3 was found lene leads to the results in Fig. 20. The singlet state prefers
to be pyramidal. Because of the ability of 3 B1 CH2 to bond planar geometry since the overlap of the πl and πr orbitals
an H to either the lobe or p orbital, the first constant for leads to a strong pi bond. However, for the triplet state, the
pyramidal distortion of CH3 is quite small. πl and πr orbitals must be orthogonalized to each other,
and this state prefers the 90◦ twisted geometry.
C. Ethylene According to Fig. 20, the energy to twist the N state of
ethylene by 90◦ is 65 kcal, breaking the pi bond. This bar-
VB theory allows us to start with two methylene radi- rier has been observed experimentally from studies of the
cals, CH2 , in the ground state, and, by forming ethylene, kinetics for cis–trans isomerization dideuterated ethylene.
H2 C CH2 , we can form both a sigma bond and a pi bond,

FIGURE 19 Twisted ethylene, where only a σ bond may be

FIGURE 17 Options for bonding to the 3 B 1 state of CH2 . formed.
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Valence Bond Theory 419

geometry; the adiabatic excitation energy for θ = 0◦ is

91 kcal.

SEE ALSO THE FOLLOWING ARTICLES

BONDING AND STRUCTURE IN SOLIDS • HYDROGEN BOND

• KINETICS (CHEMISTRY) • QUANTUM CHEMISTRY

BIBLIOGRAPHY

FIGURE 20 Energy profile for the singlet N state and the triplet T Cooper, D. L., Gerratt, J., and Raimondi, M. (1987). Modern valence
state of ethylene as the molecule is twisted about the C C bond. bond theory, Adv. Chem. Phys. 67, 319.
Coulson, C. A. (1961). “Valence,” Oxford Univ. Press, London and
New York.
As the molecules are rotated, the strength of the pi bond Klein, D. J., and Trinajstić, N., eds. (1990). “Valence Bond Theory and
is weakened, and the CC bond length increases. Thus, for Chemical Structure,” Elsevier, Amsterdam.
the N state, RCC = 1.34 Å at θ = 0◦ and RCC = 1.50 Å at Matsen, F. A., and Pauncz, R. (1986). “The Unitary Group in Quantum
Chemistry,” Elsevier, Amsterdam.
θ = 90◦ . McWeeny, R., and Sutcliffe, B. T. (1969). “Methods of Molecular Quan-
In the T state, the optimum geometry is twisted, tum Mechanics,” Academic Press, New York.
θ = 90◦ , since triplet pairing of the orbitals prefers that Pauling, L. (1969). “The Nature of the Chemical Bond,” Cornell Univ.
the pi orbitals not overlap. As the molecule is twisted to- Press, Ithaca, New York.
ward the planar geometry, the CC bond length increases Pauncz, R. (1979). “Spin Eigenfunctions,” Plenum, New York.
Schaefer, H. F., III, ed. (1977). “Methods of Electronic Structure Theory,”
from 1.50 Å at θ = 90◦ to 1.57 Å at θ = 0◦ , and the Plenum, New York.
energy barrier is 25 kcal. Note that Fig. 20 shows the Slater, J. C. (1963). “Quantum Theory of Molecules and Solids,” Vol. 1.
T -to-N energy separation at θ = 0, using the ground-state McGraw-Hill, New York.