Chemical Equilibrium

Charles D. Mickey
Texas A8M University at Galveston
Galveston. TX 77553

Many chemical reactions do not proceed to completion;

instead, they establish a dynamic equilihrium in which two
opposing reactions occur a t the same rate.' For example,
mixing solutions containing cerium(1V) and iodide ions gives
rise to the reaction
2Ce& + 31Gqr=2Cef&, + I&
On the other hand, when cerium(II1) is added to a solution of
triiodide ion, significant quantities of cerium(1V) and iodide
ions are produced. The extent of either reaction is easily
gauged by the intensity of the orange-red color of the triiodide
ion. The concentration of this colored ion rapidly reaches a
constant level that is independent of the route hy which it is
formed. I t makes no difference whether Ce4+ and I- or Ce3+
and 1; are selected as the original reactants; the same condi- The variation in conwmratim of reactam and pmducts as ahlnction of time.
tion of equilihrium will result. In the beginning, if Ce4+ and (a)Initially, staidllmlric amolntJofCe4+and I-are mixedandallowedtoreadl
equilibrium. (b)Staichiometric amounts of bat and ;I are allowed to react at
I- are the original reactants, the concentrations of Ce4+ and the same temperature. In both instances, the final equilibrium concenhations
I- will he high, and consequently the forward reaction will of all species are the same.
proceed rapidly. No reverse reaction is possible a t the start,
since Ce3+ and I:, are not yet present. As Ce3+ and I; are
formed, the reverse reaction will begin slowly and gradually
increase in rate as Ce3+ and 1, accumulate. Meanwhile the
forward reaction is slowing down as Ce4+ and I- are heing used
the other to the left (called the reverse reaction), in which D
and E react to form A and B. Accordine t o the Law of Mass
Action, the rate of the forward reactLon ;r proportronal lo the
-
C
concentrations ofthe reactants A and R,whilr the rate of the
up, as shown in Figure 1. I4
Conditions of chemical equilihrium that most chemical rrwr.*e rrnctron rsproportlonal to the<oncmtrationof Uand
reactions can attain may he compared to a person running on E Thus, the forward reaction has the rate 0
a treadmill, which moves faster as the runner increases his Rater = kf[A][B]
speed. When the runner and the treadmill are in equilihrium,
the runner is apparently stationary to an observer. If the and the reverse reaction has the rate
runner increases his speed, he advances a short distance. Rate, = k,[D][E]
However, as the treadmill also moves faster, the runner again
appears to he stationary; although, his position is in advance where brackets, [ 1, represent the molar concentrations of the
of his previous stationary position. enclosed suhstances, and kf and k , are proportionality con-
In a reversible reaction, such as stants called specific rate constants.
Guldherg and Waage assumed that equilihrium results
2NOw + Oxg, * 2N02(d %hen the rates of the forward and reverse reactions are equal,
the equilibrium amounts of NO, 02, and NO2 remain constank L.e.,
yet like the runner and the treadmill, the reactions proceed Rater = Rote,
in opposite directions a t the same rate.
Therefore, a t equilihrium,
The Law of Mass Action
kr[Al[Bl= k,[DlIEl
In 1864, the Norwegian chemists Cato M. Guldberg and
Peter Waaze ~ r o o o s e dthat the rate of a chemical reaction is Writing this equation in a more useful form gives
proportion& to the active masses of the reacting substances; kr - [Dl [El
the molecular concentration of a substance in solution or in k. [A1 IBI
the gas phase is used as a measure of its actiue mass.2 The Inasmuch as kt and k , are hoth constants, their ratio kflk, is
significance of this statement, which is called the Law of Mass also a constant, hence
Action (the rate law in kinetics) is more apparent as the
quantitative notions of chemical equilihrium are developed.
For example, consider the general reversible reaction in which ...
in which K., is called the equilibrium constant. Althoughthe
an equilibrium exists between four suhstances A, B, D, and
E kinetic arguments used for the derivation of this equilibrium
constant are not applicable to complex multistep reactions,
A+B*D+E they are valid for simple one-step himolecular reactions.
Two reactions are proceeding, one to the right (called the
forward reaction), in which A and B react to form D and E and This feature is aimed as a review uf basic chemical prmeiples
and as a reappraisal ol the state of the art. Comments, sug-
' Mickey, C. D., J. CHEM. EDUC., 57,659 (1980) geatims for tupirs, and contributionr should be sent to the
Glasstone, S.,"Textbook of Physical Chemistry," D. Van Nos-
trand Company, Inc., New York, 1946, p. 817.
I feature editor. I
Volume 57. Number 11, November 1980 1 801
The Equilibrium Constant and Ideal Behavior and a t equilibrium,
The expression Rr = R,
therefore,
. .. .
is only rigorously valid in situations where all reactants and krICOnl[H~0I3= kr[H30+]Z[CO$-]
products behave like ideal eases or are comnonents of an ideal hence
Bo~[Link] example, just as conductiviiy in concentrated
solutions of strong electrolytes fails to indicate complete
ionization, because of the interference of ions with the motions
of other ions, the presence of high concentrations of ions in- Alternately, assume that the reaction proceeds by the fol-
terferes with the reactions of any ion. If the rates of reactions lowing two-step mechanism:
in concentrated solutions of strong electrolytes are calculated
and compared with the measured rates of these same reac- COac,) + 2HzOu1= HsOt,) + HCO,I,l (Step 1)
tions, there are discrepancies which increase with the increase HCO,I,I + H 2 0 =
~ HBOLI+ CO$(aql (Step 2)
in concentration. Moreover. these discrenancies will he re- For the first step
flected in the equilihrium cdnstant. 1f thlactiuity of the re- Rr = kr[C021[Hz012
acting particle is substitued for its concentration or partial
pressure a correct rate of reaction is found and the equilihrium R, = k,[H3Otl[HCO3-I
constant will he rieorouslv valid. The correction factor used At equilihrium, Rr = R,, and since the ratio of two constants
as a multiplier octhe actual pressure or concentration to is a third constant
produce the actiuity is called the actiuity coefficient (7). The
experimentally determined value of the actiuity coefficient
kr -
- - - [H3Ot1[HC0;l
varies, not only from one substance to another, but also with
kr '- [C0z11H~012
Similarly, for the second step:
pressure, conc&tration, and temperature. he magnitude of
the actiuity coefficient is always less than one and approaches R; = k;[HCOJ[Hz0]
unity as the partial pressure or concentration decreises. The R; = k:[H30+][COf]
actiuity (a) of a reaction component is its molar concentration
or partial pressure times an actiuity coefficient (y),or a = y M A t equilibrium, R i = R,'and
for solutions and a = y P for gases. The actiuity of a pure
liquid or a pure solid, at, constant temperature, is defined as
unity.
One of the great theoretical outcomes of chemical thermo- The product of two constants is a third constant; therefore,
dynamics was the rigorous derivation of equilihrium constants the product
using actiuities, rather than molarities or ~ a r t i anressures.
l
~ l t h o u g hit is not possible within the icopi d [Link], it
can be shown that the thermnd\[Link] the nrecediw-
equilibrium-constant expression is
K - UDaE
eq--
Consequently, the equilibrium-constant expression turns out
aADB to be the same; whether based on kinetic arguments or the
Freauentlv. as in this discussion. eauilihrium constants are balanced equation. Thus, for the general reaction:
based bn milarities or partial pressures instead of the more
exact activities, for three reasons: (1)the measurement of rA+sB=xD+zE
reagents are usually made in grams and put into solutions in in which r, s, x, and z represent the coefficients of A, B, D, and
terms of erams or moles per liter: (2) the activitv coefficient E, respectively, in the balanced equation, the formulation of
of any ion changes not oily with its own concentration, hut Keq is
with that of other ions in the solution; (3) all substances for
which equilibria are calculated are either in dilute solutions
of their kinds of ions and molecules or are weak electrolytes,
so the approximations secured by the use of molarities or There are several different but interrelated types of eqni-
partial pressures instead of activities are sufficiently accu- librium constants, with the symbol K., generally used to
rate.
represent any of the various kinds. However, special desig-
General Form of the Equillbrlum Constant nations for equilibrium constants are frequently used t o
Fortunately, i t is not necessary to know the mechanism or characterize a particular equilihrium system. The symbol K p ,
rate laws for a reversible reaction to he able to write the for example, indicates a particular equilihrium constant in
equilibrium-constant expression. Even if a reversible reaction which the quantities of gaseous reactants and products are
proceeds through a series of complicated steps, each individual expressed in terms of their partial pressures. Concentrations
step is reversible and, a t equilihrium, the reversible reactions can he related to partial pressures through the ideal gas law
proceed a t the same rate in both directions. Thus, the equi- (PV = nRT); therefore, the partial pressure for any gaseous
librium-constant expression can be derived from the balanced reactant or product, that behaves ideally, is proportional to
equation for the overall reaction. Consider the reaction its concentration. Hence, for the gas phase equilibrium:

COacaqi + 3 H z 0 ~ 1 +2H@&l+ CO&I N21g1 + 3 H w * 2NHl(g~

If the forward reaction is a single-step termolecular reaction, the equilibrium-constant expression is
its rate will he expressed as:
Ratef= kr[C02][H20I3 P-m%
K - 3.52 = X 10W7 at 1000DK

Likewise, if the reverse reaction is a single-step trimolecular The symbol K c represents a particular equilihrium constant
reaction, its rate will be given by the equation: in which the quantities of reactants and products are ex-
pressed in terms of their molarities. The Kc value for the
Rate. = k,[H30+I2[CO$-] previous reaction is
802 / Journal of Chemical Education
 concentration, which affect the rate of any reaction will also
affect the equilihrium; that is, these same parameters can
change the halance between the two opposing reactions. T o
Two different reactions will generally have different equi- understand the nroblem more clearlv. " . aeain consider the
lihrium constants. At 1000°K the reartion involving carbon analogy hetwee'a chemical system in equilihrium and a
monoxide, oxygen, and carhon dioxide -
oersou runnine on a treadmill which increases its speed as the
person advances. If the person while running and apparently
2COIgl + 02(g1 = 2COlld
remaining stationary with respect to some fixed point, in-
has the equilibrium constant value creases his speed he advances; hut as he does so the speed of
treadmill also increases and aeain the runner comes to an
apparent stationary position. For the second time, the runner
and the treadmill are in astateof equilihrium, but the runner
The fact that in the latter reaction K, is greater than Kc in the has now orcuyied a position farthe; forward. If, on the other
former reaction means that at 1000°K carbon monoxide and hand, the runner tires he runs slower. Momentarily he shifts
oxygen are more completely converted to carhon dioxide than his position backward; hut since the treadmill i i readjusted
. .. are to ammonia. Thus, the maenitude
nitroeen and hvdroeen to a slower rate, the runner will soon assume a new position
of theequilibrium runstant may he used to gauge theexcent of eauilihrium. nurine" the short interval that the runner ad-
tt, which a eiven reartion proeresses toward completion. If all
a
other factors are equal, vaiue of Keg > 1indicates a high
degree of conversion of reactants to products and a value of
vances or falls hack, the position of equilibrium is shifted.
In a analoeous manner. the eauilihrium position of a
chemical reaccon may be sGfted; and it is customary w speak
K., < 1indicates a low degree of conversion. of a shift in euuilibrium to the riahr or to the left with refer-
The Forward and Reverse Reactions ence to'the chemical equation f& the reaction taking place.
Thus, in the eauilihrium between nitroeen, hydrogen,
. . and
Since equations for chemical reactions may he written in ammonia as represented by the equation-
a variety of different but equivalent ways, each value for an
equilihrium must always he accompanied by the specific N w + 3 H w * 2NH31g)
equation which it represents. For example, in the reaction all these substances are present in definite amounts and the
CuL, + +A&, * CU&I + 2Agb reaction is proceeding in both directions. If now, t)y some in-
fluence, the equilibrium is affected so that more ammonia is
The equilibrium constant is formed; the equilihrium id &hifledto the right. During the
change from one equilibrium pusition to another, the reaction
proceeds mumenurrily ft~iterfrom left to right than from right
Suppose the reaction is written as to left. This situation is analoguus to the momentary shift in
the position of the runner on the treadmill when he is inspired
CUKI+ 2Ag?.1* Cuf.~+ 2 A g h to run faster.
consistency is maintained and ambiguity avoided, if the Le ha teller's Principle and Chemical Equlllbrlum
equilibrium constant is written as
Extensive studies of reversible reactions and the equilibria
associated with them led the French chemist, Henri Louis Le
Chatelier (1888), to make a simple generalization, commonly
Quantitatively, for any reversible reaction the value of the referred to as Le Chatelier's Principle:
eauilihrium constant for the reverse reaction is the reciprocal A system at equilibrium, when subjected to any stress (such as
i f t h e equilibrium constant for the forward reaction. 1;other change in temperature, pressure, or concentration of matter) so that
words, equilibrium is disturbed, will tend to adjust itselfso as to remoue the
stress and re-establish equilibrium.
Of the three stresses, only a change in temperature will affect
the magnitude of the equilihrium constant. For example,
As illustrated in the last two equations, i t is customary to
exclude the concentration terms for solids from the equilib- Reaction Temp ( O K ) K
rium expression. The concentrations of the silver and copper Nzie] + 3H21g)% 2NHxs1 623 2.66 x lo-'
solids &e constant, hence the respective equilihrium-constant Nxg) + 3H21g)= 2 N H w 123 6.59 x lo-3
N Z I ~+I 3Hzw = 2NH31x) 1000 2.37 x
expressions are simplified by comhining the constants. Sim-
ilarly, the concentration of a pure liquid is constant, hence its The Effect of Temperature on an Equillbrium
concentration term is also excluded from the equilibrium- All chemical reactions are accompanied hy energy changes.
constant expression. For example, consider the reaction Some reactions are exothermic-produce heat durine the
reaction; others are endotherrnic-ibsorb heat from thesur-
roundings. In the reaction
the equilihrium constant is expressed by Nz1.1 + 3H2(.) * 2NH3 + 22.08 keal
nitrogen and hydrogen, in comhining to from ammonia, pro-
duce heat. When ammonia decomposes into nitrogen and
hydrogen (the reverse reaction), an equivalent amount of heat
Combining the two constants in this equation gives must he ahsorhed. When this system is at equilibrium, no heat
change occurs.
A quantitative relationship between the equilibrium con-
stant and temuerature can he derived from the Arrhenius
Faclors Influencing equation for the specific rate constant, since the equilihrium
- Equillbrium
.
At equilibrium a chemical reaction is proceeding in the
constant. K.,. is eaual to the ratio krlk.. . . rate
. . The soecific
constant foi'the foiward reaction is
forward and reverse directions with equal velocities, thus it
is expected that the parameters, such as temperature and k c = *@-EaIRT

Volume 57, Number 11, November 1980 1 803

while the corresponding expression for the reverse reaction the position of the equilibrium shifts to the left.
is Converselv. removal of a comonnent from an eauilibrium
k, = A , ~ - E o / R T system favors the reaction whirh'replaces it. Fur example, the
removal of sulfur trioxide from the enuilibrium svstem shifts
Substitution shows the temperature dependence of K,,, the position of equilihrium to the right. The forward rate will
momentarily be greater than the reverse rate; the system is
temporarily out of equilihrium and sulfur trioxide molecules
will he produced faster than they are used up in the reverse
reaction. Similarly, if part of the sulfur dioxide or oxygen is
removed, the reverse reaction, forming more sulfur dioxide
and oxygen, will be favored.
The Effect of Pressure on Equilibrium: A Special Case of
(where Z, a constant, is the ratio of AyIA,). Thus, for exn- Changing Concentration
thermic reactions K,, decreases as temperature increases, and
for endothermic reactions K., increases as temperature in- Change of pressure is insignificant for liquids and solids
creases. In other words, increasing the temperature will shift because of their low compressihilitv, but i t is extremelv im-
the position of equilibrium to the left for an exothermic re- portant for gases because the molarity of a gas, a t constant
action; whereas, increasing the temperature will shift the temperature, is directly proportional to its partial pressure
position of equilihrium to the right for an endothermic reac- (PV = nRT).Therefore, as the external pressure on agaseons
tion. This simplified derivation supports the generalization system increases, the substances undergo compression and
of Le Chatelier. the molarity increases. 1.e Chatelier's principle indicates that,
According to Le Chatelier's principle, if heat is added to the if a .stress is placed on a rerrrsihle system by increasing the
nitrogen, hydrogen, ammonia system (increase of tempera- oressure. that rhemiral rhanee will he favored whirh will tend
~~-~~~

ture), the system will change in such a way as to minimize the to reduce the pressure. For a gaseous system, the increase in
stress. T o relieve the stress (increase of temoerature). . . the
oressure is achieved bv increasine the total number of mole-
system will absorb heat, i.e., the formation of nitrogen and cules per unit volume. This procesi will favor the net chemical
hvdrocen from ammonia will be favored since this reaction chance that will reduce the total number of molecules ner unit
ahsorl~sheat. In reality, pan of the heat is used u ) incrense the volume.
temperature of the svstem and pan is used toshifi the eoui- Consider the reversible reaction
2C01,l + 02id = 2c02ig)
The Effect of Changlng Concentration on the Position of A total of three moles of carbon monoxide and oxygen form
Equilibrium only two moles of carbon dioxide. The formation of carbon
Another way to put a stress on a system is to alter the cnn- dioxide will therefore decrease the total number of molecules
centration of one or more of the components. This can be ac- in the system, and the total gaseous pressure will therefore be
complished by adding or removing one or more of the equi- reduced. Thus, increasing the total external pressure on the
librium species. For example, consider the equilibrium system will favor the conversion of carbon monoxide and
oxygen to carbon dioxide. Conversely, a decrease in the total
external pressure will favor the dissociation of carbon dioxide
to carbon monoxide and oxygen.
If PC15 is injected into a closed system a t 523"K,i t disso-
ciates to an equilibrium state:
pC15~ =PCIw + Claig)
A stress can be placed on this system by adding sulfur dioxide, Since there are two moles of gaseous product compared to only
oxveen.
" - . or both. In either event. the oroduct of the molar one mole of gaseous reactant, an increase in the external
concentrations in the denominator of the equilibrium-con- pressure will cause a shift in the equilibrium to the left, i.e.,
stant expression exceeds the equilibrium value, and the ratio less PCls dissociates: whereas a decrease in the external
of the molar concentrations is now less than [Link] the molar pressurewill favor the dissociation of PClb. In other words,
concentration of sulfur dioxide is increased. the reaction rate there is a shift in the eauilihrium t o the rieht.
to the right will increase, and the change which tends to use Certain gaseous reactions are not affecied by changes in
up sulfur dioxide and oxygen and thus remove the stress will pressure, for example:
be favored. This conforms to Le Chatelier's principle which
indicates that the equilibrium system will shift so as to min-
imize the stress. Sulfur dioxide and oxygen will he used up In this rase there are two moles of reactants and two moles of
faster than they are formed, and the molar concentration of product. Changes in the external pressure have no effect on
sulfur trioxide d l increase. However, as the molarity of sulfur this system hecause thereareequal numbersof m(~leculeson
trioxide increases, the rate of its dissociation into sulfur huth sides of the equation.
dioxide and oxygen will also increase. Eventually, the forward Catalysts and Equilibrium
and reverse reactions will attain equal rates and equilihrium
will be re-established. The stress nlaced on the svstem. when While catalysts are used to increase the rate of a reaction,
the concentration of sulfur dioxide was increased, will have they cannot change the numerical value of the equilibrium
been removed by changes in the molarites of all the substances constant and hence cannot change the relative amounts of
such that the value of K,, is restored. Note that when the reactants and products present a t equilibrium. However, the
concentration of sulfur dioxide is increased. the net chances catalyst may greatly reduce the timenecessary for theestab-
whichurrur in the system are such that theconcentratiooof lishment of equilil~[Link] is extremely important from an
oxygen is decreased while the concentration of sulfur trioxide industrial viewpoint, since the rate a t which aproduct can be
is increased. In other words, oxygen can he used up mnre produced is a primary consideration. Catalysts may be used
completely and sulfur trioxide can he produced more effi- effectively in manv reactions which allow conversion of onlv
ciently byincreasing the concentration bf sulfur dioxide. On a small percentage of reactants into products (position df
the other hand, the introduction of more sulfur trinxide into equilibrium shifted far to the left) because, from a production
the system favors the reverse reaction, more sulfur dioxide and standpoint, it is far mnre important to ohtain a small yield in
oxygen are formed while some sulfur trioxide is consumed, i.e., a few minutes than to obtain a large yield in several days.
804 1 Journal of ChemicalEducation