1

)(
cz BIBLIOGRAPHY
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A. Introductory Electrochemistry Texts

Al C. N. Reilley and R. W. Murray, Electroanalytical Principles, New
York: Interscience, 1963.
A2 E. H. Lyons, Jr., Introduction to Electrochemistry, Boston: D. C.
Heath, 1967.
A3 B. B. Damaskin, The Principles of Current Methods for the Study of
Electrochemical Reactions, New York: McGraw-Hill, 1967.
A4 J. B. Headridge, Electrochemical Techniques for Inorganic
Chemists, London: Academic Press, 1969. .
A5 J. Robbins, Ions in Solution (2): An Introduction to Electrochemistry,
London: Oxford University Press, 1972.
A6 W. J. Albery, Electrode Kinetics, London: Oxford University Press,
lW5.
A7 N. J. Selley, Experimental Approach to Electrochemistry, New York:
John Wiley, 1976.
A8 D. R. Crow, Principles and Applications of Electrochemistry, 2nd ed,
London: Chapman and Hall, 1979.
A9 D. Hibbert and A. M. James, Dictionary of Electrochemistry, 2nd ed,
New York: John Wiley, 1985.
AlO T. Riley and C. Tomlinson, Principles of Electroanalytical Methods,
New York: John Wiley, 1987.
All J. Koryta, Ions, Electrodes and Membranes, 2nd ed, New York:
John Wiley, 1991.

B. More Advanced Texts

Bl P. Delahay, New Instrumental Methods in Electrochemistry, New
York: Interscience, 1954.
B2 H. S. Hamed and B. B. Owen, Physical Chemistry of Electrolytic
Solutions, New York: Reinhold,1958.
B'3 G. Charlot, J. Badoz-Lambling, and B. Tremillon, Electrochemical
Reactions, Amsterdam: Elsevier, 1962.

427
428 Appendix 1
B4 D. A. MacInnes, The Principles of Electrochemistry, New York:
Dover, 1966 (corrected reprint of 1947 edition).
B5 G. Kortum, Treatise on Electrochemistry, 2nd ed, Amsterdam:
Elsevier, 1965.
136 B. E. Conway, Theory and Principles of Electrode Processes, New
York: Ronald Press, 1965.
B7 K. J. Vetter, Electrochemical Kinetics, New York: Academic Press,
1967.
B8 J. O'M. Bockris and A. Reddy, Modern Electrochemistry, New York:
Plenum Press, 1970.
139 R. A. Robinson and R. H. Stokes, Electrolyte Solutions, 2nd ed (rev),
London: Butterworths, 1970.
B10 J. S. Newman, Electrochemical Systems, Englewood Cliffs, NJ:
Prentice-Hall,1972.
Bll L. I. Antropov, Theoretical Electrochemistry, Moscow: Mir, 1972.
B12 A. J. Bard and L. R. Faulkner, Electrochemical Methods, New
York: John Wiley, 1980.
B13 R. Greef, R. Peat, L. M. Peter, D. Pletcher, and J. Robinson,
Instrumental Methods in Electrochemistry, Chicester: Ellis
Horwood, 1985.
B14 J. Koryta and J. Dvorak, Principles of Electrochemistry, New York:
John Wiley, 1987.
c. Specialized Books and Monographs
Cl W. Ostwald, Electrochemistry, History and Theory, Leipzig: Veit,
1896. Republished in English translation for the Smithsonian
Institution, New Delhi: Amerind Publishing, 1980.
C2 V. G. Levich, Physiochemical Hydrodynamics, Englewood Cliffs,
NJ: Prentice-Hall, 1962.
C3 R. N. Adams, Electrochemistry at Solid Electrodes, New York:
Marcel Dekker, 1969.
C4 C. K. Mann and K. K. Barnes, Electrochemical Reactions in
Nonaqueous Systems, New York: Marcel Dekker, 1970.
C5 A. Weissberger and B. W. Rossiter, eds, Physical Methods of
Chemistry, Vol. 1 (Techniques of Chemistry), Parts IIA and lIB
(Electrochemical Methods), New York: John Wiley, 1971.
C6 J. S. Mattson, H. B. Mark, Jr., and H. C. MacDonald, Jr.,
Electrochemistry; Calculations, Simulation, and Instrumentation
(Computers in Chemistry and Instrumentation, Vol. 2), New York:
Marcel Dekker, 1972.
C7 Yu. V. Pleskov and V. Yu. Filinovskii, The Rotating Disc Electrode,
New York: Consultants Bureau, 1976.
CB J. O'M. Bockris and S. U. M. Khan, Quantum Electrochemistry,
New York: Plenum Press, 1979.
Bibliography 429

C9 A. J. Fry and W. E. Britton, eds, Topics in Organic Electrochemistry,

New York: Plenum Press, 1986.
C10 R. J. Gale, ed, Spectroelectrochemistry, Theory and Practice, New
York: Plenum Press, 1988.
Cll H. D. Abrwia, ed, Electrochemical Interfaces: Modern Techniques
for In-Situ Interface Characterization, New York: VCH Publishers,
1991.
C12 J. O'M. Bockris and S. U. M. Khan, Surface Electrochemistry, New
York: Plenum Press, 1993.

D. Electroanalytical Methods
D1 1. M. Kolthoff and J. J. Lingane, Polarography, 2nd ed, New York:
Interscience, 1952.
D2 J. J. Lingane, Electroanalytical Chemistry, 2nd ed, New York:
Interscience, 1958.
D3 W. C. Purdy, Electroanalytical Methods in Biochemistry, New
York: McGraw-Hill,1965.
D4 L. Meites, Polarographic Techniques, 2nd ed, New York: John
Wiley, 1965.
D5 J. Heyrovsky and J. Kuta, Principles of Polarography, New York:
Academic Press, 1966.
D6 H. Rossotti, Chemical Applications of Potentiometry, Princeton, NJ:
Van Nostrand, 1969.
D7 R. G. Bates, Determination of pH: Theory and Practice, 2nd ed, New
York: John Wiley, 1973.
DB Z. Galus, Fundamentals of Electrochemical Analysis, Chichester:
Ellis Harwood, 1976.
D9 G. Dryhurst, Electrochemistry of Biological Molecules, New York:
Academic Press, 1977.
D10 C. C. Westcott, pH Measurements, New York: Academic Press,
1978.
Dll J. Vesely, D. Weiss, and K. Stulik, Analysis with Ion-Selective
Electrodes, Chichester: Ellis Horwood, 1978.
D12 A. M. Bond, Modern Polarographic Methods in Analytical
Chemistry, New York: Marcel Dekker, 1980.
D13 J. A. Plambeck, Electroanalytical Chemistry, New York: John
Wiley, 1982.
D14 J. Koryta and K. Stulik, Ion-Selective Electrodes, 2nd ed, London:
Cambridge University Press, 1983.

E. Organic Electrosynthesis
El M. R. Rifi and F. H. Covitz, Introduction to Organic
Electrochemistry, New York: Marcel Dekker, 1974.
430 Appendix 1

E2 N. L. Weinberg, ed, Technique of Electroorganic Synthesis

(Technique of Chemistry, Vol. V), New York: John Wiley, 1974 (Part
1), 1975 (Part Il).
E3 D. K. Kyriacou, Basics of Electroorganic Synthesis, New York: John
Wiley, 1981.
FA K. Yoshida, Electrooxidation in Organic Chemistry, New York:
John Wiley, 1984.
E5 T. Shono, Electroorganic Chemistry as a New Tool in Organic
Synthesis, Berlin: Springer-Verlag, 1984.
E6 A. J. Fry, Synthetic Organic Electrochemistry, 2nd ed, New York:
John Wiley, 1989.
E7 H. Lund and M. M. Baizer, eds, Organic Electrochemistry, 3rd ed,
New York: Marcel Dekker, 1991.
E8 T. Shono, Electroorganic Synthesis, San Diego: Academic Press,
1991.

F. Experimental Methods
F1 D. J. G. Ives and G. J. Janz, eds, Reference Electrodes, Theory and
Practice, New York: Academic Press, 1961.
F2 W. J. Albery and M. L. Hitchman, Ring-Disc Electrodes, Oxford:
Clarendon Press, 1971.
F3 D. T. Sawyer and J. L. Roberts, Jr., Experimental Electrochemistry
for Chemists, New York: John Wiley, 1974.
F4 E. Gileadi, E. Kirowa-Eisner, and J. Penciner, Interfacial
Electrochemistry--An Experimental Approach, Reading, MA:
Addison-Wesley, 1975.
F5 D. D. MacDonald, Transient Techniques in Electrochemistry, New
York: Plenum Press, 1977.
F6 P. T. Kissinger and W. R. Heineman, eds, Laboratory Techniques in
Electroanalytical Chemistry, New York: Marcel Dekker, 1984.
G. Technological Applications of Electrochemistry
G1 J. O'M. Bockris and S. Srinivasan, Fuel Cells: Their
Electrochemistry, New York: McGraw-Hill,1969.
G2 C. L. Mantell, Batteries and Energy Systems, New York: McGraw-
Hill,1970.
G3 F. A. Lowenheim, ed, Modern Electroplating, New York: John
Wiley, 1974.
G4 S. W. Angrist, Direct Energy Conversion, Boston: Allyn and Bacon,
1976.
G5 V. S. Bagotzky and A. M. Skundin, Chemical Power Sources, New
York: Academic Press, 1980.
G6 D. Pletcher, Industrial Electrochemistry, London: Chapman and
Hall,1982.
Bibliography 431
G7 N. L. Weinberg and B. V. Tilak, eds, Technique of Electroorganic
Synthesis (Technique of Chemistry, Vol. V), Part III, New York:
John Wiley, 1982.
G8 H. H. Uhlig and R. W. Revie, Corrosion and Corrosion Control, New
York: John Wiley, 1984.
G9 H. V. Ventatasetty, ed, Lithium Battery Technology, New York:
John Wiley, 1984.
G10 R. E. White, ed, Electrochemical Cell Design, New York: Plenum
Press, 1984.
Gll Z. Nagy, Electrochemical Synthesis of Inorganic Compounds, New
York: Plenum Press, 1985.
H. Electrochemical Data
HI W. M. Latimer, Oxidation Potentials, 2nd ed, Englewood Cliffs, NJ:
Prentice-Hall, 1952.
H2 B. E. Conway, Electrochemical Data, Amsterdam: Elsevier, 1952.
H3 R. Parsons, Handbook of Electrochemical Data, London:
Butterworths, 1959.
H4 A. J. de Bethune and N. A. S. Loud, Standard Aqueous Electrode
Potentials and Temperature Coefficients at 25C, Skokie, IL:
Hampel, 1964.
H5 M. Pourbaix, Atlas of Electrochemical Equilibria, New York:
Pergamon Press, 1966.
H6 G. J. Janz and R. P. T. Tomkins, Nonaqueous Electrolytes
Handbook, New York: Academic Press, 1972.
H7 A. J. Bard and H. Lund, eds, The Encyclopedia of the
Electrochemistry of the Elements, New York: Marcel Dekker, 1973.
H8 L. Meites and P. Zuman, Electrochemical Data. Part I. Organic,
Organometallic, and Biochemical Systems, New York: John Wiley,
1974.
H9 D. Dobos, Electrochemical Data, Amsterdam: Elsevier, 1975.
H10 G. Milazzo and S. Caroli, Tables of Standard Electrode Potentials,
New York: John Wiley, 1977.
Hll L. Meites and P. Zuman, eds, CRC Handbook Series in Organic
Electrochemistry, Boca Raton, FL: CRC Press, 1977-.
H12 L. Meites, P. Zuman, E. B. Rupp and A. Narayanan, eds, CRC
Handbook Series in Inorganic Electrochemistry, Boca Raton, FL:
CRC Press, 1980-.
H13 A. J. Bard, R. Parsons, and J. Jordan, eds, Standard Potentials in
Aqueous Solution, New York: Marcel Dekker, 1985.
H14 A. J. Bard, R. Parsons, and J. Jordan, eds, Oxidation-Reduction
Potentials in Aqueous Solution, Oxford: Blackwell, 1986.
432 Appendix 1
1. Review Series
11 J. O'M. Bockris and B. E. Conway, eds, Modern Aspects of
Electrochemistry, New York: Plenum Press, from 1954.
12 P. Delahay (Vols. 1-9), C. W. Tobias (Vols. 1- ), and H. Gerischer
(Vols. 10- ), Advances in Electrochemistry and Electrochemical
Engineering, New York: John Wiley, from 1961.
13 A. J. Bard, ed, Electroanalytical Chemistry, New York: Marcel
Dekker, from 1966.
14 E. B. Yeager and A. J. Salkind, eds, Techniques of Electrochemistry,
New York: John Wiley, from 1972.
15 G. J. Hills (Vols. 1-3) and H. R. Thirsk (Vol. 4- ), Senior Reporters,
Electrochemistry, A Specialist Periodical Report, London: Royal
Society of Chemistry, from 1971.
16 Analytical Chemistry, Fundamental Annual Reviews (April issue
of even-numbered years), Washington: American Chemical
Society.
 2
-zc>< SYMBOLS AND UNITS
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Table A.t The International System (SI) of Units

Physical Quantity Unit Symbol

Fundamental units:
Length meter m
mass kilogram kg
time second s
electric current ampere A
temperature kelvin K
amount of substance mole mol
luminous intensity candela cd
Derived units:
force newton N (kg m s-2)
energy joule J (Nm)
power watt W (J s-l)
pressure pascal Pa (N m- 2)
electric charge coulomb C (A s)
electric potential volt V (J C-l)
electric resistaunce ohm n (V A-l)
electric conductance siemens S (A V-I)
electric capacitance farad F (C V-I)
frequency hertz Hz (s-l)

433
434 Appendix 2

Table A.2 Values of Physical Constants

Constant Symbol Value

pennittivity of free space () 8.8541878 x 10-12 C2J-1m-1
electronic charge e 1.602189 x 10- 19 C
Avogadro's number NA 6.02204 x 1023 mol- 1
Faraday constant F 96484.6 C mol- l
gas constant R 8.3144 J moI-lK-1
Boltzmann constant k 1.38066 x 10-23 J K-l
Planck constant h 6.62618 x 10-34 J s
gravitational acceleration g 9.80665 m s-2

Table A.3 List of Symbols

Symbol Name Units

a activity none
a radius m
A area m2
Ci molar concentration, species i mol L-1 (M)
mol m- 3 (mM)
C differential capacity F m-2
d density kgm- 3
DI diffusion coefficient, species i m 2s- 1
E energy J
E cell potential V
E1I2 half-wave potential V
E electric field strength V m- l
Ii frictional coefficient, species i kg s-1
F force N
G Gibbs free energy J mol- l
H enthalpy J mol- l
electric current A
Symbols and Units 435

Symbol Name Units

iD diffusion-limited current A
iL limiting current A
1 ionic strength mol L-1
1 a.c. current amplitude A
ID diffusion current constant rnA mM-1
(mg s-1)-213s -1I6
j volume flux m 3s- 1
j current density A m- 2
J molar flux density mol m- 2 s- 1
k rate constant variable
kD mass-transport rate constant m s-l
kij potentiometric selectivity coefficient none
K equilibrium constant none
L length m
m mass kg
mi molal concentration, species i mol kg-I
M molecular weight g mol- 1
n number of moles mol
ni kinetic order, species i none
N number of molecules none
p pressure bar (105 Pa)
q heat J
Q electric charge C
r,R radial distance m
ro microelectrode radius m
R resistance n
S entropy J mol-1K-l
t time s
ti transference number, species i none
T temperature K
436 Appendix 2
Table A.3 List of Symbols (continued)

Symbol Name Units

Ui mobility, species i m2V- 1s- 1
U mass flow rate kg s-l
U internal energy J mol- 1
v velocity m s-l
V volume m3
v potential scan rate V s-l
w work J
x distance m
XA ion atmosphere thickness m
(Debye length)
XD diffusion layer thickness m
XH hydrodynamic distance parameter m
XR reaction layer thickness m
Xi mole fraction, species i none
Zi charge, species i none
Z impedance n
(l cathodic transfer coefficient none
(l degree of dissociation none
C1.i electrokinetic coefficient variable
(l,~,y,o stoichiometric coefficients none
(l,~ phase labels none
~ anodic transfer coefficient none
y surface tension Nm- 1
'W activity coefficient, species i none
(molar scale)
Yim activity coefficient, species i none
(molal scale)
y,.x activity coefficient, species i none
(mole fraction scale)
Y mean ionic activity coefficient none
Symbols and Units 437

Symbol Name Units

dielectric constant none
Tl coefficient of viscosity kg m-1s- 1 (Pa-s)
Tl overpotential V
l'} polar angle rad
e exp[F(E - EO)IRTJ none
1C conductivity Sm- 1
A reaction zone parameter none
A molar conductivity S m 2mol- 1
Il chemical potential J mol- 1
v kinematic viscosity m 2 s- 1
Vi moles of ion i per mole of salt none
Vi stoichiometric coefficient, species i none
X (DoIDR) 112 none
p resistivity Om
p space charge density C m- 3
a surface charge density C m- 2
't characteristic time s
4> current efficiency none
q> azimuthal angle, phase angle rad
<l> electric potential V
CJ) angular frequency rad s-1
~ zeta potential V
 ELECTROCHEMICAL
DATA

Table A.4 Standard Reduction Potentials at 25C.

Main group elements:

Half-Cell Reaction
2 H + + 2 e- -+ H2(g) 0.0000
Li+ + e- -+ Li(s) -8.045
Na+ + e- -+ Na(s) -2.714
K+ + e- -+ K(s) -2.925
Rb+ + e- -+ Rb(s) -2.925
Cs+ + e- -+ Cs(s) -2.923
Be2+ + 2 e- -+ Be(s) -1.97
Mg2+ + 2e- -+ Mg(s) -2.356
Ca2+ + 2 e- -+ Ca(s) -2.84
Ba2+ + 2 e- -+ Ba(s) -2.92
Al3+ + 3 e- -+ Al(s) -1.67
C02(g) + 2 H+ + 2 e- -+ CO(g) + H20 ~.106
C02(g) + 2 H+ + 2 e- -+ HCOOH ~.199
2 C02<g) + 2 H+ + 2 e- -+ H2C204 ~.475
Pb2+ + 2 e- -+ Pb(s) ~.1251
Pb02(S) + 4 H+ + 2 e- -+ Pb2+ + 2 H20 1.468
N03-+3H++2e- -+ HN02+H20 0.94
N03- + 4 H+ + 3 e- -+ NO(g) + 2 H20 0.96
N03- + 10 H+ + 8 e- -+ NH4+ + 3 H20 0.875
PO(OH)3 + 2 H+ + 2 e- -+ HPO(OHh + H20 ~.276
HPO(OH)2 + 2 H+ + 2 e- -+ H2PO(OH) + H20 ~.499

438
Electrochemical Data 439

Half-Cell Reaction EON

HPO(OH)2 + 3 H+ + 3 e- ~ P(s) + 3 H2O -0.454
P(s)+3H++3e' ~ PH3 -0.111
AsO(OH)s + 2 H+ + 2 e- ~ As(OH)a + H2O 0.560
As(OH)a + 3 H+ + 3 e- ~ As(s) + 3 H2O 0.240
As(s) + 3 H + + 3 e- ~ AsHS(g) -0.225
02(g) + H+ + e- ~ H02 -0.125
02(g) + 2 H+ + 2 e- ~ H202 0.695
H202 + H+ + e- ~ HO + H2O 0.714
H202 + 2 H+ + 2 e- ~ 2 H2O 1.763
&.208 2- + 2 e- ~ 2 8042- 1.96
8042- + H20 + 2 e- ~ 8Os2- + 2 OH- -0.94
28042- +4H++ 2 e- ~ 82062- + 2 H20 -0.25
2 802(aq) + 2 H+ + 4 e- ~ 820S2- + H2O 0.40
802(aq) + 4 H+ + 4 e- ~ 8(s) + 2 H2O 0.50
84062- + 2 e- ~ 2 &.20a2- 0.08
8(s) + 2 H+ + 2 e- ~ H2S(aq) 0.14
F2(g) + 2 e- ~ 2 F- 2.866
CI04- + 2 H+ + 2 e- ~ CIOs- + H2O 1.201
CIOs- + 3 H+ + 2 e- ~ HCI02 + H2O 1.181
CIOs- + 2 H+ + e- ~ CI02 + H2O 1.175
HCI02+2H++2e- ~ HOCI+H20 1.701
2 HOCI + 2 H+ + 2 e- ~ CI2(g) + 2 H2O 1.630
CI2(g) + 2 e- ~ 2 CI- 1.35828
CI2(aq) + 2 e- ~ 2 CI- 1.396
Br04- + 2 H+ + 2 e- ~ BrOs- + H2O 1.853
2 BrOs- + 12 H+ + 10 e- ~ Br2(l) + 6 H2O 1.478
2 HOBr + 2 H+ + 2 e- ~ Br2(l) + 2 H2O 1.004
Br2(l) + 2 e- ~ 2 Br 1.0652
Br2(aq) + 2 e- ~ 2 Br 1.0874
10(OH)5 + H+ + e- ~ 103- + 3 H2O 1.60
2 lOs- + 12 H+ + 10 e- ~ 12(S) + 6 H2O 1.20
440 Appendix 3

Table A.4 Standard Reduction Potentials at 25C (continued)

Main group elements:

Half-Cell Reaction
2HOI+2H++2e- ~ lis)+2H20 1.44
lis) + 2 e- ~ 2 l- 0.5355
Is- + 2 e- ~ 31- 0.536
liaq)+2e- ~ 21- 0.621

Transition and posttransition elements:

Half-Cell Reaction
V02+ + 2 H+ + e- ~ V02+ + H20 1.000
V02+ + 2 H+ + e- ~ \13+ + H20 0.337
\13+ + e- ~ V2+ -0.255
V2+ + 2 e- ~ V(s) -1.13
Cl"2072- + 14 H+ + 6 e- ~ 2 Cr3+ + 7 H~ 1.38
Cr3+ + e- ~ Cr2+ -0.424
Cr2+ + 2 e- ~ Cr(s) -0.90
Mn04- + e- ~ Mn042- 0.56
Mn04- + 8 H+ + 5 e- ~ Mn2+ + 4 H20 1.51
Mn02(S) + 4 H+ + 2 e- ~ Mn2+ + 2 H20 1.23
Mn3+ + e- ~ Mn2+ 1.5
Mn2+ + 2 e- ~ Mn(s) -1.18
Fe3+ + e- ~ Fe2+ 0.711
Fe(phen)3+ + e- ~ Fe(phen)2+ 1.13
Fe(CN)63- + e- ~ Fe(CN)64- 0.361
Fe(CN)64- + 2 e- ~ Fe(s) + 6 CN- -1.16
Fe2+ + 2e- ~ Fe(s) -0.44
Co3+ + e- ~ Co2+ 1.92
CO(NH3)63+ + e- ~ CO(NH3)62+ 0.058
Co(phen)33+ + e ~ Co(phen)3 2 + 0.327
Co(C204)33- + e- ~ CO(C204)34- 0.57
Electrochemical Data 441

Half-Cell Reaction
C02+ + 2 e- --+ Co(s) ....().2:l7
NiOis) + 4 H+ + 2 e- --+ Ni2+ + 2 H20 1.593
Ni2+ + 2 e- --+ Ni(s) ....().257
Ni(OH>2(s) + 2 e- --+ Ni(s) + 2 OH- ....().72
Cu2+ + e- --+ Cu+ 0.159
CuCI(s) + e- --+ Cu(s) + CI- 0.121
Cu2+ + 2 e- --+ Cu(s) 0.340
Cu(NHa)42+ + 2 e- --+ Cu(s) + 4 NHa ....().oo
Ag2+ + e- --+ Ag+ 1.980
Ag+ + e- --+ Ag(s) 0.7991
AgCI(s) + e- --+ Ag(s) + CI- 02223
Zn2+ + 2 e- --+ Zn(s) ....().7626
Zn(OH)42- + 2 e- --+ Zn(s) + 4 OH- -1.285
Cd 2+ + 2 e- --+ Cd(s) ""().4025
2 Hg2+ + 2 e- --+ Hg22+ 0.9110
Hg22+ + 2 e- --+ 2 Hg(l) 0.7960
Hg2CI2(S) + 2 e- --+ 2 Rg(l) + 2 CI- 0.26816

Data from Bard, Parsons, and Jordan (RI3).

442 Appendix 3

Table A.S Biochemical Reduction Potentials

Half-Cell Reaction E'/V

Reduction of a carboxyl group to an aldehyde:
1,3-diphosphoglycerate + 2 e- -0.286
-+ 3-phosphoglyceraldehyde + HP04 2-
acetyl-CoA + 2 H+ + 2 e- ~ acetaldehyde + coenzyme A -0.412
oxalate + 3 H+ + 2 e- ~ glyoxal ate -0.462
gluconate + 3 H+ + 2 e- ~ glucose -0.47
acetate + 3 H + + 2 e- ~ acetaldehyde -0.598
Reduction of a carbonyl group to an alcohol:
dehydroascorbic acid + H+ + 2 e- ~ ascorbate 0.077
glyoxylate + 2 H + + 2 e- ~ glycolate -0.090
hydroxypyruvate + 2 H + + 2 e- ~ glycerate -0.158
oxaloacetate + 2 H + + 2 e- ~ malate -0.166
pyruvate + 2 H+ + 2 e- ~ lactate -0.190
acetaldehyde + 2 H + + 2 e- ~ ethanol -0.197
acetoacetate + 2 H+ 2 e- ~ ~-hydroxybutyrate -0.349
Carboxylation:
pyruvate + C02 (g) + H+ + 2 e- ~ malate -0.330
a-ketoglutarate + C02(g) + H+ + 2 e- ~ iso-citrate -0.363
succinate + C02(g) + 2 H+ + 2 e- ~ a-ketoglutarate + H20 -0.673
acetate + C02(g) + 2 H+ + 2 e- ~ pyruvate + H20 -0.699
Reduction of a carbonyl group with formation of an amino group:
oxaloacetate + NH4+ + 2 H+ + 2 e- ~ aspartate + H20 -0.107
pyruvate + Nl4+ + 2 H+ + 2 e- ~ alanine + H20 -0.132
a-ketoglutarate + NH4+ + 2 H+ + 2 e- ~ glutamate + H20 -0.133
Reduction of a carbon-carbon double bond:
crotonyl-CoA + 2 H+ + 2 e- ~ butyryl-CoA 0.187
fumarate + 2 H+ + 2 e- ~ succinate 0.031
Electrochemical Data 443

Half-Cell Reaction E'/V

Reduction of disulfide:
cystine + 2 H+ + 2 e- ~ 2 cysteine -D.340
glutathione climer + 2 H+ + 2 e- ~ 2 glutathione -D.340
Other reductions of biochemical interest:
02(g)+4H++4e- ~ 2 H20 0.816
cytochrome c (Fe3 +) + e- ~ cytochrome c (Fe 2+) 0.25
FAD+ + H+ + 2 e- ~ FADH -D.20
NAD++H++2e- ~ NADH -D.320
2 H + + 2 e- ~ H2(g) -D.414

Reduction potentials at 25C, pH 7 standard state; data from H. A. Krebs,

H. L. Kornberg, and K. Burton, Erg. Physiol. 1957,49,212.
444 Appendix 3
Table A.6 Some Formal Reduction Potentials

EO'/V
Couple 1MHCI04 1MHCl
Ag(l)lAg( 0) 0.792 0.228 0.77
As(V)1As(III) 0.577 0.577
Ce(IV)/Ce(III) 1.70 1.28 1.44
Fe(IIl)lFe(II) 0.732 0.700 0.68
Ag(l)lAg( 0) 0.792 0.228 0.77
As(V)1As(III) 0.577 0.577
Ce(IV)/Ce(III) 1.70 1.28 1.44
Fe(IIl)lFe(II) 0.732 0.700 0.68
H(I)IH(O) -0.005 -0.005
Hg(II)IHg(1) 0.907
Hg(l)IHg(O) 0.776 0.274 0.674
Mn(IV)/Mn(II) 1.24
Pb(II)lPb(O) -0.14 -0.29
Sn(lV)/Sn(II) 0.14
Sn(Il)/Sn( 0) -0.16

Data from E. H. Swift and E. A. Butler, Quantitative

Measurements and Chemical Equilibria, San Francisco:
Freeman, 1972.

Table A. 7 Reference Electrode Potentials

Electrode EO'IV (dE/dT)/mV K-l

Calomel (0.1 M KCD 0.336 -0.08
Calomel (1.0 M KCD 0.283 -0.29
Calomel (satd. KCl) 0.244 -0.67
Ag/AgCl (3.5 M KCl) 0.205 -0.73
Ag/AgCI (satd. KCl) 0.199 -1.01
Electrochemical Data 445

Table A.8 Molar Ionic Conductivities

Ion AD Ion AD Ion AD

H+ 349.8 Pb2+ 139.0 103- 40.5
Li+ 38.7 Mn 2+ 107. 104- 54.6
Na+ 50.1 Fe2+ 107. Mn04- 62.8
K+ 73.5 Co2+ 110. HC03- 44.5
Cs+ 77.3 Ni 2+ lOB. H2P04- 36.
Nli4+ 73.6 Al3+ 189. HC02- 54.6
(CH3)4N+ 44.9 Cr3+ ~1. CH3C02- 40.9
(C2HS)4N+ 32_7 Fe3+ ~. C2HSC02- 35.8
(C3H 7)4N+ .23.4 OH- 199.2 C6HSC0 2- 32.4
Ag+ 61.9 F- 55.4 C032- 138.6
Mg2+ 106.1 Cl- 76.3 8042- 160.0
Ca2+ 119.0 Br 78.1 &P32- 174.B
Sr2+ 118.9 I- 76.B Cr042- 170.
Ba2+ 127.3 CN- 7B. HP042- 114.
Cu2+ 107.2 N02- 72. C20 42- 148.3
Zn 2+ 105.6 N03- 71.5 P30s3- 25O.B
Cd2+ 108.0 ClO3- 64.6 Fe(CN)63- 302.7
Hg2+ 127.2 ClO4- 67.4 Fe(CN)64- 442.

Conductivities from Robinson and Stokes (B9) and Dobos (H9) in units of
10- 4 S m 2mol- 1, aqueous solutions at infinite dilution, 25 DC.
446 Appendix 3

Table A.9 Solvent Properties

Liquid Vapor Dielectric

Solvent Range/oC Pressure b Constant Viscosity
water 0 3.2 78.4 0.89
propylene carbonate (PC) -49 to 242 0.0 64.4 2.5
dimethylsulfoxide 19 to 189 0.1 46.7 2.00
(DMSO)
N ,N-dimethylformamide -60 to 153 0.5 36.7 0.80
(DMF)
acetonitrile -44 to 82 11.8 37.5 0.34
nitromethane -29 to 101 4.9 35.9 0.61
methanol -98 to 65 16.7 32.7 0.54
hexamethylphosphor- 7to233 0.01 30.d 3.47d
amide (HMPA)
ethanol -114 to 78 8.0 24.6 1.08
acetone -95 to 56 24.2 20.7 0.30
dichloromethane -95 to 40 58.1 8.9 0.41
trifluoroacetic acid -15 to 72 14.4 8.6 0.86
tetrahydrofuran (THF) -108 to 66 26.3 7.6 0.46
1,2-dimethoxyethane -58 to 93 10.0 72 0.46
(glyme, DME)
acetic acid 17 to 118 2.0 6.2d 1.13
p-dioxane 12 to 101 4.9 22 1.2

a Data at 25C from J. A. Riddick and W. B. Bunger, Organic Solvents,

3rd ed, New York: Wiley-Interscience, 1970.
b Vapor pressure in units of kPa.
C Viscosity in units of 10-3 kg m-ls-l.
d 20C.
Electrochemical Data 447

Table A.1O Potential Range for Some Solutions

Potential RangeN (us. s.c.e.)

Solvent Electrolyte Pt Hg
Propylene carbonate E4NCI04 1.7 to-1.9 0.5to-2.5
Dimethylsulfoxide NaC104 0.7 to-1.8 0.6to-2.9
E4NCI04 0.7 to-1.8 0.2to-2.8
BU4NI -0.4to-2.8
Dimethylformamide NaCI04 1.6to-1.6 0.5to-2.0
E4NCI4 1.6to-2.1 0.5to-3.0
E4NBF4 -to-2.7
BU4CI04 1.5 to-2.5 0.5to-3.0
BU41 -0.4 to-3.0
Acetonitrile NaCI04 1.8to-1.5 0.6to-1.7
E4NCI04 0.6to-2.8
E4NBF4 2.3 to- -to-2.7
BU4NI -O.6to-2.8
BU4PF 6 3.4to-2.9
Acetone NaCI04 1.6 to-
E4NCI04 -to-2.4
Dichloromethane BU4NCI04 1.8 to-1.7 0.8to-1.9
BU4NI 0.2to-1.7 -O.5to-1.7
1,2-Dimethoxyethane BU4NCI04 0.6to-2.9

Data from C. K. Mann, Electroanal. Chem. 1969,3, 57.

 4
-cz
><
LAPLACE TRANSFORM
W
Q. METHODS
Q.
cc

The method of Laplace transforms provides a powerful aid to the

solution of differential equations. l The method is particularly useful in
solving the coupled partial differential equations which are encountered
in electrochemical diffusion problems. Here we will introduce the
technique and demonstrate the method by deriving a few of the results
quoted in the text.
Laplace Transformations
The Laplace transform of a function F(t) is defined by

f(s) = L- F(t) exp(-st) dt (A. I)

Not all functions possess a Laplace transform. Clearly, F(t) must be

finite for finite t and F(t) exp(-st) must go to zero as t ~ The Laplace
00.

transformation can be thought of as an operation in linear algebra:

f(s) = L[F(t)]
which is reversible by the inverse operation
F(t) = L-llfls)]
The Laplace transformation is a linear operation, that is, sums or
differences of functions are transformed as
L[F(t) + G(t)] = f(s) + g(s) (A.2)
Multiplicative constants are unaffected by Laplace transformation:
L[a F(t)] = a f(s) (A.3)

1 F. E. Nixon, Handbook of Laplace Transformations: Tables and Examples,

Englewood Cliffs, NJ: Prentice-Hall, 1960; R. V. Churchill, Modern Operational
Mathematics in Engineering, 2nd ed, New York: McGraw-Hill, 1963; P. A.
McCollum and B. F. Brown, Laplace Transform Tables and Theorems, New York:
Holt, Rinehart, and Winston, 1965; M. G. Smith, Laplace Transform Theory,
London, D. Van Nostrand, 1966.

448
Laplace Transform Methods 449
The Laplace tranform of a constant is
L(a) = als
Functions of variables other than t behave as constants in the
transformation
L[H(x)] = H(x)ls
The utility of Lapace transforms in the solution of differential equations
is that the transform of a derivative is a simple function
L[dF(t)/dt] = s f{s) - F(O) (AAa)
L[d 2F(t)/dt 2 ] = s2f{s) - s F(D) - (dFldt)o (A4b)
A short selection of Laplace transforms are found in Table All.
Two properties of the Laplace transformation are sometimes useful
in finding the inverse transform. The shift theorem allows the zero of s
to be displaced by a constant:
L-llfts + a)) = F(t) exp(~t) (A5)
The convolution theorem is useful when the inverse transformation of
f(s)cannot be found, but f(s) can be written as the product of two
functions, f{s) = g(s)h(s), the inverse transforms of which can be found.
If
G(t) = L-lfg(s)]
H(t) = L-l[h(s)]

then

(A.6)

The specific solution to a differential equation depends on the initial

and boundary conditions on the problem. The solution to a differential
equation using Laplace transform methods in general follows the steps:
(1) Transform the differential equation to remove derivatives with
respect to one of the variables. An ordinary differential equation
will then be an algebraic equation and a partial differential
equation with two independent variables will become an ordinary
differential equation.
(2) Transform the initial and boundary conditions.
(3) Solve the resulting system of algebraic equations or ordinary
differential equations, using the transformed boundary conditions
to evaluate constants.
(4) Take the inverse transform to obtain the solution to the original
differential equation.
450 Appendix 4

Table A.ll Some Laplace Transforms

F(t) f{s) F(t) f{s)

a (a constant) als sin at a

a 2 + s2

t s-2 cos at s.
a 2 + s2
t n- 1 _a_
s-n sinh at s2-a 2
(n -I)!
~
l/'fii s-1I2 cosh at s2-a 2
_I_
2fiTiC s-3/2 exp at s-a
F(t) f{s)
exp(at) - exp(bt) 1
a-b (s-a)(s-b)
ifI
exp(at) erfW -IS(s - a)
1
exp(at)[l- erfYat]

1- exp(at)[l- erfYat] s (-IS + ifI)

~ exp(-l/4at) exp (-Vs/a)
1tat 3
.b
,1tt
exp(-l/4at) (l/-IS) exp (-Vs/a)

1- erf(lJ2W) (1/s) exp (-V sial

Consider as an example the ordinary differential equation

d2F(t) = a 2F(t)
dx 2
with boundary conditions F(O) = 0, (dF/dx)o = a. Taking the Laplace
transform, using eqs (A.2) - (A.4), we have
s2f{s) - a + a 2f(s) = 0
from which we obtain
Laplace Transform Methods 451
(ts) =
a
a 2 + s2
The inverse transform from Table A,11 gives
F(t) = sin at
We really didn't need a fancy method to solve this problem, but other
cases arise which are not quite so simple.

Solutions of the Diffusion Equation

Now let us apply Laplace transform methods to the solution of the
one-dimensional diffusion equation
aC(X,t) = D a2C(X,t) (A.7)
at ax2

We can do step (1) of the solution procedure in general. Writing the

Laplace transform of C(x,t) as c(x,s), the transformed diffusion equation
is
2
s C(X,s) _ C(X,O) = D a c(x,s) (A,B)
ax2

We need initial and boundary conditions to solve eq (A,B), and these differ
from one problem to another.
Derivation of eq (3.22). Let us start with the problem posed in
3.3. We considered a solution layered on pure solvent so that the initial
condition was C =C* for x < 0, C = 0 for x > O. The boundary condition is
C -7 C* as x -7 - 0 0 , C -7 0 as x -7 +00. We will divide the problem into two
regimes, - 0 0 < X < 0 and 0 < x < +00, with the requirement that C(x,t) and
J(x,t) be continuous at x = 0 for t > O. Thus for x > 0, we have

D a2c(x,S) () 0
sex,s =
ax 2
the general solution to which is
c(x,s) =A(s) exp(-YslD) + B(s) exp(+YslDx) (A.9a)
where A(s) and B(s) are to be determined from the boundary conditions.
One of the boundary conditions requires c(x,s) -7 0 as x -7 00 so that B(s) =
O.
For x < 0, eq (A,B) gives

D ic'(x,s)
dX 2
s
,
C (x,s) +
C*
=
452 Appendix 4

The general solution to this differential equation is

c'(x,s) = C*ls +A'(s) exp(-VsIDx) +B'(s) exp(+VsIDx) (A.9b)
The boundary condition requires c'(x,s) ~ C*ls as x ~ --00 so thatA'(s) = 0.
We now apply the continuity restraints to determine A(s) and B'(s). If
C(O,t) = C'(O,t), then C(O,S) = c'(O,s). Thus we have
C(O,S) =A(s)
c'(O,s) = C*ls + B'(s)
so that
A(s) - B'(s) = C*ls
The equal fluxes at x = means that
dC(O,s) dC'(O,s)
---=
dX dX
Differentiating eqs (A.9) and setting x = 0, we have
-VsIDA(s) = +VsIDB'(s)
Thus
A(s) =-B'(s) =C*/2s
Equations (A.9) then become

C(x,s) = ~ exp (- fk Ixl) x>o

c'(x,s) = c;- - ~; eXP(-fklxl) x<o

Taking the inverse transforms, we have
C(x,t) =~[1-erf~] x>o
2 2Wt

C'(x,t) =C* - ~[1-

2
erf---L-]
2Wt
x<o

Since the error function is an odd function of the argument, i.e., erf(-'I') =
-erf('I'), we see that these two functions are in fact identical:
C(x,t) =C*2 [1- erf 2,Dt
.~]
(3.22)

Derivation of eqs.(4.2). In typical electrochemical applications of

the diffusion equation, the concentrations of the diffusing species are
uniform at the beginning of the experiment, C(x,O) = C* and, at later
Laplace Transform Methods 453
times, approach the initial concentration at sufficient distance from the
electrode, C(x,t) ~ C* as x ~ 00. With the electrode as x = 0, we need not
consider negative values for x. Thus eq (AB) is
2
D a c(x,s) ( ) C* - 0
s C x,s + -
ax 2
The solution consistent with the boundary condition (at x ~ 00) is
c(x,s) = 9- + A(s) exp (- VIi x) (A10)

where A(s) must be determined by the boundary condition at x = O. Ifwe

have two species, 0 and R, which are involved in an electrode process,
each transformed concentration will have the form of eq (A.10). If the
initial concentrations are Co(x,O) = Co*, CR(O,t) = 0, then eq (A.10) gives
Co(x,s) = Cf +A(s)exp(-ffox) (Alla)

CR(X,S) = B(s) exp (- ~ DR x) (Al1b)

For a reversible electrode process, the surface boundary conditions are:

(1) the concentration ratio atx = 0, governed by the Nernst equation
Co(O,t) = e = exp nF(E - EO) (A.12a)
CR(O,t) RT
and (2) the continuity restriction
Jo(O,t) = - JR(O,t)
or
-Do aCo(O,t) = DR aCR(O,t) (A12b)
ax ax
The boundary conditions transform to
coCO,s) = e CR(O,S) (A.13a)
and
-Do o<:o(O,s) =DR aCR(O,S) (A13b)
ax ax
Differentiating co(x,s) and CR(X,S) with respect to x and setting x = 0, we
have on substitution in eq (A13b),
YsDo A(s) = - YSDR B(s)
454 Appendix 4

or
B(s) =- ~A(s) (AI4)
where
~= "IDo/DR
Setting x = 0 in eqs (All) and substituting in eq (A.I3a) gives
Co*/s + A(s) = eB(s) = - ~e A(s)
so that
A(s) =_ Co*
+ ~e)
s(1
Thus the transformed concentrations are
Co*
( ) = -s-
cox,s [1 exP{-Ys7i50x}]
1 + ~e

CR(X,S) = ~~o* exp{-Vs7l5'Rx}

1 + ~e
Taking the inverse transform, we have
( ) -C
Cox,t *~e+erf(x/2YDot)
- 0 (4.2a)
1 + ~e

CR(x,t ) -- C0 * ~ [1- erf(x/2Y DRt }] (4.2b)

1 + ~e

Derivation of eq (4.20). The Laplace transform of eq (4.19) is

( ) - C* = D [d C(r,S) + .2.
2
scr,s rdC(r,S)]
--
dr 2 dr
This differential equation can be converted to a more familiar form by
the substitution
vCr,s) = r c(r,s)
2
s vCr,s) _ rC* = D d vCr,s)
dr 2
Remembering that the range of r is ro to 00, the solution analogous to eq
(AIO) is
Laplace Transform Methods 455
Reverting to the transformed concentration function, we have
c(r,s) = ~ + A~) exp [-VI (r-rol]
This expression is consistent with the boundary condition
C(r,t) -+ C*, c(r,s) -+ C*/s as r -+ 00

The surface boundary condition,

C(ro,t) = 0, t > 0
transforms to c(ro,s) = O. Thus we find A(s) = -roC*/s and have
c(r,s) = ~ II-~exp [-VI (r-rol])
Taking the reverse Laplace transform, we have
C(r,t) = C* [I-E.Q(I- erf r- ro)~ (4.20)
r 2Wt~
Derivation of eq (4.26). In double potential step
chronoamperometry, the electrode is polarized for a time 't at a
sufficiently negative potential that C o(O,t) = 0; the potential is then
stepped to a positive potential so that CR(O, t - 't) = O. This problem is
easily solved using Laplace transforms by noting that eq (4.2b) gives the
initial concentration distribution of R for the second potential step. Thus
substituting eq (4.2b) with t = 't and e = 0 into eq (A.IO), we have
~C *
CR(X,S) = +[I-e1~)] +A(S)ex~-ff.x)
where the transform variable s corresponds to (t - 't). The boundary
condition CR(O,t) =0 for t > 't implies that CR(O,S) = O. Thus
(cCo*ls) + A(s) = 0
so that
A(s) = - ~Co*ls
We need the flux of R at the electrode in order to calculate the current.
Thus we compute the derivative with respect to x
CkR(O,S) ~Co* ~Co*
---=- +--
ax s "1tDR't YDRS
and take the inverse transform to obtain
aCR(O,t) ~Co* ~Co*
-a-x- = - "1tDR't + J"=1tD~R(;::;:t=-='t=<=)
456 Appendix 4
Since the current is

we get
i = nFACo*fl5Qiii(-L-..l..) t >t (4.26)
vt-t Yt
Derivation of eq (4.27). In a constant current experiment such
as chronopotentiometry, the flux of 0 at the electrode surface is constant
up to the transition time when Co(O,t) -+ 0 and the potential swings
negative. Thus the boundary condition is
Do OCo(O,t) ---.L
ax nFA
Taking the Laplace transform, we have
Do aco(O,s) =~
ax nFAs
=0, we have
Differentiating eq (A.10) and setting x
-Doh/Do A(s) =nJAs
Solving for A(s) and substituting in eq (A. 10) with x =0:
cO<O,s) =C0 * .
I
S nFAsYsDo
Taking the inverse transform, we get
CO<O,t) =Co* _ 2ifi
nFAVreDo
Apparently, Co(O,t) goes to zero when
nFA VreDo Co* =2ifi
so that the transition time is given by
fC = nFA VreDo Co*/2 i (4.27)
Derivation of eq (4.29). For a linear potential scan experiment,
the boundary conditions are similar to those used in deriving eq (4.2)
except that the potential is time-dependent. Thus we can proceed as
before up through eq (A.14), but A(s) cannot be so simply evaluated. We
can write the transformed current as
Laplace Transform Methods 457

i(s) = nFADo (aco(x,s))

ax %=0
Substituting eq (A.lla) for CO(x,s), we have
i(s) = - nFAV sDo A(s)
Solving for A(s), substituting into eqs (A.ll), and setting x = 0, we have
Co i(s)
co(0)
,s = - - - - - = =
s nFA VsDo
i(s)
CR(0 ,s )
= ---'--===-
nFA VSDR
We now use the convolution theorm, eq (A.6), with h(s) = i(s), g(s) = s-1/2 to
obtain

Co(O,t) = Co. - 1
nFA Y7r.Do
t i(t) dt
10 yt-t

For a nernstian process, the ratio of the surface concentrations is

Co(O,t) = 9(t) = exp nF(Ei - vt _EO)
CR(O,t) RT
Substituting the surface concentrations into this expression and
rearranging, we have

nFA fit1JO Co = t ~dt (4.29)

1 + ~9(t) 10 yt-t
where ~ = VDo/DR.
Derivation of eq (5.31). We are concerned here with the flux of 0
at the electrode surface when Co(O,t) = 0 and 0 is formed from Y in an
equilibrium prior to electron transfer. We start with diffusion equations
in Y and 0, similar to eqs (5.2) but including the time derivatives. With
the new functions of eqs (5.3), we obtain the differential equations
aC(x,t) = D a2C(X,t)
at ax 2
458 Appendix 4

dC'(X,t) = D iC'(x,t) _ (k i + k_l ) C'(X,t)

dt dx 2
We will assume that the equilibrium strongly favors Y so that K = kl/k_1
1 . Taking Laplace transforms, we obtain simple differential
equations which are readily solved to give
c(x,s) = C*/s + A(s) exp -Ysil5 x
c'(x,s) = A'(s) exp -yes + k_I)ID x
With eq (5.6b), the boundary condition, CO(O,t) = 0, gives
CO(O,s) = 6[-9-+ A (S)] -l;K A '(s)=O
Since Y is not electroactive, Jy(O,t) = 0 and eq (5.6a) gives

( dCO) =-A(s)~rr _A'(S).yS + k-I =0

dXx=o VD D
Solving the simultaneous equations, we have
A(s) = C* = _ A'(s) K 2s + Kki
S(l + /
A /

S ) KV s
'V K% + Kki
Neglecting K compared with 1 and assuming that K 2 s Kkl,l the
transformed flux of 0 is
;o(O,s) = -C* w s +fKki.
YKklS
Taking the inverse Laplace transform and converting to current, we
have
(5.31)

Derivation of eqs (6.36). Allowing for a finite electron transfer

rate, the surface boundary conditions are

D o dCo(O,t) -- - D R dCR(O,t) -- k c C0 (0)

,t - k a CR(0 ,t)
dx dx
Transforming the boundary conditions, we again have eq (A.13b), but
instead of eq CA.13a), we get

1 This approximation is equivalent to neglecting the very small amount of 0

initially present near the electrode; thus the result if only approximate at short times.
Laplace Transform Methods 459

Do oco(O,s) =kceo(O,s) - kaCR(O,S)

ax
Thus, with co(x,s) and CR(X,S) given by eqs (A.ll), and B(s) = -x A(s), we
have
- VsDo A(s) = kc[Co*ls +A(s)] + ka~A(s)
or
A(s) = _ keCo*
VDos(A +-IS)
where
A = kc!V Do + ka/V DR
Substituting A(s) into eqs (A.ll) with x = 0, we have
coCO,s) = C~* [1- Wo ke
Do (A +-IS)
]

CR(O,s) = keCo*
VDR seA + -IS)
Taking the inverse transforms, we have
Co(O,t) = Co* - kcCo* (1- exp(A2t}[1- erf(A Vt)))
'A.VDo

CR(O,t) = keCo* !1-eXP('A.2t}[1-erf('A.Vt)J)

'A.VDR
Defining
(('A.Vt) = 'A.fi[i exp('A.2t)[1- erf('A.Vt)]
we have
Co(O,t) = Co* _~[l_t{'A.Vt)] (6.36a)
1 + ~9 'A.fi[i

CR(O,t) = ~Co* [l_t{'A.Vt)] (6.36b)

1+~9 Afi[i
where we have used the relation kalke = 9.
Derivation of eqs (6.47). When the boundary condition is
determined by a sinusoidal current

let) = 10 sin rot

460 Appendix 4

the flux of 0 at the electrode surface is

- Do dCO(O,t) =- ~ sin rot
dX FA
Taking the Laplace transform, we have
Do dCO(O,S) = 10 0)
dX FA s2+ 0)2
Substituting the first derivative of eq (A.ll), evaluated at x = 0, we get
_ VsDoAs = 10 0)
FA s2+ 0)2
Solving for A(s) and substituting in eq (A.ll) with x = 0, we have
co(O,s) = Co* _ 10 [ 0) ]
s FAVDo VS(s2 + 0)2)
The inverse transform of this function cannot be found in tables, so we
have recourse to the convolution theorem, eq (A.6), taking
g(s) = _ 0 ) _ => G(t) = sin rot
s2+c02
h(s) = l => H(t) = _1_
VS f1ti
Thus

L-1 [ 0) ] = t_1- sinroCt-'t)d't

VS(s 2 + co2) Jo iii
U sing the trigonometric identity
sin roCt - 't) = sin rot cos CJ)'t - cos rot sin CJ)'t
the integral becomes

sin rot
fit
t ~ cos
Jo ft
CJ)'t d't - ~ t ~ sin
fit Jo ft
CJ)'t d't

The factor of 11ft in the integrand represents a transient response to the

application of the sinusoidal current which dies off to give a steady-state
sinusoidal variation in the concentrations. Since we are interested only
in the steady state, the limits on the integrals can be extended to infinity,
obtaining
Laplace Transform Methods 461

Thus we have
CO<O,t) = Co. _ 10 {sin rot - cos rot)
FAY2roDo (6.47a)
Equation (6.47b) for CR(O,t) results from a similar development.
 5
-c>< DIGITAL SIMULATION
z
W
Il.
METHODS
Il.
<

The theoretical description of an electrochemical experiment

usually requires the solution of a set of coupled partial differential
equations based on the diffusion equation. In experiments which
include forced convection, such as r.d.e. voltammetry, a driving term is
added to each equation as in eq (4.43). When a diffusing species is
involved in a chemical reaction, reaction rate terms must be added to the
equation describing its concentration. The set of equations often has
time-dependent boundary conditions and can be devilishly difficult to
solve. In some fortunate cases, such as those treated in Appendix 4, the
use of Laplace transforms leads to closed-form analytical solutions, but
more often solutions are obtained in terms of infinite series or
intractable integrals which must be evaluated numerically. In the
1950's and 1960's, a great deal of effort was expended by theorists in
obtaining mathematical descriptions of electrochemical experiments.
While the results provide an invaluable aid to understanding (we have
quoted many of these results), one often finds that the theoretical results
available in the literature do not quite cover the experimental case at
hand. If the problem seems to be of sufficient generality and interest, it
may be worthwhile attempting an analytical approach. More often,
however, electrochemists have turned to the digital computer to
simulate experiments. The details of digital simulation are beyond the
scope of this text, but a brief outline of the strategy is in order. For
further details see reviews by Feldberg,l Maloy,2 or Britz.3
In general the problem to be solved involves equations of the form
2
ae a C- + kInetIc. and/or d
- =D - nvmg terms
at ax 2
together with a set of initial and boundary conditions. The
concentrations are functions of time and distance from the electrode and

1 s. W. Feldberg, Electroanalytical Chemistry 1969, 3, 199.

2 J. T. Maloy in Laboratory Techniques in Electroanalytical Chemistry, P. T.
Kissinger and W. R. Heineman, eds, Kew York: Marcel Dekker, 1984.
3 D. Britz, Digital Simulation in Electrochemistry, Lecture Notes in Chemistry, Vol.
23, Heidelberg: SpringerVerlag, 1981.

462
Digital Simulation Methods 463

the general strategy in a digital simulation is to divide the time and

distance axes into discrete elements of size ot and Ox, respectively. The
first step in the development of a simulation program is to convert the
differential equations into finite difference equations.
Thus Fick's first and second laws,
J(x,t) = -D aC(x,t)
ax
aC(x,t) aJ(x,t)
---=----
at ax
which describe the diffusional part of the problem, can be written in
approximate form in terms of the finite differences, Ox and ot:
J(x,t) '" -D C(x + 0xI2,t) - C(X - 0xI2,t)
Ox
C(X,t + ot) - C(x,t) J(X + 0xI2,t) - J(x - &X/2,t)
ot Ox
Combining the two expressions, we have
C(x,t + Ot) = C(x,t) + .D.aL[C(x + Ox,t) - 2C(x,t) + C(X - Ox,t)] (A.15)
(axf
If the spatial boxes, of equal width Ox, are labeled 1,2,3 .. .j. .. and the time
boxes of width ot, are labeled 1,2,3 ... k ... we can rewrite eq (A.15) as
C(j,k+l) = C(j,k) + D[C(j+I,k) - 2C(j,k) + C(j-l,k)] (A. 16)
where D = Dotl(ox)2 is a dimensionless diffusion coefficient. Thus eq
(A.16) models the diffusion process as follows: during the time interval
ot, an amount DC(j,k) moves from boxj to each of the adjacent boxes. But
meanwhile DC(j-I,k) and DC(j+l,k) move from the adjacent boxes into
box j; the change in concentration in box j is the sum of these
contributions. Clearly, we can't take more out of a box than was there to
begin with, so that we require D s; 0.5.
The net flux at the electrode (related to the current) is determined by
the changes in concentrations in the j = 1 box (adjacent to the electrode)
which are required to satisfy the surface boundary condition. For
example, for a reversible electrode process, the boundary condition
corresponds to the surface concentration ratio CoiCR = e, specified by the
Nernst equation. The equilibrium surface concentration of 0 can be
written as
Co(eq) =_e_[Co(I,k) + CR(I,k)]
1+8
464 Appendix 5
The net flux then corresponds to the difference between Co(1,k) and the
equilibrium surface concentration
SCo(k) =Co(1,k) - 9CR(1,k) =- SGR(k)
1+9
The surface concentrations then are corrected to
Co(1,k + 1) =Co(1,k) - SGo(k) (A.17a)
CR(1,k + 1) =CR(l,k) + SCo(k) (A. 17b)
Since the current is given by
i =nFAJo(O)
the simulation current is proportional to SCo(k).
In an experiment where the electrode potential is time-dependent
(e.g., cyclic voltammetry), the potential (and thus the concentration ratio
9) will be different for each time increment. If the simulated experiment
involves two or more electron-transfer processes, these are handled
independently and the current contributions added to get the total
current. Experiments with slow electron-transfer kinetics can be
simulated by including Butler-Volmer electron-transfer rate equations
in place of the above expression which assumes that equilibrium is
attained instantaneously.
If species A is consumed in a first-order chemical reaction,
A~B

the contribution to the rate equations is

aCB(X,t) = _ aCA(X,t) = kCA(X,t)
at at
In terms of the finite differences, these expression are
CB(X,t + at) - CB(X,t) =_ CA(X,t + at) - CA(X,t) = kCA(x,t)
at at
or, using the indicesj and k,
CAV,k+1) = CAV,k) - kCAV,k) (A.1Ba)
CBV,k+1) =CBV,k) + kCAV,k) (A.1Bb)
where k = kSt is the dimensionless rate constant. In practice, k must be
small (~ 0.1) in order to accurately model the system; for a given value of
k, this places a restriction on 8t. This restriction can be somewhat
relaxed (k ~ 1) by using an analytical solution for the extent of reaction
during a time increment, e.g., for a first-order process
(A.19a)
Digital Simulation Methods 465

CB(j,k+l) = CB(j,k) + CA(j,k) [1- exp (-k)] (A. 19b)

Analytical expressions can be used for more complex reaction schemes,

or, for still more complex schemes, the extent of reaction can be
estimated using the modified Euler method. 1
For a cyclic voltammetry simulation, the time increment is
determined either by the scan rate with v ot '" 1 mV, or, when coupled
chemical reactions are considered, by the rate constant. The number of
time increments to be used in the simulation is determined by
nt = tlot (A.20)
where t is the total time of the experiment to be modeled. The size of the
spatial increment is determined by
&cD- o-tlD
= yr- - (A.21)

If the solution is isotropic at the beginninuf the experiment, the

diffusion layer grows to a thickness of about 6Y Dt during the time of the
experiment. Thus the number of spatial boxes required in the
simulation is determined by
nx&c = erlDnt Ot
or
nx = 6V Dnt &X&cf
nx = 6VDnt (A.22)
or nx '" 4 fflt ifD = 0.45.
Even with the use of analytical expressions such as eq (A.19) to
model the effects of chemical reactions, nt can be very large for schemes
with fast reactions. Since computer execution time increases as the
product of nt and nx, there is a practical upper limit to rate constants.
One solution to this problem is to use variable-width increments in the
simulation. For very fast reactions, the reaction layer, XR, is thin and, in
the simulation, most of the action takes place in the first few spatial
boxes adjacent to the electrode. Thus some saving in execution time can
be realized if the size of the spatial boxes is allowed to increase with
increasing distance from the electrode. 2 This approach leads to a
different D for each box and a somewhat more complex diffusion
algorithm. A still more efficient approach is to expand the time grid as
well for boxes far from the electrode. 3 Thus boxes in which not much is
happening are sampled less frequently.
The overall structure of the simulation program then is as follows:

1 D. K. Gosser and P. H. Rieger, Anal. Chern. 1988,60, 1159.

2 T. Joslin and D. Pletcher, J. Electroanal. Chern. 1974,49, 171.
3 R. Seeber and S. Stefani, Anal. Chern. 1981,53, 1011.
466 Appendix 5
(1) Set concentrations to initial values.
(2) Correct each concentration in each box for the results of the
chemical reactions using eqs (A.1B) or (A.19).
(3) Correct each concentration in each box for the results of diffusion
using eq (A.16).
(4) Change the concentrations in box 1 to satisfy the surface boundary
condition, e.g., using eqs (A.17) for a nernstian process; the changes
correspond to the flux and thus to the current.
(5) Go to the next time increment and adjust time-dependent
parameters such as the electrode potential.
(6) Repeat steps (2) - (5) for the required number of time increments.
 6
-zc>< ANSWERS TO
W
Il.
SELECTED PROBLEMS
Il.
<C

U (a) PtIFe 2+, Fe3+) I I Mn04-, Mn2+, H+IPt

(b) Fe3+ + e- ~ Fe2+
Mn04- + 8 H+ + 5 e- ~ Mn2+ +4 H20
(c) 5 Fe 2+ + Mn04- + 8 H+ ~ 5 Fe3+ + Mn2+ + 4 H20
(d) EO = 1.51- 0.771 = 0.74 V
(e)E =0.56 V
(f) !lGo =-357 kJ mol-I, K =3 x 1062

1.2 (a) 1.0662 V

(b)-O.607V
(c)-O.76V

1.4 Ksp =1.6 x 10-8

1.5 Ksp =4.5 x 10-18, pH =7.00

1.7 E =0.077, 0.085, 0.107, 0.145, 0.302,0.458,0.491 V

1.8 1.27 x 10-4 M

1.9 K =9.8 x 1018

LlO (b) pH 5.0

lJ.1 flux = 2.2 x 10-3 mole Na+ s-l; firing rate =2.2 s-l
L12 (a) E' =+0.043, +0.353, -0.154 V
(b) !lG' ;;; -8.3, -68.1, +29.7 kJ moP
(c) K =28, 8.6 x 1011, 6.2 x 10-8

L13 (a) !lGo ;;; -130 kJ mol- 1

(b) !lGo =-76 kJ mol- 1
(c) !lGo =-206 kJ mol- 1

Ll4 (a) !lGo =-35 kJ mol- 1

467
468 Appendix 6

(b) !l.GO = +234 kJ mol- 1

(e) !l.Go = -458 kJ mol- 1

1.15 pH = 10.386 0.008

1.16 [Na+] = (1.12 0.03) x 10-4 M

1.17 (a) kH Na = 7.8 x 10- 12

(b) pH 11.19 solution would give apparent pH 11.14

1.18 (a) Zn(s) + 2 OH- ~ ZnO(s) + H20 + 2 e-

Ag20(S) + H20 + 2 e- ~ 2 Ag(s) + 20H-
Ag20(S) + Zn(s) ~ 2 Ag(s) + ZnO(s)
(b) 1100 J g-1

2.8 (a) Qoo = 2.0 IlC

(b) io = 1.0 rnA
(e) t = 0.092 s

2.9 (a) y(NaCl)

(b) y(NaF)fy(NaCl)
(e) y(NaF)

2.11 Y(exptl) = 0.905, 0.875, 0.854, 0.826, 0.807, 0.786

Y(eq 57) = 0.889, 0.847, 0.816, 0.769, 0.733, 0.690
Y(eq 56) = 0.903, 0.872, 0.851, 0.821,0.800,0.776

2.12 [KOH] = 0.988 M, y = 0.742

2.14 E = 0.767 V

3.1 (a) L fA = 29.05 m- 1

(b) A = 14.66 x 10-4 S m 2mol- 1
(e) A = 390.7 x 10-4 S m 2mol- 1
= =
(d) ex 0.0375, K 1.5 x 10-5

3.2 N = 133.4 x 10-4 S m 2mol- 1

3.3 s(calc) = 2.88 x 10-4 S m1l2mol-3/2
s(expt) = 3.03 x 10-4

3.4 s = 1.94 x 10-3 S m1l2mol-3/2

3.5 0.203
Answers to Selected Problems 469

3.6 1.4 x 10-4 M

3.7 K = 1.6 x 10-4

3.8 u = 1.046 x 10-7, 1.145 x 10-7 m2V- 1s-1
r = 274, 334 pm
f = 4.60 x 10-12, 5.60 x 10- 12 kg s-l
D = 8.96 x 10- 10, 7.36 x 10- 10 m2s- 1

3.12 D = 2.45 x 10- 11 m 2s- 1, t '" 6.5 years

3.13 D = 1.59 x 10-9 m 2s-1

3.14 teu = 0.366

3.16 [Ba(OH)2] = 0.0422 M, A = 411 x 10-4 S m 2mol- 1

3.18 [Na+]a = 0.0319 M, [Na+]~ = 0.0281 M, ~<l> = 3.3 mV

4.4 E1I2 = 0.764 V

4.5 A square wave signal is required.

4.7 (a) Gain> 10 4

(b) Gain> 4 x 104
(c) Scan rate is 2 ppm smaller when output voltage is -1 V.
(d) i = 100 j.4A, RcelJ < 10 kn, nominal current correct to 0.001%

4.8 Co = 0.14 mM

4.12 4.75 j.4A

4.14 (a) El/2 = -0.693 V

(b)R = 1480 n

4.15 Diameter greater than 0.5 mm

4.16 Electrode radius less than about 2.3 ~

4.20 13 '" 2.4 eV (Figure 4.42a), 13 '" 2.1 eV (Figure 4.42b)

4.26 13 '" 4 x 10 12

4.27 (a) p =2, El/2 =-0.258 V

(b) 13 "" 1035
470 Appendix 6

5.1 k1K = 0.008 s-l

5.2 (a) CA> 10-6 M

(b) A = 1 cm2

5.7 (a) (iL - i)/i = 82(1 + 28 1)/(2 + 82)

(b) E1I2 = (E 1 + E2)/2
(c) The Heyrovsky-Ilkovic equation is obtained when E2 E1
(d) E3/4 -E1/4 = 42.9,33.8,30.3,28.5 mV for E2 -E1 = 0, 50,100,
and 200 mY. The Tomes criterion for a reversible two-electron
wave gives 28.2 mY.

5.8 k = 0.8 s-l

5.10 (b) k = 1.0 s-l

5.11 (a) 60
(b) 1.3
(c) 5.1

5.12 (a) DEl/2 = 17.8,61.6 mV

(b) DEl/2 = 101.9,41.8 mV

6.2 i - nFA ( kcCo* - kaCR* )

- 1 + kalkn + kclkn

6.5 Jo = 0.0079 A m-2 , (Xapp = 0.58, ko = 2.2 x 10-10 m s-l

6.9 (a) E1I2 _EO = -24.7 mV

(b) kolkn = 0.141

6.10 (b) ko = 2.1 x 10-4 m s-l

6.12 ko = 5.8 x 10-5 m s-l

6.13 Resistive component: Rs = IZrl cos cp

Capacitive component: 1/roCs = IZrl sin cp

6.14 (b) Width at half height = 90.6 mY.

6.15 (b) Width between extrema = 67.6 mY.

6.16 (a) ko s 10-5 m s-l
(b) ko s 0.0002 m s-l
(c) ko s 0.002 m s-l
Answers to Selected Problems 471

7.2 t = 27.5 days

7.3 (a) 22 min

0.10, 0.14, and 0.12 mM at t = 5, 10, and 25 min
(b) GB(t) =

7.6 126C

7.7 (a)0.234C
(b)48.5 J.!M

7.8 (a) R = 1000 Q

(b) Rcell < 9 kQ

7.9 3.51 roM

7.10 5-mL sample, 2 rnA current give t = 241 s, uncertainty is 0.6%

7.12 Hydrogen reduction current: j = 0.27 A m- 2 on Pt (cp = 0.997),j = 1.9

rnA m- 2 on Cu (cp = 0.9992)

7.13 Optimum current = 133 A

Cost = (raw materials + capital and labor + energy)
Cost = (1.00 + 0.84 + 0.91) = $2.75 per kilogram
With doubled energy costs, optimum current = 91 A
Cost = $3.57 per kilogram

7.15 (a) Ec = -0.73 V, Corrosion rate = 0.5 mg Zn m- 2 s- l , Hydrogen

evolution rate = 0.18 mL m- 2 s- l
(b) Corrosion rate = 2.2 mm yearl
 AUTHOR INDEX

An author's work is mentioned on page numbers given in roman type,

biographical sketches on page numbers given in bold, and literature
citations on page numbers in italics.

Abruiia, H. D. 429 Britz, D. 462

Adams, R. N. 171,237,286,309, 428 Brooks, M. A 236, 239
Alberts, G. S. 293, 309 Brown, B. F. 448
Albery, VV.J.236,239,277,309,42~430 Bronsted, J. N. 98, 105
Alder, R. 253,308 Bruckenstein S. 261,309
Allendoerfer, R. D. 261,309,322,367 Buck, R. P. 40, 54
Amatore, C. 303, 309 Bungenberg de Jong, H. G. 81, 105
Anderson, T. N. 89, 105 Bunger, VV. B. 446
Angrist, S. VV. 430 Burbank, J. 51,54
Antropov, L. I. 428 Burnett, R. VV. 236, 239
Arrhenius, S. A 126 Burton, K 443
Austen, D. E. G. 259, 308 Butler, E. A 444
Badoz-Lambling, J. 427 Butler, J. A V. 318, 367
Baer, C. D. 215,238,342,367 Butler, J. N. 107
Bagotzky, V. S. 430 Cairns, E. J. 45, 50, 54
Baizer, M. M. 430 Camaioni-Neto, C. 306,309, 342,367
Bard, A J. 428, 431, 432, 441 Carlisle, A 4, 113, 371
Barendrecht, E. 388, 389,422 Caroli, S. 431
Barker, G. C. 202, 2M, 238 Carroll, J. B. 261,309
Barnes, K K 428 Casanova,J. 391, 422
Bates, R. G. 429 Cawley, L. P. 85, 105
Bauer, H. H. 200,238 Chapman, D. L. 60, 61, 105
Bell, R. P. 277, 309 Charlot, G. 427
Belleau, B. 395, 422 Chateau-Gosselin, M. 236, 239
Bernal, I. 259, 261,308 Christie, J. H. 206, 238
Bezems, G. J. 308, 309 Chung, Y. K 306, 309
Bier, M. 85, 105 Churchill, R. V. 448
Birke, R. L. 235,239, 281,309 Colton, R. 253, 308
Bockris, J. O'M. 333, 367, 369, 415, 428, Compton, R. G. 258,308
430,431 Connelly, N. G. 247, 263,308,309
Bond,A. M. 207,215,232,238,239,253, Conway,B.E.42~431
308,341,366,367,429 Cooke, W. D. 175,237
Brdi&a, R. 198,238,278,280,309,287 Cottrell, F. G. 156, 237
Brezina, M. 236, 239 Covitz, F. H. 429
Britton, vv. E. 169,237,428 Crow, D. R. 232,239,427

472
Author Index 473
Cruikshank, W. 371, 372, 377, 421 Gerischer, H. 432
Curran, D. J. 387, 422 Geske, D. H. 259,308
Dalrymple-Alford, 193, 238 Gibbs, O. W. 377,421
Damaskin, B. B. 427 Gileadi, E. 430
Daniell, J. F. 4 Given, P. H. 259,308
Davis, D. G. 181,238 Goldberg, I. B. 258, 308
Davy, H. 4 Gosser, D. K 266,309,465
de Bethune, A J. 431 Goto, M. 193,238
de Montauzon, D. 226,238,247,308 Gouy, L.-G. 60,61, 105
de Smet, M. 79, 80, 105 Grahame, D. C. 60,87,88,89,105
Debye,P.J. W.90,91,105, 124,147 Greef, R. 428
DeFord, D. D. 383,421 Gregory, D. P. 45,54
Delahay, P. 26, 54, 179, 181,237,292, Gritzer, G. 171,237
309, 427, 432 Gross, M. 247,308
Deryagin, B. V. 73, 105 Grove, W. R. 48, 49, 54
Despic, A R. 333,367, 369,415 Grunwald, R. A 236, 239
Dietz, R. 361, 367 Grzeszczuk, M. 365, 367
Dobos, D. 431, 445 Guggenheim, E. A 142, 147
Donnan, F. G. 142, 147, 158 Haber, F. 36, 54
Dordesch, K V. 45, 54 Hajdu, J. 391,422
Drazic, D. 333,367,369,415 Hall, C. M. 402
Dryhurst, G. 171, 237, 429 Hamaker, H. C. 69, 105
Dukhin, S. S. 73, 105 Hamed, H. S. 97, 105, lO7,427
Dvorak, J. 428 Harrar, J. E. 383, 421
Ebsworth, E. A V. 20, 54 Harris, M. D. 236, 239
Edison, T. A. 52 Hawkridge, F. M. 173, 237
Ehlers, R. W. 97, 105 Hawley, M. D. 247, 293,308,309
Eisenberg, M. 50, 54 Headridge,J.B.427
Engles, R. 394, 422 Healy, T. W. 70, 105
Enke, C. G. 113, 146 Heineman, W. R. 389,422,430
Erdey-Gruz, T. 318,367 Heinze,J.218,220,222,238
Erman,P.113,115,146,371 Helmholtz, H. von 60, 61, 105
Falkenhagen, H. 124, 147 Henderson, P. 139, 147
Faraday, M. 4,52,371,421 Hershberger, J. W. 305, 309
Faulkner,L. R. 204,238,266,309,428 Heubert, B. J. 322,367
Feldberg,S. W.286,293,294,303,304, Heydweiller, A 126, 147
309,462 Heyrovsky, J. 157,158, 165, 194,232,
Fick, A E. 130 237,239,429
Filinovskii, V. Yu. 428 Heroult, P. L. T. 402
Fillenz, M. 236, 239 Hibbert, D. 427
Flato, J. D. 232,239 Hills, G. J. 432
Fraenkel, G. K 259, 261, 308 Hitchman, M. L. 430
Frost, A. A 20, 54 Hittorf, J. W. 116, 117, 146
Frumkin, A N. 324, 367 Hogg, R. 70, 105
Fry, A J. 169,237,428,430 Hoijtink, G. J. 225,238
Fuoss, R. M. 122, 146 Holler, F. J. 113, 146
Furman, N. H. 39,54,175,237 Howell, J. O. 222,238
Furstenau, D. W. 70, 105 Huston, R. 107
Gale, R. J. 429 Huckel, E. 90, 91, 105
Galus, Z. 171, 237, 429 Ilkovic, D. 157, 158, 196,237,238
Galvani, L. 4 Ingram, D. J. E. 259,308
Gardner, A. W. 202, 238 Ishii, D. 238
Geary, C. G. 107 Israel, Y. 348,367
Geiger, W. E. 247,308,363,365,367 Ives, D. J. G. 430
474 Author Index
James, A. M. 427 Manecke, G. 327, 367
Janata, J. 39,54 Mann, C. K 169,237, 428, 447
Janz,G.J.43~431 Mantell, C. L. 430
Jefti~L.293,294,303,309 Marcoux, L. S. 286, 309
Jensen, B. S.299,309 Marcus, R. A. 316, 319, 367
Jones, R. D. 207,238 Mark, H. B., Jr. 389, 422, 428
Jordan,J.431,441 Martinchek, G. A. 261,309
Joslin, T. 465 Marzlutf, W. F., Jr. 281, 309
KekuIe, A. 396 Mattson, J. S. 428
Kern, D. M. H. 279,309 Mazorra,M.235,239
Khan, S. U. M. 428 McAllister, D. L. 171,237
Kim, S. 306, 309 McBreen, J. 45, 54
Kirowa-Eisner, E. 204, 234, 238, 239, McCollum, P. A. 448
245,430 McCormick, M. J. 253, 308
Kissinger, P. T. 430 McKinney, T. M. 258,308
Klemenciewicz, Z. 36, 54 Meites, J. 384, 421
Klingler, R. J. 305, 309 Meites, L. 194, 233, 238, 239, 348, 367,
Kochi, J. K 305,309 384,421,429,431
Kohlrausch, F. 114, 115, 126, 146, 147 Meng, Q. 306, 309
Kolbe, H. 395, 396,422 Milazzo, G. 431
Kolthotf, I. M. 207, 234,238, 429 Miller, J. W. 383, 421
Kornberg, H. L. 443 Milner, P. C. 53, 54
Kortum, G. 428 Mohammad, M. 391, 422
Koryta, J. 236,239, 427, 428, 429 Mohilner, D. M. 60, 105
Kosaka, T. 394, 422 Moraczewski, J. 363,367
Kosower, E. M. 391, 422 Morris J. R. 204,238
Koutecky, J. 278,309 Murray, R. W. 39, 54, 427
Krebs, H. A. 443 Myland, J. C. 341,367
Kublik, Z. 389, 422 Nagy, Z. 431
Kuta, J. 171,237, 429 Narayanan, A. 431
Kyriacou, D. K 430 Nernst, W. 11, 158,318
Laitinen, H. A. 207,238,392,422 Neto, C. C. see Camaioni-Neto, C.
LaMer, V. K 98, 105 Newman,J.220,238
Latimer, W. M. 18,431 Newman, J. S. 428
Le Bel, J. A. 396 Nicholson, R. S. 183, 187, 238, 296, 298,
Le Chatelier, H. 401 309, 348, 366, 367
Leclanche, G. 45 Nicholson, W. 4, 113, 371
Lehnhotf,N.S.215,238,266,309 Nishiguchi, I. 395, 422
Lemoine, P. 247,308 Nixon, F. E. 448
Leon, L. E. 233,239 O'Brien, P. 342, 367
Levich, V. G. 212, 238, 428 O'Halloran, R. J. 366, 367
Lewis, G. N. 18 O'Neill, R. D. 236, 239
Lingane,J.J.230,234,238,384,421,429 Ohkawa, M. 395, 422
Lingane,P.J.217,238 Oldham, K B. 193,215,217,238,274,
Loud, N. A. S. 431 309,341,367
Loveland, J. W. 128, 147 Onsager,L. 77,105,122, 123, 146
Lowenheim, F. A. 430 Orpen, A. G. 263, 309
Lund, H. 430, 431 Ostapczuk, P. 389, 422
Lyons, E. H., Jr. 427 Osteryoung, J. 204,234,238,239,245
MacDonald, D. D. 430 Osteryoung, R. A. 206,238, 390, 422
MacDonald, H. C., Jr. 428 Ostwald, F. W. 5,48,54, 156,428
MacInnes, D. A. 427 Overman, R. F. 56
Maki, A. H. 259, 308 Owen, B. B.427
Maloy, J. T. 462 Parker, V. D. 191,238,299,309
Author Index 475
Parsons,R.60,105,324,367,431,441 Selley, N. J. 427
Patriarche, G. J. 236,239 Shain, I. 183, 187, 190,238,289,293,296,
Peat, R. 428 298,309,389,422
Penciner, J. 430 Shannon, R. D. 121, 146
Peover,~.E.259,308,361,367 Shaw, D. J. 69,70,85,105
Perkins, R. S. 89, 105 Shedlovsky, L. 113, 146
Peter, L.~. 428 Shedlovsky, T. 113, 146
Pinson,J.303,309 Shimizu, K 390, 422
Plambeck, J. A. 429 Shono,T. 394, 395,422,430
Plante, G. 52 Siegerman, H. 236, 239
Pleskov, Yu. V. 428 Simon, A. C. 51, 54
Pletcher, D. 428,430,465 Skundin, A. ~. 430
Poilblanc, R. 226,238,247,308 Smith, D. E. 322, 356, 365, 366, 367
Pourbaix,~.26,54,431 Smith, ~. G. 448
Prada!; J. 236, 239 Somo~,Z.380,421
Prade~va,J.236,239 Soos, Z. G. 217,238
Purdy, W. C. 429 Spiro, ~. 116, 146
Reddy, A. 428 Srinivasan, S. 430
Reeves, R. ~. 60, 105 Steckhan, E. 394, 422
Reilley, C. N. 175,237,427 Stefani, S. 465
Reinmuth, W. H. 179,237, 259, 261, 290, Steihl, G. L. 292, 309
308 Stem, O. 60,61, 105
Revie, R. W. 431 Stock, J. T. 177,237
Riddick, J. A. 446 Stokes, G. G. 121
Riddiford, A. C. 213,238 Stokes, R. H. 428, 445
Rieger, A. L. 263, 309 Stone, N. J., see N. S. Lehnhoff
Rieger,P. H. 258,259, 261,263,266,308, SWrzbach, ~. 220, 222, 238
308,309,322,367,465 Streitwieser, A. 226, 238
Rifi, ~. R. 392, 422, 429 Stulik, K. 429
Riley, T. 427 Sweigart, D. A. 215, 238, 266,306,309,
Robbins, J. 427 342,367
Roberts, J. L., Jr. 430 Swift, E. H. 444
Robinson, J. 428 Szebelledy, L.380,421
Robinson, R. A. 428, 445 Tachikawa, H. 266, 309
Roe, D. K. 167,238 Tafel, J. 325, 326,367
Rogers, J. R. 391, 422 Talmor, D. 244
Rosair, G. ~. 263, 309 Tanaka, N. 377,421
Rossiter, B. W. 428 Testa, A. C. 290, 309
Rossotti, H. 429 Thiebault, A. 303, 309
Roston, D. A. 389, 422 Thirsk, H. R. 432
Rupp, E. B. 431 Thomas, U. B. 53,54
Rutgers, A. J. 79, 80, 105 Tilak, B. V. 430
Ruzic, I. 366, 367 Tilset, ~. 299, 309
Rysselberghe, P. van 26, 54 Tiselius, A. 84, 105, 117
Sack, H. 124,147 Tobias, C. W. 432
Safford, L. K. 350, 367 Tome', J. 158,237
Salkind, A. J. 432 Tomkins, R. P. T. 431
Sand,H.T.S.182,238 Tomlinson, C. 427
Saveant,J.~.303,308,309 Trasatti, S. 337, 367
Sawyer,D.T.233,239,430 Tremillon, B. 427
Schafer, R. 394, 422 Tropp, C. 280,309
Schwartz, W. M. 289, 309 Turner, J. A. 206,238
Scott, C. J. 263,309 Uhlig, H. H. 418,422,431
Seeber, R. 465 Underwood, A. L. 237,239
476 Author Index
van't Hoff, J. H. 396
Vandenbalck, J. L 236,239
Verhoef, J. C. 388,422
Vesely, J. 429
Vetter, K J. 327, 330, 367, 428
Visco, S. J. 308,309
Volmer, M. 318,367
Volta, A 4, 371
Vukovic, M. 206, 238
Waller, A G. 258, 308
Wawzonek,S.39,54,392,422
Weaver,M.J.350,367
Weinberg, N. L. 395, 422, 429,430
Weiss, D. 429
Weissberger, A. 428
Westcott, C. C. 429
Weston, E. 7
Whewell, W. 4
White, R. E. 431
Wien, M. 124, 147
Wiese, G. R. 70,105
Wiesner, K 278, 280, 309
Wightman, R. M. 215, 223,238
Willihnganz, E. 51,54
Winograd, N. 171, 237
Wipf, D. O. 215,238
Wise, J. A. 389, 422
Wopschall, R. H. 190, 238
Yeager, E. B. 124, 147,432
Yoshida, K 430
Zana, R. 124, 147
Zhan~ Y.266,309,342,367
Zoski, C. G. 215, 217,238,341,367
Zuman, P. 236,239,247,308,431
 SUBJECT INDEX

a.c. cyclic voltammetry 366 Karl Fischer titration 387

a.c. polarography 322, 356-366 polarography 231-236, 281
EC mechanism 362-366 potentiometric titration 42-44
irreversible process 360-362 stripping voltammetry 389-390
second-harmonic 358 of cyanide ion 245
activation free energy 316 of hydroxide ion 234
activity 9 of metal ions 223
of solvent 100-102 ofthiols 235
activity coefficients 9, 17 chemical kinetics 247-249
experimental determination 96-98 chemical potential 91
from Debye-Hiickel theory 91-95 electrochemical potential 134
mean ionic activity coefficients 93 chlor-alkaIi process 404-407
molal & mole fraction scales 99-100 chronoamperometry 179-181
adsorption CE mechanism 287
effect on cyclic voltammetry 189-190 double potential step 180, 289
effect on polarography 198-199 EC mechanism 288-289
aluminum production 401-2 EC' mechanism 292-293
anodic stripping voltammetry 389-390 ECE mechanisms 293, 294, 295
anodization 400 capacitive charging current 180, 220
band theory of solids 1 irreversible process 346-348
biamperometric titrations 388 time scale 250
biochemical half-cell potentials chronocoulometry 241, 369
table 442 chronopotentiometry 181-183
Butler-Volmer equation 318 current reversal 182, 290-291
calomel electrode 31, 170 EC mechanism 290-291
catalytic current 280 time scale 250
cathodic stripping voltammetry 390 colloids 68-73, 81-85
CE mechanism 256, 274-278, 287, 296 electrophoresis 82-85
charge-transfer resistance 326-327, 354 electroviscous effect 81
chemical analysis sedimentation potential 82
a.c. polarography 358 stability of 69-71
amperometric titration 177-178 surface pH 72
biamperometric titration 388 surface potential 64, 72
conductometric titration 127-128 conductance 109
constant current coulometry 384 measurement 110-113
constant potential coulometry 380 relation to conductivity 109
coulometric titration 385 relation to resistance 109
dead-stop titration 388 conductivity 109-124
electrogravimetry 377-379 electrolyte charge type from 127
electrolysis methods 376-390 equilibrium constants from 125
ion-selective electrodes 40-42 at high electric field strength 124

477
478 Subject Index
at high frequency 124 diffusion 128-136
ionic conductivity 115 Fick's first law 130
of pure water 126 Fick's second law 131
relation to diffusion 134 flux 130
relation to mobility 119 random walk model 128-130
theory of 122-124 to a microdisk electrode 216-219
units 109 to a planar electrode 153-162
conductometric titrations 128 to a spherical electrode 162-165
convection 152 diffusion coefficient 130
r.d.e. forced convection 208 relation to conductivity 135
conventions relation to frictional coefficient 134
potential scale zero 12 relation to mobility 133-135
sign of current 151, 195 diffusion layer thickness 158, 195, 211
sign of potential 7 diffusion-limited current 152-164, 196
sign of work 5 digital simulation 462-466
writing half-cell reactions 11 Donnan membrane potential 141-143
corrosion 412-421 double layer
corrosion inhibitors 420 effect on
differential aeration 419 colloid stability 68
passivation 417-418, 421 electron-transfer rate 323-324
prevention of corrosion 420-421 interfacial tension 86-88
reaction of metal with air 416 Gouy-Chapman theory 59-68
reaction of metal with water 413-416 surface pH 72, 410
sacrificial anodes 420 thickness of 66, 92
corrosion potential 414 double layer capacitance 88-90, 110,351
Cottrell equation 156 effect on
coulometric titrations 387 chronoamperometry 180, 220
coulometry 380-388 cyclic voltammetry 185, 223
constant potential coulometry 380 polarography 197, 202-206
constant current coulometry 384 dropping Hg electrode 172, 194-201
current-potential curve 155-162 effect of potential on drop time 86
cyclic voltammetry 183-194 homogeneous kinetics at 272
adsorption effects 189-190 see polarography
capacitive charging current 185, 223 dry cell 45
CE mechanism 296 Ebsworth diagrams 20
EC mechanism 296-300 EC mechanism 256, 279, 288-291, 296-
EC' mechanism 300 300, 362-366
ECE mechanisms 301-308 EC' mechanism 256, 280-281, 292-293,
derivative presentation 190-192 300
irreversible,quasi-reversible 348 ECE mechanisms 256, 282-287,293-295,
ohmic potential drop 185 301-308
semiderivative presentation 192-194 Edison cell 52
time scale 250 EE mechanism 332-334, 342-345
Daniell cell 2 efficiency of fuel cells 47
dead-stop titration 388 electric migration 152
Debye length 66, 92 electrical circuits
Debye-Falkenhagen effect 124 a.c. bridge 112
Debye-Huckel theory 90-98 cell equivalent circuit 110, 351
comparison with experiment 95-98 current source 168
extensions from 102-104 electrometer 30
limiting law 95 constant current source 386
relation to conductivity 122 for measuring a cell potential 28, 29
dielectric constant 61, 169 potentiometer 29
table 446 operational amplifier 30, 166
Subject Index 479
current follower 165 electrolysis 391
ramp generator 167 analytical applications 376-390
voltage follower 165 current efficiency 374
coulometer 382 electroseparation 374-375
potentiostat 165 electrosynthesis 390-396
galvanostat 386 industrial processes 396-412
voltage integrator 167, 382 electrometer 30
Wheatstone bridge 112 electromotive force 6
electrocapillarity 86-88 electron spin resonance 258-264
electrochemical cell potentials electron-transfer rate 316-319, 321-324,
measurement of 27 360,366
electrochemical cells Frumkin effect 324
conductance cells 113 Marcus theory 319-322
for coulometry 380 electroosmosis 75
Daniell cell 2, 151 electroosmotic pressure 75
Edison cell 52 electrophoresis 82-85
for electrogravimetry 379 electrophoretic painting 400
electrolysis cells 5, 151 electroplating 398-400
equivalent circuit 110,351 electrorefining 403
fuel cells 47-50 electrosynthesis 390-396
galvanic cells 2 Kolbe hydrocarbon synthesis 395-396
lead-acid cell 51 oxidation of olefins 394-395
Leclanche cell (dry cell) 45 reduction of aromatics 392
mercury cell 46 reductive elimination reactions 391
nickel-cadmium cell 53 equation
production of aluminum 402 Boltzmann distribution law 62
production of Cl2 & NaOH 405 Butler-Volmer equation 318
production of lead tetraalkyls 411 Cottrell equation 156
silver cell 47 Debye-Huckel limiting law 95
silver-zinc cell 58 Einstein relation 135
sodium-sulfur cell 53 Fick's first law 130
storage batteries 50-54 Fick's second law 131
thermodynamics 5 Gibbs-Duhem equation 86, 101
three-electrode configuration 165 Henderson equation 140
for voltammetry 173 Heyrovsky-Ilcovic equation 157
Weston cell 7-12, 29 Ilkovic equation 196
electrochemical potential 134 Kohlrausch equation 114
electrodes Levich equation 212
anode 4 Lingane equation 230
auxiliary electrode 165 Nernst equation 10-13
cathode 4 Nernst-Einstein equation 135
in conductance cell 113 Nernst-Planck equation 134
for stripping analysis 389 Ohm's law 76
see indicator electrodes Ostwald's dilution law 126
see reference electrodes Poiseuille's equation 76
electrogravimetric analysis 377-379 Poisson equation 61
electrokinetic phenomena 73-80 Poisson-Boltzmann equation 63
electroosmosis 75 Sand equation 182
electroosmotic pressure 75 Stokes law 82
streaming current 73 Tafel equation 325
streaming potential 74 equilibrium constants
theory of 76-79 from cell potential data 14
zeta potential 75, 79-80, 83 from conductance data 125
from polarographic data 227-231
480 Subject Index
error function 131-132 rotating platinum electrode 207
exchange current 318 rotating ring-disk electrode 214
faradaic impedance 110, 351-356 static Hg drop electrode 206-207
Faraday's laws of electrolysis 371, 380 industrial processes 396-412
Fermi level 1 anodization 400
ferrocene electrophoretic painting 400
as a potential reference 171 electroplating 398-399
rate of oxidation 350 electrorefining 403
Fick's laws of diffusion 128 hydrometallurgical processes 403
Flade potential 417 organic syntheses 412
formal potentials production of
table 444 adiponitrile 409-410
Franck-Condon principle 319 alkalies & alkaline earths 403
free energy-oxidation state diagrams aluminum 401-402
19-21 chlorates and bromates 407
frictional coefficient 120 Cl2 and NaOH 404-407
relation to diffusion coefficient 134 fluorine 407
Frost diagrams 19-21 lead tetraalkyls 410-412
Frumkin effect 324 manganese dioxide 408
fuel cells 47-50 perchlorates 407
galvanic cells 2 potassium dichromate 408
Gibbs free energy potassium permanganate 408
of activation 316-317 infrared spectroscopy 265-268
from cell potential data 14, 224-227 ion-selective electrode 35-39, 143-146
relation to electrical work 5 ionic conductivity
Gouy layer 60 table 445
Gouy-Chapman theory 59-68 ionic radii
half-cell potentials crystal radii 121
table 438 Stokes law radii 120-121
half-cell reactions 8 ionic strength 63
half-wave potential 157, 212 kinetic current 274
correlation with IR frequencies 226 kinetic zones
correlation with MO theory 224 CE mechanism 275-276
stability constants from 227-231 EC' mechanism 292-293
table 233 kinetics of electron transfer 315-324
Hall-Heroult process 401 Kohlrausch law of independent ionic
Helmholtz layer 60 migration 115
heterogeneous rate constants 316 Kolbe hydrocarbon synthesis 395
Heyrovsky-IlcovU: equation 157 Laplace transforms 448-461
history of electrochemistry table 450
double layer theory 60 Latimer diagrams 18
conductivity 114-115 lead-acid cell 51
electrolysis & Faraday's laws 371 Lec1anche cell 45
origins 3-4 liquid junction potentials 2, 136-141
polarography 194 London force 69
hydrodynamic layer thickness 209 lyotropic series 71
hydrogen evolution kinetics 334-337 Marcus theory 319-322
indicator electrodes 171-172 mass transport rate constants 159, 211,
dropping Hg electrode 172, 194-201 218
glass electrode 35 maximum suppressor 200-201
ion-selective electrode 35-39, 143-146 mechanisms 247
microelectrodes 215-223 CE 256, 274-278, 287, 296
quinhydrone electrode 56 EC 256, 279, 288-291, 296-300, 362-366
rotating-disk electrode 172, 207-215 Ee' 256, 280-281, 292-293, 300
Subject Index 481
ECE 256, 282-287, 293-295, 301-308 overpotential (overvoltage) 317
EE 332-334, 342-345 oxidation state diagrams 19
bond cleavage 251 peak polarogram 183
electrophilic attack 252 pH measurements 40
multi-electron processes 249 phase angle 352
multi-step processes 328-334 planar diffusion 153-162
reactions of olefin radical cations polarography 176, 194-201,231-234
394 a.c. polarography 322, 356-366
rearrangement 253 adsorption effects 198-199
reductive elimination reactions 391 analytical applications 231-234
reduction of aromatic anodic waves 235
hydrocarbons, nitro and capacitive charging current 197,
carbonyl compounds 293 ID2-200
mechanistic data on CE mechanism 274
hydrogen evolution 334-337 criteria for reversibility 345
oxidation of current maxima 201
p-aminophenol291 differential pulse 204
ArCr(CO)2(alkyne) 263 EC mechanism 279
iron 333 EC' mechanism 281
(mesitylene)W(CO)3 266 ECE mechanisms 282
Mn(CO)3(dppm)CI 253 instrumentation 165-168
CpMn(CO>2L 305 irreversible waves 348
9-phenylanthracene 299 maximum suppressors 200
reduction of peak polarography 183
azobenzene 289 polarographic wave 157, 161
(COT)CoCp 363 pulse polargraphy 202
cyclooctatetraene 322 resolution 162, 205
triiodide ion 330 reverse pulse polarography 204
Mn3 + 327 sampled d.c. (tast) polarography 201
CpMn(NO)(CO)2 306 sensitivity 197,201-206
p-nitrosophenol 295 square wave 206
1,1,2,3,3-pentacyanopropenide 261 stability constants from 227-231
mercury cell 46 static Hg drop electrode 206
microelectrode voltammetry time scale 250
see steady-state voltammetry, cyclic total electrolysis in 198
voltammetry potential
microelectrodes 215-223 corrosion potential 414
electron transfer kinetics 338, 350 between dissimilar conductors 1
homogeneous reactions at 272 Donnan membrane potential 141-
mobility 143
electrophoretic mobility 82-84 electrochemical cell potential 6
ionic mobility 118-119 ferrocene as a potential standard
relation to conductivity 119 171
relation to diffusion coefficient 133 Flade potential 417
molecular orbital theory 224 formal potentials 17, 154
N ernst diffusion layer 158 half-cell potentials 11-16
Nernst equation 10-13 half-wave potential 157,212
nickel-cadmium cell 53 ion-selective membrane 37, 143146
ohmic potential drop Latimer diagrams 18
in cyclic voltammetry 185, 191, 193 liquid junction potential 2, 136-141
in steady state voltammetry 213, measurement 27
220,222 potential of zero charge 87-90, 324
Onsager reciprocal relations 77 sedimentation potential 82
osmotic pressure 142 standard reference half-cell 12
482 Subject Index
surface potential 64, 66 spherical diffusion 162-165,216-219
ultrasonic vibration potential 124 square scheme 263, 305, 307, 364
zeta potential 75, 79-80, 83 standard states 9,17,21,91
potential range for solvents 447 static Hg drop electrode 206
potential-pH diagrams 25-26 steady-state voltammetry 176, 212, 220
potentiometric titration 42-44 CE mechanism 274-278
potentiostat 165-166 coupled homogeneous reactions 269
predominance area diagrams criteria for reversibility 345
(Pourbaix diagrams) 26-27, 413 EC mechanism 279
r.d.e. voltammetry EC' mechanism 280-281
see steady-state voltammetry ECE mechanisms 282-287
stripping analysis 389 EE process 342-345
rate laws 247 irreversible/quasi-reversible 338
rate of electron transfer in time scale 250
oxidation of ferrocene 351 Stem model for double layer 60
reduction of Stokes' law 120
(COT)CoCp 363 Stokes' law radii 120-121
cyclooctatetraene 322 storage batteries 50-54
Mn porphyrin complex 342 streaming current 73
substituted stilbenes 361 streaming potential 74
reaction layer thickness 251, 270-273 stripping voltammetry 389-390
reference electrodes 31, 170-171 supporting electrolyte 153, 170
Ag/AgCI electrode 32, 170 surface charge density 66, 86, 89
calomel electrode 31, 170 surface tension
hydrogen electrode 12 effect of potential on 86-88
Luggin probe 168 symmetry factor 319, 333
table of potentials 444 table
residence time 250, 338 biochemical half-cells 442-443
resistance 109 conductivities, mobilities and
resistivity 109 diffusion coefficients 136
reversibility formal potentials 444
operational definition 28 half-cell potentials 438-441
reversibility, criteria for ion atmosphere thickness 66
a.c. polarography 360 ionic conductivity 445
cyclic voltammetry 188, 348 Laplace transforms 450
steady-state voltammetry 158, 345 list of symbols 434-437
rotating platinum electrode 207 parameters for extended Debye-
rotating ring-disk electrode 214 Huckel theory 104
rotating-disk electrode 172, 207-215 physical constants 434
homogeneous reactions at 270 polarographic data 234
Sack effect 124 potential range 447
salting-out effect 69-71 reference electrode potentials 444
sedimentation potential 82 SI units 433
silver cell 47 solvent properties 446
silver-zinc cell 58 Stokes law and crystal radii 121
silver/silver chloride electrode 32, 170 Tafel plot 325-326
sodium-sulfur cell 53 tast polarography 201
solvents thermodynamics 5
choice of 168-169 thickness
properties 169 ion atmosphere thickness 66
table of properties 446,447 diffusion layer thickness 158, 195,
spectroelectrochemistry 257 210
electron spin resonance 258-264 hydrodynamic layer 209
infrared spectroscopy 265-268 reaction layer thickness 251, 270
Subject Index 483
time scales for experiments 250 diffusion coefficient 130
titration for variables used in text 434-437
amperometric titration 177 heterogeneous rate constants 159,
biamperometric titration 388 316
conductometric titration 128 kinematic viscosity 208
coulometric titration 385 resistivity 109
dead-stop titration 388 SI units 433
Karl Fischer titration 387 van der Waals attraction 69
potentiometric 42, 176 vapor pressure 169
Tomes:riteria for reversibility 158, 345 table 446
transfer coefficient 317-323, 324, 333 viscosity 169
transference numbers 116-118 table 446
Hifforf method 116-117 voltammetry
moving boundary method 117 differential pulse 204
transition state theory 316 linear potential sweep 183
transition time 182 square wave 206
transport impedance 355 see steady-state voltammetry, cyclic
transport processes 128 voltammetry
ultrasonic vibration potential 124 Warburg impedance 355
units Wheatstone bridge 112
cell potential and free energy 7 Wien effect 124
concentration 62 work
conductivity 109 electrical work 5-6
surface tension - area work 86
zeta potential 75, 79-80, 83