)(

cz

a..
a..

<C

BIBLIOGRAPHY

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
B2
B'3

P. Delahay, New Instrumental Methods in Electrochemistry, New

York: Interscience, 1954.
H. S. Hamed and B. B. Owen, Physical Chemistry of Electrolytic
Solutions, New York: Reinhold,1958.
G. Charlot, J. Badoz-Lambling, and B. Tremillon, Electrochemical
Reactions, Amsterdam: Elsevier, 1962.
427

428
B4
B5
136
B7
B8
139
B10

Bll
B12
B13
B14

Appendix 1
D. A. MacInnes, The Principles of Electrochemistry, New York:
Dover, 1966 (corrected reprint of 1947 edition).
G. Kortum, Treatise on Electrochemistry, 2nd ed, Amsterdam:
Elsevier, 1965.
B. E. Conway, Theory and Principles of Electrode Processes, New
York: Ronald Press, 1965.
K. J. Vetter, Electrochemical Kinetics, New York: Academic Press,
1967.
J. O'M. Bockris and A. Reddy, Modern Electrochemistry, New York:
Plenum Press, 1970.
R. A. Robinson and R. H. Stokes, Electrolyte Solutions, 2nd ed (rev),
London: Butterworths, 1970.
J. S. Newman, Electrochemical Systems, Englewood Cliffs, NJ:
Prentice-Hall,1972.
L. I. Antropov, Theoretical Electrochemistry, Moscow: Mir, 1972.
A. J. Bard and L. R. Faulkner, Electrochemical Methods, New
York: John Wiley, 1980.
R. Greef, R. Peat, L. M. Peter, D. Pletcher, and J. Robinson,
Instrumental Methods in Electrochemistry, Chicester: Ellis
Horwood, 1985.
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.

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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

Electrochemistry, New York: Marcel Dekker, 1974.

to

Organic

430
E2
E3

FA
E5
E6
E7

E8

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

F. Experimental Methods
F1
F2
F3
F4
F5
F6

D. J. G. Ives and G. J. Janz, eds, Reference Electrodes, Theory and

Practice, New York: Academic Press, 1961.
W. J. Albery and M. L. Hitchman, Ring-Disc Electrodes, Oxford:
Clarendon Press, 1971.
D. T. Sawyer and J. L. Roberts, Jr., Experimental Electrochemistry
for Chemists, New York: John Wiley, 1974.
E. Gileadi, E. Kirowa-Eisner, and J. Penciner, Interfacial
Electrochemistry--An Experimental Approach, Reading, MA:
Addison-Wesley, 1975.
D. D. MacDonald, Transient Techniques in Electrochemistry, New
York: Plenum Press, 1977.
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: McGrawHill,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.

Appendix 1

432

1. Review Series
11
12
13
14
15

16

J. O'M. Bockris and B. E. Conway, eds, Modern Aspects of

Electrochemistry, New York: Plenum Press, from 1954.
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.
A. J. Bard, ed, Electroanalytical Chemistry, New York: Marcel
Dekker, from 1966.
E. B. Yeager and A. J. Salkind, eds, Techniques of Electrochemistry,
New York: John Wiley, from 1972.
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.
Analytical Chemistry, Fundamental Annual Reviews (April issue
of even-numbered years), Washington: American Chemical
Society.

-zc><
w

a..
a..

til(

SYMBOLS AND UNITS

Table A.t The International System (SI) of Units

Physical Quantity

Fundamental units:
Length
mass
time
electric current
temperature
amount of substance
luminous intensity
Derived units:
force
energy
power
pressure
electric charge
electric potential
electric resistaunce
electric conductance
electric capacitance
frequency

Unit

Symbol

meter
kilogram
second
ampere
kelvin
mole
candela

m
kg
s
A
K
mol
cd

N (kg m s-2)
newton
J
(Nm)
joule
W (J s-l)
watt
Pa (N m- 2)
pascal
coulomb C (A s)
V (J C-l)
volt
n (V A-l)
ohm
siemens S (A V-I)
F (C V-I)
farad
Hz (s-l)
hertz

433

434

Appendix 2

Table A.2 Values of Physical Constants

Symbol

Constant
pennittivity of free space
electronic charge
Avogadro's number
Faraday constant
gas constant
Boltzmann constant
Planck constant
gravitational acceleration

()

NA
F

R
k
h
g

Value
8.8541878 x 10-12 C2J-1m-1
1.602189 x 10- 19 C
6.02204 x 1023 mol- 1
96484.6 C mol- l
8.3144 J moI-lK-1
1.38066 x 10-23 J K-l
6.62618 x 10-34 J s
9.80665 m s-2

Table A.3 List of Symbols

Symbol

Name

a
a
A
Ci

activity
radius
area
molar concentration, species i

C
d
DI

differential capacity
density
diffusion coefficient, species i
energy
cell potential
half-wave potential
electric field strength
frictional coefficient, species i
force
Gibbs free energy
enthalpy
electric current

E
E
E1I2

Ii
F
G
H

Units
none
m
m2
mol L-1 (M)
mol m- 3 (mM)
F m-2
kgm- 3
m 2s- 1
J
V
V
V m- l
kg s-1
N
J mol- l
J mol- l

435

Symbols and Units

Symbol

iD
iL
1
1

ID
j
j
J
k
kD
kij

L
m
mi

M
n
ni

q
Q
r,R
ro
R
S
t
ti

Name
diffusion-limited current
limiting current
ionic strength
a.c. current amplitude
diffusion current constant
volume flux
current density
molar flux density
rate constant
mass-transport rate constant
potentiometric selectivity coefficient
equilibrium constant
length
mass
molal concentration, species i
molecular weight
number of moles
kinetic order, species i
number of molecules
pressure
heat
electric charge
radial distance
microelectrode radius
resistance
entropy
time
transference number, species i
temperature

Units
A
A
mol L-1
A
rnA mM-1
(mg s-1)-213s -1I6
m 3s- 1
A m- 2
mol m- 2 s- 1
variable
m s-l
none
none
m
kg
mol kg-I
g mol- 1
mol
none
none
bar (105 Pa)
J
C

m
m

J mol-1K-l
s
none
K

436

Appendix 2

Table A.3 List of Symbols (continued)

Symbol
Ui
U

v
V

v
w
x
XA
XD
XH
XR
Xi
Zi

Z
(l
(l
C1.i
(l,~,y,o
(l,~

y
'W
Yim

y,.x
Y

Name

Units

mobility, species i
mass flow rate
internal energy
velocity
volume
potential scan rate
work
distance
ion atmosphere thickness
(Debye length)
diffusion layer thickness
hydrodynamic distance parameter
reaction layer thickness
mole fraction, species i
charge, species i
impedance
cathodic transfer coefficient
degree of dissociation
electrokinetic coefficient
stoichiometric coefficients
phase labels
anodic transfer coefficient
surface tension
activity coefficient, species i
(molar scale)
activity coefficient, species i
(molal scale)
activity coefficient, species i
(mole fraction scale)
mean ionic activity coefficient

m2V- 1s- 1
kg s-l
J mol- 1
m s-l
m3
V s-l
J
m
m
m
m
m
none
none

none
none
variable
none
none
none
Nm- 1
none
none
none
none

437

Symbols and Units

Symbol

Tl
Tl
l'}

e
1C

A
A
Il

Vi
Vi

X
p
p

a
't

4>
q>

<l>
CJ)

Name
dielectric constant
coefficient of viscosity
overpotential
polar angle
exp[F(E - EO)IRTJ

conductivity
reaction zone parameter
molar conductivity
chemical potential
kinematic viscosity
moles of ion i per mole of salt
stoichiometric coefficient, species i
(DoIDR) 112

resistivity
space charge density
surface charge density
characteristic time
current efficiency
azimuthal angle, phase angle
electric potential
angular frequency
zeta potential

Units
none
kg m-1s- 1 (Pa-s)
V
rad
none
Sm- 1
none
S m 2mol- 1
J mol- 1
m 2 s- 1
none
none
none
Om
C m- 3
C m- 2
s
none
rad
V
rad s-1
V

ELECTROCHEMICAL
DATA

Table A.4 Standard Reduction Potentials at 25C.

Main group elements:
Half-Cell Reaction
2 H + + 2 e- -+ H2(g)
Li+ + e- -+ Li(s)
Na+ + e- -+ Na(s)

K+ + e- -+ K(s)
Rb+ + e- -+ Rb(s)
Cs+ + e- -+ Cs(s)
Be2+ + 2 e- -+ Be(s)
Mg2+ + 2e- -+ Mg(s)
Ca2+ + 2 e- -+ Ca(s)
Ba2+ + 2 e- -+ Ba(s)
Al3+ + 3 e- -+ Al(s)
C02(g) + 2 H+ + 2 e- -+ CO(g) + H20
C02(g) + 2 H+ + 2 e- -+ HCOOH
2 C02<g) + 2 H+ + 2 e- -+ H2C204
Pb2+ + 2 e- -+ Pb(s)
Pb02(S) + 4 H+ + 2 e- -+ Pb2+ + 2 H20
N03-+3H++2e- -+ HN02+H20
N03- + 4 H+ + 3 e- -+ NO(g) + 2 H20
N03- + 10 H+ + 8 e- -+ NH4+ + 3 H20
PO(OH)3 + 2 H+ + 2 e- -+ HPO(OHh + H20
HPO(OH)2 + 2 H+ + 2 e- -+ H2PO(OH) + H20

438

0.0000
-8.045
-2.714
-2.925
-2.925
-2.923
-1.97
-2.356
-2.84
-2.92
-1.67
~.106
~.199
~.475
~.1251

1.468

0.94
0.96
0.875
~.276

~.499

Electrochemical Data
Half-Cell Reaction
HPO(OH)2 + 3 H+ + 3 e- ~ P(s) + 3 H2O
P(s)+3H++3e' ~ PH3
AsO(OH)s + 2 H+ + 2 e- ~ As(OH)a + H2O
As(OH)a + 3 H+ + 3 e- ~ As(s) + 3 H2O
As(s) + 3 H + + 3 e- ~ AsHS(g)
02(g) + H+ + e- ~ H02
02(g) + 2 H+ + 2 e- ~ H202
H202 + H+ + e- ~ HO + H2O
H202 + 2 H+ + 2 e- ~ 2 H2O
&.208 2- + 2 e- ~ 2 80428042- + H20 + 2 e- ~ 8Os2- + 2 OH28042- +4H++ 2 e- ~ 82062- + 2 H20
2 802(aq) + 2 H+ + 4 e- ~ 820S2- + H2O
802(aq) + 4 H+ + 4 e- ~ 8(s) + 2 H2O
84062- + 2 e- ~ 2 &.20a28(s) + 2 H+ + 2 e- ~ H2S(aq)
F2(g) + 2 e- ~ 2 FCI04- + 2 H+ + 2 e- ~ CIOs- + H2O
CIOs- + 3 H+ + 2 e- ~ HCI02 + H2O
CIOs- + 2 H+ + e- ~ CI02 + H2O
HCI02+2H++2e- ~ HOCI+H20
2 HOCI + 2 H+ + 2 e- ~ CI2(g) + 2 H2O
CI2(g) + 2 e- ~ 2 CICI2(aq) + 2 e- ~ 2 CIBr04- + 2 H+ + 2 e- ~ BrOs- + H2O
2 BrOs- + 12 H+ + 10 e- ~ Br2(l) + 6 H2O
2 HOBr + 2 H+ + 2 e- ~ Br2(l) + 2 H2O
Br2(l) + 2 e- ~ 2 Br
Br2(aq) + 2 e- ~ 2 Br
10(OH)5 + H+ + e- ~ 103- + 3 H2O
2 lOs- + 12 H+ + 10 e- ~ 12(S) + 6 H2O

439

EON
-0.454
-0.111
0.560
0.240
-0.225
-0.125
0.695
0.714
1.763
1.96
-0.94
-0.25
0.40
0.50
0.08
0.14
2.866
1.201
1.181
1.175
1.701
1.630
1.35828
1.396
1.853
1.478
1.004
1.0652
1.0874
1.60
1.20

440

Appendix 3

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

Main group elements:

Half-Cell Reaction
2HOI+2H++2elis) + 2 e- ~ 2 l-

Is- + 2 e-

liaq)+2e-

lis)+2H20

31~

21-

1.44
0.5355
0.536
0.621

Transition and posttransition elements:

Half-Cell Reaction
V02+ + 2 H+ + e- ~ V02+ + H20
V02+ + 2 H+ + e- ~ \13+ + H20
\13+ + e- ~ V2+
V2+ + 2 e- ~ V(s)
Cl"2072- + 14 H+ + 6 e- ~ 2 Cr3+ + 7 H~
Cr3+ + e- ~ Cr2+
Cr2+ + 2 e- ~ Cr(s)
Mn04- + e- ~ Mn042Mn04- + 8 H+ + 5 e- ~ Mn2+ + 4 H20
Mn02(S) + 4 H+ + 2 e- ~ Mn2+ + 2 H20
Mn3+ + e- ~ Mn2+

1.000
0.337
-0.255
-1.13
1.38
-0.424
-0.90
0.56
1.51

1.23
1.5

Mn2+ + 2 e- ~ Mn(s)

-1.18

Fe3+ + e- ~ Fe2+

0.711

Fe(phen)3+ + e- ~ Fe(phen)2+
Fe(CN)63- + e- ~ Fe(CN)64Fe(CN)64- + 2 e- ~ Fe(s) + 6 CNFe2+ + 2e- ~ Fe(s)
Co3+ + e- ~ Co2+
CO(NH3)63+ + e- ~ CO(NH3)62+
Co(phen)33+ + e ~ Co(phen)3 2 +
Co(C204)33- + e- ~ CO(C204)34-

1.13
0.361

-1.16
-0.44
1.92
0.058
0.327
0.57

441

Electrochemical Data
Half-Cell Reaction
C02+ + 2 e- --+ Co(s)

....().2:l7

NiOis) + 4 H+ + 2 e- --+ Ni2+ + 2 H20

Ni2+ + 2 e- --+ Ni(s)
Ni(OH>2(s) + 2 e- --+ Ni(s) + 2 OHCu2+ + e- --+ Cu+
CuCI(s) + e- --+ Cu(s) + CICu2+ + 2 e- --+ Cu(s)
Cu(NHa)42+ + 2 e- --+ Cu(s) + 4 NHa

1.593
....().257

Ag2+ + e- --+ Ag+

1.980

....().72
0.159
0.121

0.340

....().oo

Ag+ + e- --+ Ag(s)

AgCI(s) + e- --+ Ag(s) + CIZn2+ + 2 e- --+ Zn(s)
Zn(OH)42- + 2 e- --+ Zn(s) + 4 OHCd 2+ + 2 e- --+ Cd(s)

-1.285
""().4025

2 Hg2+ + 2 e- --+ Hg22+

Hg22+ + 2 e- --+ 2 Hg(l)
Hg2CI2(S) + 2 e- --+ 2 Rg(l) + 2 CI-

0.9110
0.7960
0.26816

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

0.7991

02223
....().7626

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 2acetyl-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
Half-Cell Reaction

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

443
E'/V

-D.340
-D.340
0.816
0.25
-D.20
-D.320
-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

0.792
0.577
1.70
0.732
0.792
0.577
1.70
0.732
-0.005
0.907
0.776
1.24
-0.14

0.228
0.577
1.28
0.700
0.228
0.577
1.28
0.700
-0.005

Ag(l)lAg( 0)
As(V)1As(III)

Ce(IV)/Ce(III)
Fe(IIl)lFe(II)
Ag(l)lAg( 0)
As(V)1As(III)
Ce(IV)/Ce(III)
Fe(IIl)lFe(II)
H(I)IH(O)
Hg(II)IHg(1)
Hg(l)IHg(O)
Mn(IV)/Mn(II)
Pb(II)lPb(O)
Sn(lV)/Sn(II)
Sn(Il)/Sn( 0)

0.77
1.44

0.68
0.77
1.44

0.68

0.274

0.674
-0.29

0.14
-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

Calomel (1.0 M KCD
Calomel (satd. KCl)
Ag/AgCl (3.5 M KCl)
Ag/AgCI (satd. KCl)

0.336
0.283
0.244
0.205
0.199

-0.08
-0.29
-0.67
-0.73
-1.01

Electrochemical Data

445

Table A.8 Molar Ionic Conductivities

Ion

AD

Ion

AD

Ion

AD

H+
Li+
Na+
K+
Cs+
Nli4+
(CH3)4N+
(C2HS)4N+
(C3H 7)4N+
Ag+
Mg2+
Ca2+
Sr2+
Ba2+
Cu2+
Zn 2+
Cd2+
Hg2+

349.8
38.7
50.1
73.5
77.3
73.6
44.9
32_7
.23.4
61.9
106.1
119.0
118.9
127.3
107.2
105.6
108.0
127.2

Pb2+
Mn 2+
Fe2+
Co2+
Ni 2+
Al3+
Cr3+
Fe3+
OHFClBr
ICNN02N03ClO3ClO4-

139.0
107.
107.
110.
lOB.
189.

103104Mn04HC03H2P04HC02CH3C02C2HSC02C6HSC0 2C0328042-

40.5
54.6
62.8
44.5
36.
54.6
40.9
35.8
32.4
138.6
160.0
174.B
170.
114.
148.3
25O.B
302.7
442.

~1.

~.

199.2
55.4
76.3
78.1
76.B
7B.
72.
71.5
64.6
67.4

&P32-

Cr042HP042C20 42P30s3Fe(CN)63Fe(CN)64-

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.

Appendix 3

446

Table A.9 Solvent Properties

Solvent
water
propylene carbonate (PC)
dimethylsulfoxide
(DMSO)
N ,N-dimethylformamide
(DMF)
acetonitrile
nitromethane
methanol
hexamethylphosphoramide (HMPA)
ethanol
acetone
dichloromethane
trifluoroacetic acid
tetrahydrofuran (THF)
1,2-dimethoxyethane
(glyme, DME)
acetic acid
p-dioxane

Liquid
Dielectric
Vapor
Range/oC Pressure b Constant Viscosity
0
-49 to 242
19 to 189

3.2
0.0
0.1

78.4
64.4
46.7

0.89
2.5
2.00

-60 to 153

0.5

36.7

0.80

-44 to 82
-29 to 101
-98 to 65
7to233

11.8
4.9
16.7
0.01

37.5
35.9
32.7
30.d

0.34
0.61
0.54
3.47d

-114 to 78
-95 to 56
-95 to 40
-15 to 72
-108 to 66
-58 to 93

8.0
24.2
58.1
14.4
26.3
10.0

24.6
20.7
8.9
8.6
7.6
72

1.08
0.30
0.41
0.86
0.46
0.46

17 to 118
12 to 101

2.0
4.9

6.2d

1.13
1.2

22

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.

447

Electrochemical Data

Table A.1O Potential Range for Some Solutions

Solvent

Electrolyte

Propylene carbonate
Dimethylsulfoxide

E4NCI04
NaC104
E4NCI04
BU4NI
NaCI04
E4NCI4
E4NBF4
BU4CI04
BU41
NaCI04
E4NCI04
E4NBF4
BU4NI
BU4PF 6
NaCI04
E4NCI04
BU4NCI04
BU4NI
BU4NCI04

Dimethylformamide

Acetonitrile

Acetone
Dichloromethane
1,2-Dimethoxyethane

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

Hg
Pt
1.7 to-1.9
0.7 to-1.8
0.7 to-1.8
1.6to-1.6
1.6to-2.1
1.5 to-2.5
1.8to-1.5
2.3 to-

0.5to-2.5
0.6to-2.9
0.2to-2.8
-0.4to-2.8
0.5to-2.0
0.5to-3.0
-to-2.7
0.5to-3.0
-0.4 to-3.0
0.6to-1.7
0.6to-2.8
-to-2.7
-O.6to-2.8

3.4to-2.9
1.6 to1.8 to-1.7
0.2to-1.7

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

-to-2.4
0.8to-1.9
-O.5to-1.7
0.6to-2.9

-cz

><
W

Q.
Q.

cc

LAPLACE TRANSFORM
METHODS

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
transformation can be thought of as an operation in linear algebra:
00.

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)
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.
1

448

449

Laplace Transform Methods

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

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
f(s)

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 2 + s2

s-2

cos at

t n- 1
(n -I)!

s-n

sinh at

a 2 + s2
_a_
s2-a 2

l/'fii

s-1I2

cosh at

2fiTiC

s-3/2

exp at

a
s.

s2-a 2

_I_
s-a

F(t)

f{s)

exp(at) - exp(bt)
a-b

1
(s-a)(s-b)

exp(at) erfW

-IS(s - a)

ifI

exp(at)[l- erfYat]
1- exp(at)[l- erfYat]

1tat 3

s (-IS + ifI)

exp(-l/4at)

exp (-Vs/a)

.b
exp(-l/4at)
,1tt

(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

at

a2C(X,t)

(A.7)

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

s C(X,s) _ C(X,O) = D

a c(x,s)
ax2

(A,B)

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)
ax 2

() 0
sex,s =

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

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
The equal fluxes at x =

A(s) - B'(s) = C*ls

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

=-B'(s) =C*/2s

A(s)

Equations (A.9) then become

~ exp (- fk Ixl)

x>o

c;- - ~; eXP(-fklxl)

x<o

C(x,s) =
c'(x,s) =

Taking the inverse transforms, we have

=~[1-erf~]

x>o

=C* - ~[1erf---L-]
2
2Wt

x<o

C(x,t)
C'(x,t)

2Wt

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

453

Laplace Transform Methods

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
D

a c(x,s)
ax 2

( ) C* - 0
s C x,s +
-

The solution consistent with the boundary condition (at x

c(x,s) =

9- + A(s) exp (- VIi x)

~ 00)

is
(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)

DR x)

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

(Alla)
(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)

ax

ax

(A12b)

The boundary conditions transform to

coCO,s) =

e CR(O,S)

(A.13a)

and
-Do o<:o(O,s) =DR aCR(O,S)

ax

ax

(A13b)

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) =-

(AI4)

~A(s)

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

Co*

A(s) =_

+ ~e)
Thus the transformed concentrations are
s(1

Co*
( ) = -scox,s

[1

exP{-Ys7i50x}]
1 + ~e

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

1 + ~e
Taking the inverse transform, we have

*~e+erf(x/2YDot)
( ) -C
Cox,t
- 0
1 + ~e

(4.2a)

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

2
( ) - C* = D [d C(r,S) + .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
(AIO) is

00,

the solution analogous to eq

455

Laplace Transform Methods

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)~

2Wt~

(4.20)

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
CR(X,S) =

~C *
+[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)
---=-

ax

~Co*

~Co*

+-s "1tDR't YDRS

and take the inverse transform to obtain

aCR(O,t)

-a-x- = -

~Co*

~Co*

"1tDR't + J"=1tD~R(;::;:t=-='t=<=)

Appendix 4

456
Since the current is

we get
i = nFACo*fl5Qiii(-L-..l..)
vt-t Yt

t >t

(4.26)

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

---.L

Do OCo(O,t)
ax

nFA

Taking the Laplace transform, we have

Do aco(O,s)
ax

=~
nFAs

=0, we have
-Doh/Do A(s) =nJAs

Differentiating eq (A.10) and setting x

Solving for A(s) and substituting in eq (A. 10) with x

.
cO<O,s) =C0 *
I
S
nFAsYsDo
Taking the inverse transform, we get
CO<O,t) =Co* _

=0:

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

457

Laplace Transform Methods

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)

nFA VsDo

co(0)
,s = - - - - - = =
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. -

nFA Y7r.Do

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)

RT

CR(O,t)

Substituting the surface concentrations into this expression and

rearranging, we have
nFA fit1JO Co =
1 + ~9(t)

t ~dt

10 yt-t

(4.29)

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)

at

= D

a2C(X,t)
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)

dXx=o

=-A(s)~rr

_A'(S).yS + k-I =0
D

VD

Solving the simultaneous equations, we have

A(s) =

S(l + /

= _ A'(s)

C*
S

'V K% + Kki

KV

K 2s + 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.

459

Laplace Transform Methods

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~*
CR(O,s)

[1- Wo

ke
]
Do (A +-IS)

keCo*

VDR seA + -IS)

Taking the inverse transforms, we have

Co(O,t) = Co* - kcCo*

'A.VDo

CR(O,t) = keCo*

'A.VDR

(1- exp(A2t}[1- erf(A Vt)))

!1-eXP('A.2t}[1-erf('A.Vt)J)

Defining

(('A.Vt) = 'A.fi[i exp('A.2t)[1- erf('A.Vt)]

we have
Co(O,t) = Co* _~[l_t{'A.Vt)]
1 + ~9
'A.fi[i
CR(O,t) =

~Co* [l_t{'A.Vt)]

1+~9

Afi[i

(6.36a)

(6.36b)

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

=- ~ sin rot

- Do dCO(O,t)

FA

dX

Taking the Laplace transform, we have

Do dCO(O,S)

dX

10

0)

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)

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 ) _
s2+c02
h(s) = l

VS

=>
=>

G(t) = sin

rot

H(t) = _1_

f1ti

Thus
L-1 [

0)

VS(s 2 + co2)

= t_1- sinroCt-'t)d't

Jo iii

U sing the trigonometric identity

sin roCt - 't) = sin rot cos
the integral becomes
sin rot

fit

t ~ cos
Jo ft

CJ)'t

d't -

CJ)'t -

cos rot sin CJ)'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

461

Laplace Transform Methods

Thus we have

CO<O,t) = Co. _ 10 {sin rot - cos rot)

FAY2roDo

Equation (6.47b) for CR(O,t) results from a similar development.

(6.47a)

-c><
z

W
Il.
Il.

<

DIGITAL SIMULATION
METHODS

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)]

(axf

(A.15)

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

Appendix 5

464

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)
1+9

=- SGR(k)

The surface concentrations then are corrected to

Co(1,k

+ 1) =Co(1,k) - SGo(k)

CR(1,k + 1)

=CR(l,k) + SCo(k)

(A.17a)
(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)
at

= _ aCA(X,t) = kCA(X,t)
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

or, using the indicesj and k,

at

CAV,k+1) = CAV,k) - kCAV,k)

(A.1Ba)

=CBV,k) + kCAV,k)

(A.1Bb)

CBV,k+1)

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
= yr(A.21)
D- o-tlD

&c

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
(1)
(2)
(3)
(4)
(5)
(6)

Appendix 5
Set concentrations to initial values.
Correct each concentration in each box for the results of the
chemical reactions using eqs (A.1B) or (A.19).
Correct each concentration in each box for the results of diffusion
using eq (A.16).
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.
Go to the next time increment and adjust time-dependent
parameters such as the electrode potential.
Repeat steps (2) - (5) for the required number of time increments.

-zc><
W
Il.
Il.

<C

ANSWERS TO
SELECTED PROBLEMS

(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

1.7

=1.6 x 10-8
Ksp =4.5 x 10-18, pH =7.00
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

LlO

(b) pH 5.0

lJ.1

flux

1.5

L12

=9.8 x 1018

= 2.2 x 10-3 mole Na+ s-l; firing rate =2.2 s-l

(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

Appendix 6

468
(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 eAg20(S) + H20 + 2 e- ~ 2 Ag(s) + 20HAg20(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

3.5

0.203

S m1l2mol-3/2

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,

4.4

E1I2 = 0.764 V

4.5

A square wave signal is required.

4.7

(a)
(b)
(c)
(d)

4.8

Co = 0.14 mM

4.12

4.75 j.4A

4.14

(a) El/2 = -0.693

(b)R = 1480 n

4.15

Diameter greater than 0.5 mm

4.16

Electrode radius less than about 2.3

[Na+]~

= 0.0281 M, ~<l> = 3.3 mV

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

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
(b)

=2, El/2 =-0.258 V

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 =

5.11

(a)
(b)
(c)

5.12

(a) DEl/2 =
(b) DEl/2 =

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 =

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

1.0 s-l

60
1.3
5.1

(a) ko

17.8,61.6 mV
101.9,41.8 mV

2.1 x 10-4 m s-l

s 10-5 m s-l

(b) ko s
(c) ko s

0.0002 m s-l
0.002 m s-l

471

Answers to Selected Problems

7.2
7.3
7.6
7.7

t = 27.5 days

(a) 22 min
0.10, 0.14, and 0.12 mM at t = 5, 10, and 25 min

(b) GB(t) =

126C
(a)0.234C
48.5 J.!M

(b)

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

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

= 0.5

mg Zn m- 2 s- l , Hydrogen

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
Adams, R. N. 171,237,286,309, 428
Alberts, G. S. 293, 309
Albery, VV.J.236,239,277,309,42~430
Alder, R. 253,308
Allendoerfer, R. D. 261,309,322,367
Amatore, C. 303, 309
Anderson, T. N. 89, 105
Angrist, S. VV. 430
Antropov, L. I. 428
Arrhenius, S. A 126
Austen, D. E. G. 259, 308
Badoz-Lambling, J. 427
Baer, C. D. 215,238,342,367
Bagotzky, V. S. 430
Baizer, M. M. 430
Bard, A J. 428, 431, 432, 441
Barendrecht, E. 388, 389,422
Barker, G. C. 202, 2M, 238
Barnes, K K 428
Bates, R. G. 429
Bauer, H. H. 200,238
Bell, R. P. 277, 309
Belleau, B. 395, 422
Bernal, I. 259, 261,308
Bezems, G. J. 308, 309
Bier, M. 85, 105
Birke, R. L. 235,239, 281,309
Bockris, J. O'M. 333, 367, 369, 415, 428,
430,431
Bond,A. M. 207,215,232,238,239,253,
308,341,366,367,429
Brdi&a, R. 198,238,278,280,309,287
Brezina, M. 236, 239
Britton, vv. E. 169,237,428

Britz, D. 462
Brooks, M. A 236, 239
Brown, B. F. 448
Bronsted, J. N. 98, 105
Bruckenstein S. 261,309
Buck, R. P. 40, 54
Bungenberg de Jong, H. G. 81, 105
Bunger, VV. B. 446
Burbank, J. 51,54
Burnett, R. VV. 236, 239
Burton, K 443
Butler, E. A 444
Butler, J. A V. 318, 367
Butler, J. N. 107
Cairns, E. J. 45, 50, 54
Camaioni-Neto, C. 306,309, 342,367
Carlisle, A 4, 113, 371
Caroli, S. 431
Carroll, J. B. 261,309
Casanova,J. 391, 422
Cawley, L. P. 85, 105
Chapman, D. L. 60, 61, 105
Charlot, G. 427
Chateau-Gosselin, M. 236, 239
Christie, J. H. 206, 238
Chung, Y. K 306, 309
Churchill, R. V. 448
Colton, R. 253, 308
Compton, R. G. 258,308
Connelly, N. G. 247, 263,308,309
Conway,B.E.42~431

Cooke, W. D. 175,237
Cottrell, F. G. 156, 237
Covitz, F. H. 429
Crow, D. R. 232,239,427

472

Author Index
Cruikshank, W. 371, 372, 377, 421
Curran, D. J. 387, 422
Dalrymple-Alford, 193, 238
Damaskin, B. B. 427
Daniell, J. F. 4
Davis, D. G. 181,238
Davy, H. 4
de Bethune, A J. 431
de Montauzon, D. 226,238,247,308
de Smet, M. 79, 80, 105
Debye,P.J. W.90,91,105, 124,147
DeFord, D. D. 383,421
Delahay, P. 26, 54, 179, 181,237,292,
309, 427, 432
Deryagin, B. V. 73, 105
Despic, A R. 333,367, 369,415
Dietz, R. 361, 367
Dobos, D. 431, 445
Donnan, F. G. 142, 147, 158
Dordesch, K V. 45, 54
Drazic, D. 333,367,369,415
Dryhurst, G. 171, 237, 429
Dukhin, S. S. 73, 105
Dvorak, J. 428
Ebsworth, E. A V. 20, 54
Edison, T. A. 52
Ehlers, R. W. 97, 105
Eisenberg, M. 50, 54
Engles, R. 394, 422
Enke, C. G. 113, 146
Erdey-Gruz, T. 318,367
Erman,P.113,115,146,371
Falkenhagen, H. 124, 147
Faraday, M. 4,52,371,421
Faulkner,L. R. 204,238,266,309,428
Feldberg,S. W.286,293,294,303,304,
309,462
Fick, A E. 130
Filinovskii, V. Yu. 428
Fillenz, M. 236, 239
Flato, J. D. 232,239
Fraenkel, G. K 259, 261, 308
Frost, A. A 20, 54
Frumkin, A N. 324, 367
Fry, A J. 169,237,428,430
Fuoss, R. M. 122, 146
Furman, N. H. 39,54,175,237
Furstenau, D. W. 70, 105
Gale, R. J. 429
Galus, Z. 171, 237, 429
Galvani, L. 4
Gardner, A. W. 202, 238
Geary, C. G. 107
Geiger, W. E. 247,308,363,365,367

473
Gerischer, H. 432
Geske, D. H. 259,308
Gibbs, O. W. 377,421
Gileadi, E. 430
Given, P. H. 259,308
Goldberg, I. B. 258, 308
Gosser, D. K 266,309,465
Goto, M. 193,238
Gouy, L.-G. 60,61, 105
Grahame, D. C. 60,87,88,89,105
Greef, R. 428
Gregory, D. P. 45,54
Gritzer, G. 171,237
Gross, M. 247,308
Grove, W. R. 48, 49, 54
Grunwald, R. A 236, 239
Grzeszczuk, M. 365, 367
Guggenheim, E. A 142, 147
Haber, F. 36, 54
Hajdu, J. 391,422
Hall, C. M. 402
Hamaker, H. C. 69, 105
Hamed, H. S. 97, 105, lO7,427
Harrar, J. E. 383, 421
Harris, M. D. 236, 239
Hawkridge, F. M. 173, 237
Hawley, M. D. 247, 293,308,309
Headridge,J.B.427
Healy, T. W. 70, 105
Heineman, W. R. 389,422,430
Heinze,J.218,220,222,238
Helmholtz, H. von 60, 61, 105
Henderson, P. 139, 147
Hershberger, J. W. 305, 309
Heubert, B. J. 322,367
Heydweiller, A 126, 147
Heyrovsky, J. 157,158, 165, 194,232,
237,239,429
Heroult, P. L. T. 402
Hibbert, D. 427
Hills, G. J. 432
Hitchman, M. L. 430
Hittorf, J. W. 116, 117, 146
Hogg, R. 70, 105
Hoijtink, G. J. 225,238
Holler, F. J. 113, 146
Howell, J. O. 222,238
Huston, R. 107
Huckel, E. 90, 91, 105
Ilkovic, D. 157, 158, 196,237,238
Ingram, D. J. E. 259,308
Ishii, D. 238
Israel, Y. 348,367
Ives, D. J. G. 430

474
James, A. M. 427
Janata, J. 39,54
Janz,G.J.43~431
Jefti~L.293,294,303,309

Jensen, B. S.299,309
Jones, R. D. 207,238
Jordan,J.431,441
Joslin, T. 465
KekuIe, A. 396
Kern, D. M. H. 279,309
Khan, S. U. M. 428
Kim, S. 306, 309
Kirowa-Eisner, E. 204, 234, 238, 239,
245,430

Kissinger, P. T. 430
Klemenciewicz, Z. 36, 54
Klingler, R. J. 305, 309
Kochi, J. K 305,309
Kohlrausch, F. 114, 115, 126, 146, 147
Kolbe, H. 395, 396,422
Kolthotf, I. M. 207, 234,238, 429
Kornberg, H. L. 443
Kortum, G. 428
Koryta, J. 236,239, 427, 428, 429
Kosaka, T. 394, 422
Kosower, E. M. 391, 422
Koutecky, J. 278,309
Krebs, H. A. 443
Kublik, Z. 389, 422
Kuta, J. 171,237, 429
Kyriacou, D. K 430
Laitinen, H. A. 207,238,392,422
LaMer, V. K 98, 105
Latimer, W. M. 18,431
Le Bel, J. A. 396
Le Chatelier, H. 401
Leclanche, G. 45
Lehnhotf,N.S.215,238,266,309
Lemoine, P. 247,308
Leon, L. E. 233,239
Levich, V. G. 212, 238, 428
Lewis, G. N. 18
Lingane,J.J.230,234,238,384,421,429
Lingane,P.J.217,238
Loud, N. A. S. 431
Loveland, J. W. 128, 147
Lowenheim, F. A. 430
Lund, H. 430, 431
Lyons, E. H., Jr. 427
MacDonald, D. D. 430
MacDonald, H. C., Jr. 428
MacInnes, D. A. 427
Maki, A. H. 259, 308
Maloy, J. T. 462

Author Index
Manecke, G. 327, 367
Mann, C. K 169,237, 428, 447
Mantell, C. L. 430
Marcoux, L. S. 286, 309
Marcus, R. A. 316, 319, 367
Mark, H. B., Jr. 389, 422, 428
Martinchek, G. A. 261,309
Marzlutf, W. F., Jr. 281, 309
Mattson, J. S. 428
Mazorra,M.235,239
McAllister, D. L. 171,237
McBreen, J. 45, 54
McCollum, P. A. 448
McCormick, M. J. 253, 308
McKinney, T. M. 258,308
Meites, J. 384, 421
Meites, L. 194, 233, 238, 239, 348, 367,
384,421,429,431
Meng, Q. 306, 309
Milazzo, G. 431
Miller, J. W. 383, 421
Milner, P. C. 53, 54
Mohammad, M. 391, 422
Mohilner, D. M. 60, 105
Moraczewski, J. 363,367
Morris J. R. 204,238
Murray, R. W. 39, 54, 427
Myland, J. C. 341,367
Nagy, Z. 431
Narayanan, A. 431
Nernst, W. 11, 158,318
Neto, C. C. see Camaioni-Neto, C.
Newman,J.220,238
Newman, J. S. 428
Nicholson, R. S. 183, 187, 238, 296, 298,
309, 348, 366, 367
Nicholson, W. 4, 113, 371
Nishiguchi, I. 395, 422
Nixon, F. E. 448
O'Brien, P. 342, 367
O'Halloran, R. J. 366, 367
O'Neill, R. D. 236, 239
Ohkawa, M. 395, 422
Oldham, K B. 193,215,217,238,274,
309,341,367
Onsager,L. 77,105,122, 123, 146
Orpen, A. G. 263, 309
Ostapczuk, P. 389, 422
Osteryoung, J. 204,234,238,239,245
Osteryoung, R. A. 206,238, 390, 422
Ostwald, F. W. 5,48,54, 156,428
Overman, R. F. 56
Owen, B. B.427
Parker, V. D. 191,238,299,309

475

Author Index
Parsons,R.60,105,324,367,431,441
Patriarche, G. J. 236,239
Peat, R. 428
Penciner, J. 430
Peover,~.E.259,308,361,367

Perkins, R. S. 89, 105

Peter, L.~. 428
Pinson,J.303,309
Plambeck, J. A. 429
Plante, G. 52
Pleskov, Yu. V. 428
Pletcher, D. 428,430,465
Poilblanc, R. 226,238,247,308
Pourbaix,~.26,54,431

Prada!; J. 236, 239

Prade~va,J.236,239

Purdy, W. C. 429
Reddy, A. 428
Reeves, R. ~. 60, 105
Reilley, C. N. 175,237,427
Reinmuth, W. H. 179,237, 259, 261, 290,
308
Revie, R. W. 431
Riddick, J. A. 446
Riddiford, A. C. 213,238
Rieger, A. L. 263, 309
Rieger,P. H. 258,259, 261,263,266,308,
308,309,322,367,465
Rifi, ~. R. 392, 422, 429
Riley, T. 427
Robbins, J. 427
Roberts, J. L., Jr. 430
Robinson, J. 428
Robinson, R. A. 428, 445
Roe, D. K. 167,238
Rogers, J. R. 391, 422
Rosair, G. ~. 263, 309
Rossiter, B. W. 428
Rossotti, H. 429
Roston, D. A. 389, 422
Rupp, E. B. 431
Rutgers, A. J. 79, 80, 105
Ruzic, I. 366, 367
Rysselberghe, P. van 26, 54
Sack, H. 124,147
Safford, L. K. 350, 367
Salkind, A. J. 432
Sand,H.T.S.182,238
Saveant,J.~.303,308,309

Sawyer,D.T.233,239,430
Schafer, R. 394, 422
Schwartz, W. M. 289, 309
Scott, C. J. 263,309
Seeber, R. 465

Selley, N. J. 427
Shain, I. 183, 187, 190,238,289,293,296,
298,309,389,422
Shannon, R. D. 121, 146
Shaw, D. J. 69,70,85,105
Shedlovsky, L. 113, 146
Shedlovsky, T. 113, 146
Shimizu, K 390, 422
Shono,T. 394, 395,422,430
Siegerman, H. 236, 239
Simon, A. C. 51, 54
Skundin, A. ~. 430
Smith, D. E. 322, 356, 365, 366, 367
Smith, ~. G. 448
Somo~,Z.380,421

Soos, Z. G. 217,238
Spiro, ~. 116, 146
Srinivasan, S. 430
Steckhan, E. 394, 422
Stefani, S. 465
Steihl, G. L. 292, 309
Stem, O. 60,61, 105
Stock, J. T. 177,237
Stokes, G. G. 121
Stokes, R. H. 428, 445
Stone, N. J., see N. S. Lehnhoff
SWrzbach, ~. 220, 222, 238
Streitwieser, A. 226, 238
Stulik, K. 429
Sweigart, D. A. 215, 238, 266,306,309,
342,367
Swift, E. H. 444
Szebelledy, L.380,421
Tachikawa, H. 266, 309
Tafel, J. 325, 326,367
Talmor, D. 244
Tanaka, N. 377,421
Testa, A. C. 290, 309
Thiebault, A. 303, 309
Thirsk, H. R. 432
Thomas, U. B. 53,54
Tilak, B. V. 430
Tilset, ~. 299, 309
Tiselius, A. 84, 105, 117
Tobias, C. W. 432
Tome', J. 158,237
Tomkins, R. P. T. 431
Tomlinson, C. 427
Trasatti, S. 337, 367
Tremillon, B. 427
Tropp, C. 280,309
Turner, J. A. 206,238
Uhlig, H. H. 418,422,431
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

Karl Fischer titration 387

polarography 231-236, 281
potentiometric titration 42-44
stripping voltammetry 389-390
of cyanide ion 245
of hydroxide ion 234
of metal ions 223
ofthiols 235
chemical kinetics 247-249
chemical potential 91
electrochemical potential 134
chlor-alkaIi process 404-407
chronoamperometry 179-181
CE mechanism 287
double potential step 180, 289
EC mechanism 288-289
EC' mechanism 292-293
ECE mechanisms 293, 294, 295
capacitive charging current 180, 220
irreversible process 346-348
time scale 250
chronocoulometry 241, 369
chronopotentiometry 181-183
current reversal 182, 290-291
EC mechanism 290-291
time scale 250
colloids 68-73, 81-85
electrophoresis 82-85
electroviscous effect 81
sedimentation potential 82
stability of 69-71
surface pH 72
surface potential 64, 72
conductance 109
measurement 110-113
relation to conductivity 109
relation to resistance 109
conductivity 109-124
electrolyte charge type from 127
equilibrium constants from 125
at high electric field strength 124

a.c. cyclic voltammetry 366

a.c. polarography 322, 356-366
EC mechanism 362-366
irreversible process 360-362
second-harmonic 358
activation free energy 316
activity 9
of solvent 100-102
activity coefficients 9, 17
experimental determination 96-98
from Debye-Hiickel theory 91-95
mean ionic activity coefficients 93
molal & mole fraction scales 99-100
adsorption
effect on cyclic voltammetry 189-190
effect on polarography 198-199
aluminum production 401-2
anodic stripping voltammetry 389-390
anodization 400
band theory of solids 1
biamperometric titrations 388
biochemical half-cell potentials
table 442
Butler-Volmer equation 318
calomel electrode 31, 170
catalytic current 280
cathodic stripping voltammetry 390
CE mechanism 256, 274-278, 287, 296
charge-transfer resistance 326-327, 354
chemical analysis
a.c. polarography 358
amperometric titration 177-178
biamperometric titration 388
conductometric titration 127-128
constant current coulometry 384
constant potential coulometry 380
coulometric titration 385
dead-stop titration 388
electrogravimetry 377-379
electrolysis methods 376-390
ion-selective electrodes 40-42

477

478
at high frequency 124
ionic conductivity 115
of pure water 126
relation to diffusion 134
relation to mobility 119
theory of 122-124
units 109
conductometric titrations 128
convection 152
r.d.e. forced convection 208
conventions
potential scale zero 12
sign of current 151, 195
sign of potential 7
sign of work 5
writing half-cell reactions 11
corrosion 412-421
corrosion inhibitors 420
differential aeration 419
passivation 417-418, 421
prevention of corrosion 420-421
reaction of metal with air 416
reaction of metal with water 413-416
sacrificial anodes 420
corrosion potential 414
Cottrell equation 156
coulometric titrations 387
coulometry 380-388
constant potential coulometry 380
constant current coulometry 384
current-potential curve 155-162
cyclic voltammetry 183-194
adsorption effects 189-190
capacitive charging current 185, 223
CE mechanism 296
EC mechanism 296-300
EC' mechanism 300
ECE mechanisms 301-308
derivative presentation 190-192
irreversible,quasi-reversible 348
ohmic potential drop 185
semiderivative presentation 192-194
time scale 250
Daniell cell 2
dead-stop titration 388
Debye length 66, 92
Debye-Falkenhagen effect 124
Debye-Huckel theory 90-98
comparison with experiment 95-98
extensions from 102-104
limiting law 95
relation to conductivity 122
dielectric constant 61, 169
table 446

Subject Index
diffusion 128-136
Fick's first law 130
Fick's second law 131
flux 130
random walk model 128-130
to a microdisk electrode 216-219
to a planar electrode 153-162
to a spherical electrode 162-165
diffusion coefficient 130
relation to conductivity 135
relation to frictional coefficient 134
relation to mobility 133-135
diffusion layer thickness 158, 195, 211
diffusion-limited current 152-164, 196
digital simulation 462-466
Donnan membrane potential 141-143
double layer
effect on
colloid stability 68
electron-transfer rate 323-324
interfacial tension 86-88
Gouy-Chapman theory 59-68
surface pH 72, 410
thickness of 66, 92
double layer capacitance 88-90, 110,351
effect on
chronoamperometry 180, 220
cyclic voltammetry 185, 223
polarography 197, 202-206
dropping Hg electrode 172, 194-201
effect of potential on drop time 86
homogeneous kinetics at 272
see polarography
dry cell 45
Ebsworth diagrams 20
EC mechanism 256, 279, 288-291, 296300, 362-366
EC' mechanism 256, 280-281, 292-293,
300
ECE mechanisms 256, 282-287,293-295,
301-308
Edison cell 52
EE mechanism 332-334, 342-345
efficiency of fuel cells 47
electric migration 152
electrical circuits
a.c. bridge 112
cell equivalent circuit 110, 351
current source 168
electrometer 30
constant current source 386
for measuring a cell potential 28, 29
potentiometer 29
operational amplifier 30, 166

Subject Index
current follower 165
ramp generator 167
voltage follower 165
coulometer 382
potentiostat 165
galvanostat 386
voltage integrator 167, 382
Wheatstone bridge 112
electrocapillarity 86-88
electrochemical cell potentials
measurement of 27
electrochemical cells
conductance cells 113
for coulometry 380
Daniell cell 2, 151
Edison cell 52
for electrogravimetry 379
electrolysis cells 5, 151
equivalent circuit 110,351
fuel cells 47-50
galvanic cells 2
lead-acid cell 51
Leclanche cell (dry cell) 45
mercury cell 46
nickel-cadmium cell 53
production of aluminum 402
production of Cl2 & NaOH 405
production of lead tetraalkyls 411
silver cell 47
silver-zinc cell 58
sodium-sulfur cell 53
storage batteries 50-54
thermodynamics 5
three-electrode configuration 165
for voltammetry 173
Weston cell 7-12, 29
electrochemical potential 134
electrodes
anode 4
auxiliary electrode 165
cathode 4
in conductance cell 113
for stripping analysis 389
see indicator electrodes
see reference electrodes
electrogravimetric analysis 377-379
electrokinetic phenomena 73-80
electroosmosis 75
electroosmotic pressure 75
streaming current 73
streaming potential 74
theory of 76-79
zeta potential 75, 79-80, 83

479
electrolysis 391
analytical applications 376-390
current efficiency 374
electroseparation 374-375
electrosynthesis 390-396
industrial processes 396-412
electrometer 30
electromotive force 6
electron spin resonance 258-264
electron-transfer rate 316-319, 321-324,
360,366
Frumkin effect 324
Marcus theory 319-322
electroosmosis 75
electroosmotic pressure 75
electrophoresis 82-85
electrophoretic painting 400
electroplating 398-400
electrorefining 403
electrosynthesis 390-396
Kolbe hydrocarbon synthesis 395-396
oxidation of olefins 394-395
reduction of aromatics 392
reductive elimination reactions 391
equation
Boltzmann distribution law 62
Butler-Volmer equation 318
Cottrell equation 156
Debye-Huckel limiting law 95
Einstein relation 135
Fick's first law 130
Fick's second law 131
Gibbs-Duhem equation 86, 101
Henderson equation 140
Heyrovsky-Ilcovic equation 157
Ilkovic equation 196
Kohlrausch equation 114
Levich equation 212
Lingane equation 230
Nernst equation 10-13
Nernst-Einstein equation 135
Nernst-Planck equation 134
Ohm's law 76
Ostwald's dilution law 126
Poiseuille's equation 76
Poisson equation 61
Poisson-Boltzmann equation 63
Sand equation 182
Stokes law 82
Tafel equation 325
equilibrium constants
from cell potential data 14
from conductance data 125
from polarographic data 227-231

480
error function 131-132
exchange current 318
faradaic impedance 110, 351-356
Faraday's laws of electrolysis 371, 380
Fermi level 1
ferrocene
as a potential reference 171
rate of oxidation 350
Fick's laws of diffusion 128
Flade potential 417
formal potentials
table 444
Franck-Condon principle 319
free energy-oxidation state diagrams
19-21
frictional coefficient 120
relation to diffusion coefficient 134
Frost diagrams 19-21
Frumkin effect 324
fuel cells 47-50
galvanic cells 2
Gibbs free energy
of activation 316-317
from cell potential data 14, 224-227
relation to electrical work 5
Gouy layer 60
Gouy-Chapman theory 59-68
half-cell potentials
table 438
half-cell reactions 8
half-wave potential 157, 212
correlation with IR frequencies 226
correlation with MO theory 224
stability constants from 227-231
table 233
Hall-Heroult process 401
Helmholtz layer 60
heterogeneous rate constants 316
Heyrovsky-IlcovU: equation 157
history of electrochemistry
double layer theory 60
conductivity 114-115
electrolysis & Faraday's laws 371
origins 3-4
polarography 194
hydrodynamic layer thickness 209
hydrogen evolution kinetics 334-337
indicator electrodes 171-172
dropping Hg electrode 172, 194-201
glass electrode 35
ion-selective electrode 35-39, 143-146
microelectrodes 215-223
quinhydrone electrode 56
rotating-disk electrode 172, 207-215

Subject Index
rotating platinum electrode 207
rotating ring-disk electrode 214
static Hg drop electrode 206-207
industrial processes 396-412
anodization 400
electrophoretic painting 400
electroplating 398-399
electrorefining 403
hydrometallurgical processes 403
organic syntheses 412
production of
adiponitrile 409-410
alkalies & alkaline earths 403
aluminum 401-402
chlorates and bromates 407
Cl2 and NaOH 404-407
fluorine 407
lead tetraalkyls 410-412
manganese dioxide 408
perchlorates 407
potassium dichromate 408
potassium permanganate 408
infrared spectroscopy 265-268
ion-selective electrode 35-39, 143-146
ionic conductivity
table 445
ionic radii
crystal radii 121
Stokes law radii 120-121
ionic strength 63
kinetic current 274
kinetic zones
CE mechanism 275-276
EC' mechanism 292-293
kinetics of electron transfer 315-324
Kohlrausch law of independent ionic
migration 115
Kolbe hydrocarbon synthesis 395
Laplace transforms 448-461
table 450
Latimer diagrams 18
lead-acid cell 51
Lec1anche cell 45
liquid junction potentials 2, 136-141
London force 69
lyotropic series 71
Marcus theory 319-322
mass transport rate constants 159, 211,
218
maximum suppressor 200-201
mechanisms 247
CE 256, 274-278, 287, 296
EC 256, 279, 288-291, 296-300, 362-366
Ee' 256, 280-281, 292-293, 300

481

Subject Index
ECE 256, 282-287, 293-295, 301-308
EE 332-334, 342-345
bond cleavage 251
electrophilic attack 252
multi-electron processes 249
multi-step processes 328-334
reactions of olefin radical cations
394
rearrangement 253
reductive elimination reactions 391
reduction of aromatic
hydrocarbons, nitro and
carbonyl compounds 293
mechanistic data on
hydrogen evolution 334-337
oxidation of
p-aminophenol291
ArCr(CO)2(alkyne) 263
iron 333
(mesitylene)W(CO)3 266
Mn(CO)3(dppm)CI 253
CpMn(CO>2L 305
9-phenylanthracene 299
reduction of
azobenzene 289
(COT)CoCp 363
cyclooctatetraene 322
triiodide ion 330
Mn3 + 327
CpMn(NO)(CO)2 306
p-nitrosophenol 295
1,1,2,3,3-pentacyanopropenide 261
mercury cell 46
microelectrode voltammetry
see steady-state voltammetry, cyclic
voltammetry
microelectrodes 215-223
electron transfer kinetics 338, 350
homogeneous reactions at 272
mobility
electrophoretic mobility 82-84
ionic mobility 118-119
relation to conductivity 119
relation to diffusion coefficient 133
molecular orbital theory 224
N ernst diffusion layer 158
Nernst equation 10-13
nickel-cadmium cell 53
ohmic potential drop
in cyclic voltammetry 185, 191, 193
in steady state voltammetry 213,
220,222
Onsager reciprocal relations 77
osmotic pressure 142

overpotential (overvoltage) 317

oxidation state diagrams 19
peak polarogram 183
pH measurements 40
phase angle 352
planar diffusion 153-162
polarography 176, 194-201,231-234
a.c. polarography 322, 356-366
adsorption effects 198-199
analytical applications 231-234
anodic waves 235
capacitive charging current 197,
ID2-200
CE mechanism 274
criteria for reversibility 345
current maxima 201
differential pulse 204
EC mechanism 279
EC' mechanism 281
ECE mechanisms 282
instrumentation 165-168
irreversible waves 348
maximum suppressors 200
peak polarography 183
polarographic wave 157, 161
pulse polargraphy 202
resolution 162, 205
reverse pulse polarography 204
sampled d.c. (tast) polarography 201
sensitivity 197,201-206
square wave 206
stability constants from 227-231
static Hg drop electrode 206
time scale 250
total electrolysis in 198
potential
corrosion potential 414
between dissimilar conductors 1
Donnan membrane potential 141143
electrochemical cell potential 6
ferrocene as a potential standard

171

Flade potential 417

formal potentials 17, 154
half-cell potentials 11-16
half-wave potential 157,212
ion-selective membrane 37, 143146
Latimer diagrams 18
liquid junction potential 2, 136-141
measurement 27
potential of zero charge 87-90, 324
sedimentation potential 82
standard reference half-cell 12

482
surface potential 64, 66
ultrasonic vibration potential 124
zeta potential 75, 79-80, 83
potential range for solvents 447
potential-pH diagrams 25-26
potentiometric titration 42-44
potentiostat 165-166
predominance area diagrams
(Pourbaix diagrams) 26-27, 413
r.d.e. voltammetry
see steady-state voltammetry
stripping analysis 389
rate laws 247
rate of electron transfer in
oxidation of ferrocene 351
reduction of
(COT)CoCp 363
cyclooctatetraene 322
Mn porphyrin complex 342
substituted stilbenes 361
reaction layer thickness 251, 270-273
reference electrodes 31, 170-171
Ag/AgCI electrode 32, 170
calomel electrode 31, 170
hydrogen electrode 12
Luggin probe 168
table of potentials 444
residence time 250, 338
resistance 109
resistivity 109
reversibility
operational definition 28
reversibility, criteria for
a.c. polarography 360
cyclic voltammetry 188, 348
steady-state voltammetry 158, 345
rotating platinum electrode 207
rotating ring-disk electrode 214
rotating-disk electrode 172, 207-215
homogeneous reactions at 270
Sack effect 124
salting-out effect 69-71
sedimentation potential 82
silver cell 47
silver-zinc cell 58
silver/silver chloride electrode 32, 170
sodium-sulfur cell 53
solvents
choice of 168-169
properties 169
table of properties 446,447
spectroelectrochemistry 257
electron spin resonance 258-264
infrared spectroscopy 265-268

Subject Index
spherical diffusion 162-165,216-219
square scheme 263, 305, 307, 364
standard states 9,17,21,91
static Hg drop electrode 206
steady-state voltammetry 176, 212, 220
CE mechanism 274-278
coupled homogeneous reactions 269
criteria for reversibility 345
EC mechanism 279
EC' mechanism 280-281
ECE mechanisms 282-287
EE process 342-345
irreversible/quasi-reversible 338
time scale 250
Stem model for double layer 60
Stokes' law 120
Stokes' law radii 120-121
storage batteries 50-54
streaming current 73
streaming potential 74
stripping voltammetry 389-390
supporting electrolyte 153, 170
surface charge density 66, 86, 89
surface tension
effect of potential on 86-88
symmetry factor 319, 333
table
biochemical half-cells 442-443
conductivities, mobilities and
diffusion coefficients 136
formal potentials 444
half-cell potentials 438-441
ion atmosphere thickness 66
ionic conductivity 445
Laplace transforms 450
list of symbols 434-437
parameters for extended DebyeHuckel theory 104
physical constants 434
polarographic data 234
potential range 447
reference electrode potentials 444
SI units 433
solvent properties 446
Stokes law and crystal radii 121
Tafel plot 325-326
tast polarography 201
thermodynamics 5
thickness
ion atmosphere thickness 66
diffusion layer thickness 158, 195,
210
hydrodynamic layer 209
reaction layer thickness 251, 270

Subject Index
time scales for experiments 250
titration
amperometric titration 177
biamperometric titration 388
conductometric titration 128
coulometric titration 385
dead-stop titration 388
Karl Fischer titration 387
potentiometric 42, 176
Tomes:riteria for reversibility 158, 345
transfer coefficient 317-323, 324, 333
transference numbers 116-118
Hifforf method 116-117
moving boundary method 117
transition state theory 316
transition time 182
transport impedance 355
transport processes 128
ultrasonic vibration potential 124
units
cell potential and free energy 7
concentration 62
conductivity 109

483
diffusion coefficient 130
for variables used in text 434-437
heterogeneous rate constants 159,
316
kinematic viscosity 208
resistivity 109
SI units 433
van der Waals attraction 69
vapor pressure 169
table 446
viscosity 169
table 446
voltammetry
differential pulse 204
linear potential sweep 183
square wave 206
see steady-state voltammetry, cyclic
voltammetry
Warburg impedance 355
Wheatstone bridge 112
Wien effect 124
work
electrical work 5-6
surface tension - area work 86
zeta potential 75, 79-80, 83