3

Chem., 313 (1991) 3-16

Elsevier Sequoia S.A., Lausanne

J. Electroanal.

JEC 01600

Steady-state microelectrode
to homogeneous kinetics

voltammetry

as a route

Keith B. Oldham
Electr~hemica~

~bu~at~~es,

Trent ~nj~rsity,

Peter~~~~gh

~Can~u~

(Received 13 November 1990; in revised form 3 April 1991)

Abstract

It is demonstrated that, under propitious circumstances, information concerning the kinetics of

homogeneous reactions can be gamed by studying how features of steady-state voltammograms depend
on the size of the voltammetric microelectrode. Applications to CE, EC, ECE and EC mechanisms are
discussed.

INTRODWCTION

The advantages of steady-state volta~et~

compared with traditional transient
voltammetries include much greater freedom from interferences arising from capacitive currents, uncompensated resistance and instrumental imperfections [If. Microelectrodes [2-71 provide one of the simplest methods for achieving steady-state
voltammetry.
It has been demonstrated [8,9] that the kinetics of electron-transfer reactions are
accessible from steady-state voltammetric studies at electrodes of a variety of small
sizes. This article shows that the kinetics of preceding or succeeding homogeneous
reactions may be elucidated in a similar way. It is assumed that the microelectrode
is a hemisphere of radius a (or can be treated as if it were [lo]), and that a
heterogeneous electron-transfer reaction occurring at its surface is coupled, in some
way, to the homogeneous reaction.
Throughout this article the term isomer will be used loosely. This word is
employed in the first three applications to refer to each of two species that may be
genuinely isomeric, e.g.
~22-0728/91/$03.50

0 1991 - Elsevier Sequoia S.A. All rights reserved

HeC.COOH
II
H-C-COOH

HO0C.C.H

H . ! . COOH

(1)

or they may be related to each other by solvation, e.g.

HCHO(aq)

+ H,O(l)

or by a complexation
FeCl++

Cl-

H,C(OH),(aq)

(2)

exchange e.g.

FeClT

(3)

involving ligands present in excess. In the final application, the meaning of isomer
is stretched even further to cover structurally similar species that diffe; in oxidation
state.
Before considering the electrochemistry itself, a general result will be derived.
CODIFFUSION

OF INTERCONVERTING

ISOMERS

Let P and Q be solute species that interconvert by a mechanism

only first-order (or pseudo-first-order) reaction steps
P

k,
k-7

that involves

(4)

with homogeneous rate constants k, and k-i. In this section we derive the
steady-state concentration profiles of isomers P and Q when these are being
conveyed to or from a hemispherical (or spherical) electrode by diffusive transport
with diffusion coefficients D, and DQ.
Ficks second law for the spherical diffusion of species P becomes modified to

pp

a2

= Dpar2cp

20,
r

3
=pp

k,c, + k_,cQ

when isomeric interconversion occurs. Here cp and co are the concentrations of the
isomers and r denotes the radial coordinate. Under steady-state conditions the local
concentration of P does not change, so that ac,/& equals zero, and therefore

Similarly
2DQ d
The solution to these simultaneous differential equations will be sought in terms of
the isomer concentrations cp and c& at the electrode surface and the total bulk
concentration cb = cb + c& where we use superscripts s and b to denote
conditions at the surface of the electrode and in the bulk of the solution. Note that
rs = a.

With the definitions

g = D,c, + DQcQ, h = D,c, - DQcQ, A = (k,/DP)
:k_,/DQ)
and /.L
= (kl/DP)
- (k_,/DQ),
eqns. (6) and (7) become

rd2g+2dg=()

(8)

dr

dr2

on addition and
d=h
dh
rs+2x-Xrh-prg=O

(9)

after subtraction.

Equation (8) solves easily to

g=gb-u(gb-gS)/r

(10)

so that eqn. (9) may be rewritten

(11)

r$+2$-hrh=p[ag+(r-a)gb]
Standard methods [ll] permit this inhomogeneous ordinary differential
be solved, giving

after recognition that h must remain finite as r -+ co.

From eqns. (10) and (12) and the identities cP = (g + h)/2D,
h)/2DQ we may now express the concentration profiles as

+ (kc, - k_&)a
XD,r

exp{(a

- r)JT;}

equation to

and co = (g -

(13)

and
co=$(3L+$)(l_;)+$(*+~);

(k-lc,-klcb)uexp((u_r)~)

hDar

(14)

On letting r --+ co, these equations show, as expected, that the bulk solution is at
equilibrium in the steady state, so that
k,cb, = k_,c;

kk-,

= k, + k_, Cb

(15)

Hence

(16)

and the first right-hand term in eqns. (13) and (14) may be simplified accordingly.
For example, eqn. (13) becomes

Our prime interest is in the fluxes of the isomers at the electrode surface. These
are easily determined from Fieks first law j = - D(dc/dr) with r then set equal to
a. For isomer P we find

(18)
with a similar result for Q.
THE EQUIDIFFUSIYITY SIMPLIFICATION

In the last section the diffusion coefficients of P and Q were regarded as distinct.
This distinction could be maintained but the equations become simpler, while still
retaining all the essentials of the problem, when the isomers have similar diffusivities. Setting D, = Do = D, eqn. (18) becomes
jS,

-Dk_,cb
ka

(G+k,j/-+-k-q&;

(19)

where k = k, + k _ l. Similarly

Moreover, we shall assume that other species, formed by electron transfer to or

from the codiffusing isomers, also share the same diffusion coefficient D.
THE CE MECHANISM

Consider species A to be electroinactive,

whereas its isomer B is oxidized
(reduced) by an n-electron heterogeneous transfer to species Z, which diffuses away
from the electrode
A-

k,

k_,

-ne_
+n e-

The electroinacti~ty of isomer A implies that ji

and B, we then find from eqn. (19) that
s _ v%k_,cb
cA -

(21)
is zero. Replacing P and Q by A

+ k_,av%c,

$%k + k_,afi

Cw

nFcb
---8
t 1,

,&

i,a

Fig. 1. How the dependence of the limiting current density i, on the radius of a microelectrode at which
a CE mechanism occurs can be analyzed to obtain the rate constants. Note that k = k, + k_,.

This result, when substituted

into the analogue

of eqn. (20) reveals

that

(23)
after some algebra.
The current density
reaction), i.e.
i =

nFD
a

(positive

when anodic)

is - nFjg (n is negative

Jr I
b

-Kc

and has its maximum value (the limiting current density

polarized to such an extreme value that cS, = 0. Thus

for a cathodic

(24
i,) when the electrode

is

(25)
after rearrangement.
Figure 1 shows how this equation may be further rearranged to
provide a linear graph from measurements
of the limiting current density as a
function
of electrode radius. The slope and intercept
permit the homogeneous
kinetics to be elucidated.

The most useful situation arises when the equilibrium constant between A and B
favours the electroinert isomer A so that

Then, provided the microelectrode

radius a is such that, approximately

then the limiting current density is independent of a, whereas it is inversely

proportional to a outside this range.
This result is true irrespective of the degree of reversibility of the electron-transfer process. However, if the process is reversible, the Nernst law

applies. One shows easily that the #ncentration

if Z is absent from the bulk solution. Therefore

profile of product Z is cz = a&/r

i=nFjg=-nFD

If one subtracts eqn. (24) from eqn. (25) and divides by eqn. (29), one finds

which may be combined with the Nernst eqn. (28) to produce

Hence the preceding isomerization does not affect the shape of the reversible
voltammogram but does influence its position on the potential axis.
THE ErC MECHANISM

Now transfer attention to the mechanism

A

-rte-

V
+n e-

k,
k-2

(32)

in which the product Y of a reversible electrooxidation (or electroreduction, in

which case n is negative) isomerizes to Z. Both Y and Z are absent from the bulk
solution. These two species are the codiffusing pair so, by analogy with eqns. (19)
and (20)

where now k = k, + k_,,

and
(34)

Likewise, from the concentration

profile
(35)

one finds that

(36)
The fact that jg = 0 establishes the result
c; =

ak&
ak_, + JDk

(37)

with the help of eqn. (35); then substitution into eqn. (33) shows that
j$=

$[

alr:+z]

(38)

The current density may be expressed either as

(39)
so that
iL

-i=

nFD
cs
a
A

(40)

or as
i = nFj$ =

(41)

The Nernst equation

(42)
may now be combined with eqns. (41) and (40) into
(43)
The succeeding homogeneous reaction evidently does not affect either the height
or the shape of the reversible steady-state voltammogram, but it does influence its

position on the potential axis. The halfwave potential (where i = iL/2) is

E

where K, = k,/k_,. The constant in this equation is the hdfwave potential when
a is large, and corresponds to the classical macroelectrode value of E1,,2, namely
E, = (Rllj/nF) ln(1 + K,). Even with a microelectrode, we see that the voltammetry
is scarcely affected by the succeeding isomerization when K, is small. When this
equilibrium constant is large, however, there exists a wide range of electrode radii
that satisfy the inequality

In this range eqn. (44) shows that E,,, is dependent on a according to

whereas outside this range the halfwave potential is virtu~ly independent of

electrode radius. Figure 2 illustrates the behaviour graphically and shows how E,,,.

Fig. 2. Dependence of the halfwave potential of an EC ekctron

microelectrode radius.

transfer on the

k?garithmof the

11

versus a data may be analyzed to determine the rate constants

their quotient, K,.
THE EFE,

k,

and k_,

and

MECHANISM

Next consider the mechanism

A

(E;)

&
+n e-

k,
Q

k-2

(G)

(47)

in which the product P of a reversible electron-transfer reaction must isomerize to Q

before a further reversible oxidation (or reduction, n then being negative) to Z is
possible. For simplicity, the same number of electrons is assumed to be transferred
in each electrochemical step. Only species A is present in the bulk solution.
Using the same approach that has been used in prior sections, the surface fluxes
of the four species are found to be
(48)

where, once more, k = k2 + k_,,

ji_;

and

SC-

(50

The diffusion away from the electrode of each P or Q corresponds to the transfer
of n electrons, whereas 2n electrons are transferred for every Z that leaves the
electrode. It follows that the current density is given by
i = nF( jg +j;S) + 2nFji = nF( jg - ji)

(52)

the second equality following from the conservation requirement that ji + j$ +jS, +
jg be zero.
Because the interconversion of P and Q is a homogeneous reaction, the amount
of this isomerization taking place at the electrode surface will be negligible. This
means that j: + j; = 0 and j; + ji = 0, whereby eqns. (48)-(51) reveal that
es\+ (1+ k~~/~~c~

- (k_*~/~~c~

= c;

(53)

and
c;+

(l+

k_,a/&%)cs,-

(k&%%)cp==O

(54)

Next, note that because both electron transfers are reversible, each may be
allocated a potential-dependent equilibrium constant via Nernsts law:
K,(E)

=exp{

-$(E-SF))

= 2

(55)

12

and
K,(E)

=e+(E-E30,I

(56)

= 4

EF and Ef being the corresponding standard potentials.

The unknown surface concentrations of the four species are contained in eqns.
(53)-(56). These four equations can therefore be solved simultaneously to provide
expressions for the four surface concentrations. Only those of A and Z, namely
c;=

([l+K,(E)+k_,a/Lz]c~j
x([l

+K,@)][l

+&@)I

+K,(E)[1+K,(E)]&~

(I+K,(E)]k-,a/v%}-

(57)

and

will be reported. Combination

leads to

of these expressions with eqns. (52), (48) and (51)

+[l+K,(E)]k_,a,d=}-

(59)

as the final, very complicated, result for the current density corresponding to the
E,CE, mechanism. As expected, when K,(E) = 0, eqn. (59) reduces to the expression for the current in the EC mechanism, implicit in the preceding section.
The limiting current density can be found from eqn. (59) by letting both K,(E)
and K,(E) approach infinity. The result, which is

nFDci

i, -_ ~

1+

1 f &%/ak,

shows that for microelectrodes of radius a -=xm/k,

the limiting current density
is nFDci/u,
whereas it equals twice this value for a large enough electrode. Figure
3(a) illustrates how this behaviour may be linearized.
Of course, if K,(E) z=-K,(E), the volt~mo~am
splits into two distinct waves.
The opposite circumstance, when K3( E) B K,( E ), is more interesting. Then the

13

(b)

Fig. 3. For an ECE mechanism, similar information is available (a) from the limiting current density i,
and (b) from the halfwave potential E,,,, when the radius LI of the microelectrode is varied.

current density reduces to

ilF@
j = ___
a

1+ 2k,a/m
i 1+

[~/K,(E)]

+ k,a/m

(61)
I

which describes a single wave of normal sigmoidal shape but with a halfwave
potential that shifts with microelectrode size according to the equation
g(E,,,

- Ef)

= ln[ K,( E1/2)] = -ln[l

+ k,a/m]

(62)

which is illustrated in Fig. 3(b) and shows how kinetic information may be
extracted.
In the foregoing it has been assumed that neither the disproportionation
P+Q-+A+Z

(63)

nor the converse conproportionation reactions occur homogeneously. The likelihood

of such bimolecular reactions diminishes as ck is lowered.
THE EC MECHANISM

The EC symbol is given [12] to a mechanistic scheme known alternatively as

catalytic regeneration. If the product Z of an electron transfer reaction is
reconverted to the reactant A by a homogeneous pseudo-first-order reaction of rate
constant k _ 1
(64)

Fig. 4. The dependence on l/a,

to catalytic regeneration.

then analogues
j;=

-;($

the reciprocal of the electrode radius, of the limiting current density due

of eqns. (19) and (20) apply with k, set to zero. That is

-C;)-pJC;

(65)

and

and since these two surface fluxes must sum

follows that cS = cb - cS
The currentzdensity
i;easily found to be

to zero

to satisfy

conservation,

it

(67)
The limiting

current

density,

which corresponds

to CA= 0, is therefore

i, = nF
and varies with electrode size as illustrated
in Fig. 4. Evidently
the catalytic rate
constant k_, is easily found by measuring the current density for several electrode
sizes.
CONCLUSIONS

The kinetics of all the mechanisms

that we have considered may be elucidated, at
least in part, by studying how the steady-state
voltammograms
respond to changes
in electrode size. The technique is most successful for rate constants whose magnitude is comparable
with D/a.
Radii of microelectrodes
are limited to values
greater than about 0.1 pm by fabrication
difficulties (but see ref. 13). There is no

15

corresponding upper limit, but the time required to reach a steady state [14]
becomes excessive for microelectrodes much larger than about 10 pm. Hence these
methods should be ideal for reactions with first order rate constants in the 102-lo4
S ~ range.
Of course, there exist several other electrochemical methods for investigating
homogeneous reactions. These are discussed in several reviews [12,15-171, where
also will be found examples of systems that conform to the various mechanisms. In
addition, the literature [e.g. 18, 191 contains derivations with objectives similar to
those reported here.

GLOSSARY

i,

cx
cx
Cb
csc
D
Dx
eE
EZ
E l/2
F
g, h
i
i,
_i
A
k
km
k-m
K,
K,(E)
n
P, Q
r
R
t
T
y, z
A, II

radius of (hemi)spherical microelectrode, m

reactant species
local concentration of species X, mol mP3
concentration of X in the bulk of the solution, mol me3
total bulk concentration, mol me3
concentration of X at the electrode surface, mol me3
common diffusion coefficient of all relevant species, m2 s-
diffusion coefficient of species X, m2 s-r
an electron
electrode potential, V
conditional potential of the mth reaction, V
halfwave potential, V
Faradays constant, 96485 C mol-
D,c, + DQcQ, mol m-l s-r
current density, A m-
limiting current density, A mP2
local flux, mol me2 s-
flux of species X at electrode surface, mol me2 s-i
sum of the rate constants (e.g. k, + k_,) for the relevant reaction, s-l
rate constant for the forward direction of the mth reaction, s-r
rate constant for the backward direction of the mth reaction, s-i
equilibrium constant of the mth reaction, = k,/k_,
potential dependent equilibrium constant of mth reaction
number of electrons transferred (negative for a reduction)
arbitrary or intermediate species
radial coordinate, m
gas constant, 8.3144 J K-i mol-
time, s
temperature, K
product species
(WW

f (L/Do),

me2

16
REFERENCES
1 A.M. Bond, K.B. Oldham and C.G. Zoski, Anal. Chim. Acta, 216 (1989) 177.
2 R.M. Wi~tman
and D.O. Wipf, in A.J. Bard (Ed.), El~~oan~ytic~
Chemistry,
Vol. 15, Marcel
Dekker, New York, 1989, p. 267.
3 G.A. Brydon and K.B. Oldham, J. Electroanal.
Chem., 122 (1981) 353.
4 J.O. Howell, Curr. Sep., 8 (1987) 2.
5 S. Ports and M. Fleischmann,
Anal. Chem., 59 (1987) 1391A.
6 R.M. Wightman, Science, 240 (1988) 415.
7 M. Fleischmann,
S. Pans, D.R. Rolison and P.P. Schmidt (Eds.), Ultramicroelectrodes,
Datatech
Systems, Morganton,
NC, 1987.
8 K.B. Otdham, C.G. Zoski, A.M. Bond and D.A. Sweigart, J. Electroanal.
Chem., 248 (1988) 467.
9 K.B. Oldham, J.C. Myland, C.G. Zoski and A.M. Bond, J. Electroanal.
Chem., 270 (1989) 79.
10 K.B. Oldham and C.G. Zoski, J. Electroanal.
Chem., 256 (1988) 11.
11 G.M. Murphy, Ordinary
Differential
Equations
and their Solutions, Van Nostrand,
Princeton,
NJ,
1960.
12 A.J. Bard and L.R. Faulkner, Electrochemical
Methods, Wiley, New York, 1980, Ch. 11.
13 R.M. Penner, M.J. Heben, T.L. Longin and N.S. Lewis, Science, 250 (1990) 1118.
14 C.G. Zoski, A.M. Bond, E.T. Allinson and K.B. Oldham, Anal. Chem., 62 (1990) 37.
15 P.H. Reiger, Electrochemistry,
Prentice-Hall,
Englewood Cliffs, NJ, 1987, Sections 5.6-5.9.
16 M. Sluyters-Rehbach
and J.H. Sluyters, in C.H. Bamford and R.G. Compton (Eds.) Comprehensive
Chemical Kinetics, Vol. 26, Elsevier, Amsterdam,
1986, pp. 317-349.
17 C.M.A. Brett and A.M.F.C. Ohveira-Brett,
in ref. 16, pp. 411-421.
18 M. Fleischmann,
F. Lasserre and J. Robinson, J. Electroanal.
Chem., 177 (1984) 115.
19 M. Fleischmann,
F. Lasserre, J. Robinson and D. Swan, J. Electroanal.
Chem., 177 (1984) 97.