.

Journal of Electroanalytical Chemistry 439 1997 7380

Double potential-step chronoamperometry and chronocoulometry at an
ultramicrodisk electrode: Theory and experiment
1
Jun-Sheng Yu
)
, Zu-Xun Zhang
Department of Chemistry, Nanjing Uniersity, Nanjing, 210093, Peoples Republic of China
Received 30 December 1996; received in revised form 19 April 1997
Abstract
The theoretical equations describing the reversible couple for double potential-step chronoamperometry and chronocoulometry at a
microdisk electrode are derived. The experimental chronoamperometric and chronocoulometric responses at a platinum microdisk
electrode with radius 10 mm in the ferrocyaniderferricyanide system for the time range of current measurement from 300 ms to 500 ms
agree well with the theory and demonstrate the advantages of the ultramicroelectrodes in electrochemical transient study. q1997 Elsevier
Science S.A.
Keywords: Double potential-step; Chronoamperometry and chronocoulometry; Ultramicroelectrode
1. Introduction
The application of voltammetric ultramicroelectrodes in
electrochemical and electroanalytical investigations has
w x
grown rapidly over the past 15 years 116 . As a result of
their micrometer-sized dimensions, ultramicroelectrodes
have many advantages in comparison with conventional-
sized electrodes made of the same material; including
enhanced mass transport, increased temporal and spatial
resolution, decreased influence of solution resistance. The
unique properties of ultramicroelectrodes have been shown
in the fields for which conventional-sized electrodes are
difficult to use; for example, in vivo electrochemical anal-
w x w x
ysis 1,2,13,14 , fast voltammetry 5,8,17,18 , and low
w x w x
temperature 19 and solid electrochemistry 2023 . The
unique electrochemical response at ultramicroelectrodes
has also been given much attention. Non-linear diffusion is
the predominant mode of mass transport at ultramicroelec-
w x
trodes 2,3,2426 , the corresponding diffusion partial dif-
ferential equations are more complicated. In the early work
some empirical expressions and digitally simulated solu-
tions for the voltammetric response on the microdisk elec-
)
Corresponding author. Fax: q86 253317761.
1
Dedicated to Professor Keith B. Oldham on the occasion of his
retirement from Trent University.
w x w x
trodes were developed 2730 . Oldham 31 analyzed
w x
edge effects in semi-infinite diffusion. Heinze 32 devel-
oped a digital simulation model for the current at a mi-
w x
crodisk electrode. Aoki and Osteryoung 33,34 derived
analytical solutions for diffusion-controlled currents at mi-
w x
crodisk electrodes. Shoup and Szabo 35 studied the
chronoamperometric current at a stationary finite electrode
using both analytical and digital simulation techniques and
presented a simple analytic expression for the current with
w x
an accuracy of 0.6%. Bond and Oldham et al. 36,37
obtained analytical solutions to the problem of steady-state
transport to an inlaid disk electrode. Recently, Cope and
w x
Tallman 38,39 presented an integral equation method for
computing the transient current at microelectrodes. So far,
the theory of various electrochemical techniques at mi-
crodisk electrodes has been established, such as square
w x w x
wave voltammetry 40 , cyclic voltammetry 24 , normal
w x
and reverse pulse voltammetry 9 , reverse pulse voltam-
w x
metry 41 , and staircase sweep and differential staircase
w x
voltammetry 42 . The theory of these methods lays a
foundation for understanding the specific electrochemical
properties of ultramicroelectrodes and utilizing them.
As the total electrode capacitance is very low at ultra-
microelectrodes, the measurement of faradaic currents is
possible after very short periods of electrolysis. In this
sense, ultramicroelectrodes are very suitable for transient
0022-0728r97r$17.00 q 1997 Elsevier Science S.A. All rights reserved.
. PII S0022- 0728 97 00258- 1
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 74
w x
techniques. Aoki and Osteryoung 43 verified their
.
chronoamperometric curves for longer times 50 ms to 3 s
on various radii of microdisk electrodes. Hepel and Ostery-
w x
oung 25 examined the behavior of the chronoamperomet-
ric transients at ultramicrodisk electrodes for short times of
.
current measurement down to 130 ms with an 8-bit
analog to digital converter. Although these studies are
excellent, unrevised chronoamperometric equations are
used in their work. Double potential-step chronoamperom-
w x w x
etry 4446 and chronocoulometry 4749 are two pow-
erful techniques for the study of chemical reactions follow-
ing the electrode reaction, reactant and product adsorption
at conventional-sized electrodes. A major reason, charac-
teristic of the methods, is that the faradaic and charging
currents are easily separated. These techniques will be
more beneficial at ultramicroelectrodes. Because of their
very small size, power requirements are minimized for
w x
ultramicroelectrodes. Galus et al. 50 developed an ex-
pression for double-step chronoamperometry from a con-
ventional-sized spherical electrode and compared theoreti-
cal and experimental results with a circular disk electrode
. w x
r s225 mm . Ewing et al. 51 derived an approximation
0
equation for chronoamperometry at their carbon fiber elec-
trodes and examined the experimental responses. Thor-
w x
mann et al. 52,53 characterized the fabrication quality of
several ultramicroelectrodes and microelectrode arrays
sealed with epoxy and glass by chronocoulometry.
In this work, we present a study of theory and experi-
ment for double potential-step chronoamperometry and
chronocoulometry. The theory work is on the basis of the
w x
Aoki and Osteryoung 33,34 theory about diffusion-con-
trolled current at microdisk electrodes and uses their re-
w x
vised equations 34 for chronoamperometry. The experi-
mental investigations were carried out using an instrument
designed by ourselves. The times of current measurement
selected were between 300 ms and 500 ms. The range is
w x
situated just between Aoki and Osteryoungs longer 43
w x
and Hepel and Osteryoungs short times 25 of current
measurement.
2. Theoretical
2.1. Boundary alue problem
Consider the simple electrode reaction:
Ryne
y
sO 1 .
occurring at a stationary microdisk electrode with radius
r . In a solution containing R, but no O initially, R and O
0
are soluble in the solution. c
)
denotes the bulk concentra-
R
tion of reactant R. For linear and non-linear diffusion we
have the diffusion equation:
2
E c r , z,t E c r , z,t . .
R R
sD
R 2
E t E r
2
1 E c r , z,t E c r , z,t . .
R R
q q 2 .
2
r E r E z
2
E c r , z,t E c r , z,t . .
O O
sD
O 2
E t E r
2
1 E c r , z,t E c r , z,t . .
O O
q q 3 .
2
r E r E z
where c , c are the local concentration of R and O,
R O
respectively, z represents the dimension normal to the
electrode surface and r is the radial coordinate measured
from the center of the microdisk electrode. The initial and
boundary conditions on the partial differential equations,
. .
Eq. 2 and Eq. 3 , for mass transfer in all cases consid-
ered are:
zG0, r G0, t s0: c r , z,t sc
)
, c r , z,t s0 4 . . .
R R O
z`, r G0, t G0: c r , z,t sc
)
, c r , z,t s0 5 . . .
R R O
zG0, r `, t G0: c r , z,t sc
)
, c r , z,t s0 6 . . .
R R O
E c r , z,t .
O
zs0, r Fr , t G0: D
0 0
E z
E c r , z,t I .
R
syD s 7 .
R
E z nFA
E c r , z,t .
O
zs0, r )r , t G0: D
0 0
E z
E c r , z,t .
R
syD s0 8 .
R
E z
zs0, r Fr , t -t : c r , z,t s0 9 . .
0 R
zs0, r Fr , t )t : c r , z,t s0 10 . .
0 O
where I is the total current; A is the electrode area; and t
.
is the time for the duration of the potential step Fig. 1 . It
.
is assumed that: 1 the electrode reaction takes place so
Fig. 1. The potentialtime program for the double potential-step experi-
ment. E sinitial potential; E sfront step potential; E sback step
i f b
potential; t sduration of the potential step.
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 75
rapidly that the Nernst equation is obeyed at the electrode
surface:
nF c 0, r ,t .
X
O
0
usexp EyE s 11 . .
RT c 0, r ,t .
R
where E
0
X
is the formal potential of the reversible couple;
.
2 the diffusion coefficients of substances O and R have a
. .
common value D; 3 adsorption effects are negligible; 4
the electrode potential is adjusted to a value E sufficiently
i
0
X
.
negative of E that no current flows; 5 at t s0, the
potential is stepped to a value E sufficiently positive of
f
E
0
X
that R at the electrode surface is immediately oxidized
.
and the concentration is zero. Reaction 1 then proceeds
to the right at a rate limited by the diffusion of R to the
electrode. After a time, t , the potential is stepped back to a
0
X
.
value E sufficiently negative of E in general E sE ,
b b i
and the concentration of O at the electrode surface is
immediately reduced to zero. The resulting current is
limited by the rate of diffusion of O back to the electrode.
According to the initial and boundary conditions as well as
. .
the above-mentioned assumption, Eq. 2 and Eq. 3 may
be solved simultaneously. By applying complicated opera-
w x
tions Aoki and Osteryoung 34 have obtained:
)
L c 0, r ,t sc rsqL f t L I t r 4nFr D . . . .
R R 1 0
12 .
L c 0, r ,t syL f t L I t r 4nFR D 13 . . . . .
O 1 0
where L is the operator of the Laplace transformation; s is
.
the variable of the Laplace transformation; f t is a certain
1
function about t dependent on the type of diffusion in Eq.
. .
2 and Eq. 3 .
2.2. Double potential-step chronoamperometric equations
.
Taking the inverse Laplace transform of Eq. 12 and
. .
Eq. 13 , then combining Eq. 11 yields:
I u yu .
t
)
f t yu dus c 14 . .
H
1 R
4nFr D 1qu
0
0
.
The Laplace transform of Eq. 14 is given by:
yu
)
L Ir 4nFr D ssL c L f t 15 . . .
0 R
1qu
where:
L f t s1r sL f t 4 . .
1
Applying the convolution theorem and carrying out the
.
inverse Laplace transformation of Eq. 15 , we have:
I 4D t yu dl .
t
s f du 16 .
H
)
/
4nFr Dc r du
0
0 R 0
where:
lsur 1qu 17 . .
For the case of the stationary disk microelectrode, the
w x
function f is defined by 34 :
f G s1q0.71835G
y1r2
q0.05626G
y3r2
.
y0.00646G
y5r2
for G)0.88 and:
1r2
1r2
f G s pr4G qpr4q0.094G 18 . . .
2
.
for G-1.44, where Gs4Dtrr , Eq. 16 is applicable to
0
various techniques with changing potential. When the po-
tential has the double step form, as in Fig. 1, for t )0, we
have:
E t sE yd t yt E yE 19 . . . .
f f b
.
where the function d t yt is given by:
d t yt s0 for t -t .
20 .
s1 for t Gt
. .
From Eq. 19 , for 0-t Ft , Eq. 17 is written as:
1
l s 21 . X
f
0
1qexp ynF E yE rRT
.
f
. .
Substituting Eq. 21 into Eq. 16 and carrying out the
.
integration with attention to the step function in Eq. 21
yields the front step current I as:
f
I sy4nFDr c
)
l f G 22 . .
f 0 R f f
where G s4Dt rr
2
, t Ft , When various potential step
f f 0 f
values of E are applied on an ultramicroelectrode, then a
f
series of values of l will be produced, corresponding the
f
.
values of f G for the time t related to E . If the potential
f f
step value of E is adjusted to a value sufficiently positive
f
0
X
.
of E , then, from Eq. 21 , l f1 is obtained; therefore
f
.
we obtain a simplified form of Eq. 22 :
I sy4nFDr c
)
f G 23 . . .
f 0 R f
s
Similarly, at t )t , we have the back step current expres-
sion as:
)
I s4nFDR c l f G q l yl f G yp 24 . . . .
b 0 R f b b f b
where:
G s4Dt rr
2
, ps4Dtrr
2
, t )t 25 .
b b 0 0 b
and:
1
l s 26 X .
b 0
w 1qexp ynF E yE
.
b
When the value of E is sufficiently positive of E
0
X
and the
f
value of E is sufficiently negative of E
0
X
, then l f1 and
b f
.
l f0, and substituting l , l into Eq. 24 , we have:
b f b
)
I s4nFDr c f G yf G yp 27 . . . .
b 0 R b b s
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 76
Fig. 2. The chronoamperometric curves for a double potential-step at a
platinum ultramicrodisk electrode with radius 10 mm. Asfront step
curves; Bsback step curves. E s0.500, 0.250, 0.200V from the top to
f
the bottom for curves A and from the bottom up to the top for curves B;
E s0V. vsexperimental data; linesstheoretical curves calculated
b
. . from Eq. 22 and Eq. 24 .
. .
From Eq. 23 and Eq. 27 , we obtain a ratio of back step
. .
current I to front step current I as:
b f
I f G f G yp . . .
b b b s
s y 28 .
I f G f G . . .
f f f
s
When the selection of the values of t and t is symmetri-
b f
cal; that is, the relation of t and t all holds as t ytst ,
b f b f
.
then Eq. 28 may be written as:
I f G . .
b b s
s y1 29 .
I f G . .
f f
s
or:
I f G qp . .
b f s
s y1 30 .
I f G . .
f f
s
Double potential-step chronoamperometric curves cal-
. .
culated from Eq. 22 and Eq. 24 are shown in Fig. 2 for

several values of E at an ultramicrodisk electrode r s10

f 0
.
mm , with E s0 V at 258C. Curves A in Fig. 2 represent
b
the chronoamperometric characteristics of the front step
current I and time t. Curves B in Fig. 2 display the
f
chronoamperometric relation of the back step current I
b
and time t. Fig. 3 shows chronoamperometric transients
. .
calculated from Eq. 22 and Eq. 24 in coordinates
I-t
y1r2
for various values of E and E s0.0 V at 258C.
f b
2.3. Double potential-step chronocoulometric equations
.
We let Q t represent the charge on the microelectrode
at time t, by definition:
t
Q t s I u du 31 . . .
H
0
.
In the following discussion, we assume that all charge Q t
all is indicated with positive value. Taking Laplace trans-
.
forms of Eq. 31 yields:
sL Q t sL I t 32 . . .
. . .
Substituting Eq. 17 and Eq. 32 into Eq. 15 , then
taking the inverse transform and applying the convolution
theorem, we obtain the general result:
t
) 2
Q t s4nFDr c lf 4D t yu rr du 33 . . .
H
0 R 0
0

When the electrode potential is changed as in Fig. 1 at

.
0Ft Ft , the potential was stepped from E to E then
i f
.
Eq. 33 may be written as:
t
) 2
Q t Ft s4nFDr c l f 4D t yu rr du . .
H
f 0 R f 0
0
s4nFDr c
)
l q 34 .
0 R f f
When E is sufficiently positive of E
0
X
, then l f1, we
f f
have:
Q t Ft s4nFDr c
)
q 35 . .
f 0 R f
where:
t
2
q s f 4D t yu rr du 36 . .
H
f 0
0
.
where q can be obtained by substituting Eq. 18 into Eq.
f
.
36 and carrying out the integration.
Fig. 3. Theoretical chronoamperometric transients in the coordinates
I-t
y1r2
for a double potential-step at microelectrode. Front step lines, E :
f
as0.500 V; bs0.300 V; cs0.270 V; ds0.250 V; es0.200 V. Back
X X X X X
. step lines, E s0V for a , b , c , d , e , calculated from Eq. 22 and Eq.
b
. 24 .
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 77
Similarly, at t st , we obtain:
Q t st s4nFDr c
)
q 37 . .
r 0 r t
where:
t
2
q s f 4D tyu rr du 38 . .
H
t 0
0
for t )t , the potential E was stepped from E to E , we
f b
have:
t
) 2
Q t )t s4nFDr c l f 4D t yu rr du . .
H
0 R f 0

0
t
2
ql f 4D t yu rr du 39 . .
H
b 0
5
t
When the value of E is sufficiently positive of E
0
X
, and
f
the value of E is sufficiently negative of E
0
X
, then l f1
b f
.
and l f0, Eq. 39 may be simplified as:
b
Q t )t s4nFDr c
)
q 40 . .
0 R
where:
t
2
qs f 4D t yu rr du 41 . .
H
0
0
. .
From Eq. 37 and Eq. 39 , we can easily obtain the back
step charge:
. . Q t )t sQ yQ t )t
b t
. 4D t yu t
)
s4nFDr c l f
H 0 R f
2
r 0
0
. . 4D t yu 4D t yu
t
yf duyl f du 42 . H b
2 2 5 /
r r t
0 0
again, with E sufficiently positive of E
0
X
and E suffi-
f b
0
X
.
ciently negative of E , l f1 and l f0, Eq. 42 may be
f b
written:
Q t )t s4nFDr c
)
q 43 . .
b 0 R b
where:
t
2 2
q s f 4D tyu rr yf 4D t yu rr du . . 4 H
b 0 0
0
44 .
.
where q , q, q are calculated similarly to q in Eq. 36 .
t b f
Fig. 4 shows a comparison of the theoretical dimension-
less chargetime curves with the dimensionless at a con-
ventional-sized electrode and a microelectrode for a double
. .
potential-step. In Fig. 4 x and x represent the
Q L Q s
dimensionless charge on conventional-sized and microme-
ter-sized electrodes, respectively:
1r2 )
'
x sQ p r 2nFAD c . .
Q L R
L
and:
x sQ r 4nFDr c
)
. .
Q s 0 R
s
where Q is the charge on the conventional-sized elec-
L
trode, Q the charge on the microelectrode, and A is the
s
Fig. 4. Theoretical dimensionless chronocoulometric curves for a double
potential-step, 1sfor a conventional-sized electrode; 2sfor a microelec-
trode.
area of the conventional-sized electrode. In Fig. 4, curve 1
is a theoretical chronoamperometric curve for the conven-
tional-sized electrode, and curve 2 for the ultramicrodisk
electrode. As seen in Fig. 4, an evident difference appears
between both curves.
. . .
In addition, from Eq. 35 , Eq. 37 , Eq. 40 and Eq.
.
43 , we have:
Q t -t q .
f f
s 45 .
Q t st q .
t r
Q t )t q .
s 46 .
Q t st q .
t t
Q t )t q .
b b
s 47 .
Q t -t q .
f f
. .
Eqs. 45 47 can indicate whether the system under
study is the effect of chemical reactions on electrode
reactions or not.
3. Experimental
The instrument used in the work is a microcomputer-

ized electrochemical system designed and assembled in

.
the laboratory . The instrumentation includes an IBM
.
PCrAT 80286-16B microcomputer system, an Epson
LQ-1600K graphic printer, a fast-response potentiostat

11
settling time 2 ms or less, input impedance above 10
.
V , a high-speed data acquisition system with a 12 bit
analogdigital converter and a sample-and-hold amplifier

with 25 ns aperture time 69kHz data acquisition fre-

.
quency, signal acquisition rate 15 ms or less . The current
amplifier can detect currents down to 10
y11
A. Electro-
chemical sweep potential waveforms are generated through
.
the potentiostat by two digitalanalog DA converters a
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 78
.
12-bit and a 14-bit DA converter, respectively . Software
for in situ data acquisition and data processing and the
sweep waveform routines were written in 80286 assembly
language. In a double potential-step experiment, the instru-
ment can apply the potential step amplitude from y2.000
V to 2.000 V, resolution G1.0 mV. Any step amplitude
may be selected within this potential range. The potential
.
step duration t see Fig. 1 can be changed from 20 ms to
59 s. The current sampling time is less than 15 ms at each
datum point, the final data are the average result for
several runs. In the instrument the sampling interval may
be selected from 15 ms to 1000 ms, the current sampling
may be carried out either at the same sampling interval for
a experiment or at different sampling intervals for a differ-
ent time domain.
The working microdisk electrode was made from plat-
inum wire 10 mm in radius which was heat sealed into a
drawn glass tube. The tip of the electrode was ground
carefully using emery paper so as to expose only a disk of
platinum to the solution and then polished with 0.05 mm
alumina powder. The radius of the electrode was deter-
mined with the aid of a microscope.
All chemicals used were of analytical grade. The exper-
.
y3
imental system was K Fe CN in 0.50 mol dm KCl.
4 6
All experimental solutions were prepared in twice-distilled
water.
The cell employed was an H-type cell thermostated at
25"0.18C. It was equipped with the working electrode, an
auxiliary electrode of platinum wire, a saturated calomel
.
reference electrode SCE and a tube for passing nitrogen
gas. The experimental solutions were deaerated with nitro-
gen for 1015 min to remove dissolved oxygen prior to
the potential step.
4. Results and discussion
4.1. Chronoamperometry
In the chronoamperometric experiments, the initial po-
tential was set at E s0 V, and background currents were
i
sampled at E . Then the potential was stepped from E to
i i
E . Here the potential ranges of E were applied from
f f
0.200 V to 0.500 V, the duration of the potential-step t
was 500 ms, at every selected potential, when t st , the
potential was stepped back to E s0 V, meanwhile the
i
current was sampled at the very end of the potential step.
The double potential-step chronoamperometric curves for
y2 y3
.
the solution of 1.00=10 mol dm K Fe CN in the
4 6
0.50 mol dm
y3
KCl at a 10 mm radius platinum microdisk
electrode for different values of the potential step are
shown in Fig. 2 and chronoamperometric transients of
theory and experiment in the coordinates I-t
y1r2
are pre-
sented in Fig. 5 for two pairs of curves at E s0.500 V
f
and E s0.0 V in Fig. 2. Because the total current signal
b
.
is a smaller value nA level at an ultramicrodisk electrode,
Fig. 5. Theoretical and experimental chronoamperometric transients in the
coordinates I-t
y1r2
for double potential-step at a platinum ultramicro-
electrode with radius 10 mm. asfront step line, E s0.500V; bsback
f
step line E s0V. 'sexperimental data; vstheoretical values calcu-
b
. . lated from Eq. 22 and Eq. 24 .
the current amplifier has to be set at a larger gain factor for
the measurement, so the first point of current sampling
started 300 ms after the potential step. As can be seen in
Fig. 2, during the potential front step, the oxidized currents
.
produced from reaction 1 decline rapidly to a steady-state
current as time t increases. The major reason is that
electrode capacitance is very small and non-linear diffu-
sion is the predominant mode of mass transfer at ultrami-
croelectrodes. While the potential was stepped back the
reduction current decreased very quickly. This is because
the product of the oxidation reaction diffuses quickly away
from the electrode surface, so that the current is down to
approximately zero. According to the current changing
characteristics, the current sampling interval is set at 1 ms
for the first 6 data points after the potential front step and
back step, while for the following data points the sampling
interval was 2 ms. Chronoamperometric curves between
300 ms and 500 ms were obtained in Fig. 2. The results in
Fig. 2 also show that the experimental chronoamperomet-
ric curves are in good agreement with the theoretical
. .
values from Eq. 22 and Eq. 24 under the same condi-
tion. Fig. 2 demonstrates that chronoamperometry is a
good method for the electrochemical study of transient
processes at ultramicroelectrodes, owing to the small ca-
pacitance current, fast current response and steady-state
current.
4.2. Chronocoulometry
In chronocoulometric experiments, the charge Q can be
obtained by integrating the current measured for the dou-
ble potential-step. Fig. 6 shows the experimental chrono-
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 79
coulometric data and theoretical curves for the solution of
y2 y3
.
y3
1.00=10 mol dm K Fe CN in 0.50 mol dm
4 6
KCl at a platinum ultramicrodisk electrode for the double
potential-step. The experimental curves have all been cor-
rected by the background signal at E s0. The points
i
represent the experimentally determined forward and back
step charge. The continuous curves represent theoretical
. .
curves calculated from Eq. 34 and Eq. 39 . As predicted
by the theory, at larger potential-step amplitude, the
chargetime curves are very close to each other. The
reason for this is that chronoamperometric curves quickly
decrease to the steady-state value at an ultramicroelectrode
and the charge value is only the integration of the current.
In Fig. 6 the maximum error between the experimental
results and calculated values for the charge is below 0.5
nC.
. .
According to Eq. 35 and Eq. 43 , if the value of Q
f
obtained for a time less than t is plotted against q and on
f
the same graph Q is plotted against q , the results should
b b
be two straight lines of equal slope. The results in Fig. 7
verify this prediction. In Fig. 7, points represent experi-
mental data and continuous curves represent the values
. .
calculated from Eq. 35 and Eq. 43 . The upper curves
.
are Q t -t corresponding to q , the lower curves are
f f
.
Q t )t corresponding to q . The parameters used in
b b
experiments and calculation are E s0.500 V, E s0.000
f b
V, E
0
X
s0.241 V, l s0.9999f1, l s0.00007f0, D
f b
s6.34=10
y6
cm
2
rs, c
)
s1.00=10
y2
mol dm
y3
. The
R
.
slope of the upper straight line calculated from Eq. 35 is
24.22 nCrs
1r2
and the experimental slope of points line is
24.47 nCrs
1r2
. Similarly, the slope for the lower straight
.
1r2
line calculated from Eq. 43 is 24.47 nCrs , and the
experimental slope is 24.47 nCrs
1r2
. These values and the
results in Fig. 7 demonstrate that the agreement between
Fig. 6. The chronocoulometric curves for a double potential-step at a
platinum ultramicrodisk electrode with radius 10 mm. E s0.500 V,
f
0.300 V, 0.270 V, 0.250 V from the top to the bottom curves. E s0 V,
b
Ds6.34=10
y6
cm
2
rs. v sexperimental data; lines stheoretical
. . curves calculated from Eq. 34 and Eq. 39 .
Fig. 7. Charge vs. q and charge vs. q plots for the curve E s0.500 V
f b f
and E s0 V in Fig. 4. Upper: Q vs. q plots; lower: Q vs. q plots.
b f f b b
vsexperimental data; linesstheoretical values calculated from Eq.
. . 35 and Eq. 43 . See text for the other parameters.
the experiment and the expected behavior at an ultrami-
crodisk electrode in the absence of adsorption is excellent.
Fig. 7 also shows that the intercepts of each line of dashes

at the Q axis are very small values upper 0.47 nC, lower
.
0.74 nC . This charge includes the charge consumed by the
ultramicroelectrode electrolyte double-layer capacitance
when the potential is changed from its initial to its final
value or vice versa, and, partly, the contribution of the
experimental error. From this we conclude that the ultrami-
croelectrode is a useful tool for the double potential-step
transient technique, due to the very small electrode
double-layer charge. In particular, it is applicable to the
study of reactant or product adsorption and chemical reac-
tion following the electrode reaction.
Acknowledgements
Support of this work from the Natural Science Founda-
tion of China and by the Science and Technology Commit-
tee of the Jiangsu Province of China are gratefully ac-
knowledged.
References
w x . 1 R.N. Adams, Anal. Chem. 48 1976 1126A.
w x . 2 R.M. Wightman, Anal. Chem. 53 1981 1125A.
w x 3 M. Fleischmann, F. Lasserre, J. Robinson, D. Swan, J. Electroanal.
. Chem. 177 1984 97.
w x 4 J. Cassidy, R.B. Khoo, S. Pons, M. Fleischmann, J. Phys. Chem. 89
. 1985 3933.
w x . 5 M.I. Montenegro, D. Pletcher, J. Electroanal. Chem. 200 1986 371.
w x . 6 S. Pons, M. Fleischmann, Anal. Chem. 59 1987 1391A.
( ) J.-S. Yu, Z.-X. ZhangrJournal of Electroanalytical Chemistry 439 1997 7380 80
w x 7 M. Fleischmann, S. Pons, D. Rolison, P.P. Schmidt, Ultramicroelec-
trodes, Datatech, Morgantown, NC, 1987.
w x . 8 R.M. Wightman, Science 240 1988 415.
w x 9 L. Sinru, J. Osteryoung, J.J. ODea, R.A. Osteryoung, Anal. Chem.
. 60 1988 1135.
w x . 10 R.M. Wightman, L.J. May, A.C. Michael, Anal. Chem. 60 1988
769A.
w x . 11 R.M. Wightman, D.O. Wipf, in: A.J. Bard Ed. , Electroanalytical
Chemistry, vol. 15, Marcel Dekker, New York, 1989, p. 267.
w x . 12 C.P. Andrieux, P. Hapiot, J.M. Saveant, Chem. Rev. 90 1990 723,
and references cited therein.
w x . 13 P.A. Broderick, Electroanalysis 2 1990 241.
w x . 14 A.G. Ewing, T.G. Strien, Y.Y. Law, Acc. Chem. Res. 25 1992
440.
w x 15 R.J. Tait, P.C. Bury, B.C. Finnin, B.L. Reed, A.M. Bond, Anal.
. Chem. 65 1993 3252, and references cited therein.
w x . 16 J. Heinze, Angew. Chem. Int. Ed. Engl. 32 1993 1268.
w x 17 D.O. Wipf, M.R. Kristensen, R.M. Wightman, Anal. Chem. 60
. 1988 306.
w x . 18 T.G. Strein, A.G. Ewing, Anal. Chem. 66 1994 3864.
w x 19 W.J. Bowyer, E.E. Engelman, D.H. Evans, J. Electroanal. Chem.
. 262 1989 67.
w x 20 A.M. Bond, M. Fleischmann, J. Robinson, J. Electroanal. Chem. 180
. 1984 257.
w x 21 R.A. Reed, L. Geng, R.W. Murray, J. Electroanal. Chem. 208
. 1986 187.
w x 22 L. Geng, R.A. Reed, M. Longmire, R.W. Murray, J. Phys. Chem. 91
. 1987 2908.
w x . 23 J.F. Parcher, C.J. Barbour, R.W. Murray, Anal. Chem. 61 1989
584.
w x 24 K. Aoki, K. Akimoto, K. Tokuda, H. Matsuda, J. Osteryoung, J.
. Electroanal. Chem. 171 1984 219.
w x . 25 T. Hepel, J. Osteryoung, J. Phys. Chem. 86 1982 1406.
w x . 26 J.O. Howell, R.M. Wightman, J. Phys. Chem. 88 1984 3915.
w x . 27 J.B. Flanagan, L. Marcoux, J. Phys. Chem. 77 1973 1051.
w x . 28 C.R. Ito, S. Asakura, K. Nobe, J. Electrochem. Soc. 119 1972 698.
w x 29 G.P. Sato, M. Kakihana, H. Ikeuchi, K. Tokuda, J. Electroanal.
. Chem. 108 1980 381.
w x 30 G.P. Sato, M. Kakihana, H. Ikeuchi, K. Tokuda, J. Electroanal.
. Chem. 117 1981 201.
w x . 31 K.B. Oldham, J. Electroanal. Chem. 122 1981 1.
w x . 32 J. Heinze, J. Electroanal. Chem. 124 1981 73.
w x . 33 K. Aoki, J. Osteryoung, J. Electroanal. Chem. 122 1981 19.
w x . 34 K. Aoki, J. Osteryoung, J. Electroanal. Chem. 160 1984 335.
w x . 35 D. Shoup, A. Szabo, J. Electroanal. Chem. 140 1982 237.
w x 36 A.M. Bond, K.B. Oldham, C.G. Zoski, J. Electroanal. Chem. 245
. 1988 71.
w x . 37 K.B. Oldham, J. Electroanal. Chem. 313 1991 17.
w x . 38 D.K. Cope, D.E. Tallman, J. Electroanal. Chem. 285 1990 79.
w x . 39 D.K. Cope, D.E. Tallman, J. Electroanal. Chem. 396 1995 265,
and references cited therein.
w x 40 D.P. Whelan, J.J. ODea, J. Osteryoung, K. Aoki, J. Electroanal.
. Chem. 202 1986 23.
w x . 41 Z. Stojek, J. Electroanal. Chem. 256 1988 283.
w x . 42 J.-S. Yu, Z.-X. Zhang, J. Electroanal. Chem. 427 1997 7.
w x . 43 K. Aoki, J. Osteryoung, J. Electroanal. Chem. 125 1981 315.
w x 44 D.D. Macdonald, Transient Techniques in Electrochemistry, Plenun
Press, New York, 1977, p. 69.
w x 45 A.J. Bard, L.R. Faulkner, Electrochemical Methods, Fundamentals
and Applications, Wiley, New York, 1980.
w x . 46 W.M. Schwarz, I. Shain, J. Phys. Chem. 69 1965 30.
w x . 47 F.C. Anson, Anal. Chem. 38 1966 54.
w x . 48 J.H. Christie, J. Electroanal. Chem. 13 1967 79.
w x 49 J.H. Christie, R.A. Osteryoung, F.C. Anson, J. Electroanal. Chem.
. 13 1967 236.
w x 50 Z. Galus, J.O. Schenk, R.N. Adams, J. Electroanal. Chem. 135
. 1982 1.
w x . 51 A.G. Ewing, M.A. Dayton, R.M. Wightman, Anal. Chem. 53 1981
1842.
w x 52 W. Thormann, P. Van den Bosch, A.M. Bond, Anal. Chem. 57
. 1985 2764.
w x . 53 W. Thormann, A.M. Bond, J. Electroanal. Chem. 218 1987 187.