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ELSEVIER

Journal of Electroanalytical Chemistry 402 (1996) 1l-17

Quantitative analysis of a mixture with reversible electrode processes by cyclic voltammetry and linear sweep voltammetry
Pingsan Zhao 1, Shen Yun, Zhongmin Hu, Deyao Qi
Department of Chemistry and Chemical Engineering, Shanghai University of Technology, Shanghai 200072, People's Republic of China
Received 5 October 1994; in revised form 23 June 1995

Abstract

The theories of the linear sweep voltammetry (LSV) and cyclic voltammetry (CV), including branch cyclic voltammetry (BACV), of a mixture containing two components whose electrode processes are reversible and independent are described. The digital simulation method is used to simulate the theoretical linear sweep and cyclic voltammograms at spherical electrodes. A mixture of Pb 2+ and Cd 2+ at hanging mercury drop electrodes is used to test the theories. Both theory and experiment show that, in the presence of a species which is reduced at more positive potentials, it is difficult to determine the concentration of another species; considerable error could be caused in LSV, but CV based on the reverse branch of a cyclic voltammogram and BACV show less error. The allowed concentration of the more positively reduced species with a 10% relative error in CV and BACV is about four to twenty times more than that in LSV. However, in the presence of a species that is reduced at more negative potentials, LSV shows far less error than BACV and CV. The theoretical and experimental results are consistent.
Keywords: Digital simulation; Quantitative analysis; Reversible electrode processes; Cyclic voltammetry; Linear sweep voltammetry
1. Introduction

Cyclic voltammetry (CV) is usually used to diagnose various electrode reaction mechanisms and to monitor intermediate products [1,2]. In 1984, Oldham and Zoski [3] established an analytical method, branch addition cyclic voltammetry (BACV), based on CV. They added the forward and reverse branches of the cyclic voltammogram to obtain a new voltammogram with a trough and a crest. The difference in currents at the trough and crest is directly proportional to concentration and to the square root of sweep rate. In BACV, the charging current is virtually eliminated, thus allowing a low detection limit and improving the analytical accuracy [3,4]. Compared with dc polarography, linear sweep voltammetry (LSV) has many advantages [5] including improved sensitivity and a much shorter measurement time. However, when several components coexist in solution, the preceding electrode processes often interfere with the measurement of an analyte [5,6]. Several methods have been proposed to minimize a n d / o r eliminate this interference

Present address: Department of Marine Science, University of Georgia, Athens, GA30602, USA. Elsevier Science S.A. SSDI 0 0 2 2 - 0 7 2 8 ( 9 5 ) 0 4 2 1 4 - 8

[6,7], but most require rather arbitrary extrapolation procedures to establish a baseline for the determination of peak height [5]. Both sensitivity and resolution are very important for the quantitative analysis of a mixture. The introduction of pulse and square-wave techniques increases the sensitivity substantially by eliminating the charging current and also improves the symmetry of the voltammogram [8,9]. However, it does not produce much improvement in resolution and, moreover, pulse polarography is relatively slow. Many authors have concentrated on enhancing resolution by means of complex mathematic methods which transform the original linear sweep, pulse and square-wave voltammograms, for example the separation of overlapping peaks by semidifferential transformation [10] and resolution enhancement by Fourier transformation [11,12]. All these methods require not only complex mathematic treatment, but also knowledge of or assumptions about peak shape parameters, electrode reaction mechanism etc. before the treatment can start. Simple, fast and accurate methods are needed for the analysis of a mixture. Here we present a theoretical and experimental study of CV and LSV of a mixture containing two components whose electrode processes take place reversibly and independently. Two new CV-based methods

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P. Zhao et al. / Journal of Electroanalytical Chemistry 402 (1996) 11 17

for minimizing the influence of the preceding electrode process are presented: the first is BACV and the second is CV based on the reverse branch of a cyclic voltammogram. We also present a comparison of the effect of a following electrode process on the current peak height measurement of the determinant in LSV and CV.

The dimensionless current in Eqs. (2) and (4) is given by the expression [2]
2Do(Co,l-gcl l)

IR =

1 + gDo/D R + 2 g "Do/k s

(5)

where g = exp( E - E ) (6)

2. Theory

2.1. The concentration iteration and current function equations

The theory for LSV and CV is complicated, and it is difficult to obtain an exact analytical expression except for a reversible process at a planar electrode [13,14]. However, the digital simulation method proposed by Feldberg [15] can easily be used to simulate linear sweep and cyclic voltammograms under almost all conditions. At a spherical electrode, the following concentration iteration equations can be deduced: for j > 1

Here k s is a standard rate coefficient, a is the transfer coefficient, E is the electrode potential and E is the standard electrode potential; all these parameters are dimensionless. For a reversible process (k s ~ zc), Eq. (5) becomes

1R = 2 0 0 ( C'O,I -- g c l ,I )(1 + g D o / D R )

(7)

The current given by Eqs. (5) or (7) is dependent on the sweep rate V. Therefore we set

CI+ O.JI
=

ct,j + D O

(N+j)2(c~.j+,-c~.j)-(N+j

- l ) 2 ( c o) . ' _ c !O,j_,)

[(N+ j ) 3 - ( N + j - 1)3]/3
(la)

el+ R.)1 ( N - j)2(c~.j+, - CtR.j) -- ( N - j + l)2(clR.j-- (.'~.) ,) = clR.j + D R

[ ( N - j + l) 3- ( N - j)3]/3
(lb)

and for j = 1
el+

O.1l

CI

O,I .~_

N 2 1 o + ( N + 1)2 Do(C~).2 [(N+ 1)3-N3]/3 N2IR+(N+I)2DR(C~,: [(N+l)3_N31/3

c' O,I) (2a)

where v is dimensionless. The voltammogram for BACV is obtained by adding the forward and reverse branches of the cyclic voltammogram. Consider a system containing two components Ol and 0 2. Each electrode reaction O 1 + n l e - ~ R~ or 0 2 + n2e~R2, where n~ and n 2 are the electron numbers, is reversible and independent. The voltammograms of the mixture for LSV, CV and BACV can be obtained by adding the voltammograms of O~ and 0 2. Fig. 1 shows the reversible cyclic voltammograms of O l and 02 and their mixture at spherical electrodes where (a) represents the forward branches and (b) the reverse branches. In fact a cyclic voltammogram consists of two linear sweep voltammograms with the forward branch corresponding to LSV. Fig. 2 shows the reversible voltammograms of BACV of the mixture at spherical electrodes.

1+ 1 =

C l

CR.,

R.l

q._

' CR,I)
(2b)

2.2. Influence of the preceding electrode process

Three methods can be used to determine species 0 2 in the presence of the more positively reduced species O~. The first is LSV, which is based on the forward branch of the cyclic voltammogram in Fig. l(a). This figure illustrates the difficulty in determining the real peak height ( I C ) r of species 0 2 in the presence of the more positively reduced species O 1 because the reference current (dotted curve in Fig. l(a)) must be extrapolated. In such a case, the flat part between the peaks of Ol and 0 2 and the initial part of the voltammogram can usually be taken as the baseline for measuring the peak height of 0 2 in LSV if no correction procedures are applied. The corresponding two measurements of peak height to baseline are represented by 1~ and I ~ in Fig. l(a). The second method is the CV based on the reverse branch of the cyclic voltammogram in Fig. l(b) where the species 0 2 can be determined from the peak height I ~ of the second peak. This method is

All variables and parameters in the preceding equations are dimensionless (each parameter can be made dimensionless by the method described in Ref. [6], p. 675), where c represents concentration, 1 and j represent time and space, O and R represent oxidized and reduced species, D is the diffusion coefficient and N is the radius of the spherical electrode (in space steps). Thus c~.j is the dimensionless concentration of the oxidized species at the jth space and lth time step, and so on. At a planar electrode ( N ~ oc), the preceding equations can be simplified as follows [2,9]: For j > 1

c!+l=,.s

l l - 2c~ + Ci I. j - , ) c! .,.,+ Di(c,.j+

(3)

and for j = 1

el+l=i.l CIi., "Jf-Di(c[. 2 -- C[.l) -I-If

where i represents O or R.

(4)

P. Zhao et al. / Journa I of Electroanalytical Chemistry 402 (1996) l 1 - 17

13

Table 1 Concentration effect of a more positively reduced species O~ on the peak m e a s u r e m e n t o f the analyte 0 2 u n d e r conditions o f constant peak potential difference and electron n u m b e r cI BACV CV LSV

AI 2
0 0.01 0.1 0.5 1 10 20 0.6664 0.6662 0.6643 0.6561 0.6461 0.4873 0.3448

~/%
-- 0.03 - 0.32 - 1.54 - 3.04 - 26.88 - 48.26

1~2
0.4627 0.4627 0.4625 0.4615 0.4604 0.4398 0.4177

~/%
-0.00 - 0.04 - 0.26 - 0.50 -- 4.95 - 9.72

1~2
0.4508 0.4497 0.4441 0.4260 0.4074 0.2005 0.0657

el%
-- 0.24 - 1.49 - 5.50 - 9.63 - 55.52 - 85.42

I~'2
0.4508 0.4522 0.4653 0.5236 0.5964 1.9155 3.3983

el%
-0.31 3.22 16.15 32.30 324.91 653.84

D O = D R = 0.45, nt = n 2 = 2, N = 500, the p e a k potential difference A E p between species O~ and 0 2 is 2 0 0 mV, the concentration of the analyte O 2 is set at 1, c t is die concentration o f the m o r e positively reduced species O~ and e is the relative error in the p e a k height or current difference o f 0 2 . The remaining symbols are illustrated in Figs. 1 a n d 2.

expected to be more accurate than LSV because the segment CD due to species O~ is fairly flat and species O~ has little effect on the peak shape and peak height of species 0 2. The third method is based on the voltammogram of BACV in Fig. 2 where A I 2 is used as an analytical parameter. It can be seen from Fig. 2 that when the concentration e 1 of species O~ increases from zero to five times of that of species O 2, AI2 changes insignificantly. Therefore BACV will also be more accurate than LSV. The three methods are compared using the four parameters A I 2 , I ~ 2 , I~2 and I~2 in Tables 1 and 2. Table 1 shows the concentration effect of a more positively reduced species O~ on the peak measurement of the analyte 02 under conditions of constant peak potential difference (AEp = 200 mV) and electron number (n 1 = n 2 = 2) where e is the relative error. The value of e for the current difference A I 2 of 0 2 c a n be calculated using the following equation:

applied to the remaining analytical parameters I ~ , I~2 and I ~ . In Table 1, the concentration of the analyte 02 is fixed as 1 and the concentration c~ of the interferent O l is changed from zero to 20. As ct increases, the error in the peak height or current difference of the determinant 02 increases. For example, in BACV e is - 3 . 0 1 % and - 4 8 . 2 6 % respectively when ct is equal to and 20 times larger than the concentration of the analyte 02 (see Table 1, third column). Comparing the relative error of the different measuring methods at the same concentration of the interferent, Table 1 shows that the error caused by the presence of the more positively reduced species decreases in the following sequence: CV < BACV << LSV( I~2 ) < L S V ( I ~ ) Therefore CV and BACV are more accurate than LSV regardless of whether I~2 or I ~ is used as the analytical parameter in LSV. Table 2 shows the effect of the peak potential difference and electron number of species O~ and 0 2 on the allowed concentration of the intefferent when e is set at 10%. As the peak potential difference AEp and the electron numbers n 1 n 2 decrease, the allowed concentration of the interferent decreases, i.e., the influence of preceding elec-

e/%

A I 2 -- ( A l 2 ) t

X 100

(a6), where (AI2) t represents the true current difference due to species O 2 in the absence of the interferent O~ (c~ = 0), i.e. the true value of A I 2. Similar error equations can be

Table 2 The dependence o f the allowed concentration o f the interferent with a 10% relative error in the p e a k height or current difference o f the analyte on the peak potential difference AEp and the electron n u m b e r s n I and n 2 o f species O I and 0 2

AEp/mV

nI

n2

Allowed concentration o f interferent BACV AI 2 CV I~2 9 a 20 12 20 12 LSV 1~,2 0.23 0.7 0.36 1 0.23 LSV 1~,' 2 0.23 0.23 0.32 0.3 0.23 39 28 33 20 52 a/ l p 2 c l~ BACV A11 1 1.5 2 3 0.85 LSV ll~ 1 > 1a > 1000 a 60 > 1000 a > 18

200 200 200 200 100

1 1 2 2 2

l 2 1 2 2

1 2.2 1.7 3.4 1

D O = D R = 0.45, N = 500 and the concentration of the analyte is set at 1. 1~,2/1~,2 is defined as the result o f the allowed concentration o f the interferent O~ in one method divided b y that in the other method. The r e m a i n i n g s y m b o l s are illustrated in Figs. 1 a n d 2. a At this concentration, the relative error is less than 10%, and when a lower concentration is set in LSV, or a h i g h e r concentration in CV, the peak o f interest disappears.

14
(~)
.5

P. Zhao et al. / Journal of Electroanalytical Chemistry 402 (1996) 11-17

Table 3 Effect of the concentration of a more negatively reduced species 02 on the peak measurement of species O t under conditions of constant peak potential difference and electron number. ca
I

BACV A11 e/% -- 0.03 - 0.33 - 3.31 - 28.92

LSV 1~,L 0.4508 0.4508 0.4508 0.4508 0.4508 0.4513 e/% -0.00 0.00 0.00 0.00 0.11

0 400

300

200

100 E-E/mV

-100

-200

0 0.01 0.1 1 10 1000

0.6693 0.6691 0.6671 0.6471 0.4757 No peak

The concentration of species O~ is set at l and c 2 represents the concentration of the more negatively reduced species O~. See Table 1 for conditions and Figs. 1 and 2 for symbols.
192---.-.-. T - V

" . . . . . . . . . . .
co 0 ,t

t' 01

--.5

400

300

200

t00

-100

-200

E-E/mV Fig. 1. The theoretical reversible cyclic voltammograms of a more positively reduced species O l ( . . . . . . ), a more negatively reduced species 02 ( . . . . . ) and their mixture ( ) at a spherical electrode: (a) forward branch; (b) reverse branch. The concentration of O~ and 02 is 1; D o = D ~ = 0 . 4 5 ; n l = n z = 2 ; N=500.

trode process b e c o m e s stronger. F o r e x a m p l e , in C V based on the reverse branch o f a cyclic v o l t a m m o g r a m , the allowed concentration of the more positively r e d u c e d

species Ot decreases f r o m 20 to 12 times greater than the concentration o f the analyte 0 2 w h e n ,:IE e decreases from 200 to 100 m V and n~ = n 2 = 2 (see Table 2, fifth column), and it decreases from 20 to 9 times greater w h e n both n I and n 2 decrease f r o m 2 to 1 and A E r, = 200 m V (see Table 2, fifth column). It can be seen f r o m Table 2 that, under various conditions, the a l l o w e d concentration o f the m o r e positively reduced species O 1 in B A C V or C V is larger than that in L S V , and therefore one can c o n c l u d e that C V and B A C V are m o r e accurate than L S V . M o r e over, two more conclusions can be obtained f r o m Table 2: (1) C V is far better than B A C V ( c o m p a r e third and fourth c o l u m n s in Table 2); (2) C V is preferable to smaller peak separations (see Table 2, eighth column). F o r e x a m p l e , the allowed concentration o f the m o r e positively reduced species is 20 times larger in C V than in L S V w h e n A E p = 2 0 0 m V and n j = n 2 = 2 , but is 52 times larger w h e n A E p = 100 m V and n l = n 2 = 2 (see Table 2, last column).
2.3. I n f l u e n c e o f the f o l l o w i n g e l e c t r o d e p r o c e s s

t.5
,g .5

~@

~-5 r-~--____2
~ 1

-.5

-1
-1.5 400 i 300 i 200 ~ 1oo i o i -too

-200

E-E*/mV

Fig. 2. The theoretical reversible voltammograms for BACV of a mixture containing two species O~ and 02 at a spherical electrode. The concentration C2 of 02 is set at 1 and the concentration C l ofO l is set at 0, 1, 2, 3, 4 and 5 as shown in the figure. Other conditions are as in Fig. 1.

Fig. 1 shows that the presence o f 0 2 has little effect on the baseline for measuring O I and the peak h e i g h t I~,] o f 0 1 , i.e. the s e g m e n t A B in the v o l t a m m o g r a m o f 0 2 (Fig. l(a)) is a zero baseline. Thus the f o l l o w i n g electrode process has little effect on the p r e c e d i n g process in L S V . H o w e v e r , it is difficult to d e t e r m i n e O~ by the C V based on the reverse branch o f the cyclic v o l t a m m o g r a m in Fig. l(b). Therefore only a c o m p a r i s o n o f L S V and B A C V is presented. Table 3 shows the c o n c e n t r a t i o n effect and the ninth and tenth c o l u m n s in Table 2 s h o w the effect o f peak potential difference and electron number. It can be seen f r o m Tables 2 and 3 that L S V is far m o r e accurate than B A C V . For e x a m p l e , w h e n the concentration C z o f the m o r e negatively reduced species is 1000 times m o r e than that of the analyte O~, the relative error is 0.11% in L S V but peak 02 disappears in B A C V under the s a m e conditions (see last line of Table 3).

P. Zhao et al. / Journal of Electroanalytical Chemistry 402 (1996) 11-17

15

3. Experiments

3.1. Reagents
0.1 M KC1 was used as the supporting electrolyte. Solutions (0.01 M) of Pb 2+ and Cd 2+ were prepared from nitrate. The reagents used were analytical grade and all water was treated with an ion exchanger and redistilled.
1.5

<(

_-

3.2. Instrumentation
All experiments were carried out with a PARC model 273A potentiostat controlled by a model 50 z IBM P S / 2 computer with model 270 electrochemical analysis software (PARC). The working electrode was a PARC model 303 SMDE and the reference electrode was AgCI l a g 10.1 M KC1.
.5

L.SV II~,)

)3.pO
4

i
4.5

i
5

-log(c/toO1 1-1) Fig. 4. The influence of the more negatively reduced ion Cd 2+ on the determination of Pb 2+ in LSV and BACV ([Pb 2+ ] = 2X 10 -4 M; sweep rate, 100 mV s - i) O BACV; LSV. The broken line and the number on this line signify the allowed concentration of the more negatively reduced species Pb 2 (logarithmic value) in BACV for a 10% relative error. The solid curves join the points.

3.3. Experimental procedures

One drop of 0.5 M HC1 and 5 ml of 0.1 M KC1 were added to the electrolyte cell and the solution was deaerated for 15 min. Solutions of reduced species (Pb 2 and/or Cd 2 ) were injected into the bulk solution by a microinjector and the cyclic voltammograms were recorded. Two series of measurements were performed: (1) the concentration of C d 2+ w a s fixed and the concentration of P b 2+ w a s changed to test the influence of the preceding electrode process (Fig. 3); (2) the concentration of Pb 2 was fixed and the concentration of Cd 2+ was changed to test the influence of the following electrode process (Fig. 4).

3.4. Method for obtaining BACV voltammograms

Because the 270 software does not include the BACV method, we have written our own BASICprogram. After the CV experiments were complete, we stored the voltammogram data on a diskette and then exited from 270 software and ran our own program to generate a BACV voltammogram. Typical CV and BACV voltammograms for a mixture at a hanging mercury drop electrodes are shown in Fig. 5.

I t - " ~
. . . . . . . . .

V(aI~)
/"

~,,,~ LSV(I ~-e) i "~ cv ( I ~

~.~ . _- . =--.

.____p_Acv_

=L <
~. . . . . .

~k____jt.

.....

i '1

I I ~ ,

v-,

!i
0 I I I I

i::
~ I 1

3.5

4 -log(c/tool

4.5 1-1)

Fig. 3. The effect of the more positively reduced ion Pb 2+ on the determination of Cd 2+ in LSV, CV and BACV ([Cd 2+ ] = 5X 10 5 M; sweep rate, 1 0 0 m V s - l ) O AI 2 in BACV; , I~2 in CV; B, 1~,2 in LSV; E3, I ~ in LSV. The broken lines and the numbers on these lines indicate the allowed concentrations of the more positively reduced species Pb 2+ (logarithmic value) in different methods for a 10% relative error. The solid curves join the points.

-t
I I I I
I I ,

-200

-300

-400

-500 -600 E/mY

-700

-800

-900

Fig. 5. The voltammograms of CV and BACV for the mixture of Pb 2+ and Cd2+: lPb 2+ ] = 1.0x 10 -4 M; [Cd 2+ ] = 5.0X 10 -4 M; sweep rate, 100 m V s -I .

16
4. Results and discussion

P. Zhao et al. / Journal of Electroanalytical Chemistry 402 (1996) 11- l 7

As shown in Fig. 5, the potential difference between the anodic and cathodic peaks of ions Pb 2+ or Cd 2+ is 30 mV, indicating reversible electrode processes. The two electrode processes take place independently and the peak potential difference between Pb 2+ and Cd 2+ is 200 inV. Therefore the mixture of Pb 2 and Cd 2+ corresponds to the theory shown in Table 1 and can be used to test it.
4.1. Influence o f the preceding electrode reaction

presence of 10 ppm indium, a cadmium peak of 5 ppm was obtained which was difficult to measure if the forward sweep was used but which could be measured readily if the reverse sweep was used. Therefore the main contribution making the determination of cadmium in the presence of indium possible is the reverse scan technique rather than the derivative technique, as Rooney stated.
4.2. Influence o f the following electrode reaction

Fig. 3 shows the effect on the determination of C d 2+ of the more positively reduced species Pb 2+ where [Cd 2 ] is fixed at 5 x 10 -5 M and [Pb 2+] is varied from 2 10 -5 to 7 x 10 -4 M. The allowed concentration of the interferent for a 10% relative error in the peak height or current difference of the analyte for different methods can be obtained from Fig. 3 (see the broken lines and the numbers on these lines in Fig. 4 and also see the first line in Table 4). Its ratio with respect to the concentration of the determinant is shown in the second line of Table 4. It is quite clear that a higher concentration of the interferent is allowed in CV and B A C V than in LSV. This is generally consistent with the theoretical results (see the last line in Table 4). There is one difference between the theoretical predictions and the experimental system as shown in Figs. 1 and 5: the experimental peak height of the reverse branch of the cyclic voltammogram is higher than that of the forward branch, while the theoretical peak height in both branches is equal. The larger peak on the reverse sweep in the experimental voltammograms arises because the electrode reaction products are insoluble in solution but soluble in mercury, and the diffusion coefficients of the metals in mercury are larger than those of the metal ions in solution [16,17], whereas equal diffusion coefficients were assumed in the theories. Therefore the absolute values of theoretical and experimental results are slightly different. However, the CV, BACV and LSV data are compared based on the same conditions in theory and experiment, and good agreement is obtained as described above. Rooney [18] used the second-derivative linear sweep voltammogram to determine a small peak in the presence of a large wave. Rooney's experiments showed that in the

Fig. 4 shows the effect of the more negative reduced species of CO 2+ o n the determination of Pb 2+. It is quite clear that in the experimental concentration range shown in Fig. 4, l~l is barely influenced but AI~ is strongly affected. These data are consistent with the theoretical results shown in the last two columns of Table 4.

5. C o n c l u s i o n In a mixture containing two components whose electrode reactions take place reversibly and independently, the more negatively reduced species can be determined more accurately by CV (based on the reverse branch of CV voltammogram) and B A C V than by LSV. The allowed concentration of the more positively reduced species for a 10% relative error in the peak height or in the current difference of the analyse is eight times more by CV and six times more by BACV than by LSV according to experiments. However, the more positively reduced species can be determined far more accurately by LSV than by BACV. Compared with the other methods and techniques discussed in Section 1, CV based on the reverse branch of a cyclic voltammogram and B A C V are relatively simple and fast methods. Moreover, the charging current can be eliminated to some extent in BACV. The determination of current difference in B A C V is easier than that of peak height in LSV and CV, and the data for current difference in B A C V have a higher reproducibility than the data for peak height in LSV and CV. In the present work, only experiments in which the peak potential difference A E p is 200 mV and n] = n 2 = 2 are presented. According to the theory, as the peak potential separation decreases CV based on the reverse branch of

Table 4 The allowed concentration ofa the concentration of analyte. Method Parameter 104c' Experimental ratio Theoretical ratio

interferent for a 10% relative error in the peak height or current difference of a determinant C' and its ratio with respect to BACV AI2 3.98 8.0 3.4 CV I~2 5.75 11.5 20.0 LSV I~2 0.589 1.2 1.0 LSV 1~,' 2 0.742 1.4 0.3 BACV AIj 1.26 0.6 3.0 LSV 1~1 100 a 50 a > 1000

See Figs. 1, 2 and 5 for symbols. a At this concentration or ratio, the relative error is less than 10%.

P. Zhao et al. / Journal of Electroanalytical Chemistry 402 (1996) 11-17

17

the cyclic v o l t a m m o g r a m is far m o r e f a v o r a b l e t h a n B A C V a n d the e x p e r i m e n t a l s y s t e m s c o r r e s p o n d i n g to this case are u n d e r i n v e s t i g a t i o n .

Acknowledgment W e are m o s t grateful to Dr. C.G. Z o s k i for h e r c o m m e n t s a n d a d v i c e o n the manuscript.

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[1] [2] [3] [4] [5] G.A. Mabbott, J. Chem. Educ., 60 (1983) 697. P.T. Kissinger and W.R. Heineman, J. Chem. Educ., 60 (1983) 702. K.B. Oldham and C.G. Zoski, Anal. Chem., 55 (1983) 1992. P. Zhao and D. Qi, Acta Chim. Sin., 45 (1987) 1163. A.M. Bond (Ed.), Modem Polarographic Methods in Analytical Chemistry, Dekker, New York, 1980, p. 207.

[6] A.J. Bard and L.R. Faulkner (Eds.), Electrochemical Methods: Fundamentals and Applications, Wiley, London, 1980, p. 232. [7] P.S. Polcyn and I. Shain, Anal Chem., 38 (1966) 370. [8] J. Osteryoung and J.J. O'Dea in A.J. Bard (ed.), Electroanalytical Chemistry, Vol. 14, Dekker, New York, 1986, p. 209. [9] J. Osteryoung and R. Osteryoung, Anal. Chem. Symp. Ser., 25 (1986) 3. [10] M. Palys, T. Korba, M. Bos and W.E. Van Der Linden, Talanta, 38 (1991) 723. [1 l] S.O. Engblom, J. Electroanal. Chem., 296 (1990) 371. [12] I. Pizeta, M. Lovric and M. Branica, J. Electroanal. Chem., 296 (1990) 395. [13] R.S. Nicholson and R.I. Shain, Anal. Chem., 36 (1964) 706. [14] J.C. Myland and K.B. Oldharn, J. Electroanal. Chem., 153 (1983) 43. [15] S.W. Feldberg in A.J. Bard (Ed.), Electroanalytical Chemistry, Vol. 3, Dekker, New York, 1969, p. 199. [16l K. Tokuda, N. Enomoto and H. Matsuda, J. Electroanal. Chem., 159 (1983) 23. [17] J.C. Myland, K.B. Oldham and C.G. Zoski, J. Electroanal. Chem., 206 (1986) 1. [18] R.C. Rooney, J. Polarogr. Soc., 9 (1963) 45.