J. Electroanal. Chem.

, 178 (1984)21-43 21
Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

THE GALVANOSTATIC DOUBLE-PULSE METHOD IN THE STUDY OF

THE KINETICS OF STEPWISE ELECTRODE REACTIONS

O.A. KOPISTKO and N.V. GRUSHINA

lnstttute of Orgamc Catalysts and Electrochemtstry, Kazakh S. S.R. Aeademv of Sctences, 480100, Alma - A ta,
K. Marx Street, 142 (U.S.S.R )
(Received 21st October 1983; in revised form 16th May 1984)

ABSTRACT

Analysis of the kinetics of the overall electrode reaction

Me ° - 3 e - = M e 3+
proceeding through the three consecutive charge-transfer steps
Me ° - e = Me +
Me + - e- = M e 2 +
Me 2+ - e = Me 3+
involving non-adsorbed intermediates under transient single- and double-galvanostatlc conditions has
been made. Curves of "q-t were plotted and change of intermediate concentrations with time were
calculated numerically for different ratios of exchange current densities. It is shown that when the time of
reaching the steady-state, caused by the rate levelling of single-electron steps considerably exceeds the
time of double-layer charging by the short duration current impulse, the employment of the galvanostatic
double-pulse method allows the stepwise electrode process under non-stationary conditions to be
investigated and information about the kinetics of the fastest steps in the reaction sequence to be
obtained. Comparison of the conclusions of the analysis and experiment has been carried out by the
galvanostatic double-pulse method in the stepwise electrode reaction Bi ° - 3 e = Bl(lll) on an amalgam
electrode in 2 M HCIO 4 solutions.

(I) INTRODUCTION

The galvanostatic double-pulse method (GDP) was introduced by Gerischer and

K r a u s e [1] i n o r d e r to s t u d y t h e k i n e t i c s o f f a s t n o n - c o n s e c u t i v e a n d a d s o r p t i o n f r e e
e l e c t r o d e p r o c e s s e s w h e n it is d i f f i c u l t t o s e p a r a t e d i f f u s i o n o v e r v o l t a g e f r o m
charge-transfer overvoltage.
Further development of GDP [2-10] dealt with qualitative evaluation of con-
centration polarization effects on the one hand [2-4] and with analysis of restrictions
o f u s i n g t h e m e t h o d c a u s e d b y i m p e r f e c t i o n o f e q u i p m e n t a n d cells ( p a r a s i t i c
c a p a c i t i e s a n d i n d u c t i v i t i e s , o h m i c d r o p o f p o t e n t i a l ) o n t h e o t h e r [ 5 - 1 0 ] . L o r e n z et
al. [11] i n v e s t i g a t e d a p p l i c a t i o n o f G D P t o t h e e l e c t r o d e p r o c e s s w i t h t w o c h a r g e -
transfer steps that were complicated by intermediate adsorption in order to de-
t e r m i n e k i n e t i c p a r a m e t e r s o f t h e s t e p s as well as d o u b l e - l a y e r a n d a d s o r p t i o n

0022-0728/84/$03.00 ~'~ 1984 Elsevier Sequoia S.A.

22

pseudocapacity. These scientists used a mathematical treatment of G D P for the

equivalent circuit (Fig. 1) suggested previously [12-16] which is valid with the
following simplifying assumptions:
(1) small departure of potential from equilibrium;
(2) neglect of diffusion processes;
(3) adsorption of intermediate obeys the Langmuir isotherm;
(4) exchange current densities of the steps are considerably different.
Circuit element are assumed to be independent of time, potential, and other
parameters and are set in conformity with kinetic and thermodynamic parameters of
partial steps of charge-transfer. However, besides the observance of simplifying
assumptions such an approach requires knowledge of an adequate equivalent circuit
which can be derived from a most probable, a priori, unknown mechanism of the
electrode reaction under study. The latter makes it difficult to use GDP.
This work presents the general kinetic analysis of the overall electrode reaction
Me ° - 3 e - = Me 3+ (1)
occurring through three consecutive steps
Me ° - e - = Me + (2a)
Me + - e - = Me 2+ (2b)
Me 2 + - e - = Me 3+ (2c)
in the absence of adsorption of intermediates under single- and double-transient
galvanostatic conditions. Comparison of the conclusions of the analysis was made by
the galvanostatic double-pulse method in the three-step electrode reaction
Bi ° - 3 e - = Bi(IlI) (3)
on an amalgam Bi°(Hg)/Bi 3+ electrode in noncomplexing 2 M HC10 4 solutions,
because the stepwise character of this reaction was proved previously on amalgam
and solid metal by stationary methods [17,18].

(II) THEORETICALCONSIDERATIONS

Vetter [19] was the first the consider the two-step electrode reaction
St-- e - = Sm; Sm-e-= So (4)

.Q"

Fig. 1. Equivalentcircmt.
 23

for a redox systems under steady-state conditions. Plonski [20] presented analysis of
the two-step reaction (4) under transient galvanostatic conditions and Bachmann
and Bertocci [21], and Plonski [22], under transient potentiostatic conditions.
A three-step electrode process under steady-state conditions was analysed by
Hurd [23] and in detail by Losev and Gorodetskii [24]. The present analysis is made
under the following simplifying assumptions: during the pulse current, Me ° con-
centration in the amalgam is constant; no competitive chemical or disproportiona-
tion reactions of intermediate take place; there are no double-layer effects.
The rates of partial steps of charge-transfer (2a)-(2c) can be represented as

• ( [Me °] /3,F71 [Me +1 --%FTI /

(5a)
i , = ' m l ~ [ M e ioeXp R T [Me+]0 exp RT )

[Me+] exp/72F~1 [Me2+] e x p - - -ot 2 Frl }

12 = i02 [Me+lo RT [Me2+lo RT
(Sb)

[Me 2+ ] /73F~I [Me 3+ ]

i 3=t03 [ Me2+]exp R T -[Me3+]o
- exp - RT } (5c)
where top io2, i03 were exchange current densities; cq, ct2, or3, ~1, f12, f13 are
cathodic and anodic transfer coefficients of partial steps; [Me +], [Me 2+], [Me +]0,
[Me+]0 are intermediate ion concentrations during the flow of current and in
equilibrium.
The external current is the sum of the three partial currents
1 = l1 + i 2 + i3 (6)

(IL 1) Steady-state conditions

Under the steady-state conditions the rates of all three steps (2a)-(2c) are equal

i I --- i 2 = i 3 = ½i (7)
Solution of eqns. (5a)-(5c) in conjunction with eqn. (7) gives the general expression
for the stationary polarization curve of the three-step process [24]:

exp (/71 + ¢2 + ¢3 ) ~ exp - ( a] + a z + a 3 ) F'iloo ]

t=3 RT ]
'01l exp[ (/~2 + i(~3)-R-"T ] + i0-2l . -- Otl) " - - ~ J +i031 . -- + RT]
(8)
where */o~ is the charge-transfer overvoltage under steady-state conditions.
Analysis of eqn. (8) is given in refs. 23 and 24. In the case of i02 < i03 < i01 (A)
and for the region of cathodic and anodic overvoltages determined by the conditions
24

of eqns. (9) and (10)

io, [ Vna }
/-~2e x p [ - ( a, q- f 1 2 ) - ' ~ - J >> 1 (9a)
iol [ , F a F a
io--Texp[ -~'a' + f 1 2 ) ~ ] >> 17m
+ etx poI_
[ - (1
3 + al f13)~] (9b)

io3 [, _, Fn~l
io-"-~exp[t % +/-~3)-~-~ ] >> 1 (lOa)

'o3 [, Frl k ] io3 [ (1 + f13 + OL3)FT~k ]

io7 exp[ I,a2 + f 1 3 ) ~ ] >> i0--Texp[ RT (10b)

eqn. (8) transforms to

[ (1 + f l 2 ) F ~ ] (11)
t~, = 3io2 exp RT

i k = - 3i02 exp
[ (l+a2)F*l~]
RT (12)

for anodic and cathodic polarizations respectively.

For high cathodic and anodic overvoltages eqn. (8) transforms to

i k -- - 3i03 exp RT

i. = e__[ &Fn~ 1 (14)

respectively. In the case of io3 < i02 < i01 (B) for cathodic overvoltages eqn. (8)
transforms to

i k -- - 3i03 exp RT
For low, moderate and high anodic overvoltages determined by the conditions of
eqns. (16)-(18)
io3 [ (1 +/3 3 + a,)F~ L ]
l~oTeXp[ RT , << 1 (16a)
io3 [ (f13 + a2)F~l~ 1 << 1 (16b)
io---2exp[ RT 1
io, [ - ( a, + fl2 ) F ~ 1
7~o2exp[ RT ~ >> 1 (17a)

im [ - ( 1 + a, + fl3)Frl a ] i01 [ -- (0/1 "]- fl2)F~: I (17b)

T~o2exp[ RT << 7-~o2exp [ RT
 25

(Ol exp,[ --(O/1 -t- /~2)Fna ] << 1 (18a)

102 t RT l
'Ol [-(l+al+B3) n~ <<1 (18b)
exp RT

three linear regions appear on the stationary polarization curve which are described
by the equations

(2 + fl3)F*/~ (19)
i a = 3io3 exp RT

(1 + f12) F*/a (20)

l. = 3io2 exp RT

i a = 3101 exo,- fll F ~ (21)

F o r the charge-transfer resistance R , = (d~/~/di)n~o =0 from eqn. (8) it is possible

to obtain [24]
RT(1 + 1 + 1)
R,,=-~ iol io-~ ~ (22)

It is to be noted that the given analysis is valid only under steady-state conditions.

(11.2) The moment of switching on the current (Cd = O)

At the moment of switching on the current t = 0 intermediate ion concentrations

are approximately equal to equilibrium concentrations and the eqns. (5a)-(5c) can
be written as

( fllF*l° exp - alF*/° ) (23a)

i I = iol exp RT R~---~

• [ fl2FTl° - a2F~/° ] (23b)

:2 = :o21exp ~ exp RT ]
f13 F*/o -- a3 F*lo
i3=to3(exp ~ exp ~ ) (23c)

where T0 is the overvoltage at the moment when t = 0.

Solution of eqns. (23a)-(23c) in conjunction with eqns. (6) gives the general
expression for the non-stationary polarization curve of a three-step electrode process
• [ flxFTIo -oqF~lo I ( flzF~° -°t2FTl° I
i=tox/eX p ~ exp RT ] + i o 2 exp ~ exp RT ]

( fl3F*l° exp F- r a3
/~° ) (24)
+ i03 exp RT RT
26

When a I = a 2 = a 3 = fla = f12 = f13 = 0.5 eqn. (24) transforms to

• + 1 (25)
*/o = In 2(ira + io2 + i03) + 4(ira + i02 + 103) 2

If i >> 2(i m + io2 + io3 ) then eqn. (25) is simplified to

2.3.2RT 2.3.2RT .
no - -ff log i -ff log(i0, q- i02 q- i03 ) (26)

Relationship (26) is analogous to the Tafel plot with the slope 0.118 V and its
extrapolation to 7/0 = 0 gives the value of log(i01 + io2 + i03).
The derived equations (24)-(26) enable us to obtain kinetic p a r a m e t e r s of
single-electron steps. It is to be noted that under steady-state conditions the overall
electrode process is limited by the slowest step and analysis of data according to the
stationary equation (8) yields information a b o u t the slowest steps of the overall
process, while the e m p l o y m e n t of non-stationary equations (24)-(26) permits the
kinetics of the fastest steps to be determined which can be quasi-equilibrium under
steady-state conditions. An expression for the charge-transfer resistance at the
m o m e n t when t = 0 can be obtained from eqn. (24) after expansion of the exponents
in series under 7/0 << R T / F with further differentiation

i m + i02 + i03
Expression (27) differs from (22) which is valid only for stationary conditions. Hence
the apparent kinetic parameters obtained near the equilibrium by stationary and
non-stationary methods (for instance, by impulse methods which analyse the kinetics
as t --* 0) must differ.
Indeed, in some cases under similar experimental conditions reference data on
kinetic parameters of electrode processes [25] differ depending on the m e t h o d of
study of the kinetics of the electrode process.

(II. 3) Reaching the steady-state

Let us consider the process of reaching the steady-state in the case when
intermediate ion concentrations [Me +]0 and [Me2+]o are not zero neglecting the
diffusion of Me +, Me 2+ and Me 3+ ions.

(II.3.a) Ca = O. Using the condition of mass balance for the intermediates we have
the system of differential equations

d [ M e + ] = i, - i 2 (28a)
dt F
d i M e 2+ ] = i 2 - i, (28b)
dt F
 27

The system (28a)-(28b) should be solved in conjunction with eqn. (6) and taking
into account eqns. (5a)-(5c) under the following boundary conditions: at t = 0;
[Me+ ]= [Me+]0; [Me2÷]= [Me2+]0; ~ = 70; as t ~ oo; [Me + ] ~ [Me+]~; [Me 2÷]
--+ [Me2+]oo; 7/--+ r/oo

(II.3.b) C a --/: O. In this case the system (28a)-(28b) should be solved in conjunction
with the equation

i=il +i2+ i3+ Cdd~

dt (29)

under the following boundary conditions: at t = 0 ; [Me÷] = [Me+]0; [Me2+] =

[Me2+]0; ~ = 0. as t ~ ~ ; [Me ÷ ] ~ [Me+]~; [Me 2 ÷ ] ~ [Me2+]~; ~/~ ~ .

(II.3.c) Ca4: O. The current has the form of two rectangular impulses with high
amplitude and short duration of the first impulse. The total system of equations
considering the diffusion of both Me + and Me 2+ intermediates and Me 3+ ions in
the course of electrolysis has the form
d[Me + ] il--i 2 ( 0[Me+] )
(30a)
dt ~ + D1 . x=o

d[Me2+l '2-i3 (3[Me2+l)

(30b)
dt - F + D2 . . a S x=o

d[Me 3+ ] i 3
dt - F + D3 .
(0[Me3+])
. 0 X x=o
(30c)

i = i 1 + i 2 + i 3 + Ca-~tt = i [ f ( t ) ] (31)

where D 1, D 2, D 3 a r e the diffusion coefficients of Me +, Me 2÷ and M e 3+ ions

respectively. The terms D n(3[Men + ] / 0 X ) x=0 take account of the mass-transfer of
metal ions due to diffusion. The general mathematical approach to this problem
consists in the solution of Fick's equations (32a)-(32c) for the non-stationary
diffusion
O[Me + ] O2[Me + ] O[Me 2+ ] 02[Me 2+ ]
Ot D, OX 2
(a); 3t D2 OX 2
(b);

0[Me 3+ ] D3 02tMe3+][ (c) (32)

3t 3X 2

with initial and boundary conditions

[Me+l( X, O ) = [ M e + l o ; [Me+I( t, o o ) = [ M e + l o ; l a [ M e + ] ] l \
\ 0X / x=o
28

given by (30a)
0[Me 2+ ]
[Me2+](X, 0)= [Me2+]o; [Me2+](t, ~ ) = [Me2+]o; (
OX x=o
given by (30b)
and
0[Me 3+ ]
[Me3+](X, O) = [Me3*]o; [Me3+](t, o¢) = [Me3+]o; (
0X )x=o
given by (30c)
The equations (30a)-(30c) and (32a)-(32c) form a mixed system of differential
equations in partial and ordinary derivatives. The exact solution of Fick's equations
(32a)-(32c) with the above mentioned boundary conditions leads to very com-
plicated integral equations, the numerical calculation of which requires special
algorithms and much computer time [26,27]. To simplify the calculations to a good
approximation it can be assumed [26] that [Me+I(0, t), [Me2+](0, t), and [Me3+](0, t)
are constant during a very short time interval. In this case, instead of eqns.
(32a)-(32c) we have
O[Me ] [Me+]o-[Me+],
(33a)
ax ,x-0 ( b,i
0[Me +]
ax
)
j x-o
[Me2+]0-[Me2+],
~D2t
(33b)

(0[Me3+]) [Me3+]0 - [Me3+]t

OX x=o = vf~D3t (33c)

Finding solutions in the analytical form for cases (II.3.a)-(II.3.c) is not possible
and hence the equations have to be solved numerically.

(111) NUMERICALCALCULATIONS

Throughout the computation, intermediate ion concentrations were taken to be

equal, [Me+]o = 10 -9 and [Me2+]o = 10 -11 mol cm3; Cd = / ~ F / c m 2 and independent
of electrode potential. The transfer coefficients a, and fl, were assumed to be 0.5. The
two exchange current density variants were taken to be (A/cm2): (A) io~ = 10-2;
io2 --- 10-4; io3 = 10-3; (B) iol = 10-2; io2 = 10-3; io3 --" 10-4; the temperature was
set at 25 o C.
For the variant (II.3.c) diffusion coefficients of Me ÷, Me 2+ and Me 3÷ ions were
set at 10 -5 cm2/s and Me 3+ concentration at 10 -5 mol cm 3. Duration of the
charging current impuse, tl, was in all cases 2.0 #s, the il/i 2 ratio was 5 : 36. The
condition (d~/dt),, = 0 was selected by the iterative method to an accuracy of
0.01%.
The calculations were performed by Adams method [28,29].
 29

(11I. 1) Results of numerical calculations

Figures 2 and 3 give overvoltage and intermediate ion concentration dependences

with time for Ca = 0 and for the ratios of the exchange current (A) and (B). It should
be noted that with current increase in the anodic process for both variants the curves
of T/-t from monotonically growing towards the steady-state overvoltage alter to
monotonically descending.
Cathodic curves of ~ - t for ratio (B) are S-shaped. It should be noted that the
time for reaching the steady-state (relaxation time ~') decreases with increase in i,
this decrease being greater for (B) than for (A).
Change of intermediate ion concentrations with time is generally smooth, however
dependences [Me2+]/[Me2+]o-t for ratio (A) pass through the m a x i m u m for not
too high currents (Fig. lc). The cathodic curves of ~ - t for Ca ~ 0 (Figs. 4 and 5) and
for ratio variant (A) increase monotonically towards the steady-state overvoltages

~,o E ¢o,o ¢
--.IX

L~ I l l \ ~ t c

, I5,.11/\

60 - 6 20 2,0

7
¢20 8 40 ~,0

~8o ~ ' - 9 60 8,0

Fig. 2. Dependences of '0-t (a), [Me+ ]/[Me * ] 0 - t (b), [ M e : + I / [ M e 2~ ]-t (c) for Ca = 0 Exchange
current density values correspond to case (A). Current densiues for curves (103 A /cm2), cathodic: (1)
9946; (2) 17.54; (3) 4.92, (4) 1.27; anod~c: (5) 1 15; (6) 5 14; (7) 43.37; (8) 10907; (9) 576.95.
30

for the variant (B) they are double-S-shaped, that is unusual. The anodic vt-t curves
are characterized by the appearance of a m a x i m u m with increase in the anodic
current densities for both variants (A) and (B). A similar effect for the two-step
m e c h a n i s m was first shown by Plonski [20]. Consider the condition of appearance of
the m a x i m u m on the ~ - t curves.
It is obvious that the m a x i m u m must appear if
(~/0-~) > 0 (34)
Using eqns. (11) and (26), we obtain
2RT, 3i m
(T/° - T/°~) = ---F---t°g (io, + 102 "4-'03) > 0 (35)

T h e inequality (35) is valid when 3~o] > (Zo] + ~o2 + Zo3) or

io] > ½(io2 + io3) (36)

4,O

48OH O,8 i

II , 2
420 I1~~ 3 0,/~
f
0 )o v,-s o t/ s

6
60 2,o 20
f 7

120

/8O

8 s
tOO
Fig 3. Dependences of O - t (a), [Me + ]/[Me + ] 0 - t (b), [Me 2 + ]/[Me 2+ ] o - t (c) for C,a = 0 Exchange
current density values correspond to case (B). Current densities for curves (103 A / c m 2 ) , catho&c: (1)
32.3; (2) 4.6; (3) 2.1; (4) 0.256; anodic: (5) 1 51; (6) 8.46: (7) 87.2; {8) 14760.
 31

Similarly, the condition of the appearance of a maximum on the cathodic curve

must be
io3 > ½(i0, + io2) (37)
The critical anodic overvoltage above which the maximum should appear is derived
from the solution of eqn. (1l) together with eqn. (26).

~lcr= 2.3ff-~log( im + i°2 + t°3 (38)

Relationship (38) is exactly fulfilled if the general equation (8) is approximated well
enough by eqn. (11) in the region of ~"~ determined by conditions (9a) and (9b).
Figure 6 presents, for the variant (A), the curves of ~/-t, [Me+]/[Me+]0-t and
[Me2+]/[Me2+]0-t for C d = 3 0 # F / c m 2 and applications of the double-pulse
galvanostatic current (curves 1'-4'), compared with 7/-t curves calculated for Cd = 0
and t 1 = 0 (curves 1-4) and with an account of the diffusion effect (curves 1 " - 4 " ) .
The comparison of 7/o and (T/0)t, values for t 1 = 2/~s (Fig. 6) allows the proximity of
these values and the increase in the discrepancy between them with growth of the
current densities of the first impulse to be seen. For all the curves of Figs. 6b and 6c

2OO
~ -

~---- t
112O,~s

,oo

- FI
Ii

Fig. 4. Dependences of ~ - t for Cd = 30 ~ F / c m 2 Case (A). Current densities for curves (103 A/cm2),
anodlc: (1) 1423.8; (2) 161.7; (3) 69.74; (4) 26.2; (5) 5.14; cathodic: (6) 99 46; (7) 17.54; (8) 2.09: Abscissa
for curves (ms/div): ( 1 - 5 ) 0 0 5 ; (6)0.1; (7)0.4; (8)0 8.
32

change in the [Me+l/[Me+]0 and [Me2+]/[Me2+]0 values at t I = 2/~s is negligible

compared with stationary values of the latter (their numerical values are given in the
legend to Fig. 6). However, the given systematic error will increase at other equal
conditions with decrease in equilibrium intermediate concentrations. Thus, contribu-
tion of the Faradaic current to the total current during passing of the charging
current impulse grows with increasing i, and at high (r/0),, change in Me + and Me 2+
intermediate concentrations should be taken into account even for a minimum, short
duration of the charging current impulse. Hence it follows that validity of the
obtained non-stationary equations (24)-(27) is limited by certain limiting values of
kinetic parameters of charge-transfer steps, amplitude and duration of the charging
current pulse.
Now, we determine the upper limit of the exchange current densities of the fastest
step in the reaction sequence where G D P is successfully applied to stepwise
processes. A reasonable criterion of the absence of the effect of the process of the
double layer charging by a high-amplitude short pulse can be as follows
~->~ 100 t t (39)

S
!

20O

¢00

0 r

¢00
I
W
I
I
200:

Fig. 5. Dependences of ~ - t for Ca = 30 /~F/cm 2. Case (B) Current densities for curves (103 A/cm2),
anodic: (a) 1476.0; (2) 87.23; (3) 33.403; (4) 8.463; cathodic: (5) 32 33; (6) 10.03; (7) 0.95. Abscissa for
curves (ms/div): (1) 0.02; (2-4) 0.2; (5) 0.1; (6) 0.25; (7) 2.0.
 33

where ~" is the time at which the stationary (or close to it) state is reached.
Obviously, the functional dependence of ~" on exchange currents of partial steps of
charge-transfer and equilibrium concentrations of intermediates are to be de-
termined. The numerical analysis of the (30a)-(30b), (31), (33a)-(33b) system is
tabulated in Tables 1 and 2.
The data of Table 1 show the time at which the stationary overvoltage value ( , ) is
reached at fixed values of anodic and cathodic current densities depending in
general on the exchange currents of partial steps but determined by the slowest step
of the reaction sequence.
This unexpected conclusion is, however, quite natural because the velocity of a
consecutive process is determined by the slowest step. Table 2 shows the relaxation
time (z) to depend linearly on excessive equilibrium intermediate concentrations:
r = k l [ M e + ] o , if [Me+]o >> [Me:+]o and ~"= k:[Me2+]o, if [Me2+]o >> [Me+]o .
The result for the cathode process is similar. Assuming a minimum duration of
the charging pulse t 1 = 2 /~s, eqn. (39) can be written as

t >~ 0.2 ms (40)

~' o,,95ol- ,~" o.~ool-/, ~'

,oo ,~'~ "
/ ~1~
,. ,_v_z_ . I 0,g975 r / J o,goot/ /I
5-0 " .J" i t ) ~-" ~ i

o ~_, ~ ~ l H 3~-g-s4ooo~
, ~ ~ tl/J;
~ "
i ~ 2 t/r~ ~,oo l~.~----=~]~k,~

\ ,I ~,,o,oo
tOO Pt \ <°"I- \k!.
II / I \l':'"
#
/, ~,0200 I/
It, ':"'
/ ,,o~o V
~1~1
]'
I
Fig. 6. Dependences of r t - t (a), [Me + ] / [ M e + ] 0 - t (b) [Me 2+ I / [ M e 2+ ] o - t (c) calculated when using the
double rectangular current. The exchange current densities correspond to case (A), C a = 30 / t F / c m 2.
t I = 2.0 #s for curves 1 ' - 4 ' and 1 " - 4 " ; t I = 0 for curves 1 - 4 (single pulse current, C a = 0). Current
densities of the first pulse ( A / c m 2) for the curves, anodic: (1) 3.04; (2) 0.50; cathodic: (3) 0.17; (4) 0.82.
Current densities of the second pulse ( A / c m 2) for curves, anodic: (1) 0.58; (2) 0.16; cathodic: (3) 0.0049;
(4) 0.029. D 1 = D 2 = D 3 = 0 for curves 1 - 4 and 1 ' - 4 ' . D 1 = D 2 = D 3 = 10 -5 c m / s for curves 1 " - 4 " .
Stationary values of [Me + ] ~ / [ M e + ]o and [Me 2+ ]o~/[Me 2+ ]o for the curves: (1) 83.7 and 9.15; (2)
13.32 and 4.14; (3) 0.2 and 1.39; (4) 0.1 and 8.37.
34

Then the upper value of the exchange current density of the slowest step and the
lowest value of the concentration of the Me + (or Me 2÷) intermediate can be
determined from data of Tables 1 and 2 a s 10 4 m//cm 2 and 10-1° mol c m 3.
Assuming the region of stationary overvoltages to be In~l ~ 15 m V ( a t h i g h v a l u e s o f
In~l the value of z strongly decreases (Figs. 2-5), that violates condition (40)) and
the error= 10% we find from Tables 1 and 2 that the maximum value of the
exchange current density of the fastest step should not exceed 10 -t A/cm 2 at
[Me+]0 = 10 -l° m o l c m 3.

TABLE 1
Dependent of cathode, ~- , and anode, ~-+, relaxation times on the exchange current of partial steps of
charge-transfer a
Equilibrium concentrations of intermediates: [Me + ]0 = 10--1° mol cm -3; [Me2+ ]0 = 10 12 mol cm 3:
t_ = 5.02 × 10 - 4 A / c m 2 ; 1+ = 5.56 × 10 - 4 A / c m 2

104 tol 104/02/ 104103// + ('O0)q// + 'O~// "r+// -(no)q~~ - ~ / / 'r/

c m - 2//A Acm 2 A cm -2 mV mV ms mV mV ms
10 1 10 6.8 17.0 3.4 6.1 15.4 1.9
100 1 10 1.3 15.0 3.7 1.2 15.0 2.2
103 1 10 1.0 15.0 4.2 0.1 15.0 2.2
104 1 10 < 0.1 15.0 4.2 < 0.1 15 0 2.2
105 1 10 < 0.1 15.0 4.2 < 0.1 15.0 2.2
100 0.1 10 1.3 43 9.6 1.2 50 2.4
100 0.01 10 1.3 71 13.4 1.2 88 2.5
100 1 1 1.4 19 4.5 1.3 38 3.1
100 1 0.l 1.4 34 9.6 1.3 150 2.2
100 0.1 1 1.4 46 12 1.3 60 2.3
100 0.01 0.1 1.4 78 34 1.3 150 45
1 1 10 11.8 41 42 10.7 20 2.2
10 0.001 0.01 14.1 104 80 12.7 263 1.0
10 1 100 1.3 16 2.5 1.2 13.8 1.6
10 1 103 0.1 16 2.5 0.1 13.4 2.28
10 1 104 <0.1 16 2.5 <0.1 134 2.28
10 1 10 6.8 17 3.4 6.1 15.4 1.92
10 102 10 1.2 3.0 0.005 1.1 2.9 0.005
10 103 10 0.1 2.8 0.005 0.1 2.7 0.005
10 104 10 < 0.1 2.8 0.005 < 0.1 2.7 0.005

~" was evaluated as the time for reaching 95% of -q~ from "q-t curves.

TABLE 2
Dependence of "r+ on equilibrium concentrations of intermediates Me + and Me 2÷ at i_ = 5.02× 10 4
A / c m 2, variant (A)

[Me+]o/molcm 3 10 9 10 9 10 8 10-,~ 10 10 10-11 10 11 10 l~

[Me2,-]o/molcm 3 10-13 10 12 10 11 lO-li 10 11 10-11 10-10 10-9
~'~/ms 37 37 370 37 37 0.46 4.6 46
'r/ms 48 48 480 48 4.8 0.37 3.7 37
 35

For metal ion electrodes the fastest step is usually the ion transfer step [18]. F o r
[Me °] = 10 -5 mol cm 3 we obtain the standard value for ksh of the fastest first step
from the equation i = Fksh[Me°]'~,[Me+]/~1 or ksh ~< 10 c m / s .
Thus the equation for non-stationary charge-transfer resistance, eqn. (27), m a y be
used to obtain the exchange current density of the fastest step of ion transfer
provided its k~h does not exceed 10 c m / s . It is to be noted that evaluation of the
upper limit of ksh of the fastest step does not involve any assumptions of ideality of
the form of impulses or residual self-inductance of the cell circuit and miscompensa-
tion of ohmic drop.
Figure 6 shows the diffusion effect on the stepwise process to be negligible at
registration times of cell response comparable with the charge time of double-layer
capacity (coincidence of curves 1 ' - 4 ' and 1 " - 4 " , Fig. 6a). In fact, the diffusion
becomes of importance with increase in the electrolysis time (Fig. 7). The diffusion
of intermediate ions and stable metal ions retards reaching of the steady-state (Fig.
7, curves 2 and 3) both for cathode and anode processes (see Fig. 7, if t >_ 8 - 1 0 ms).
It leads to the conclusion that correct e m p l o y m e n t of the expression for the
stationary charge-transfer resistance of the stepwise process (22) is limited both by
strict linearization demands [30] and the permissible range of the time of response
observation.

(IV) EQUIVALENT CIRCUIT AND COMPARISON OF THE GDP WITH IMPEDANCE METHOD

The circuit (Fig. 1) used in refs. 12-16, which is valid at small departures from
equilibrium and is formally similar for processes involving adsorption steps, can be
an analogue of the electrode process with consecutive mechanism of charge-transfer

140

I I I I
~0 ¢5 t/ms

Fig. 7 Dependences of */-t, calculated when using the double rectangular current. Diffusion effect. Case
(A), C a = 30 p,F/cm2, t I = 2 p,S. Current densities of the first pulse (102 A/cm 2) for the curves, anodic:
(1,2) 1.95; cathodic: (3,4) 1.80. Current densities of the second pulse (104 A/cm2): for the curves: (1,2)
5.56; (3.4) 5.02; D1= D2 = D 3 = 0 ( c u r v e s 1, 4 ) D1= D 2 = D3 = 10- 5 cm2/s (curves 2, 3).
36

without adsorption of the intermediates. However, the physical character of its

elements is different. For the stepwise process in the linearization region
R ' = (~'/o)q/i2 (41)
R " = no~/i2 (42)
Ca = iltl/(~lo ),, (43)

1/R'= 1/R 1+ 1/R 2 + 1/R 3 = ( F/RT)(tol + io2 + to3 ) (44)

R " = ( 1 / 9 ) ( R 1 + R 2 + R3) = ( R T / 9 F ) ( 1 / i o l + 1/io2 + 1/i03 ) (45)
R 1 = (RT/F)(1/iol) (46)
R 2 = (RT/F)(1/io2) (47)
R 3 = (Rr/F)(1/io3) (48)
C 1 is the non-adsorption pseudocapacity caused by the process of reaching the
steady-state. Cd is the double-layer capacity. Ro,n is the solution resistance.
The element of the circuit, C 1, is formally analogous to the adsorption pseudo-
capacity caused by intermediate adsorption during the electrode process [13,14].
However, in the case of the stepwise process involving no adsorption, element C l
appears due to a Faradaic process of charge-transfer through the interphase and
establishment of the stationary intermediate concentrations at the electrode inter-
phase (different from equilibrium concentrations, i.e. [Me+]oo 4:[Me+]0 and
[Me2+]oo 4: [Me2+]0).
Resistance R' is determined by eqn. (41) under the condition (dv//dt),, = 0; it
corresponds to the parallel connection of the partial charge-transfer steps (2a)-(2c)
as t --, 0 and is related to the exchange current steps by eqn. (44).
Resistance R" is determined by expression (42) and corresponds to the stationary
resistance of the stepwise process (2a)-(2c)as t ~ oo (neglecting the diffusion) and is
related to the partial charge-transfer steps by eqn. (45). The circuit (Fig. 1) presents
a full description of the impedance of three-step electrode process without adsorp-
tion. The elements of the circuit (Fig. 1) and hence, the kinetic parameters of
charge-transfer steps can be measured by other relaxation methods, e.g. the imped-
ance method. In this case R' and the exchange current of the fastest step can be
determined from the relationship between the active component of the Faradaic
impedance and ~0 by the usual extrapolation of the R , - 1 / o a 1/2 dependence to
oa ~ oo. In order to calculate the exchange current densities of the two-step electrode
process involving the adsorption of an intermediate, Lorenz et al. [11] used the
following equations for R' and R"
R" = ( R T / F ) ( 1 / i o , ) (49)
R" = ( RT/4F)(1/io2 ) (50)
Relationship (49) used in ref. 11 neglects the contribution of the exchange current
densities of the slowest charge-transfer steps, and relationship (50) neglects that of
 37

the fastest steps. Hence, the relationships of types (44) and (45) are more exact,
especially for the systems with close values of exchange current densities of partial
steps.
It is noteworthy that the time for reaching the steady-state (relaxation time)
"r = f ( i o , , a,, fl,, i, [Me+]0, [Me2÷]0) can be sufficiently great (Figs. 2-7). Hence, it is
possible to study the kinetics of the stepwise electrode reaction (1) under conditions
far from the steady-state by relaxation methods. Here the galvanostatic double-pulse
method is very useful when the time of double-layer charging is about 10 -6 s.

(v) EXPERIMENTAL

All experiments were performed in a double-walled 150 ml Pyrex cell thermo-

stated at 25 °C. High purity mercury and bismuth (99.9999%) were used to prepare
the amalgam. The working electrode was the amalgamated surface of a bismuth rod
in fluoroplastic isolated with a working area of 4.46 × 10 -2 cm 2. An amalga,ated
bismuth plate with an exposed area of about 10 cm 2 was used as an auxiliary
electrode.
A saturated calomel electrode was used as reference outside the cell and was
electrolytically connected to the working electrode by a Luggin capillary tube filled
with the test solution. The working solutions were prepared from A.P. Bi203
calcined at t - 8 0 0 ° C , highly refined HCIO 4 and fresh bidistilled water. The
solutions were de-aerated with a mixture of highly refined helium and electrolytic
hydrogen and were used under excess pressure in the cell.
The cell and other glassware were cleaned with chromic acid.
The galvanostatic double-pulse method was carried out using two double-channel
currrent pulse generators G5-30A and G5-56 which gave rectangular current pulses
with a rise time about 5 x 10-8 s. To compensate for the ohmic drop a bridge circuit
was used [3]. The overvoltage-time transients were recorded on a storage oscillo-
graph of the $8-13 type with a maximum sensitivity of 0.5 m V / d i v .

(vI) EXPERIMENTAL RESULTS

The present measurements were made on an amalgam bismuth electrode

Bi°(Hg)/Bi 3+ at t = 2 5 ° C in a series of solutions containing 1 0 - 3 - 1 0 2 M Bi 3+
and 2 M HCIO 4.

( VI. 1) Transient curves

The oscillograms of ,/-t curves, obtained by using two rectangular current pulses,
are shown in Fig. 8. Cathodic ~ - t curves increase monotonically from values of
(~/0),1 towards the steady-state overvoltages. Anodic ,/-t curves have a similar form.
The duration of charging current impulse t 1 is 2-7/~s for all the curves, the time of
reaching the steady-state greatly exceeding t 1, i.e. the condition tl << ~- is fulfilled.
38

F r o m the e x p r e s s i o n

Cd = i l t l / ( ~ t o ) t ' (51)

the d o u b l e - l a y e r c a p a c i t y , C,, was c a l c u l a t e d . Its v a l u e is 25 _+ 3 / ~ F / c m 2.

T h e c a p a c i t y o f the B i ° ( H g ) / B i 3+ e l e c t r o d e was c a l c u l a t e d f r o m the s l o p e o f the
d e c a y t r a n s i e n t c u r v e s at the m o m e n t o f s w i t c h i n g o f f the c u r r e n t a f t e r the ~ - t
c u r v e s r e a c h e d the s t e a d y - s t a t e o v e r v o l t a g e , as a m e t h o d to e v a l u a t e the a d s o r p t i o n
p s e u d o c a p a c i t y b y a d s o r p t i o n o f the i n t e r m e d i a t e s [13,31]. T h e v a l u e s o f c a p a c i t y
t h u s o b t a i n e d f r o m c a t h o d i c a n d a n o d i c d e c a y t r a n s i e n t c u r v e s d o n o t d e p e n d o n the
d e c a y o v e r v o l t a g e s a n d t h e y are f o u n d to be 31 + 7 / z F / c m z (Fig. 9).

(VI.2) Stationary polarization curves

T h e s t e a d y - s t a t e o v e r v o l t a g e s , r/~, t o g e t h e r w i t h the c o r r e s p o n d i n g c u r r e n t d e n s i -
ties f o r m the s t a t i o n a r y p o l a r i z a t i o n c u r v e s in T a f e l c o o r d i n a t e s (Fig. 10) a n d in
r t ~ - i c o o r d i n a t e s (Fig. 11). T h e s t a t i o n a r y c a t h o d i c r / ~ - l o g i c u r v e s are c h a r -
a c t e r i z e d b y a single T a f e l line w i t h a s l o p e close to 0.118 V. S t a t i o n a r y a n o d i c

~t

.9'
,I
~0' I I I I I I I

.3'
f
Fig. 8. The cathodic (1,1')-(2,2') and the anodic (3,3)-(4,4') oscillograms of r/-t curves, obtained on a
Bl°(Hg)/Bi 3+ electrode in 2 M HCIO4 +10 -2 M B13+ solutions by the double pulse galvanostatic
method, q (A/cm2), t I (p,s) and 12 (A/cm 2) for curves (1, 1'): q = 0.551; t I = 3.0; t 2 = 2.66×10-2; for
curves (2, 2'): q = 0.25; t 1 = 3.0; l 2 = 1.09 × 10-2; for curves (3,3'): q = 0.19; t 1 = 2.0; t2 = 5.31 × 10-3;
for curves (4, 4'): q = 0.16; t 1 = 2.0; t 2 = 4.47×10 -2. Abscissa for curves (1, 2) 0.5 ms/div; (1'-2') 5
#s/div; (3,4) 5 p.s/div; (3'-4') 1 ms/div. Ordinate axis for curves (1,1',2,2') 50 mV/div; (3,3') 20
mV/div; (4,4') 10 mV/div.
 39

hO
II
0 ~) L O0
u. 3 0 V OVJ
@
,2 20

I I I
20 30 40~/mV
Fig. 9. The dependences of Cde~ on decay stationary overvoltages for the cathodic ( O ) and the anodlc (O)
polarizations. [Bi(III)] = 10 3 M.

0,¢

0,2 - .z"4
- - q

0,3

Fig. 10. (a) Experimental (O, ,,, V, X) curves of ~0-1og t, obtained from 71oovalues (curves O, &) and (%)t,
values (curves V, X) on a Bi°(Hg)/Bi 3+ electrode in 2 M HCIO 4 solutions. Concentrations of Bi(llI)
( M ) : 10 -3 and 10 -2 for curves (O, V, ( ~ ) , and (A, X, ®) respectively. The calculated stationary ( © )
and nonstationary (zx) ~0-1ogt dependences. Plots (~) and ® were obtained without extrapolations to
t 1 = 0. (b) The dependence of log t-log[Bi 3+ ] at q~ = 0.144 V vs. NHE.
40

~/~-log i curves are characterized by an extended Tafel line with a slope close to
0.038 V, however this value increases slightly with increase in i~. With % = f12 = 0.5,
the relationships (11) and (13) show experimentally observed Tafel slopes. The
cathodic order for Bi 3+ ions was found to be 0.92 - 1.0 at ¢p = 0.144 V with respect
to the N H E (Fig. 10b), and the anodic one to be zero. The plots of stationary
cathodic and anodic dependencies of 7/~-i (Fig. 11) obtained near equilibrium are
symmetrical and retain linearity up to 14-16 mV, but curve at higher I~P- The slope
of the ~oo-i dependence near equilibrium gives the value of the stationary charge-
transfer resistance (for [Bi 3+] = 10 2 M): R s t = ( d ~ / ~ / d t ) , ~ o = 52 V A - 1 c m 2.

(VI.3)Non-stationarypolarizationcurves
Overvoltages (B0)q at the moment of full charging of the double-layer by the
current impulse i 1 of t I duration together with the corresponding current-pulse
densities i 2 form non-stationary polarization curves ~/0-1og I (Fig. 10) and ~0-i (Fig.
11).
Figure 10(a) shows the slope of non-stationary cathodic and anodic T0-1og i
dependences at I~10[< 0.080 V to be close to 0.118 V, but they rapidly increase when

2040 t~
t5 7,5
¢0 5
5 2,5

I I I I
3,0 2,0 j-3,o
/ ~ 2¢~5 /~mAcro-

~ tF "'°
/ jl
Fig 11. Experimental (zx, O) curves of B - t , obtained from ~o~ values (curve zx) and (Bo)q values (curve
0) on a Bi°(Hg)/Bl 3+ electrode in 2 M HCIO4 + 10 2 M Bi 3÷ soluuon. The calculated stationary (A)
and non-stationary (O) ~ - i dependences.
 41

I*/0l> 0.080 V. However, usage of (*/0)t, values corrected by extrapolation of */-t

curves to t I = 0 to plot ,/o-log i curves when I*/01 > 0.080 V makes it possible to
extend - 0.118 V-sloped linear parts of */0-log i dependences to the I*/01 > 80 mV
region. These observations show that it is necessary to take account of the influence
of concentration polarization during charging of the double-layer by a short-layer by
a short current impulse, tl = 2 - 7 #s, at high overvoltages. Extrapolation of the
anodic and cathodic Tafel lines */o-log i to 770 = 0 yields equal values of i0ex" All this
is in good accord with relationship (26). Non-stationary */0-i dependences (Fig. 11)
obtained near equilibrium are linear and symmetrical at 17701 < 10 mV and their slope
gives the value of the non-stationary charge-transfer resistance, R n = (d*/o/di)no~ o
= 3.6 V A -1 cm 2 for [Bi 3+] = 10 -2 M.

(VII) DISCUSSION

The stationary polarization data obtained show the overall electrode process (3)
to proceed through the consecutive charge-transfer steps
Bi ° - e =Bi ÷ (52a)
Bi + - e - = Bi 2÷ (52b)
Bi 2+ - e - = Bi 3+ (52c)
Exchange current densities of steps (52c) and (52b) obtained by extrapolation of
Tafel lines */~-log i to ,/~ = 0 are equal to 3i02 = 2.24 × 10 -4 A / c m 2 and 3io3 = 5.31
× 10 -4 and for [Bi(III)] = 10 -2 M respectively.
The exchange current density of step (52a) cannot be calculated from stationary
*/~-log i curves because there are no sections of the Tafel line on the anodic curves
due to limitation of the overall process by the ion transfer step (52a). This
phenomenon is caused the quasi-equilibrium of step (52a) due to its fastest rate.
Using the equations derived for the non-stationary polarization curve of the three-step
process (24)-(26) and Tafel non-stationary dependences (Fig. 10a) the exchange
current density of step (52a) was calculated to be lO1 = 6.88 × 10 -3 A / c m 2 for
[Bi 3+] = 10 -2 M.
The transfer coefficients of all the three charge-transfer steps we are found to be
close to 0.5.
The value of to1 was verified additionally by calculation from the data obtained
near equilibrium (Fig. 11) using the derived equation for the non-stationary charge-
transfer resistance (27) and was found to be i01 = 6.85 × 10 -3 A / c m 2. Thus, the
proximity of the values of exchange current densities of the fastest step determined
by non-stationary measurements near and far from equilibrium can be easily seen.
The absence of maxima on the experimental anodic , / - t curves (Fig. 8) can be
explained by the fact that */cr is not reached in the region of anodic current densities
under study. Figure 10 shows that */or calculated from the ordinate of the point of
intercept of */o~-log i and */0-log i curves lies in the region of anodic current density
not achieved experimentally.
42

Equation (38) predicts the Tcr value to be +90 mV (using the values of the
exchange current densities for [Bi 3÷] = 10-2 M), but the deviation of the slope of
the Too-log l curves to the side of higher values at higher i a shifts Tcr to higher values.
Figures 10 and 11 show the stationary Too-log i and Too-t and nonstationary T0-1og i
and T0-i polarization curves of the three-step electrode process calculated with the
help of experimental kinetic parameters of partial charge-transfer steps according to
eqns. (8) and (24) respectively.
It can be seen from Figs. 10 and 11 and the coincidence of calculated and
experimental curves is sufficiently good.
The closeness of the values of Bi°(Hg) electrode capacity calculated from eqn.
(51) and Cdec obtained from overvoltage decay curves to double layer capacity
values, and also the independence of Cdec of potential (fig. 9) testify to the [13,31]
absence of appreciable adsorption of the intermediates in the course of the electrode
reaction (52).
The material presented shows the effectiveness of the double-pulse galvanostatic
method in the kinetic study of stepwise processes in those cases when the time of
reaching the steady-state essentially exceeds the time of charging of the double-layer
capacity by the preliminary high amplitude current impulse of short duration and
when the influence of the concentration polarization is insignificant. It is therefore
possible to study stepswise processes under non-stationary conditions (t--* 0) and
the kinetics of the fastest electrochemical steps in a reaction sequence that is
complicated when using the methods analysing the kinetics of stepwise processes in
the stationary state or states close to this.

(VIII) SUMMARY

(1) Analysis of the kinetics of the overall electrode process Me ° - 3 e- = Me 3+,

occurring through the single-electron steps under single- and double-galvanostatic
transient conditions, is made.
(2) The derived equations are solved numerically for different ratios of exchange
current densities.
(3) It is shown that when the time of reaching the steady-state sufficiently exeeds
the time of charging the double-layer by short duration impulse, the employment of
the galvanostatic double-pulse method allows a stepwise electrode process to be
studied under non-stationary conditions and yields information about the kinetics of
the fastest electrochemical steps in the reaction sequence.
(4) Using the galvanostatic double-pulse method, the kinetics of the Bi°(Hg)/Bi 3+
electrode in 2 M HC104 solutions are studied. It is shown that charge-transfer
proceeds through single-electron steps without involving appreciable intermediate
adsorptions. Stationary and non-stationary measurements make it possible to calcu-
late kinetic parameters of all the three single-electron steps.
 43

ACKNOWLEDGEMENT

T h e a u t h o r s express their great gratitude to Mr. A.P. C h e s n a k o v for c o m p i l i n g the

p r o g r a m for the SM-3 computer.

REFERENCES

1 H. Gerischer and M. Krause, Z. Phys. Chem. (Frankfurt), 10 (1957) 264; 14 (1958) 184.
2 H. Matsuda, S. Oka and P. Delahay, J. Am. Chem. Soc., 81 (1959) 5077.
3 P. Delahay in P. Delahay and W. Tobias (Eds.), Advances m Electrochemistry and Electrochemical
Engineering, Vol. 1, Intersclence, New York, 1961, Ch. 5.
4 S.K. Rangarajan, J. Electroanal. Chem., 32 (1971) 329.
5 D.J. Kooilman and J.H. Sluyters, J. Electroanal. Chem., 13 (1967) 152.
6 H.P. van Leeuwen and J.H. Sluyters, J. Electroanal. Chem., 42 (1973) 313.
7 D J. Kooljman and J.H. Sluyters, Electrochim. Acta, 11 (1966) 1147.
8 Z. Nagy. J. Electrochem. Soc., 125 (1978) 1809.
9 Z. Nagy, J. Electrochem. Soc., 126 (1979) 1148.
10 Z. Nagy, J. Electrochem. Soc., 128 (1981) 786.
11 H. Schweickert, A.A. El Miligy, A. Melendez and W.J. Lorenz, J. Electroanal. Chem., 68 (1976) 19.
12 D.C. Grahame, J. Electrochem. Soc., 99 (1952) 370 C.
13 E. Gilead1 and B.E. Conway in J.O'M, Bockris and B.E. Conway (Eds.), Modern Aspects of
Electrochemistry, Vol. 3, Butterworths, London, 1964, Ch. 5.
14 R. Parsons in P. Delahay (Ed.), Advances in Electrochemistry and Electrochemical Engineering, Vol.
7, lntersclence, New York, 1970, p. 177.
15 H.P. van Leeuwen and J.H. Sluyters, J. Electroanal. Chem., 39 (1972) 25.
16 R.D. Armstrong and M. Henderson, J. Electroanal. Chem., 39 (1972) 71.
17 V.V. Gorodetskl and V.V. Losev, Elektrokhimlya, 3 (1967) 1192.
18 V.V. Losev in B.E. Conway and J.O'M. Bockrls (Eds.), Modern Aspects of Electrochemistry, Vol. 7,
Butterworths, London, 1972, p. 314.
19 K.I. Vetter, Z. Naturforsch. Teil A, 7 (1952) 328, 8 (1953) 823.
20 I.H. Plonskl, J. Electrochem. Soc., 116 (1969) 944.
21 K.J. Bachmann and U. Bertocci, Electrochlm. Acta, 15 (1970) 1877.
22 I.H. Plonskl, Rev. Roum. Phys., 16 (1971) 449.
23 R.M. Hurd, J. Electrochem. Soc, 109 (1962) 327.
24 V.V. Losev and V.V. Gorodetski, Elektrokhimiya, 3 (1967) 1061.
25 R. Tamamuch~, Kinetic Parameters of Electrode Reactions of Metalhc Compounds, Butterworths,
London, 1975.
26 l.H. Plonskl, J. Electrochem. Soc., 116 (1969) 1688.
27 J.M. Kudirka and C.G. Enke, Anal. Chem., 44 (1972) 614.
28 W.E. Mdne, Numerical Solutions of Differential Equations, New York, London, 1953, Ch. 4.
29 R.W, Hamming. Numerical Methods for Scientists and Engineers, New York, San Franslsco, Toronto,
London, 1962, Ch. 15.
30 D.J. Kooijman, M. Sluyters-Rehbach and J.H. Sluyters, Electrochim. Acta, 11 (1966) 1197.
31 H. Genscher, Z. Elektrochem., 62 (1958) 256.