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J. Electroanal. Chem.

, 101 (1979) 19--28 19


© Elsevier Sequoia S.A., Lausanne -- Printed in The Netherlands

G E N E R A L EXPRESSION OF THE L I N E A R POTENTIAL SWEEP


V O L T A M M O G R A M IN THE CASE O F D I F F U S I O N L E S S
ELECTROCHEMICAL SYSTEMS

E. L AVI R ON
Laboratoire de Polarographie Organique associ~ au C.N.R.S., Facult~ des Sciences Gabriel,
211 O0 Dijon (France)
(Received 6th April 1978; in revised form 15th November 1978)

ABSTRACT

The equation of the linear potential sweep voltammogram is derived for any degree of
reversibility of the electrochemical reaction for the following methods: surface voltammetry
when both the oxidized and the reduced forms are strongly adsorbed, and a Langmuir iso-
therm is obeyed, thin layer voltammetry, and linear potential sweep coulometry. The results
are expressed in one mathematical form valid for the three cases. The transfer coefficient and
the rate constant of the electrochemical reaction can be deduced from an ~ ~perimental study
of the variations of the peak potentials as a function of the sweep rate.

INTRODUCTION

As we have shown previously, the same mathematical formulation can be


used for the following three different linear potential sweep (1.p.s.) methods,
when certain conditions, ensuring in particular that control b y diffusion is
absent, are fulfilled: (a} surface 1.p.s. voltammetry, when both the oxidized and
the reduced forms are strongly adsorbed, and when a Langmuir isotherm is
o b e y e d [1--3], (b) thin layer 1.p.s. voltammetry, when the sweep rate does not
exceed a certain limit [1,4]; and (c) 1.p.s. coulometry [5], when the sweep rate
is small enough.
We have published in previous papers the theory of the reversible [2,6,7] and
totally irreversible [2,8] cases for 1.p.s. surface voltammetry, and for a reversible
reaction in the case of 1.p.s. c o u l o m e t r y [5]. The equations for the reversible and
completely irreversible reactions in thin layer 1.p.s. voltammetry are well known
[4]. The general equation of the voltammogram for any degree of reversibility
has n o t however been derived yet. Such an equation would be useful for the
determination of the rate constant and of the transfer coefficient of the electro-
chemical reaction, as it is in the case of diffusion 1.p.s. voltammetry [9]. (In ref.
10, Srinivasan and Gileadi considered a surface reaction corresponding to physi-
cal conditions different from those of case a; the mathematical formulation is
however the same and they derived the expression of the voltammogram for the
reversible and completely irreversible cases. They also gave a general differential
equation for the current, b u t only solved it numerically to obtain the shape of
the voltammogram in a few cases.)
We present in this paper a general expression for the voltammograms of the
20

systems described above, which we will designate as diffusionless systems, there-


by meaning t h a t diffusion does n o t have to be taken into account in the mathe-
matical treatment of the problem: its only role is to homogenize the concentra-
tions in the case of thin layer voltammetry and 1.p.s. coulometry. We will dis-
cuss the application of our results to the determination of the rate constant and
of the transfer coefficient of the reaction.

MATHEMATICAL FORMULATION

We shall consider the case of a reduction O + ne ~ R. The potential E is given


by
E = E i + vt (1)
v being the algebraic value of the sweep rate in V s-1.
(1) S u r f a c e v o l t a m m e t r y

We have shown previously [2,3,6] that when a Langmuir isotherm is obeyed,


and when O and R are strongly adsorbed, the electrochemical reaction concerns
exclusively the adsorbed molecules, if the coverage is smaller than 1. A surface
standard potential E '° can be defined; its value is given by:

E '° = E ° - - ( R T / n F ) l n ( b o / b R ) (2)
bo and b R being the adsorption coefficients of O and R. We can thus write:
i = n F A k s ( F o e x p [ - - - ~ n F ( E - - E ' ° ) / R T ] -- F R exp[(1 -- a ) n F ( E - - E ' ° ) / R T ] } (3)

Fo + FR = FT (4)
i = --nFA dFo/dt (5)
ks is the rate constant of the electrochemical reaction (s-l), Fo and FR are the
surface concentrations of O and R (mol cm-2), FT is their constant sum, and A
is the area (cm2). tz, F, a, R and T have their usual significance, i is here expressed
in Amperes.
The current can be defined by the dimensionless function
@ = i / ( F 2 / R T ) n 2 V A F T = m[(Fo/FT)??- ~ - (FR/FT)~ 1 - ~ ] (6)
with
m = (RT/F)(k~/nv) (7)
~? being defined by eqn. (12).

(2) Thin layer v o l t a m m e t r y

We have, if the sweep rate is so slow that the concentrations are uniform
throughout the cell:
i = n F A k s , h {Co exp [ - - ~ n F ( E - - E ° ) / R T ] - - CR exp [(1 -- a ) n F ( E - - E ° ) / R T ] } (8)

CO + CR = CT (9)
i = --nFVdco/dt (10)
21

ks, h is the heterogeneous rate constant (cm s-l), Co and CR are the concentra-
tions (mol cm-3), CT is their constant sum, and V is the volume (cm3).

(3) L.p.s. coulometry


Equation (8) is still valid, if Co and cR are replaced by c~) and c~, the concen-
trations at the surface of the electrode. Equations (9) and (10) still hold, Co and
c~ being the concentrations in the bulk of the solution. If the potential sweep
is slow enough, Co = c~) and CR = C~, SO t h a t the problem is described by eqns.
(8) to (10). In both cases, the current can be defined by the dimensionless func-
tion:
~1 = i / ( F 2 / R T ) n 2 V V C T = m [(Co~Ca)t7 --~ - - (CR/CT)~ 1 - ~ ] (II)
with m = (RT/F)(Aks,h/Vnv), ~ being defined by eqn. (12).

(4) General formulation o f the problem


Let us designate by ×o, ×R and XT the values of Fo or Co, FR or CR, FT or CT,
by k the value of ks or Aks,h/V, and let
~7 = exp[ (nF /RT)(E -- E'°)] or exp [(nF /RT)(E -- E°)] (12)
From the two systems of eqns. (1), (3--5) or (1), (8--10), we obtain the differ-
ential equations:
d(Xo/XT)/drl + m(1 + 7 ~ ) ~ - - ( l + a ) ( X o / X w ) = m~ -~ (13)
d(XR/XT)/d~? + m(1 + ~)~-(1 +a)(XR/XT) = roT?-(1+~) (14)
By solving one of these equations, we obtain the value either of Xo/XT or of
XR/XT, and the value of @ can be calculated by introducing it into eqn. (6) or
(11), taking into account eqns. (4) or (9). The integration constant is deter-
mined by expressing the condition that when m -~ 0, i.e. when the reaction
becomes totally irreversible, the expression of @ must be identical to the
expression already calculated for this case [2,8]. This condition can be expressed
by introducing the following approximations in the general expression of @:
when m -+ 0, for the cathodic c u r v e ?~l--a < < T~a and ~ < < 1, and for the anodic
curve V-~ < < ~?!- ~ and ~ > > 1. The result of the calculations shows that it is
more convenient, in order to obtain solutions in which the integration constant
is zero, to start from eqn. (13) for the anodic curve and from eqn. (14) for the
cathodic curve.

RESULTS AND DISCUSSION

(1) General expression o f


Proceeding as indicated above, we obtain for the cathodic curve:

~c = mr~~ {1 -- m(1 + rl) exp[f(r~)l f z -(1÷~) exp[--f(z)] dz} (15)


and for the anodic curve:

~ a = - - m f l -c~ ( 7 - - m ( 1 + 7) exp[f(rl)l f z ~ exp[--f(z)l dz } (16)


o
22

with
f(7) = [m/~(1 -- ~)]7-~[1 -- ~(1 + 7)] (17)
f(z) represents the same function, with z replacing 7. m is negative for the
cathodic curve and positive for the anodic curve.

(2) L i m i t i n g f o r m w h e n m -~ 0 (totally irreversible reaction)

As stated above, when m -~ 0, 7 1 - 4 < < 7-~ and 7 < < 1 for the cathodic
curve. The integration becomes possible and yields the simple equation:
Cc = m 7 --~ e x p ( m 7 - ~ / a ) (18)
which is identical to the equation derived earlier [2,8]. (In refs. 2 and 8, the
absolute value of m was used, instead of the algebraic value.)
In the same way, when 7 -~ < < 7 1 - 4 and 7 > > 1, we obtain from (16):
Ca = - - m 7 1 - a e x p [ _ m 7 1 - ~ / ( 1 -- a)] (19)
Cc passes through a maximum when 7 ' ~ = - - a / m = c~/Im I, so that the peak poten-
tial Ep is given by:
Ep = E j - - (RT/c~nF) ln[a/Im I] (20)
E j being equal to E '° or E0.
The maximum of Ca is obtained when: 7 1 - 4 = (1 --c~)/m, whence
Ep = E j + [ R T / ( 1 -- a ) n F ] ln[(1 -- a ) / m ] (21)
(3) Shape o f the curves
When m -* oo (v -* 0), both the cathodic and the anodic peaks tend towards
the "reversible peaks", which are symmetrical with respect to the potential axis,
and which have a symmetrical shape; the width at mid-height 5o. 5, which
becomes independent of a, tends towards 90.6/n mV [1--3,5--7]. When m -* 0,
the peaks tend towards the "totally irreversible peaks" (eqns. 18 and 19). The
width of the cathodic peak is equal to 62.5/an mV, that of the anodic peak to
62.5/(1 - - a ) n mV [2,8].

(4) D e t e r m i n a t i o n o f ks(ks, h) and a


The most interesting experimental quantity is the difference AEp between
the peak potential of the anodic and cathodic peaks. Figure 1 gives n(Ep - - E j)
as a function o f l / m , calculated from eqns. (15) and (16) by numerical integra-
tion (a Hewlett-Packard 9821 A calculator was used), and the corresponding
variations of n AEp in the limiting case (m -~ 0, eqns. 20 and 21). It can be seen
that, whatever a, the relative error on n AE, when the limiting eqns. (18)--(21)
are used instead of the general eqns. (15) and (16) remains smaller than about
2% when 1 / m is larger than a b o u t 12 (see also Fig. 2). An experimental criterion
has to be found, since m is not known: as shown in Fig. 1, the condition 1 / m
> 12 can be replaced by the experimental condition AEp > 200/n mV. Either
n is known (e.g. for a l e process) or it can be deduced from the width of the
peak when v -* 0, as indicated above.
23

n ~- p~a - E J~/mV
200 2

• I

100

/i/
:-2 30
, I I
• '/ '
m-1
/
a

• 2

-100-

-200-n ~Ep,c-E~/mV
Fig. 1. n(Ep, c - - EJ) and rt(Ep, a - - E i) as a f u n c t i o n of 1/m. (Points) General eqns. (15) and
(16). (Curves) Limiting eqns. (20) and (21). (1) (~ = 0.5, (2) (~ = 0.8.

(A) AEp > 200/n mV. If values of AEp/n larger than 200 mV can be obtained
experimentally, a and k (k represents ks or A k s . h / V ) can be easily determined
by using eqns. (20) and (21). A graph o f E p = f(log v) yields two straight lines
with a slope equal to --2.3 RT/cLnF for the cathodic peak, and 2.3 R T / ( I -- a)nF
for the anodic peak. Theoretical curves E , = f(log(1/m)) = f(log v + log(nF/RTk))
are shown in Fig. 2. An experimental plot having the form of these curves was
given by Angerstein-Kozlowska et al. in a study of the adsorption of nitriles at a
platinium electrode [11]. ~ can be determined from the slope of the straight
lines, or also from the difference log Va/Vc = log me - - l o g ma = logic/(1 - - ~ ) ] ,
or a/(1 - - ~ ) = va/v¢. ~ can also be calculated from the width of the peak (see
above).
k can be calculated with the help of the equation
log k = ~ log(1 -- ~) + (1 -- ~) log ~ -- log(RT/nFv) -- ~(1 -- c~)nFAEp/2.3 R T
(22)
which is valid for n A E , > 200 mV. It can also be deduced from the values of va
and v¢ : according to eqns. (20) and (21), a/Im~l = (1 -, a)/m~ = 1 when
24

10C

log(
non~/m,~

-1 O0 -

[ I
0 logO/m) 1
Fig. 2. T h e o r e t i c a l v a r i a t i o n s o f n ( E p - E j) as a f u n c t i o n o f l o g ( l / m ) f o r ~ = 0.7.

"h (~)20 13 i u
10 8 6.6 5.6 5 4.4 4
I i I I I I i
2.6
i
2

1.4-
, /
~5

1.2

0.5

0.8

0.6 I
0 100 n,~. Ep/mV 200

Fig. 3. V a r i a t i o n s o f t h e r a t i o y = [(Ep, c - - EJ)/(Ep,a -- EJ)[ w i t h n~kEp. T h e value o f 0~ is indi-


c a t e d o n e a c h curve.
25

E--E j = 0, so t h a t :
k = c ~ n F v c / R T = (1 - - cL)nFvJRT (23)

( B ) A E p < 2 0 0 / n m V. W h e n the e x p e r i m e n t a l c o n d i t i o n s are such t h a t values o f


n A E p smaller t h a n 2 0 0 m V can o n l y b e a t t a i n e d , e.g. b e c a u s e t h e u p p e r l i m i t o f
t h e s w e e p r a t e has b e e n r e a c h e d , t h e limiting f o r m s c a n n o longer b e used. a can
in principle be d e t e r m i n e d f r o m t h e g r a p h y = ](Ep, c - - E j)/(Ep,a - - EJ)I (Fig. 3),
p r o v i d e d t h a t E j can b e d e t e r m i n e d b y e x t r a p o l a t i o n o f t h e curves n E = f ( v ) (cf.
Fig. 1). (In Fig. 3, t h e curves f o r ~ > 0.5 are s h o w n ; f o r a < 0.5 t h e r a t i o
b e c o m e s 1 / y . ) In f a c t , as s h o w n in Fig. 3, t h e d e t e r m i n a t i o n o f a will n o t be pre-
cise, b e c a u s e a small e r r o r in t h e d e t e r m i n a t i o n o f Ep,c a n d Ep,a will cause a
large e r r o r on the r a t i o y. T h e relative e r r o r o n y is
•y/y = ~(Ep,c - - E j )/(Ep,c - - E j ) + ~(Ep,a - - E j ) / ( E p , a - - E ~) ~- 5 ( A E p ) / A E p
if we a s s u m e in first a p p r o x i m a t i o n t h a t Ep, c ~- Eu, a. T h e e r r o r A y / y , c a l c u l a t e d
f o r an a b s o l u t e e r r o r o f 1 m V o n Ep, is i n d i c a t e d in Fig. 3. A c c o r d i n g t o t h e
result, o n l y a v e r y a p p r o x i m a t e value o f ~ can be d e d u c e d f r o m t h e curves. I f

nA,~
200

100

I L
5 I//m 10

Fig. 4. Variations of nAEp with 1/m. (1) a = 0.5, (2) a = 0.8, (3) a = 0.85, (4) a = 0.9.
26

TABLE 1

m-1 0.5 0.75 1 1.5 2 2.5 3 3.5 4 5


nz2kEp/ 18.8 27 34.8 48.8 61.2 72.2 82.4 91.8 100.6 116.2
m V + 0.1
mV

m-1 6 7 8 9 10 11 12 13 14
•n A E p / 130 142.4 153.8 164 173.4 182 190 197.6 204.6
mV

is n o t t o o different f r o m 0.5, this will n o t however be an obstacle to the deter-


mination o f k, as shown below.
Once ~ is known, the curves given in Fig. 4 can be used t o determine m,
hence k. As shown by these curves, when 0.3 < ~ < 0.7, the difference AEp
does n o t depend very m uc h on ~ (a similar result has been r e p o r t e d in the case
o f diffusion v o l t a m m e t r y [9]): the relative error on k is at the most about 6%
when the curve for ~ = 0.5 is used. Table 1 gives some values of nAEp as a func-
tion o f 1/m for ~ = 0.5.

EXPERIMENTAL VERIFICATION

We have examined the behaviour o f a series of molecules having a N=N


double bond, benzo(c)cinnoline, phenazine, azobenzene, for which b o t h the
oxidized and the reduced forms are strongly adsorbed and follow a Langmuir iso-
t h e r m when the superficial c o n c e n t r a t i o n is small enough [12]. The result of

, 50mY , ,~~

Fig. 5. V o l t a m m o g r a m s o f b e n z o ( c ) c i n n o l i n e . (a) 0.4 V s - 1 , (b) 6.67 V s- 1 . S t a r t i n g p o t e n -


tial - - 0 . 6 5 V. c = 3 x 10 - 6 tool 1-1.
27

Ep,a/mV I 0
-700

- 75C
-762
I

- 800

I
Ep c/mV I
-1 0 log v (,v/Vs-1)
Fig. 6. (Ep - - E j) = f(log v) f o r b e n z o ( c ) e i n n o l i n e .

-700

I.M

-750

-762:

1,1,1

°°I 0 5
I
v / V s-1 10
Fig. 7. (0) E x p e r i m e n t a l v a r i a t i o n s of Ep as a f u n c t i o n of v f o r b e n z o ( c ) c i n n o l i n e . T h e t h e o r e t -
ical curve h a s b e e n c a l c u l a t e d for ~ = 0.5 a n d k s -- 38.9 s- 1 .
28

the study of benzo(c)cinnoline at pH 8.70 will be given here as an example. The


width o f the peak at mid-height tends towards 45 mV when v -+ 0, so t hat n = 2,
and the peaks b e c o m e symmetrical (Fig. 5a). When v increases the difference
between the peak potentials increases (Fig. 5b). Figure 6 gives the variations of
Ep,a and Ep, c as a f unc t i on of log v. The slope o f the two oblique asymptotes is
equal to 60 mV/log unit, and t h e y intersect the horizontal a s y m p t o t e E'° at the
same point; b o t h results mean t h a t a = 0.5. T he value of a, calculated from the
width o f the peaks (Fig. 5b) is equal to 0.53. The value of ks obtained from
eqn. (23) with the values va = vc = 1 V s-1 is ks = 38.9 s-~. A comparison of the
experimental and theoretical values of Ep, a and Ep,c is shown in Fig. 7.

EXPERIMENTAL

A Tacussel UAP4 unit and GSTP function generator were used for the experi-
ments. The i -- E curves were r ecor de d on a T e k t r o n i x R 564B m e m o r y oscillo-
graph and photographed. The experiments were carried out in water (Britton-
Robinson buffer, supporting electrolyte NaC1 0.1 M).
The t e m p e r a t u r e was 25°C. The potentials refer to the saturated calomel elec-
trode. The delay time was equal to 6 s.

CONCLUSION

As shown by our results, 1.p.s. v o l t a m m e t r y appears as a convenient m e t h o d


for the d eter m i nat i on of the characteristics (transfer coefficient and rate con-
stant) of the electrochemical reaction in diffusionless electrochemical systems.
The limiting values of the rate constant which can be det erm i ned depend on the
limiting values of the sweep rate which can be used for each m e t h o d : from less
th an 1 mV s- 1 to m o r e than 1000 V s-1 for surface v o l t a m m e t r y , very slow
scan rates to a b o u t 1 mV s-~ for 1.p.s. c o u l o m e t r y [5], and a b o u t 1 to 10 mV s-1
f o r thin layer v o l t a m m e t r y [4].

REFERENCES

1 E. Laviron, J. Electroanal. Chem., 39 (1972) 1.


2 E. Laviron, J. Electroanal. Chem., 52 (1974) 355.
3 E. Laviron, J. Electroanal. Chem., 63 (1975) 245.
4 A.T. Hubbard and F.C. Anson in A.J. Bard (Ed.), Electroanalytical Chemistry, Vol. 4,
Marcel Dekker, New York, 1970, p. 129.
5 E. Laviron, L. Roullier and R. Gavasso, J. Electroanal. Chem., 75 (1977) 287.
6 E. Laviron, Bull. Soc. Chim. Fr., (1967) 3717.
7 E. Laviron, J. Electroanal. Chem., 52 (1974) 395.
8 E. Laviron, Bull. Soc. Chim. Fr., (1968) 2256.
9 R.S. Nicholson, Anal. Chem., 37 (1965) 1351.
10 S. Srivanasan and E. Gileadi, Electrochim. Acta, 11 (1966) 321.
11 H. Angerstein-Kozlowska, B. MacDougall and B.E. Conway, J. Electroanal. Chem., 39
(1972) 287.
12 E. Laviron, Collect. Czech. Chem. Commun., 36 (1971) 363.

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