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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
MATHEMATICAL FORMULATION
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).
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).
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.
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].
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
E--E j = 0, so t h a t :
k = c ~ n F v c / R T = (1 - - cL)nFvJRT (23)
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 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
EXPERIMENTAL VERIFICATION
, 50mY , ,~~
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
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
REFERENCES