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Gary A. Mabboil
Department of Chemistry and Geology, Clemson University. Clemson. SC 29631
~.
- E'O)
(1)
k o is the standard heterogeneous electron-transfer rate constant. (Its value is a property of the reaction between the
particular compound and the electrode surface used.) The
number of electrons transferred per molecule is n ;F is the
Faraday; R is the universal gas constant; T is the Kelvin
temperature; and En' is the formal reduction potential. (The
prime signifies that the effect on the free energy of the reactants and products embodied in activity coefficients has been
combined with the thermodynamic reduction potential to
form a term that is directly measurable but subject to solution
September 1983
697
-.
(4)
~~~~
28.0
698
(71
(aco~ax).=,,,= c&=t
(3)
where Cb 1s the concentration of the oxld.zed materlal In the bulk solullon (on moles/cm'l It seems reasonable, Inen tnat scannmg to the
same voltage would also cause the current to fa I 011 as
Rates of heterogeneous reactions are referenced to unit surface
area and have units of moi sec-' ~ m - Since
~ . the rate is expressed
as the product of kc, the rate constant, k, must have units of cm sec-'
when
concentration is aiven in mol cm-=.
'Eq-atoon (61assumes a planar e~echode.For a spher cal electfle
+ (0752) nFADoColro
(such as a hang ng mercuw drop): I, =
where ro is the radius of the electrode.
5E,,2 = Pr- RTlnF In
~~
~~
I,,,,.
11.
R&Z
I-,
Ill.
iV.
z&o
L,
O + m e R
V.
zL
-0
*-,
o t m - R
VI.
R+Z*O
k
VII,
VIII.
Volume 60
Number 9 S e ~ t e m b e r1983
699
SCAN
RATE
0.01
0.1
SCAN
1.0
10
100
RATE
4 shows the general trend that the peak current ratio follows
as a function of scan rate for each of the cases involving reversible electron transfer listed in the table. Also of some diagnostic value is the rate a t which Epl? shifts as a function of
scan rate. These trends are presented m Figure 5. (Reference
(12) gives a detailed development of each i f these cases. Polcyn and Shain also described multistep charge-transfer reactions where an intermediate oxidation state is formed (16).
Treatment of a multi-electron reaction with an intervening
chemical step has also been given (17,18). Data from other
types of electrochemical experiments is often needed to
evaluate rate constants for reactions with coupled chemical
steps.)
Measurement of the peak current is fairly simple for the
forward scan. The proper baseline can be obtained by recordine" the hackmound
current for a scan without the anal*
"
under the same conditions (same electrolyte, surface pretreatment. etc.). The reverse scan is more complicated since
the electrolysis for the forward prores~stillruntributes tuthe
total current until the scan ha3 passed the foot of the (forward)
wave again. The generally accepted approach is to assume that
the contribution of the forward process to the total current
continues to decrease with the square root of the time during
the reverse scan. The baseline curve for the return scan can
be obtained by stopping the forward scan at the switching
potential with the recorder sweeping along the x-axis as a
function of time. This is shown in Figure 6a.
A second approach is to stop the scan at a convenient spot
(at least 35 mV past E, for the forward scan) and hold the
potential until the current is relatively constant. The appropriate baseline is shown in Figure 6h (13).
700
Figure 6. Methods for determining the proper baseline for measurement of the
peak current for the reverse scan. (a) RecMding the signal versus time and
stopping lhe first scan at h.(b) Using an X-Y recorder and stopping the scan
st EL until iapproachesa steady state befwe scanning back. (c) Parameters
used lor calculation of lhe current ratio using Nicholson's method, eqn. (10).
There are occasions when neither of these two methods is
convenient. Nicholson (19) has indicated that the proper
current ratio can also be calculated using the following
equation.
i +-0.485(ih+ 0.086
(8)
Lpr
'pr
'PC
In eqn. (8), ,i is the peak current for the forward process; (id0
is the absolute current at the switching potential; and (i,.)~
is the uncorrected return peak current measured from the
current axis. (See Fig. 6c.)
There are some systems in which a coupled chemical reaction ~ i e l d electroactive
s
by-products. In these cases multiple
scans can be beneficial. For example, the product of electron
transfer in the oxidation of aniline is thought to he a free
radical that very rapidly dimerizes (13).
Acknowledgment
Often the formal potential can he evaluated by cyclic voltanmetry when one of the complexes is too unstable to permit
a direct determination of En' by potentiometric measurement
of an equimolar solution of the two forms. If either Kru or K I I
can be evaluated independently (22), then the other can be
calculated from En' data.
Practical Conslderatlons
.....
(14)
(15)
(16)
(17)
(18)
(19)
G i l m a n . S . , E l ~ r f r m ~C
I .h m . , 2.111 (1967).
Parsons. R.. J. Elsclrmnol. Chem., 21.35 (19691.
Polcyn. D..sndShain,I..Anal. C h ~ m . 3 8 . 3 7 0 . 3 7 6(1966).
Nicholmn. R.S.,sndShain,l..Awl. Chem., 37, 178 (1965).
Ssvssnt, J. M.. Elarfrmhim. A d o , 12,753 (1967).
Nicholson. R. S.. A w l . Cham., 38.1406 (1966).
(201 Kachn.C. L a n d Tauhe.C.G.. J. Arne,. Chem S m . 9 8 . 6 8 9 (1976)
Volume 60 Number 9
September 1983
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702