Nicholson 1965
Nicholson 1965
b The theory of cyclic voltammetry these determine electrode reversibility surface. Under these conditions the
has been extended to include electron indirectly b y measuring the apparent separation of cathodic and anodic peak
transfer reactions which are described standard rate constant for electron potentials is about 60/n mv., and the
b y the electrochernical absolute rate transfer from only cathodic (or anodic) reaction is reversible.
equation. Results of theoretical calcu- polarization. I n a few cases both Clearly for this case no kinetic in-
lations made it possible to use cyclic cathodic and anodic polarization give formation about the electron transfer
voltammetry to measure standard rate consistent results ( I S ) . Many of the reaction can be obtained. However, if
constants for electron transfer. Thus, relaxation techniques developed for fast frequency is increased sufficiently, a
a system which appears reversible reactions have the disadvantage that point may be reached at which the
a t one frequency may b e made to small amplitude perturbations are used, kinetics of electron transfer become
exhibit kinetic behavior a t higher and consequently differences or changes competitive with the rate of potential
frequencies, as indicated b y increased in mechanisms are not easily detected. change. Under these conditions it may
separation of cathodic and anodic A method which overcomes this dis- be possible to study the kinetics of the
peak potentials. The standard rate advantage and a t the same time gives electrode reaction, and the separation of
constant for electron transfer is de- a direct estimate of reversibility is peak potentials should be a measure
termined from this peak potential cyclic triangular wave voltammetry. of the standard rate constant for elec-
separation and frequency. The Thus, the presence of homogeneous tron transfer. Thus, a t least in princi-
method provides an extremely rapid reactions in the mechanism is readily ple, one can estimate standard rate
and simple way to evaluate electrode detected, and interpretation of results constants simply by observing cyclic
kinetics. The reduction of cadmium usually is simple. il direct estimate of polarograms on the oscilloscope, and
is used as an illustration. electrode reversibility is provided, be- then increasing the triangular wave
cause the potentials at which oxidation frequency until the separation of peak
and reduction occur are observed potentials becomes greater than 60/n
D URING RECENT’ years a number of
methods have been developed
for the measurement of electrode reac-
directly. For example, a t low fre-
quencies it may be possible with a given
system that electrochemical equilibrium
mv. The standard rate constant then
should be a calculable function of fre-
quency at this peak potential separation.
tion kinetics. I n one sense, some of always is maintained a t the electrode Unfortunately, there is no a priori way
electron transfer provided such reac- remaining terms have their usual
tions are either rapid or slow compared significance.
to the standard rate constant for elec- The potential in Equation 7 for the
-0
I , , , ,
tron transfer. The cases in which first scan (reduction) of the triangular
120 60 0 -60 -120 these conditions are not met are easily wave takes the form
-
(E E , , h mv. detected from the form of the experi-
E = E, - ut (8)
mental current-voltage curves (11).
Figure 1 . Cyclic polarograms showing The reduction of cadmium is used as and for the second scan (oxidation)
effect of charge transfer coefficient, a an illustration of the method developed
--- iC. = 0.5; CY = 0.7 here. Application to other systems is E = E, + ut - 2uX (9)
...... iC. = 0.5; a = 0.3 in progress and will be reported else-
Here, E, is the initial equilibrium poten-
where.
tial, v is dE/dt, and X is the period of
the triangular wave.
THEORY If Equations 7, 8, and 9 are combined
to make this correlation because effects the result is
of concentration polarization can be We assume the following mechanism:
treated only by mathematical analysis
kf
aco
Do - = k,(Co*/C~*)-"[Sx(t)]-* x
of the mass transport processes. Such ax
a n analysis is not available for the
O+ne*R I
kb
present case, and consequently applica- (CO, = 0 -
tions of these ideas using cyclic voltam- There k , and ka are heterogeneous rate
constants of the electron transfer, and ( C O * / ~ R * ) ~ A ( ~ o)) ~ R(10)
,
metry have been limited to simple
statements that a given system appears are assumed to be functions of potential T h e function Sx(t) is defined as
to be reversible or irreversible (7, IO). as expressed through the electrochem-
I n the study of electrode reaction ical absolute rate equation. The time t<X
mechanisms, it often is useful to be able dependence of electrode potential is the &(t) = (11)
form of an isosceles triangle. System I 2ax t>
to obtain experimentally a rapid esti-
mate of electron transfer rates. Be- is assumed to be initially in equilibrium,
Both 0 and R are to be soluble either where
cause this appeared to be possible with
cyclic voltammetry in the way just in the electrode or solution phase. a = nFv/RT (12)
described, we have attempted a theo- T o account for concentration polariza-
retical treatment of the problem which tion, diffusion to a plane electrode is Equation 10 is the final form of bound-
includes the effects of concentration assumed to be the only source of mass ary condition 6.
polarization. Our primary objective transport. Mathematical formulation By application of Laplace transform
was to determine if cyclic voltammetry of this problem follows methods the above boundary value
could be used to provide rapid and problem can be converted to the follow-
reasonably accurate determinations of aco
_- avo ing dimensionless linear integral equa-
standard rate constants for electron at - D O T ax tion with variable coefficients
transfer. Thus, the theoretical correla-
tions between peak potentials, standard X(Y) [?(CO*/cR*)sd(!/)I"=
rate constant, and rate of potential !4
scan have been emphasized, although
other correlations are possible. A seri-
ous limitation of this approach would
result if peak potential separations
depended also on the charge transfer
coefficient, C Y . This would require an
independent measure of C Y , and make the T o make Equation 13 dimensionless the
method of little use in terms of the following substitutions and changes of
stated objectives. However, through t2O,x=O variable were made:
proper selection of conditions, peak
potential separations become nearly Y = (Do/DR)"' (14)
independent of a .
Becauqe there is neither theoretical
y = at (15)
nor experimental advantage to consider-
ing more than one cycle of the applied x(y) = Do aco
a,/Co*l/?rao, (16)
triangular wave, theoretical calcula-
tions havt been limited to this case. Undefined terms have their usual
significance (11).
4 = y4s/l/*aDo (17)
ConsideratioIL also has been restricted
to the case of an situ generation of the With the electrochemical absolute For large values of $ (large k , or
reduced form of the couple under in- rate equation, Equation 6 can be trans- small v ) Equation 13 becomes independ-
vestigation. This actually has two formed t o ent of 4 and CY and reduces to the
a three-electrode potentiostat place- agreed with values calculated from the communication, 1965.
ment of the Lugg-in capillary probe in conductivity of the solution (2). By (6) DeVries, W. T., VanDalen, E., J .
close proximity with the working elec- careful placement of the Luggin probe Electroanal. Chem. 8, 366 (1964).
(7) Galus, Z., Lee, H. Y., Adams, R. N.,
trode serves to compensate for a ma- the uncompensated resistance was esti- Zbid., 5 , 17 (1963).
jority of the total cell resistance [see mated to be 3 to 4 ohms ( 2 ) , so t h a t (8) hlatsuda, H., Ayabe, Y., 2. Elektro-
Iiooman and Holbrook for the exact maximum ohmic potential losses were chem. 59. 494 11955).
relat,ionship (2) 1. Third, relatively low of the order of 1 mv. (9) Nicholbon, R . S.,'ANAL.CHEM.37,
667 (1965).
concentrations of dectroactive material The upper limit of rate constants (10) Nicholson, R. S., Shain, I., Ibid.,
can be used to keep total cell currents measurable with cyclic voltammetry p. 190.
small. This latter approach is limited, therefore depends on several factors. (11) Zbid., 36, 706 (1964).
however, by charging current. Thus, a t The most important of these is probably (12) Okinaka, Y., Talanta 11, 203 (1964).
(13) Selis. S. >I.. J . Phus. Chem. 68.
high scan rates charging current may conductivity of the solution under ~ 2538 (1964). '
become a n appreciable fraction of the investigation. With electrolytes of rea- (14) Tanaka, X.,Tamamushi, R., Electro-
total cell cuirent, especially when lo^ sonably high conductivity, it should be chem. -4cta 9,963 (1964).
concentrations of electroactive mat'erial possible to measure rate constants as RECEIVEDfor review June 28, 1965.
are used. large as 1 to 5 cm./sec. Accepted August 3, 1965. Presented in
part at the Division of Analytical Chem-
For the cadmium system investigated istry, 150th XTeeting ACS, Atlantic City,
here a concentration of 2 to 5 X 10-4Jl LITERATURE CITED N. J., September 1965. Work supported
appeared to be optimum for low cell in part by the United States Army Re-
currents without excessive charging (1) Booman, G. L., Holbrook, W. B., search Office-Durham under Contract
ANAL.CHEM.37, 795 (1963). No. DA-31-12PARO-LL308. Other sup-
current contributions. hIasimum peak ( 2 ) Zbid., 35, 1793 (1963). port was received from the National Sci-
currents n-ere of the order of 0.2-0.3 ma. 13) Delahav, P., Trachtenberg, I., J . Am. ence Foundation under Grant KO. GP-
Total solution resistance (ea. 20 ohms) Chem. Si.' 80,2094 (1958).- 3830.