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M Abbott 1983
M Abbott 1983
M Abbott 1983
Gary A. Mabboil
Department of Chemistry and Geology, Clemson University. Clemson. SC 29631
~.
Cvclic voltammetrv has become a nonular tool in the last
fifteen years for stud;ingelectrochemwal reactions. Organic
chemists have amlied the techniaue to the studv of hiusvn-
th,,tic reaction pathways ( I ) and io studies of el&tro~hemi-
callv eenerated free radicals (2). An increasing numher of
inoig&ic chemists have been using cyclic voltammetry to
evaluate the effects of liaands on the oxidation/reduction
potential of the central metal ion in complexesand multinu-
clear clusters 131.This type
. . uiinformatim plays an intrgrnl
part in many of the approaches direcwd tuwanl snlar energy
convenion 14) and in model studies of enz)mstic cataly~is15).
Knoaledge of the electrochemistry of a metal complex can he
useful in the selection of the proper oxidizing agent to put the
metal complex in an intermediate oxidation state r f i L Elec-
trochemical methoddogy has also heen exploited as a novel
means of introducing f&tional groups and removing blocking
agents (7).
There are several good texts that deal with the theory and
practice of modern voltammetry in depth (8-10). Also, many
mstrumental analysis textbooks give avery brief overview of
the method. However, the needs of a researcher interested in
applying the technique for the first time are somewhere he-
tween these two extremes. Instructors of instrumental analysis
who want to teach modern electrochemistry are faced with a
similar dilemma due to the lack of suitahle background ma-
terial for the students to read. This article is intended to help
meet those needs.
The CV Experiment
T h e voltage applied to the "working"electrode is scanned
linearly from an initial value,Ei, to a predetermined limit, Ehl,
(known as the switching potential) where the direction of the
scan is reversed (see Fig. la). The operator can halt the scan F l w 1. a) Appliedpotential program. EA, and Elp are switching potemials.
anywhere or let the instrument cycle between E h l and some b) Typical cyclic voltsm-am of 1 mMKaFe(CN)aa1a platinum elernode in
BQUKWEI 0.1 M KC1 solution.The scan rate was 100 mV/sec and the reference
other preselected value, Eh2.The current response is plotted
s l ~ c h d was
e Ag/AgCI in 0.1 M KCi solution
as a function of the applied potential. Often there is very little
difference between the first cycle and successive scans.
However, the changes that do appear on repetitive cycles are conditions.) The term ii is known as the transfer coefficient.
important keys to unlocking information about reaction It arises becauseonly a fractionof theenermthat is put into
mechanisms (as will he shown later in this paper). the system (in the form of the applied potentiall luwers the
Figure l b shows a current-voltage curve (or voltammogram) activation energy harrier. Its value \,aries from zeru to unity
for Fe(CN)r3. As the potential is scanned in the negative di- (often -0.51 depend~ngon the shape of the iree energy sur-
rection the current rises to a peak and then decays in a regular faces for the reactants and products.'
manner. The current depends on two steps in the overall The exounmtial denendence oikron the annlied .. potential
process, the movement of electroactive material to the surface accounts for the steep rise in the current. However, the elec-
and the electron transfer reaction. The electron transfer rate trolvsis of the reactant denletes its concentration near the
constant for a reduction process is a function of potential and surlace. Since the experiment ii performed at a stationary
can be described theoretically. electrode in an unstirred solution, diiiusion is the nrincipal
means of moving the reactant to the surface. This relatively
anF
k r = k" enp (%(E - E'O) (1) slow mode of mass transport cannot maintain a steady-state
concentration profile i n the region close to the elekrode.
k o is the standard heterogeneous electron-transfer rate con- Therefore, the depletion zone grows. I n a sense, the average
stant. (Its value is a property of the reaction between the distance that the ieactant molewles must travel to reach the
particular compound and the electrode surface used.) The surface increases. Consequently, the rate of mass transport,
number of electrons transferred per molecule is n ;F is the decreases. The dependence on mass transport, and the fact
Faraday; R is the universal gas constant; T is the Kelvin that a finite rate for the reverse electron transfer process is
temperature; and En' is the formal reduction potential. (The possible, prevent the current from increasing exponentially
prime signifies that the effect on the free energy of the reac-
tants and products embodied in activity coefficients has been This Is a sirnplificatlon. For a well-written and much more detailed
combined with the thermodynamic reduction potential to explanation of the significance of Me transfer coefficient and symmeby
form a term that is directly measurable but subject to solution factors see pp. 917-929 of ref.(27).
and return peakpotentials asthe formal rezuction potential tential where the current is half the value of the peak current.
for the redox couple. This is an approximation that is most This half-peak potential (for a reversible redox couple a t
accurate when the electron transfer process is reversible and 25°C) is related to the polarographic E1/2 value by the fol-
the diffusion coefficients for the oxidized and reduced forms lowing equation:
are the same. If the reaction is reversible, then the separation 28.0
in the peak potentials, AEp,will be close to 58ln mV (at 25°C). EP/2= Ei12f -mV (71
n
(This relationship can be used to evaluate n.)
By reversible, electrochemists mean that the reaction is fast (The sign is positive for a reduction process.)
enough to maintain the concentrations of the oxidized and Estimating formal reduction potentials from quasi-re-
reduced forms in equilibrium with each other a t the electrode versihle voltammograms is less reliable the farther the peak
surface. The proper equilibrium ratio a t a given potential is separation deviates from the reversible case. Theoretical work
determined by the Nernst Equation: shows that as the scan rate is increased, slow electron transfer
kinetics can make the peak potentials shift in such a manner
t b.1 .iur the rt.110~
that they are n u lungrr s\.mmrtrii. h ~ u the
cuuple. The prublrm is wursr the fart her t hr rlrctnm trmsier
where 0 is the oxidized form and R is the reduced form. c~eificient, ,I, is from 0.5.A ruugh indlrati~rlluf the rn;~gnirude
How fast is fast enough? Many systems lwk reversible when d t h e errnr that may he inrruducrd IIV wrrsginr the pair 01'
the voltage is scanned slowly hut a t higher scan rates Up cathodic and anodic peak potentials for a quasi-reversible
appears greater than 58ln mV. Reversihility is, then, a matter voltammogram can be derived from graphical data prepared
of degree and depends on the stress that is applied to the by Matsuda and Ayabe ( 1 1 ) . For an 0-value of 0.3 and peak
system. Matsuda and Ayabe indicated that for scanning vol- separations of 108,312, and 592 mV, the midpoint between
tammetry any deviations from reversible behavior will be the peaks would be on the negative side of the actual Eli2 value
imperceptible if the value of k" (in cmlsec) is greater than the by 2,44, and 104 mV, respectively. (For an a-value of 0.7 the
numerical value of 0 . 3 1 ~ "(where
~ u is the scan rate in V/sed3 error would have the same magnitude with the opposite
. . Voltammoerams
(11). " recorded a t scan rates UP to 10 Vlsec sign.)
are common. Some instruments are capable of scanning up
to 1000 Vlsec. Therefore, electron transfer reactions with rate
constants greater than 10 cmlsec will be reversible even in the The mathematics that describe a scanning experiment are quite
very fastest experiments. complicated. However, an application of Fick's First Law of Diffusion
Redox couples whose peaks shift farther apart with in- tells us that lhe current at any time is proportional to the concentration
gradient for the reactant:
creasine scan rate are categorized as auasi-reversible. (Some
authors merely say irreversible.) There are some cases in which
the oeaks are so widelv separated ( k o s 2 X 10-"112 cmlsec) A 1s the electrode area. 0, is the dnffusoon coeff~c~ent of the oxldlzed
that'no parts of the t& peaks overlap on the potential axis a t specres, 1 is tame, and x s the dlstance from lhe electrode surface An
all. These are generally known as "totally irreversible" sys- erperment in wh ch the voltage 8s stepped Instead of scanned out to
tems. A subset of this class are those reactions that yield a potential where the current is diffusion controlled is much easier to
products that cannot be recycled electrochemically to give model mathematically. (This is chronoamperometry.)in that case
back the original reactants (for example, those that involve
extensive bond breaking andlor loss of substituents to solu- (aco~ax).=,,,= c&=t (3)
tion). These are "chemically irreversible" reactions, and many where Cb 1s the concentration of the oxld.zed materlal In the bulk so-
vield no return peak a t all. lullon (on moles/cm'l It seems reasonable, Inen tnat scannmg to the
Another char&teristic of reversible systems is the depen- same voltage would also cause the current to fa I 011 as
dence of the peak height on the square root of the scan rate.' Rates of heterogeneous reactions are referenced to unit surface
At 25°C the peak current is 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
~~ ~~ ~
is the normalized current as given by the function: Ill. Reversible electron nansfer followed by an irreversible chemical
il(n3/2FADA'2CEu1/2).)
. , reaction-E,Ci mechanism
~ i c h o l s o dand ~ h a i ' nhave demonstrated that the ratio of
the anodic to cathodic neak currents can be ~ r e d i c t e dfrom
the rate constant for t i e chemical step, k , and the time, r ,
spent between Ell2 and the switching potential, EL (15). (E112
will be the midpoint between the peaks a t very high scan rates iV. Reversible chemical reaction peceding a reversible electron
where the following chemical reaction does not have time to transfer-CE, mechanism
consume a significant amount of R.) The theoretical rela-
z&o
L,
O + m e R
zL
-0
*-,
o t m - R
R+Z*O
k
I I
0.01 0.1 1.0 10 100
Figure 6. Methods for determining the proper baseline for measurement of the
SCAN RATE 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
Figwe 5. Rate of shin of potmliil as a functionof scan rate ta variws elemode st EL until iapproachesa steady state befwe scanning back. (c) Parameters
mechanisms. (Adapted with permission from Anal. Chem.. 38, 706-723 used lor calculation of lhe current ratio using Nicholson's method, eqn. (10).
cyn and Shain also described multistep charge-transfer re- In eqn. (8), ,i is the peak current for the forward process; (id0
actions where an intermediate oxidation state is formed (16). is the absolute current at the switching potential; and (i,.)~
Treatment of a multi-electron reaction with an intervening is the uncorrected return peak current measured from the
chemical step has also been given (17,18). Data from other current axis. (See Fig. 6c.)
types of electrochemical experiments is often needed to There are some systems in which a coupled chemical reac-
evaluate rate constants for reactions with coupled chemical tion ~ i e l d electroactive
s by-products. In these cases multiple
steps.) scans can be beneficial. For example, the product of electron
Measurement of the peak current is fairly simple for the transfer in the oxidation of aniline is thought to he a free
forward scan. The proper baseline can be obtained by re- radical that very rapidly dimerizes (13).
cordine" the hackmound
" current for a scan without the anal*
under the same conditions (same electrolyte, surface pre-
treatment. 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 The p-arninodiphenylamine (111) that is formed is much
potential with the recorder sweeping along the x-axis as a more easily oxidized at the applied potential and a further two
function of time. This is shown in Figure 6a. electron oxidation occurs.
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 appro-
priate baseline is shown in Figure 6h (13).