(David K. Gosser) Cyclic Voltammetry Simulation A

Preface
Cyclic voltammetry (CV) has been in the Forefront of the study of electron
t s conseyuences. With the cyclic voltarnmetric method one can
simultaneously sctivale mc.lecules by electron transfer and probe subsequent
ical reactions. The cyclic voltarnmetric response curve thus provides
ativn about elwtron transfer kinetics and thermodynamics as well as the
consequences of ekct con transfer.
Ths book jntroduces cyclic vol tarnmetry and its application to the analysis
of electrochemical reaction mechanisms. It also provides the experimentalist
-
with a siruulation-based approach for the analysis of cyclic voltammograrns.
Chapter I presents a brief summary of electrochemical principles. Emphasis
is on a conceptud approach to the reduction potential and electrode kinetics.
Chapter 2 introduces cxperimental and conceptual aspects of cyclic vol-
tammetry. The relationship hetween electrode kinetics, chemical kinetics, and
lored, find the imporpant concept of electrochemical reversibility
Chapter 3 is a survey of the use of CV for the study of reaction mechanisms in
anometallic, it~orgaruc. and pharmacological chemistry.
introduces the method of simulation by explicit finite differences,
only employed numerical method for CV analysis.
Chapter 5 describes CVSIM, a general program for the simuIation of cyclic
voltarnmetric experiments. A general program fcr the simulation of double
experiments, DSTEP, is also provided.
describes CVFIT, a program that combines CVSlM with n
A . . , , . . . . ,..- -.. .
..
. .
viii PREFACE
simplex driver to find the least-squares best fit between experimental and
simulated cyclic voltarnmograms.
CVSIM, CVFIT. and DSTEP are included on the diskette with this book.
They require the use of a PC-compatible (80 x 86) computer. A math coproces-
sor is not required, but it is recommended.
I welcome questions or comments from those utilizing the simulation
software (E mail : Gosser @ sci.ccny.cuny.edu).
Acknowledgments
Many thanks go to Philip Rieger, James Rusling, and Brenda Shaw, for their
encouragement of my interest in simulation.
Acknowledgment is due to Qindong Hnanp and Feng Zhang, my co-workers
at City College, for their many contributions to the work represented here.
Helpful discussions with Ron Birke, my colleague at City College, are
gratefully acknowledged.
I would like to thank the researchers who have used the CVSIM program,
especially Dwight Sweigart, Jay Kochi, Carlo Nervi, and Christian Amatore,
whose comments have been particularly helpful.
Finally, I wouId like to thank Edmund Immergut, of VCH, for his valuable
advice and assistance.
David K. Gosser, Jr.
May 1993
Contents
Useful Equations xi
1. The Reduction Potential and Electrode Kinetics 1
1.1 The Reduction Potential 1
1.2 Electrode Kinetics 12
References 24
2. The Cyclic Voltammetric Experiment 27
2.1 An Overview 28
2.2 The Electrochemical Cell 30
2.3 Electrochemical Mechanisms: E&C Notation 35
2 4 Distortions of the Faradaic Response 56
I
2 5 Microelectrodes and Fast Scan Voltanlnletry 59
I
2.6 Potential Step Methods and Cyciic Voltamriletry 60
5 2.7 Construction of a Fast Potentiostat 64
1'
2.8 Determination of the Number of Electrons 68
References 68
I
3. A Survey of Electrochemical Mechanisms 71
$
3.1 The CE Mechanism 72
3.2 Multielectron Transfer 75
3.3 Protonations at Equilibrium 77
x CONTENTS
3.4 Catalytic Mwhanisms SO
3.5 The Reduction of Nilrobenzoic Acid 89
3.6 Reduction of the Nit'rosonium Cation and Its Complexes
92
3.7 Reactivity of 17-, 18-, and 19-Electron Tungsten Complexes 95
3.8 Mechanisms Involving Adsorption 97
References 102 .
4. The Simulation of Electrochemical Experiments 105
4.1 The Discretized Diffusion Equation 105
4.2 Evaluation of the Boundary Conditions 108
4.3 Dimensionless Units 109
4.4 Solution Chemical Kinetics 110
4.5 A Sample Simulation Program 110
References 114
5. CVSIM: A General Program for the Simulation
of Cyclic Voltammetry Experiments 115
5.1 An Overview of CVSIM 115
5.2 Extensions of the Simulation Method 117
5.3 Accuracy of Simulations 120
5.4 Installation and Use of CVSIM and CVGRAF 123
5.5 Examples 125
References 135
6. CWIT: Simplex Data Analysis with CVSIM 137
6.1 CVFIT: Simplex Data Analysis with CVSIM 137
6.2 Instructions for the use of CVFIT 138
6.3 A Prototype Analysis: The EC Mechanism 139
6.4 Some Final Comments on Simulation Analysis 145
References 148
Appendix: Summary of Instructions for CVSJM, CVGRAF,
CVFIT,andDSTEP 149
Index 153
Useful Equations
AGO = - FE' = AG ,,.,, + SAG ,,,, + constant
Nernst Equation
Butler - Volmer Equation
k0 = stattdard heterogeneous rate constant (cm/s)
rr = cat hadic transfer coefficient
! 1 - a = anodic transfer coefficient, f l
Cyclic Voltammetry (CV)
' E, (reversible one-electron transfer)
:
C
CYCLIC VOLTAMMETRY
Figure 1-1 The conduction band model. Conduction is possibfe when parrially fillcd
valance electrons cnn be raised in energy by external fields.
potential of the electron in the conducting material. 111 thermodynamics, the
electrochemical potential is defined as the change in free energy per unit species
with everything else kept constant:
p,,,(e, conductor) = -
The units of the Fermi level free energy, usually expressed in electron volts,
can be interconverted with other units that are more useful in other contexts
(1 eV x N, = 96.485 kJ/mol = 23.06 kcal/mol = 8066 cm- ').
Mow let us turn to the process in solution, the ferricyanidejferrocyanide
transition. The free energy change associated with the transfer of an electron to
an oxidized species in solution can be viewed in the context of a thermodynamic
cycle (Figure 1-2).
The total free energy is seen to be composed of:
1. The free energy associated with transfer of the oxidized species from solution
to vacuum. This is the negative of the solvation energy, -AG,,,,,,o,,.
2. The free energy associated with the transfer of an electron to the oxidized
species jn vacuum (electron attachment), AG,,,,,. This is approxinlalely the
electron affinity (EAI of the oxidized species or the negative of the ionization
potential (IP) of the reduced species.
3. The free energy associated with transfer of the reduced species from vacuum
to solution, AG ,,,, ,,,,.
We have:
AGabs = AGel.at. + AGsolv(red) - AGsolurax) (I)
The subscript abs denotes that the referenw level for energy is established by
the electron in vacuo (the "absolute" scale). If the oxidized and reduced species
are at unit activity (at T = 298.15"K) then the free energy of reduction is a
THE REDUCTION POTENTIAL AND ELECTRODE KINETICS
e-vac
Ox ... => Red , ,
Figure 1-2 Thermodynamic cycle for reduction in solution.
standard free energy and has the usual relationship to the standard reduction
potential (also referred to absolute scale), AG,",, = -nFE,',,.
The existence of the oxidized and reduced forms of a rrdon couple thus
determine a kind of Fermi 1eveI in solution, [see Pleskov and GurevichZ for a
statistical mechanical derivation]. The Nernst equation for the half-reaction,
referenced to vacuum, is then given by*:
RT [Red]
Eaba = E L - - In -
nF [Ox]
A Le Chatelier "co~icentration" cffect raises or lowers the solution Fermi level
by the rclative concentrations of the reduced and oxidized forms.
When an electrode is placed in a solution containing the oxidized and
reduced species, the Femi levels tend to equalize. Ths is achievsd through
electron transfer between the electrode and either of the redox species. Electron
transfer from the reduced species to the electrode will raise the Fermi level of the
electrode and lower that of the sulution. Etectmn transfer from the electrode to
the oxidized species will lower the Fermi level of the electrode and raise that of
the solution. The total Fermi level energy is usually separated into a chemical
'
part (the innate Femi level of the metal) and an electrical part (energy as a result
of charging). Thus we can write
FL,ota, = FL.in*,t, - Fd
;
where #I is the electrical potential OF the electrode. At equiiihrium, the total free
"
energy change must be zero for electron transfer: the Fermi levels are equal. In
general, both Fenni levels might be expected t o move to reach equilibrium. In
'
practice, however, the electrode potential can be controlled (as in the CV
experiment) and the solution must adjust (Figure 1-3). Alternatively. iF the
electrode potential is not controlled, the solution species can determine the
t electrode Fermi level.
I t i s useful to emphasize the distinction between the electrical potential 4. and
rhe Fernli level or the electrode potential, E. The electrode potential cvns~sts of
both the chemical and electrical energy associated with bringing an electron to
The concen1raIion ltrms in Equation (2) should actually be written as activities
CYCLIC VOLTAMMETRY
Figure 1 3 Equilibration of the Fermi levels of the electrode and solution. The
electrical potential 4, of the electrode, is due to charging of the electrode. It is this
process that changes the Fermi level of the electrode from its innate value.
the electrode, whereas the electrical potential is that part of the energy due solely
t o electrostatic effects.
1.1.2 The Hydrogen Reference and the Absolute Potential
The preceding discussion used the vacuum level as the reference, to emphasize
the relationshp between gas phase properties such as TPand EA. Electrochem-
ical measurements, however, must utilize a solution-based reference. The
primary reference is based on the hydrogen ion reduction in aqueous solution:
H&,uniiaciiutg + e- + ~ ~ ( g , l atm) E0 = 0 volts
for which the potential is taken as E* = 0 volts. The potential of any other half-
reaction can in theory be obtained by constructing a complete cell with the
hydrogen reaction as the anodic (oxidation) reaction and another half-reaction
as the cathodic (reduction) reaction (Figure 1-4). AH redox reactions are thus
described by their tendency to undergo reduction relative to the hydrogen ion.
For instance, the standard potentiaI for the reduction of Fe(CN):- to F~(CN):-
is E0 = 0.356, and the reaction:
is favorable.
THE REDUCTION PO'ITNTIAL AND ELECTRODE KINETICS
I
, Figure 14 Hypothetical determination of E. Note that a difference in electrode
potentials is determined. Since the Fermi levels (FL) of the metals in contact must
equilibrate, the difference in elmtrode potentials is transmitted exactly to a difference in
'
lead electrical potentials, if the leads are of the same material.
(FL- Fd)mo, - (FL - F4)ptU, = (FL - F~) c, I, , - ( FL- F#~c~( ~I = F(& - 42)
What is the relationship between the vacuum (or absolute) potential reference
and a reference based on the hydrogen ion reduction? This is the tendency tie.,
the free energy change) for an electron to move from vacuurn to reduce the
hydrogen ion in aqueous solution. This quantity is very important in relating
electrochemical measurements and gas phase measurements or spectroscopic
measurements, and it has been measured to be about 4.42V; however, values
: around 4.8 V have aIso been r ep~r t ed. ~ - Some physical insight into the origin
of the absolute potential is obtained with a thermochemical cycle for hydrogen
reduction (Figure 1-5). The individual steps are (1) desolvation of H+, (2)
electron attachment in vacuo to give the hydrogen atom, and (3) formation of
molecular hydrogen in the standard state. The system of standard reduction
i potentials is described with respect to aqueous solutions. Much electrochemical
! work involves nonaqueous solutions, and special consideration must be given to
:
measurements in nonaqueous media.4 In cyclic voltammetric studies it is
1 common to report the redudon potential of a chosen standard, such as the
ferrocinium ion, under the conditions of the experiment. The reduction potential
of such a large ion is not expected to change appreciably with solvent.
B
1.1.3 Practical Reference Half-Celb
I
' In pr act i ~, electrode reactions other than hydrogen ion reduction are used to
construct practical reference systems. Potentials determined using these hdf-
cells can be related back to the hydrogen reference or absolute potential scale if
CYCLtC VOLTAMMETRY
- AG roc
1
Figure 1-5 Thermodynamic cycle for hydrogen ion reduction.
desired. The saturated Ag/AgC1 and Hg/Hg,CI, (calomel electrode) are com-
monly used secondary standards. The use of saturated solutions keeps the
chloride concentrations constant and thus fixes the potential.
AgCI(s) + e- = Ads) + C1-(iaq, sat KCI)
E" = 0.199 V
Hg,Cl,(s) + 2e- = 2HgO) + 2C1 -(aq, sat KCl) ED = 0.244 V
The potential of a complete cell is the difference in potential between the
cathohc and anodic cell h alf-reactions:
Ecell = Ec - Ea
. RT [Red]
E, = E: - -1n--
nF [Ox]
R T [Red]
E , = E: ---In-
nF [Ox]
where the concent ration ratios indicate general reaction quotient terms.
, The relationship between the concentrations and the potential is given by the
Nernst equation for the complete cell:
where Q is the reaction quotient:
aA + bB*cC + dD
THE REDUCTION POTENTIAL AND ELECTRODE KINETICS 7
For lzrricyanidelferrocyanide versus the silver chloride reference, this is:
Note that for a fixed reference system, the cell potential depends on the
cathodic reaction components. Again, we can note that nvnaqueous systems
pose a particular problem. For instance, if the solvent used in the reference
electrode differs greatly from the cell solution, a potential is created ljurlction
potential).
1.1.4 Formal Potentials
The E0 for a half-reaction is the potential of that renction versus the standard
hydrogen electrode, with all species at unit activity. Most reduction potentials
are not determined under such conhtions, so it is expedient to define a "formal"
reduction potential. This i s a reduction potential measured under conditions
where the reaction quotient in the Nernst equation is one and other "non-
standard" conditions are described: solvent, electrolyle, pN, and so on. Formal
reduction potentials are represented by Eo'. Reduction potentials determined by
cyclic voltanmetry are usually formal potentials. The difference between
standard and formal potentials is not expected to be great. Other definitions of
the formal potential are offered.'
1.1.5 The Chemical Interpretation of the Reduction Potential
, The process of reduction in aqueous solution has been represented by the
thermodynamic cycle in Figure 1-2, and the resulting equation.
t<
t
~ F E O = - AG ,,,,. - dAG,,, - 4.43F + constant
( 5)
Eo is the standard reduction potential based on the hydrogen reference. The
hydrogen reduction potential versus the vacuum is taken as 4.42 V. The constant
term accounts for the use of other references, such as the standard calomel
, electrode (SCE) or the Ag/AgCI electrode. (A small contributioi~ to the constant
can also wme from junction potentials due to varying solvents. etc.1 Again, we
, can note that the free energy of electron association is approximately equal to
the electron affinity and to the negative of the ionization potential.
Let us conside~ the application of Equation (5) to the one-electron reduction
i: of p-benzoquinone and to the oxidation of nitroxide spin label Tempo.
' Kebarle and Chowdhury have utilized gas phase equilibrium electron
transfer measurements to determine the thermodynamics of gas phase electron
attachment to many organic compounds, including a series of quinonm. The free
. , . , . . , , , , . .-. . "". .a-
CYCLIC VOLTAMMETRY
I
d
l
0
Figure 14 The reduction of benzoquinone reduction (top) and the oxidation of Tempo
(bottom).
energy of electron association for benzoquinone is - 1.9 eV. This number reflects
the energy of the lowest unoccupied molecular orbital (LUMO) of benzo-
quinone. The redox potential for benzoquinone in dirnethylfomarnide (DMF) is
0.0 V versus the SCE. The SAG,,,, can be estimated through Equation (5). Since
the benzoquinone [BQ) is neutral, the solvation energy change can be identified
with that of the anion. The constant term in Equation (5) is -0.241 V, to
account for the use of the SCE. The free energy of solvation that is released upon
going from the neutral to the BQ anion can then be estimated as 2.26eV.' The
energetics of the reduction of BQ are summarized in Figure I-7(top).
The energetics of solvation play an important role in the thermodynamics of
electron transfer in solution. The thermodynamics of electron transfer can be
envisioned as electron transfer from one Fermi level to another, with the Fermi
level of solution determind by the Nernst equation, and the E0 determined by
both LUMO energy and solvation changes.
Often, valence bond structures, molecular orbital diagrams, and electronega-
tivity considerations can be useful in understanding the physical and chemical
origin of the reduction potential. Electron-withdrawing groups favor reduction
(a more positive EO) by reducing the energy of the LUMO (much in the same
way that the electrode potential is lowered when electrons are withdrawn), and
electrondonating groups will tend to have the opposite effect, making reduction
more difficult (a more negative EO).
A plot of E0 versus AG,,, for benzoquinone (Figure 1-8) illustrates the
combined effect of structural changes on the molecular orbital structure as well
* The estimates here differ from those of Reference 6 because of a different choioe for the
absolute potential of the hydrogen electrode.
TEMPO' (g) TEMW (O)
TEMPO+taeO - TEMPO [a@
! Figure 1-7 Thermodynamic cycles for the reduction of benzoquinone and dhe oxida-
>I
; tion of Tempo.
! as on the solvation.' The LUMO for the quinones is a nY-type orbital centered
around the highly electronegative oxygens. Ths accounts for the large positive
electron affinity of the quinones compared to other similar compounds like p-
quinohmethane. The electronegative oxygens lower the LUMO energy.
j Kebarle and Chowdhury also studied the effect of methyl substituents on the EA
and found that for each methyl group, the EA was decreased by 1.7 kcallmol. It
can be seen from Figure 1-8 that there is no significant difference in dAG, , for
the methyl-substituted quinone series. The electron-donating methyl groups act
as an electron source that raises the LUMO of the quinones. The chloroquinone
series is quite different. The electron-withdrawing effect lowers the LUMO,
increasing the EA. It can also be seen from Figure 1-8 that dAG,,,, is not
constant for the chloroquinones. This variability is explained by the increased
'
charge delocalization caused by the electron-withdrawing effect of the chloro
1 ,
-, substituents. From the Born model of solvation, it is expected that a larger
radius will decrease solvation energy. Finally, we can look at the following
I
* For spectroscopic measurements, the equality between the ionization potential and the energy
of the highest occupied molecular orbital (HOMO) or the electron affin~ty and the LUMO energy
follows from Koopman's "theorem," which asserts they are equal and opposite (for IP/HOMO) or
$
equal (EAILUMO). This relation requires that no electronic relaxailon take place after removal of
an electron, which is not generally true. Electrochemical measurements of &%will thus also include
any similar electronic relaxation.
10 CYCLIC VOLTAMMETRY
Figure 1-8 The variation of electron affinity (EA) with reduction potential. (Adapted
from Reference 6.)
series: benzoquinone, naphthoquinone, and anthraquinone. There is apparently
no change in solvation energies here, indicating that the charge remains highly
localized on the oxygens throughout the series. However, the LUMOs do
change, as predicted by MO theory.
The energetics of the oxidation of the nitroxide spin label Tempo (in DMF)
have also been s t u d ~ d , ~ and are shown in Figure 1-7(bottom). The ionization
potential (IP) of Tempo is 7.31 eV and the oxidation potential is 0.271 V versus
the standard hydrogen electrode. The solvation energy change (cation to
neutral) is then calculated as - 2.6 eV. Both the Tempo cation and the BQ anion
have localized charge, and similar size. Barring specific solvent effects (e.g.,
solvent coordination), we expect from the Born model (Equation 61, which treats
the solvent as a dielectric continuum, that the solvation energies will be
comparable:
where
NA = Avogadro's number (6.022 x
e = elementary charge (1.602 x 10- l 9 C)
E~ = permittivity of a vacuum (8.854 x 10-l2 F/mZ)
r = radius of ion (m)
E = &electric constant of solvent
The Born equation is not expected to give very accurate results (often
calculated solvation energes are too high). However, it is useful for estimates
and qualitative predictions. Dielectric constants for some common electrochem-
ical solvents are given in the next chapter (Table 2-1).
In estimating chemical properties, it is sometimes very usefuI to combine
reduction potentials with other physical quantities. For instance, solution bond
dissociation energies for organo acids have been estimated by combining
reduction potentials with pK,
1.1.6 The Temperature Dependence of the Reduction Potential
The entropy of reduction can be obtained by measuring the reduction potential
as a function of temperature.
In such experiments the temperature dependence of the reference cell
,
potential must be taken into ~ C C O U I I ~ . ~ The most convenie~lt method of doing
this entails the use of a "nonisothermal" cell, in whch the reference is kept at a
. constant temperature whle the temperature of the remaining halF-cell reaction is
i changed.
r'
/
1.1.7 Innuence of Coupled Chemical Reactions
L
on the Reduction Potential
It is common for a chemical reaction, such as a protooation, to be part of the
h overall reduction process. For instance, in aqueous solution. p-benzoquinone is
reduced by a two-electronltwo-proton (?e-/2H +) process over a wide range of
pH values. The reduction potential is:
i Another example is ascorbic acid (H,A). s1uch aIsu undergoes a 2e-/2H
p
;; process to dehydroascorbatz (Dl:
H2A- 2H+ - 2 e - d l 3
In this case a formal potential can be written which also takes into account
, .. ....-I ----A
12 CYCLIC: VOLTAMMETRY
the presence in en01 groups of dissociable proton^,'^ with pK,, = 4.10 and
pK,, = 11.79. The resulting expression For the formal potential is:
where
F,,, = m2A] + [HA-] + [A2-]
1.2 Electrode Kinetics
Electron transfer reactions at the electrode may not be rapid enough to maintain
equilibrium concentrations of the redox couple species near the electrode
surface. It is therefore necessary to consider the kinetics of the electron transfer
process. The rate equation for heterogeneous electron transfer (Equation 8)
expresses the flux of electrons at the electrode surface (Figure 1-9):
where A is the area of the electrode (cm).
With a centimeter-based system, the heterogeneous rate constant is expressed
i n centimeters per sewnd, and concentrations are given in moles per inilliliter
(M x 10-9).
1.2.1 Transition State Theory for Electron Transfer
The main task of electrochemical rate theory is to promote an understanhug of
the physical basis of the heterogeneous rate constants k, and k - ,.
Heterogeneous electron transfer can be envisioned with the aid of transition
state diagrams. First consider the forward reaction, the transfer of an electron
from the electrode to the oxidized species in solution adjacent to the electrode. A
transition state diagram will in the first place reflect the reactant and the product
free energy. The reactants are the oxidized species in solution and the electron in
Ox
T
I cm Red
1
Figure 1-9 The flux of electrons at an electrode surface is dacribed as moles of
electrons per second through a surface area of one square centimeter.
THE REDUCTION POTENTIAL AND ELECTRODE KNT I C S 13
the electrode. We have seen that the free energy of the electron is equivalent to
the electrode potential. Thus the reactant side of the transition state diagram
(TSD) reflects the potential of the electrode. The product side of the TSD is the
free energy of the reduced species in solution. The transition state for electron
transfer must depend in some way on the physical and chemical changes that
occur as a consequence of the electron transfer. We have already seen that
solvation energy changes are a significant part of the process of electron transfer.
The transition state is a nonequilibriurn solvated state somewhere between the
oxidized and reduced forms. Often chemical or structural changes in the
molecule itself occur as a consequence of electron transfer. In such cases, we
might expect these changes to be reflected to some degree in the transition state
as well.
Transition state diagrams are sketched in Figure 1-10 for different electrode
potentials. The effeqt of changing the potential is reflected partially in the energy
of the transition state. The curves in the TSD series of Figure 1-10 are related to
the free energy relationships that have often been observed by physical organic
;
chemists for a homologous series of chemical reactions (Figure 1-11). Such
homologous reaction series often follow linear free energy relationships
(LFER), wherein in the following type of relationship ktween rate constants
'
and equilibrium constants is observed
lnIIhlkr~rcnl a 1nCktq/keq(rtfJ (9a)
where the rate and equilibrium constants of a series of homologous reactions are
I compared to a reference reaction of the series. From the constants k, = Ilk,
!
and k,/h = k , it can be easily shown that f i = ( I - a).
0, + Ox Red
Figure 1-10 Transition state diagrams for reduction at difirent electrode potentials
e -L-A. .
The fundamental equation of transition state theory is:
Together with the ratelequilibrium relationships this leads to linear free energy
relationships for the forward and reverse reactions:
In an LFER, the transition state is interpreted as resembling to some degree
the reactants and products. The degree of resemblance is given by the
coefficients a and p.
The transition state resembles to s o m e degree both the reactants and the
products. The degree of resemblance is given by the coefficient in the LFER
(Equation 9). Changes in the free energy of the reactants or the products are
reflected as fractional changes in the transition state energy. In the series of
organic reactions, the free energy is changed by substituent effects.
1.2.2 The Butler-Volmer Equation
The situation in electrochemistry is unique. The free energy of the reactants is
changed without any change in the overall reaction (without any chemical
change in the reactants or products). It is not surprising that electrochemical
kinetics have long been descrikd by an LFER that is called the Butler- Volmer
equation. If a reference rate is chosen as the rate when E = E", the forward and
reverse rates are equal (k, = A, = A,), and we have:
AGf,,,,,, = AGL, + aF[ E - EO]
A G ~ ,,,,,, = AG;,, - [I - u] F[ E - E q
Sometimes u is referred to as the cathodic or forward transfer coefficient and
f i = (1 - u) as the anodic or reverse transfer coeficient.
From transition state theory the rate is exponentially related to the free'
energy of activation, so that
whch is the Butler-Volmer equation. The standard rate constant k, is a
measure of the intrinsic energy harrier. The transfer coefficient a is generally
believed to reflect the nature of the transition state, in the same sense that is used
in physical organic chemistry. Small values (or > 0.5) are indicative of a product-
like transition state, and large values (a > 0.5) are indicative of a reactant-like
transition state. Figure 1-12 shows several eIectron transfer reactions with
corresponding d u e s of a. Anthracene12 has a = 0.55: the barrier for electron
transfer consists largely of solvation reorganization energy, and the rate of
Figure 1-1 I Linear free energy relationship obtain4 for the addition of semicarbazide
to subs tiluted benzaldehydes. The slope, analogous to thc transfer coeficient in
electrwhemistry, is 0.47. (Adapted from Reference 11.)
~6 +i- NO, a = 0.5
Figure 1-12 Electron transfer reactions and transkr coefficients.
electron transfer is fast. Both tetraalkyltjn oxidatiot~ @ = C).29)13 and alkyl
halide reduction (a = 0.3)14 occur with concurretlt s t r u~t ~r a l change (from
tetrahedral to pyramidal for the alkyltins and bond breaking for the alkyl
halides); these structural changes contribute to the barrier far electron transfer.
Cyclooctaletraene (a = 0.4) goes from a tub shape to n partially Battened state
upon redu~tion.'~.'~ An interesting pharmaceutical, Arternisinin, has a value of
a = 0.35: presumably the oxygen-oxygen bond in this endoperoxide is either
lengthened or broken upon electron transfer.
Methylcobalarnin has a large transfer coefficient (a = 0.78). The reason for
this is not as easily explained, but it can be noted that the electron trans-
fer and following chemical reaction occur in two separate activatsd steps. It
hns been suggested that in this case the transfer coefficient will k large.I4
Whereas NO: has a relatively facile reduction, with a = 0. 5, ' ~ calcuIations
based on whent structural changes indicate that the electron transfer should be
rather slow. This is indicative of a more complicated, "inner sphere'' mechanism,
in which the donor (the electrode) and acceptor (NO:) are coordinated in such a
way as to reduce the barrier to electron transfer.
1.2.3 Outer and Inner Sphere Interactions
Electron transfer. heterogeneous or homogeneous, can be classified as outer
sphere or inner sphere, according to the extent of interaction between the
electron donor and the electron acceptor (Figure 1-1 3).
Electron transfer reactions that take place with weak interactions between
reactants are outer sphere and those with strong interactions are inner sphere.
Outer sphere reactions are characterized by the relative absence of steric effects
on the rate of electron transfer, while inner sphere reactions are very senslt~ve to
Figure 1-13 Schematic representation of outer and inner sphere elcciron transfer
reactions.
THE REDUCTION POTENTIAL AND ELECTRODE KINETICS 17
ic effects, which prevent the close encounter needed for full interaction. This
observation has been suggested as the major experimental criterion for distingu-
ishing inner from outer sphere electron transfer. '
2.4 Marcus Theory
The theory that has found the most application for characterizing the nature of
' outer sphere electron transfers is that developed by R. Marcus, who was
awarded the Nobel Prize in 1992 for these contributions. As it is employed in
t stuhes, the Marcus theory provides a method by which one can relate the
', rate of electron transfer to solvation reorganization changes, structural changes,
and the overall free energy change.
Focusing on the electron transfer act, theory for electron transfer presumes a
preequiiibrium factor far complzn formation, and the following electron
D + A-[D,Aj Kc,
ID, A1 - CD+, A-1 k e ,
It is the rate of the electron transfer step, kc,, that is discussed below.
The "Marcusian" transition state diagram presents a reaction coordinate that
is composed of solvent reorganization as one moves from reactant to product.
Transition state diagrams of this sort can be applied to electrode reactions or
homogeneous electron transfer (Figure 1-14). The free energy along the
, coordinate varies as a square of the deviation from the equilibrium position. The
',physicaI meaning is that small changes in the solvent medium around the ion
T
1
G
1
(D . A1 D+ , A-1
Figure 1-14 Transition state diagram for electron transfer acoording to Marcus theory.
. . . - . A
can give rise to large changes in the electronic energy of the molecule. The
intersection of the curves gives the transition state energy. When the driving
force AG = 0, the intersection of the two curves occurs at an energy of
A G ~ = 144. This is called the intrinsic free energy barrier, where I is related lo
the optical and static dielectric constants.
In polar solvents E, << c,,,,, and the optical dielectric term dominates.
The general expression for the activation energy is given by
where w is the work required to bring the Ox and Red t o the electrode. Often the
work term is neglected. Figure 1-15 shows the variation of the activation energy
with driving force for a typical value of I, 1.00eV.
Inspection of Equation (12) (after expansion) shows that the free energy
relationship, neglecting the quadratic term. i s equivalent to the Butler-Volmer
equation, with the transfer coefficient set to 0.5. This i s shown in Figure 1-1 5 to
be true for smaIl deviations from the reduction potential. We can also note that
for the highly endoergic or exoergic regions, the transfer coefficient (the change
in activation energy per change in driving force) is given by:
Several cyclic voltammetric studies have shown the expected change in the
transfer coefficient with ~otentia1.l~ The highly exoergic region, where the
0
Hutler-
Yoirrler
Figure 1-15 Variation of activation energy with potential according to Marcus theory.
The straight ltne corresponds to a linearized version of Marcus thcory, equivalent to the
Butler-Volmer equation.
- THE REDUCTION POTENTlA L AND ELECTRODE KINETICS 19
activation energy increases with driving force, is dificult to observe with
electrochemical experiments* but has been observed in other contexts."
The theory is similar for homogeneous electron transfer, except that because
ions involved, the value of ,i is expected to be larger. Also, the work
rent as a result of the difference in work of bringing reactants and
products together in solution compared to bringing a single ion to electrode.
A term is sometimes included in reorganization energy to accommodate
changes in vibrational energies for the molecule/ion transition.
where f is the force constant and Sd is a bond length change. These are
sometimes called "inner sphere" contributions to the reorganization energy:
they are not to be confused with an "inner sphert" interactions, as described
1.2.5 Kochi's Free Energy Relationship for Electron Transfer
portance of inner sphere interactions to electron transfer was first
recognized by H. Taube, who received the Nobel Prize for work in this area. The
compIexity of the problem, however, has prevented the development of a
quantitative theory comparable to Marcus theory for outer sphere reactions. In
practical terms, inner sphere interactions generally lower the activation barrier
for electron transfer compared to outer sphere electron transfers. As a con-
. sequence, they may play important roles in electron transfer in biochsmistry and
atalysis of electrode reactions. A characteristic inner sphere reaction
ted by Kochi is the electron transfer of iridium hexachloridz with
1tin.l3 A five-coordinate transition state around the tin is indicated,
bherein the positive attraction in the ion pair stabilizes the transition state
,(Figure 1-16). In the case of inner sphere electron transfer, steric congestion
prevents the close encounter needed to stabilize the TS, and lower rates of
homogeneous electron transier are observed. In contrast to outer sphere
<electron transfer, there i s no obvious relationship between homogeneous and
,heterogeneous rates, as the interactions between D/A complexes in solution are
generally divergent from electrode-molecule interactions.
A new method to characterize inner sphere electron transfer .reactions has
been developed by KochiL3 and designated FERET (free energy
I /
+ - I f - + p{- a ; ir .]
' I
Figure 1-16 Typiiral inner sphere complex.
This is k + u x the continuum of energy levels in the electrhde (see rcfewn~u: 13a).
relationship for electron transfer). The sequence of events for electron transfer
between a general donor and acceptor can be written:
[D ' , A-] + products (fast)
The products can be either separated D' and A- or a collapsed ion pair. For
endergonic driving force, the observed rate constant is given by:
In the endergonic region, a cycle can relate the thertnodynamics and kinetics
of the electron transfer process (Figure 1-17):
The work terns w, and w, are associated with bringmg the reactants or products
together. For neutral reactants, w, can be negl ~t ed.
Another cycle involves spectroscvpic measurement oft he optical analogue of
electron transfer, the charge transfer transition energy, hvc, (Figure 1-18).
The work term for inner sphere interaction of the ion-pair can be evaluated as
follows:
[D,A]% [D', A-]*
w,* = hv, - IP, + EA, + w, (1 5)
Figure 1-17 Therrnochemical cycle for thermal electron trader.
THE REDUCTION POTENTIAL AND ELECTRODE W T [ C S
Figure 1-18 Thermochmical cycle for optical electron transfer.
'.
If a common acceptor is chosen, and a reference donor, then a comparative
work term for the ion-pair can be defined:
Aw,* - w,* - w:' = Ahv, - AIP,
(16)
Finally, utilizing a combination cycle for thermal electron transfer and
a optical charge transfer (Figure 1-19), the relative free energy of activation for
\ electron transfer can be exprsssed as follows:
This equation, a generalized free energy relationship for electron transfer
/i IFERET). has the advantage aleonsisting entirely of terms that can be evaluated
from experiment. Ths approach has been utiIized for a comparative study of the
inner sphere reactions of nitronium ions at an electrode and with aromatic
substrates in solution, providing insight into the activation process.lg
c D+ A- Is*
Figure 1-19 Overall thermochernical cycle that establishes a re energy relationship
for electron transfer.
1.2.6 Comparing Homogeneous and Heterogeneous
Electron Transfer Rates
The rates of heterogeneous and homogeneous reactions can be compared in the
context of transition state theory:
where Z is a preexponential factor that includes a preequilibrium term for
formation of the donor acceptor complex, and a frequency factor. For hetero-
geneous reactions Z,, is on the order of lo4-'cm/s, and for homogeneous
reactions Z,, is on the order of 10" M-l s-'.''
1.2.7 The Double Layer and Electrode Kinetics
In most electrochemical experiments, an inert salt is added (about 0.1-1 M) to
increase the solution conductivity and to minimize mass transport by migration.
The structure of the electrode-solution interface under such conditions has an
effect on the kinetics of electrode processes.
In general, an electrode has net charge that is related to its potential. Every
electrode material has a potential of zero charge (pzc): the potentiai at which the
net charge is zero. At potentials negative to the pzc, the electrode is negatively
charged, and at potentials positive to the pzc, the electrode has a net positive
charge.
Consider a negatively charged electrode in contact with an electrolyte
solution: positive ions will be attracted to the electrode and negative ions
repelled. Some ions may be immobilized at the surface. Themal motion is
balanoed by electrostatic forces so that there will be an excess of positive ions
near the electrode relative to the bulk solution (Figure 1-20, top). The details of
the structure will depend on solvent properties (dielectric constant) and
electrolyte charge and concentration. This is called the Gouy-Chapman-Stern
model for the double layer (charged electrode and charged solution) at the
electrode-solution interface. As a consequence of the structure of the double
layer, the potential changes decays in a gradual manner as distance from the
electrode (Figure 1-20, bottom). The electrical field (V/cm) can be very large
across the electrode-solution interface. The potential decay will be steeper as
the concentration of electrolyte is large and as the polarization is increased (the
deviation of the potential from the potential of zero charge).
The effect of the double layer on electrode kinetics is illustrated in Figure
1-21. A charged particle approaching the electrode requires work to move
through the potential drop to reach a point near enough to the electrode to
transfer an electron. This work term either increases or decreases the activation
energy compared to the ideal case, where the potential drop is infinitely steep
and there is no work associated with movement of the charged particle. Values
of k, and a or 0 determined without taking into account double-layer effects are
termed "uncorrected values." The task of double-layer theory, insofar as
REDUCTION POTENTIAL AND ELECTRODE KINETICS
X
1-20 Sketch 01 the distribution of ions near a chargcd electrode (
layer) and the corresponding potcntial drop.
MmcefrPmelecMwke
-21 Origin of the double-layer correction. An ion must move across a
:electrode
potcn-
electrode kinetics are concerned, is to determine the value of the potential drop
from the OHP (closest approach) to the solution. The Butler-Volmer equation
taking this correction ( SE) into consideration is written:
For charged species, the concentration terms in the Butler-Volmer equation
must also be modified as follows:
The parameters necessary to make a correct model of the double layer are
often not easily obtained. However, the uncorrected values of electrode kinetic
parameters may retain significance under many circumstances. For instance, for
a series of compounds studied under similar caudition~ kO and a values can be
compared. Double-layer effects are also minimized by large electrolyte concen-
trations (0.1-5 M). The 6 E term is smallest near the potential af zero charge
(pzc), and largest at extreme potential values, far from the pzc of the electrodes.
A good overview of double-layer theory is given in Bard and Faulkner's text2'
and by Rieger."
References
I . Gurney, R. W. Ions in Solution. Dover: New York, 1962.
2. Pleskov, Y. V.. Gurrvich, Y . Y . Smicodtlctor Ph~toeIectrockmistry. Consultants Bureau: New
York, 1986.
3. Antropov, L. I. Tkerw~~ical Electrochemistry. Mir: Moscow, 1972.
4. Koryi ~ 3.: Dvorak, I. Principles oj Electrochemistry, 1st ed. John Wiiey & Sons: New York,
1987.
5. Goodisman, J . Eltctrochemistry: Themeticul FouPrdationq 1st ed John Wiley M Sons: New
York, 19B7.
6. Kebarle, P.; Chowdhury, 5. C k m. Rev. 1987, 87, 514.
7. Summerman, W.: Deffner, U. Tetrahedron 1975. 31. 593.
8. Bordwell, F. G.; Cheng, .I.-P.; Harrelson, J. A,, Jr. I . Am. Chkmm. Soc. 1988, 110, 1129.
9. Hupp, J. H.; Weaver, M. J. I AOT~ CJz~am.1984, 23, 3639.
10. Harris, D. Quantitative C h i c 0 1 Anl~igsis. 2nd ed. W. H. Fmman: New York, 1987.
11. Lemer, J. E.; Grunwalk, E. Rates mi Equilihrio ojOrgotur Rcuctic~ns. Dover: New York, 1963.
12. Kojima, H.; Bard, A. J. J , Am. C h t . Soc. 1975, 97,6317.
25
13. Kochi, J. K. Angew. Chem., 1.1. Ed. Engl. Im, 27, 1227.
13a. Marcus, Rudoiph A. An~ewandte Chemie International Edition in English 1993, 32 1 1 11.
14. Saveant, J. hn. Single E/t~rrrun Trumfer a d Nut-ieophilic Subsrirwion. Advanoes in Organic
Chemistry, Vol. 26. Academ~c Press: London, 1%.
15. Allendorfer, R. D.; Rieger. P H. J. .4m. C b n SDC. 1965.87,2336.
16. Fry, A. J.; Britfon, W. E, EdF. Top~rs In Orgnrriz El e c t r ~~b s mi s f r ~, 1st ed.. Plenum Eess: New
York, 1986.
17. Lee, K. Y.; Kuchynka, D. J. ; Krxlhi, J. K. Inorg. Chem. 1990,29,4196.
18. Chem Rev. 1992, 92 (3).
19. Kochi, J. K. Acc. Chem. RPS 1992, 25, 39.
20. Brunschwig, B. S.; Logan, J.; Newton, M. D.; Sutin, N. J . Am. Ch~m SVC, 1980,102, 5798
21. Bard, A. J., Faulkuer. L. R. Electmrkmical Methods. John Wiley & Sons: New York, 1980
22 Rieger, P. H- EIc~trochemislry. Rentice-Hall: Englewood Cliffs, NJ, 1987.
CHAPTER
The Cyclic
mmetric Exp eriment
In Chapter I we explored the fundamental relationship between the electrode
;potential and a redor couple in solution. It was also pointed out that if the
,( potential of an electrode is controlled externally, the solution can be made to
; "adjust" by electron transfer to approhch equilibrium with the electrode
;'potential. In many electrochemical experiments, the solution initially has only
$:one form of a redox couple present, and the electrode is initially set at a potential
?:
.:such that this form does not undergo electron transfer. This ensures that the
jpperiment begins at zero farddaic current. The electrode potential is then
<changed to a position that favors electron transfer. The manner in which the
[&tential is changed g i v e rise to a profusion of electrochemical 4'conbolled
,potentialv techniques.
Cyclic voltammetry (CV) is a potential-controlled "reversal" electrochemical
'experiment. A cyclic potential sweep i s in~posed on an electrode and the current
response is observed. Analysis of the current response call give information
about the thermodynamics and kinetics of electron transfer at the electrode-
Solution interface, as well as the kinetics and mechanisms of solution chemical
actions initiated by the heteropneous elec~ron transfer. This chapter examines
hdarnental experimental and theoretical aspects of the CV experiment (Figure
CYCLIC VOLTAMMETRY THE CYCLIC VOLTAMMETRIC EXPERIMENT
a.
Time
b.
W
C.
Time
d.
Figure 2-2 CV waveforms,
,
Inexpensive analog instruments as well as microprocessor-controlled units
are commercially available. The equipment can include useful features such as
' IR compensation, data smoothing, background subtraction, and automated
display capabilities. Commercial instruments offer scan rates of up to several
hundred volts per second. However, units that have very high scan rate
2.1 An Overview
capability (to 106V/s) can be constructed at relatively low cost.
The clectrochemical reaction of interest takes place at the working electrode
(WE). Electrical current at the WE due to electron transfer is termed faraduic.
A potentiostat system sets the control parameters of the experiment. Its purpose
current. An auxiliary, or "counter" electrode (AE) is driven by the potentiostntic
is to jmposs on an electrode (the working electrode) a cyclic linear potentid
circuit to balance the faradaic process at the WE with an electron t r ~nuf er of
rwerp and to output the raulting mrrent-potential curve. Tbs sweep is
opposite direction (e.g if reduction takes place at the WE, oxidation takes plam
described in general by its initial (Ei), switching (E, ), final (Ed potentials,
'at the AE). The process at the AE is typically not of interest, and in most
sweep (or wan) rate (r, in V/s). The potential as a function of time is:
-experiments the small currents observed mean that the electrolytic products at
E = E~ + vt (forward sweep)
the AE have no influence on the processes at the WE.
The faradaic current at the WE is transduced to a potential output at a
E = Es - vt (reverse sweep)
selected sensitivity, expressed in amperes per volt, and recorded in a digital or
More
sweeps are possible, such as the option of a second alog form. The CV response is plotted as current versus potential. Figure 2-3a
pontential. ~ ~ l t i ~ l c cycles are sometimes used, but in many instances these ows the shape of a CV current response for a typical reduction process.
not be more idormative than a single cycle. The
linear sweep voitammetry uring the forward sweep the-oxidized form is r e du~d, while on the reverse
( L S ~ ) is ulcd for a h d f ~ d e CV. Figure 2-2 illustrates various possible weep the reduced form near the electrode is reoxidized. Chemical reaction
. . . .- I n - . .A,.-. _.d_A...
-2 . . ., . . --,.l. .. " - . . Y-YY
. . .. . .
, .
CYCLIC VOLTAMMETRY
- 1
-1.3 - 1. 4 -1.5 -1.8
PotentinI/V
Figure 2-3 CVs for (a) ferricyanide reduction and (b) methylcobalamin reduction.
coupled to the electrode reaction can drastically affect the shape of the CV
response. Compare the current response just described with that of the
reduction of methylcobalamin (Figure 2-3b}, where no reverse peak is observed.
The absence of the reverse peak indicates that a following chemical reaction has
removed the reduced species.
2.2 The Electrochemical Cell
2.2.1 Cell Design
A typical cell design for a cyclic voltammetric experiment is shown in Figure 2-
4a. The simplest approach is merely to have the three electrodes immersed in the
solution in close proximity. A Luggin capillary (Figure 2-4b) further isolates the
reference solution from the cell solution. At the outset of the experiment the d l
TIIE CYCLIC VOLTAMMETRIC EXPERIMENT
Audllary Elccbodc
worhg El mmde.
RHRmce Elmuode
Figure 24 (a) Typical electrochemical cell. (b) Lugin capillary reference.
contains solvent. electrolyte, one or more principal elcctroactive species, and
possibly added reagents that will undergo reactions with the electrolytic
.products. Before the experiment, it is necessary to remove dissolved oxygen,
which has a cathohc sip~ial tllat can interfere with observed current response,
!This is normally done by purging the solution with an inert gas such as N, or Ar.
>Removal of dssolved oxygen CWI also be effected with freeze-pump-thaw
acuum line. Electrochemical experiments cat1 be performed in glove
oxes, or in vacuum for electroactive species, that are sensitive to air
, 2.2.2 Solvents
The choice of solvent is determined by several factors, including conductance,
.,solubility of electrolyte and eleclroactive substance, and reactivity with electro-
lytic products. The solvent can also have important properties such as
decreasing usually unwanted effects (e.g., adsorption of the electroactive species
ode). Because of the importance of the solvent in electrochemicd
is sometimes desirabIe to consider the physical and chemical
e solvent in some detail. Solvent properties relevant to electro-
riments are listed in Table 2-1. The melting and boiling points
1 temperature range for most solvents (with some variation due
P
Table 2-1 Properties at Common Electrochemical Solvents
Solvent Dielmtric E: Donor Acceptor
( m ~ , bp, "c) conslant (Solvatochromatic) number number
pp --
---
H, 0 ( 0 7 1 w 78.3 1 .O
54.8
Propylene 64.96 0.491
carbonate
(- 54.5,24 1.7)
Dimethyl 46.95 0.444 0.77 f 9.3
sulfoxide
(18.5,189)
Dimethyl-
lormamide
( - 60.4,153)
Acetonitrile 35.94 0.460 0.36 18.9
(-43.8,81)
Nitrobenzene 34.78 0.3?4 0.21 14.8
(5.8,210)
Methanol 32.66 0.790
(-97.7,64.5)
Ethanol 24.55 0.654 i 37.9
( - 114.5,78.3)
Acetone 20.56 0.355 0.44 12.5
( - 94.7-56.1)
-
Swrrrc: Reference 1.
to colligative effects). The dielectric constant is primarily an indicator of solvent
polarity and solubilizing power. Other solvent properties, such as acceptor and
donor numbers, indicate the ability of the solvent to participate in electron-pair
donor-acceptor interactions. The spectral charge transfer energy (solvochroma-
tic shift) of pyridinium-N-phenoxide betaine ,dye has also been used to
characterize solvent^.^ Solvent mixtures sometimes are used to average pro-
perties. An example is the nonaqueous electrochemistry of rnethylcobalamin
where mixtures of methanol and DMF achieve a balance ketwsen solubility and
conductivity.
Low temperature studies can be very useful in electrochemical investigations.
Reactive species can be stabilized and reversible electrochemistry obtained.
Solvent properties can change drastjcally with temperature. For example, DMF
dimerizes at below -40C and has a large potential window as well as a lower
dielectric constant.
In Fry and Britton's handy review of solvenrs and electrolytes? acetonitrile,
ethanol, methanol, and methylene chloride are recommended as good oxidative
(anodic) electrochemical solvents, while acetonitrile, DMF, and dimethyl sul-
foxide (DMSO) are suggested for reductive (cathodic) electrochemistry.
Acetonitrile is suggested as the best overall nonaqueous solvent on the basis of
its electrochemical properties and its relative nontoxicity. The review of Fry and
Bntton also is a good place to start when looking for purification methods.
THE CYCLIC VOLTAMMETRIC EXPERIMENT 33
Often, to minimize evaporation of the cell solvent (and consequent changes in
concentrations), the purge gas (N,,, Ar) i s passed through the same solvent used
in the electrochemical cell. This step is particularly necessaxy for solvents with
low vapor pressures.
Mention should also be made of the increasing use of unconventional media
electrochemical experiments. Experiments in nlicellar solutions and micro-
emulsions, for instance, can solubilize or concentrate reactants in rni~elles.~
Cyclic voItammetric results have been obtained below the freezing point of
the solvent: for instance, in frozen DMSO4hS and in perchloric
2.2.3 Electrolytes
The electrolyte, added to enhance conductivity and ti-] minimize double-layer
and migration current effects, is chosen on the basis of solubility in a gven
, solvent as well as inertness toward the eIectroactive substance and its electroly-
products. There are of course many choices of electrolyte for use in aqueous
: solution. The tetraalkylammonium salts are the most commonly used non-
eous electrolytes. TetrabutyIammonium tetrafluoroborate (T3ATFB) and
tetrabutyiammoninm hexafluorophosphate (TBAHFP) are recommended by
' Fry and Britton, who note that TBAHFPin acetonitrile has a particularly large
' . useful potential hnge of + 3.4 to - 2 9 V (vs. SCE).
.2.4 Electrodes
Working Electrode [WE)
disk electrodes are most commonly employed in CV experiments (Figure
2-5). Platinum, glassy carbon, gold, silver, or amalgams* are often used. The use
:of carbon electrodes of various types has been reviewed.? The mercury drop
electrode is useful for electrochemistry in aqueous solution at large negative
Figure 2-5 Disk working zlectrode.
Recip lor s silver amalgam electrode: polish the Ag wire electrode (ca. 1 mm diameter) with
h e alumonurn oxide powder. Reduce at - I.OV(vs. SCE) for 3 minutes ih s el1containing nitric
acid (pH 1.5) and a drop of mercury. While still holding the potential, touch the eledrode surfaw lo
!he Hg drop. Rime xveral times with dei oni d water; immerse in deionized water for 50 miuutes.
Polish with aluminum oxide pwder and rinse again. The electrode can be used br months. like an?.
r Y 1 Y . U " . .^., ,:.., . . . . . . .--
potentials because of the sluggishness of the hydrogen reduction compared to
other eIectrodes. However, for nonaqueous work and for electrochemistry at
positive potentials, the solid electrodes are often preferred. The WE should also
have a facile electron transfer with the electroactjve species. The factors that
facilitate heterogeneous transfer are not always well understood, and careful
pretreatment by polishing sonicating. or holding or cycling of the WE potential
of electrodes can markedly improve performance. Electrode fouling occurs quite
easily, and frequent polishing is sometimes necessary. Deleterious effects such as
I R drop and capacitive charging time are greatly reduced as the electrode radius
is made smaller. For cyclic voltammetry, the result is that much higher sweep
rates can be achieved with ultramicroelectrodes (radius < 100pm). Most pre-
liminary studies at moderate scan rates utilize electrodes having a radius of
approximately 0.2 crn.
Reference Electrode IRE)
The most common reference elwtrode systems used in aqueous solutions are
Ag/AgCl and the calomel electrode. If aqueous-based references are used in
nonaqueous solution, however, large liquid junction is produced; and often
more serious, aqueous contamination of the nonaqueous cell occurs. Thus this
combination is not recommended. The use of an AgJAg' non-aqueous-based
reference is suggested for nonaqueous electrochemistry. To avoid large junction
potentials the RE solvent should be as close in nature as possible to the cell
solvent system. Often potentials are calibrated with a standard, such as
ierracene or cobaltocene. Suggested standards are listed in Table 2-2, along with
reduction potentials and other properties. Construction of an Ag/Agf reference
for nonaqueous use is shown in Figure 2-6. Reference electrodes can drift with
time and must be carefully maintained.
Table 2-2 Reference Conlpounds for Cyclic Voltammetry
-- ---
--
Substan& E"'(YI
D x 10'(cm2/s) Conditionsb
-- - - _ ------ ---
FdCNjG - "- 0.253 vs. AgJAgCI, D,, = 0.76 pH 3.0
1 M KC1 D,, = 0.63 0.1 M KCI
RwH, ) f +f2 +' - 0.17 vs. SCE a,, = 0.55 pH 7.0
Phosvhate buffer
Ferroaene 0.37 vs. SCE D,,, = 2.0
0.6 M TEAP in
F~(CP),/F~(CP); *
Ternpo,Tempo' ** 0.27 1 vs. Ado. 1 M
D,,, = 0.77
AeNO,/acetonitrile
acetonltrile
cl l MTBAP in
acetoni[nle
A Cp, cyclopentadienyl.
TEAP, tetraethylammonium perchlorate: TBAP, telrahulylarnmonrum perchloralc.
Swrce:
* Baur. J. E. and Wightman. R. M., J . ElectroaneL Chem.. 1991- 3W. 75-
** Summerman, W. and Mner. U., T&rah~drofl. 1975, J I . 593
THE CYCLIC VOLTAIv'IMETRIC EXPERIMENT
- Glass frlt or vycor plug
Figure 26 Nonaqueous reference electrode.
2.2.5 Potential Window and Background Subtraction
f a solvent-electrolyte-WE system have a
n can be collect& the
region, solvent or electrolyte electrolysis
reaches a level that obscures the signal. The potential window is greatly affected
lyres. Distillatiotl aid drying can extend the
it is wise to collect "background" spectra-
lvent and electrofyte present. The potential
window of the solvent -electroly te system can be established, and any obvious
impurities can be identified before they cause havoc in the interpretation of
results with the electroactjve species present. l o quantitative studies, the
background can be subtracted from equivalent experiments with the electroact-
ive substanor present. A particularly effective met hod proposed by Wightman
and Wipf utilizes a flow injection cell to obtain background and experimental
ance in the 0.5-1DmM
mprove detection limits
ignal averaging.' Such
ts dramatically, down to the nanomoiar
.3 Electrochemical Mechanisms: E & C Notation
this section we examine the CV response for the simplest electrochemical
r i kd by the E&C notation: E represents
, while C refers to a solution chemical
reaction that is coupled to an electrode reaction. Fur instance, the EC
mechanism refers to an electrode reaction followed by a chemical reaction.
Ox + e- s Red
ED', kO, rw
Red -r Products kchem
Subscripts are used to provide additional information. The subscript "T stands
for reversible (meaning that both forward aud reverse processes are fast enough
to maintain equilibrium or "Nernstian" conditions a t the surface), and "i"
represents irreversible (only the forward reaction is significantk "iw and "r" are
limiting cases of "q," or quasi-reversible (meaning that both the forward and
reverse processes take place hut are not fast enough to be considered at
equilibrium). Thus, in an E,Ci mechanism the electrode reaction is fast and
reversible and the chemical reaction is irreversible.
After "ECE" the E&C nomenclature breaks down: ECE can mean several
different things (and one cannot be sure what an "ECECCE" mechanism reiers
to !). At this point the mechanism needs to be further defined- for instance, by a
reaction sequence or schematic drawing that indicates all possible chemical and
electrochemical events considered.
We note that every reductive mechanism has an oxidative analogue. For
instance, the oxidative EC is:
Thus, all the theoretical results quoted for a reductive mechanism can be
immediately applied to the analogous oxidative process. The only dlaerence is in
the sign of the current and the direction of the potential sweep.
2.3.1 The "E," Mechanism
The simplest possible mechanism is the one-electron oxidation or reduction of a
solution chemical species at the WE. Consider a typical experiment in which
1 mM of an electroactive species in an electrolyte solution undergoes a facile,
reversible one-electron reduction with the4following parameters:
1 Experhenfa1 Settings
I
I
E, = 0.0, E, = -0.5, E, = 0.0, V = ~ V / S
Area of electrode A = 0.01 cm2 Cell temperature T = 298 K
1 Ox + e- = Red, Eo' = -0.25 V (i.e.. vs. a reference)
I
1 C,, = 1.00mM, Cred = 0.0111M 1
i
THE CYCLIC VOLTAMMETRIC EXPERWENT 37
Figure 2-7. The
. - . -
f i e voltage sweep and current response for this experiment a n shown in
- - --
: data can be represented as a current-time curve, or, since the
potentld is linearly related to time for each half-cycle, as a current-potential
curve (the usual representation). Note that reduction current is laken as positive.
1 . - .. .-
eep goes from left to right. For any CV, the direction of the initial
ep snould be indicated or at least apparent (the initial sweep potential is
always set, if possible, at a potential where zero faradaic current *rllrch
I I
4
0 ! s.!c
Time
t
Potentl a1 (\I)
Figure 2 7 .. (a) Potential waveform. (b) Current-time and icl rnlrr~nt-nn*--*:-l
Consider what happens near the working electrode in the foregoing example
(refer to Figure 2-8, which shows selected points along the CV with the
corresponding concentration profiles of Ox and Red). As the potential is swept
past the reduction potential, the oxidized form is converted to the reduced form
in proportions consistent with the Nernst equation. Because the potential sweep
is fast (relative to the rate of diffusion of material to the electrode), the oxidized
species is depleted near the electrode. As a consequence of this depletion, cyclic
voltammograms have a peak shape, in contrast to the familiar polarographic
sigmoidal wave. Sigmoidal CVs can be indicative of a catalytic regeneration of
reactant near the electrode. The peak resulting from the reduction process is
called the cathodic peak current; by convention, it is positive, and it occurs
28.5 mV negative to the EO (at 25OC). At the switching potential, the direction of
the potential sweep is reversed. A negative anodic peak current is observed as
the potential is swept past the Eo (the electron transfer is in the opposite
direction). The anodic peak occurs about 28.5 mV positive of the Eo (the exact
value depends very slightly on the switching potential). Note that the major
perturbation on the initial concentrations of Ox and Red lies within the mean
square diffusion length X, = (2Q x time)''', which is about 4Spm for this
experiment-large with respect to the double-layer thickness.
Figure 2-8 The current response and corresponding concentration profiles (A-F) for
a reversible CV. Concentrations of the oxidized (solid circles) and reduced form (open
circles) are shown as a function of distance from the electrode.
THE CYCLIC VOLTAMMETRIC EXPERIMENT
Distance/pm
Figure 28 (Contimud)
Figure 2-9 Three half-cycles. Note the slight diminution in the second cathodic p a k
current.
The initial sweep peak current for a reversible electron transfer is:
At 25C this is:
5 3 / 2 ~ ~ ~ ~ 1 / 2 ~ " 2 A
i, = 2.686 x 10 n
Y
The reverse peak current is a function of switching potential A reversible CV
is a diffusion-controlled process; that is, the rate of electron transfer is controlled
by the rate of supply of material to the electrode by di8usion.
Multiple sweeps give similar results (Figure 2-9 shows a CV with three half-
cycles), with slightly smaller currents (as the initial condition of [Ox] and [Red]
near the electrode is nearly but not quite the same for each successive cycle)
While for simple one-electron transfer no information is to be gained by
scanning more than a single cyde, if chemical reactions are coupled to the
electron transfer, more than a complete cycle may . .
be informative.
The peak potential (for the forward seeep) is*:
-
-
* Assuming that the difhsion macients of the oxidized d reduced
specks are 8qual.
- . ' . . ' a1 dausion d & t s give the exact result.
.+
-- ,.--.,-- ,, . &
43
Criterion for the E, Mechum'sm
Several criteria can be util~zed to confirm a single, reversible, electron transfer.
1. The difference in cathodic [E,,3 and anodic {E,,,) peak potentials is around
57-60mV (depending on the switching potential):
AE, = absLE,, - E,,,] w 58mV
In actual experiments the expected 58mV is rarely observed because of
small, distortions due to solution resistance effects and electronic or math-
ematical "smoothing" of data. The result i s that AE, is often 60-70mV for
reversible electron transfer.
For reversible multielectron transfer, the peak separation is 60/ n&1~.
2. The hfference between the initial sweep peak and half-peak potentialsbf the
forward sweep is 56 mV/n.
\ >. .
3. The shifted ratio of the cathodic to anodic currents is unity: i , , / i : +, = 1. In
the "shifted ratio," the anodic peak current is measured from a baseline that is
moved to a value that can be predicted from the decaying portion of the
cathodic peak. In this part of the cyclic voltammogram the current can be
predicted by assuming an inverse square root dependence of the current of
the time. The baseline is assumed to be the current that would be obtained if
the forward sweep were continued for the same amount of time that it takes
to reach the reverse peak. This procedure is illustrated in Figure 2-10. The
absolute ratio (with zero current as a baseline) depends on switching
potential and can be simulated (see Chapter 5).
4 . The forward scan peak current should be proportional to the square root of
the scan rate. This criterion is used to distinguish "diffusion-controlled"
processes from processes featuring the adsorption of the dectroactive s pi e s
onto the electrode (in which case a he a r current-scan rate relationship is
observed). A plot of the Iog i, versus log v is linear, with a slope of 0.5 for a
diffusion peak and a slope of 1 f o ~ an adsorption peak. Intermediate values of
the slope are sometimes observed, suggesting a "mixed" diffusion-adsorption
, peak. Adsorption mechanisms are discussed in more detail in Chapter 3.
The Reduction Potential and Number of EIeckons
,I. The reduction potential is given by:
~ 0 ' = ED., + %,a
2 (4)
2 If up has been determined to be 60 mV, and the reduction has been shown to
be diffusion controlled, then the number of electrons n = 1, and the diffusion
coefficient can be calculated from Equation (1). The geometric electrode area
can be found from Equation (I), or the effective area can be calibrated with a
standard with known D and n (e.g, ferrocene). Even if the diffusion coefficient
can be only roughly estimated, a reliable value of n can be found. This i s
.
" .. .L. ...-LA
, .,
CYCLIC VOLTAMMETRY
12, I I TT
i
-8L-l
P .a
I 1
-10
-0.1 -0.Z -0.3
-0.4 -0.5
0.0
, i
Potential (V)
-80
0 2 0.0 -0.2 -04 -0.6 -0.R
Potential/v
Figure 2-10 Characteristics of the Er mechanism: (a) peak potentials and currents and
(b) measurement of the shifted peak current ratio.
because the current has a square root dependence on D but is proportional to
n3I2. Conversely, if n is known, the Do, can be determined.
The determination of the number of electrons involved in an elect roc he mica^
mechanism is crucial but not always as straightforward as the discussion above
might suggest. This is because the electron transfer is not reversible. The
number of electrons can be determined utilizing potential step experiments (see
Section 2.8). Bulk electrolysis (exhaustive electrolysis of all the electroactive
species present) is sometimes helpful, but here we must be careful in i nt er p~-
tation because time scaies differ widely Thin-layer bulk electrolysis brio@ the
, , -1ysis A
more in line with the CV time scale.''
, --- -
-
THE CYCLIC VOLTAMMETRIC EXPERZMENT
45
2.3.2 Electrochemical Reversibility
Let us consider the electrochemical rate equation and its limiting case of very
fast rates, the Nernst equation:
I
nFA
- = k, C, - krC,,,
kf
- = g = erp [ g ( E - P~)]
kr
If the rate of electron transfer is slow with respect to the time scale of the
experiment, then non-Nernstian concentrations will exist at the electrode
. surface. The qualitative effect is to shift the peak wave to more negative
potentials in the case of reduction and to more positive potentials in the case of
an oxidation. The proximity to equilibrium is termed "reversibility."
Increasing the scan rate is equivalent to increasing the rate of Musion of Red
ay from the electrode (for a reductive, Ox + e- = Red, process). At faster
scan rates, steeper concentration gradients are produoed, increasing the rate of
diffusion. Red will diffuse away from the electrode faster as the scan rate is
increased. The hffusion of Red away from the electrode is a process that
, competes with the oxidation of Red. Thus for the E mechanism, the greatest
sibility is observed at slow scan rates. In this case reduction potentials are
most accurately measured at slower scan rates, where reversibility is greatest
(and distortions least). Three cyclic voltammograms with various degrees of
. reversibility are shown in Figure 2-1 1. In the reversible region the CV response
I -
---
0.0 -0.2 -0.4 -0.8 -0.0
Potential ( V)
ure 2-11 Effect of the heterogeneous rate constants, with the transfer coefficients set
0.5: circles (reversible), dashed lines (P= 0.01cm/s), squares (kO = 0.001 cm/s), and
ne (kO - 0.0001 cws).
-- . .
L - . . ,-, -.. , -., . .,-
is called Nernstian, because the forward and reverse electron transfers are fast
and occur simultaneously. In the irreversible region, the ca~hodic wave and
anodic peaks are well separated, and in each case electron transfer occurs in one
direction. The intermediate region is "quasi-reversible." Qualitatively, the
demarcation point separating quasi-reversible from irreversible has been
reached when there is no (potential) overlap between the cathodic and anodic
peak shapes.
The following criteria have been suggested for evaluation of reversibility, with
D = cm2/s and T = 298 K":
Reversible: k0 > 0.3 v l J 2 cm/s
Quasi-reversible: kO > 2 x 10- v l i 2 cmjs
Totally irreversible: k0 < 2 x v'I2cm/s
The experimentalist's attitude toward reversibility or lack of it is shaped by
his or her goals. When one desires to obtain information about either reduction
potentials or the rates and mechanisms of following chemical reactions, a
greater degree of reversibility of electron transfer allows for the use of a wide
range of scan rates, and interpretations are simpler. However, studies of the
fundamental act of electron transfer are often accomplished with totally
irreversible systems. In these cases, the transfer coefficient a and the forward rate
of electron transfer are easily measured. The transfer coefficient, being in the
exponent of the Butler-Volmer equatiotl, and reflecting the symmetry of the
barrier to electron transfer, is simply given by:
where E,,, = is the half-peak potential, and n, is the number of electrons in the
rate-determining step. In most circumstances n, = 1. Note that the symmetry of
the barrier is reflected in the "steepness" of the cathodic wave (Figure 2-L1). The
anodic transfer coefficient f i is determined by the same equation applied to an
irreversible anodic wave.
For quasi-reversible systems, the reduction potential can be obtained by
curve-fitting methods." If the peaks are symmetrically shaped, then n = 0.5,
and EO * ( E, . , - E, , J/ 2.
2.3.3 The EC Mechanism
Upon oxidation or reduction, an electroactive species may be activated toward
bond cleavage, as in the case of rnethykobalamin reduction (Figure 2-13). The
addition of an electron activates the molecule toward dissociation of a methyl
radical. The rate constant of the following reaction is 600s-' at -30C in a
DMF/propanoI solvent n-lix~ure. The cathodic transfer coefficient a for methyl-
cobalamin reduction is 0.78. At even lower temperatures, the anodic peak grows
in as a result of the lowering of the dissociatiot~ rate.
Generally speaking, the EC mechanism is recogmized by a diminished reverse
THE CYCI C VOLTMMETIUC EXPERIMENT
lor--
1
Potential (Y)
Figure 2-1 2 Effec~ of transfer coefficients for a heterogeneous rate constant k0 =O.OM1
wilh n scan rate of 1V/s.
(a) Methylcobalamin. fi) Mechanism of methylcobalamin
olution.
+
reduc
I
L ,,,-.. , A , , A , .
.. . , . .
,. . . ..... -. I...,.. .,. . .... I-.&1 ' .
peak or the lack of one. Both the chemical and electrode reactions may have
different degrees of reversibility, which affect the waveshape in characteristic
ways. However, at the outset, we will consider the case of a reversible electron
transfer followed by an irreversible chemical reaction. In this (limiting) case, the
CV peak potential will lx detennined by the E0 of the electroactive species and
the rate of the following chemical reaction. Consider the case of a reductive EC
mechanism. Let us keep the parameters that describe the experimental con-
ditions and properties of the electroactive s p 5 e s the same as in the "E"
example, adding only a following chemical reaction.
Experimental Settings
E, = 0.0, E, = -0.5,E, = 0.0 v = 1 V/S
Area of electrode A = 0.01 cm2
Cell temperature T = 298 K
Electroactiue Species Parameters
Ox + e - = Red, EO' = -0.25 V
Red =. Products k,,,,
Cox = 1.00rnM. C,,, = O.UmM
Diffiisional coefficients D,, = Dred = I x lo-' cm2/s
The following chemical reaction removes the reduced form Cronl solution as i t
is produced near the electrode. The effect is to shiR the peak to more positive
values* and to increase the peak current slightly (Figure 2- 14). Thew effects can
be understood qualitatively o n the basis of the Nernst equation (renloving Red
makes the reaction more favorable and increases the net rate of reduction).
Increasing the scan rate has the effect of making the CV more "chemically
reversible,'' until, at high scan rates, the chemical reaction is "frozen" on the time
scale of the experiment and the CV is completely reversible. The main effects of
the E,C, mechanism on the CV waveshape are summarized next.
Chmcteristics of ErCi Mechanism
1. The ratio of cathodic to anodic peak current is a function of chemical rate
constant and scan rate. The cyclic voliarnmogram can be analyzed to give
an estimate of the chcrnical rate constant.
Al %>me poinl, however, the ele~lrode reaction will be pushd Into the "'<ndcrgonic" region,
and the electron t ransf ~ can no longer be considered reversible. Also, at potentiiils negalive to E*,
the backward electron transfer ctnnk small. For a more general treaimmt of the EC mechanism, see
Chapter 6.
THE CYCLIC VOLTAMMETRIC EXFERMENT
Figure 2-14 CVs for E,Ci mechanism lor a series of increasing solution chemical rate
constants a t constant scan rate. The same effect would be observed with a constant
chemical rate constant and decreasing scan rate.
2. The peak potential of the forward scin (when k,,,RT/nFv > 4) is given by:
Several methods have been utilized to determine the rate of the following
chemical reaction from a series of CVs at different scan rates. The simplest
involves a comparison of i , , and i:,,. The cathodic peak current is measured
from the zero current baseline, while the anodic current baseline is established
by the current at whch the potential is switched. The experimental peak current
ratios can then be compared to a previously calculated theoretical "working"
curve to find the rate constant (for a first-order or pseudo-first-order reaction.'
Parker has emphasized the use of working curves based on derivative cyclic
voltammetry, which dscriminates to some d e g r ~ against capacitive back-
ground current.14
Our preference in analyzing the EC mechanism is a simulation-based rnetllod
in which the following chemical rate constant is determined by double potential
step chronoamperometry. Subsequently, CV simulation analysis can be utilized
to determine EO and a and k0 for the quasi-reversible case.
Generally, we are not fortunate enough to be presented with the E,C, limiting
case. A simplified two-hmensional "zone" diagram illustrates the situation
(Figure 2-15). AIong one dimension are changes in the heterogeneous rate
constant, and along the other dimension are changes in the homogeneous rate
constant. Cyclic voltammograms for several limiting cases are shown.
1. Irreversible. The electrode kinetics are slow and the chemical kinetics me
slow-the CV is irreversible. T!ae forward peak shifts - 59mV per tenfold
change in scan rate.
CYCLIC VOLTAMMETRY I
g
Homogeneous Rate
c:,.., 7-IC 7nnp diaorfim for he EC mechanism. Typical shapes of vollamm~grams I
r l g u l ~ r - x d YY..~ UIUP. ---. -- - --- - - --- - -
- -
are given for limiting cases.
2. Reuersible. The electrode kinetics are fast and the chemical kinetics are slow.
The peak potential is not a function of scan rate, and the CC appears as m the
E, mechanism.
3. The electrode kinetics are fast and the chemical hnetics are fast. The peak
potential shifts -30mV per tenfold change in scan rate.
4. Irreversible. The electrode kinetics are slow and the chemical kinetics are fast.
A more detailed analysis can locate intermediate regions. Reversibility ih the
zone diagram has an inverse square root dependence on scan rate in the
I
"heterogeneous" axis and an inverse scan rate dependence in the "homog-
eneous" axis. The former case obtains because increasing the scan rate is
equivalent to increasing the rate of diffusion, while in the latter case increasing
the scan rate gives less time for the chemical reaction to occur. Thus, all else
being equal, one can move around in the zone diagram by changing the scan
rate.
Klinger and Koclu have introduced a quantitative measure of reversibility in
electrochemistry as the deviation of the surface concentrations from the values
i
that would exist under Nernstian conditions.15 Reversibility thus defined is a
function of position along the cyclic voltammogram (i-e., potential). This is
11
because the heterogeneous rates are modulated several orders of magnitude
51
(through the Butler-Volmer equation) over the entire cyctic voItarnmogram. A
more detailed discussion of this is deferred until Chapter 6.
s:
!; 2.3.4 Scan Rate and the Role of Diffusion
E
We have seen that for the E, mechanism, the CV waveshape becomes more
irreversible with higher scan rates. This happens because increasing the scan rate
is equivalent to increasing the rate of diffusion of the reduced material from the
electrode. As a consequenq the diffusion process comwtes with the back
electron transfer. In fact we can write the E rnechnni ~m mnrp o-n*+nIlx~ 00
- - - - -. . . - "-.- I l . YI 1 6Vllrl(l,,J 'La
follows:
kr
OX,,, f e- = Red,,,
k,
Tlus is shown schematically in Figure 2-16. We have aIready examined in detail
the orign of the forward and reverse electron transfer rate constants. In this
scheme a diffusion rate constant k, is introduced. To understand the origin of
k,, we take a closer look at diffusion.
Cyclic voltammetric experiments are performed under conditions of so-called
semi-infinite linear diffusion. This means that the electrode dimensions are
larger than the thickness of the diffusion layer (Figure 2-1 7) and that there is a
1 bulk solution far enough from the electrode that the concentrations of all species
remain unchanged throughout the experiment. The symmetry of diffusion under
these conditions means that we need consider only diffusion perpendicular to
the electrode. No net diffusion takes place in the y or z directions, parallel to the
electrode surface.
Diffusion is described by Ficks' first law of diffusion (Equation 7), which
states that the number of particIes diffusing through a cross-sectional area per
Figure 2-16 Schematic of the EC mechanism.
CYCLIC VOLTAMMETRY
THE CYCLIC VOLTAMMETRIC EXPERIMENT 53
v5'
Figure 2-17 Representations of (a) linear and (b) spherical difftsion.
unit time (the flux, 3) is proportional to the concentration difference across the
selected area. The
constant, which describes the inherent
mobility of the particles. i s called the dltfusion coeficient (D) and is expressed in
square centimeters per second.
Taking the derivative of J with respect to distance indicates how the flux
changes with distance (the difference between particles coming in and going out)
and as a consequence describes the net accumulation of particles at a point
(Ficks' second law).
Fick's laws follow from the random nature of the motion of particles." For
linear diffusion, the net displacement of particles by diffusion has a square root
* See Bard and Faulknw (EIc.ctrockmica1 Methods) or Rieger (Ehcfrochemistry) For a more
detailed look at diffusion. Rereren~es 11 and 18. respzctivdy.
dependence on time and on the di5usion coefficient. The average net displace-
ment of a particle by diffusion can be shown to be:
Equativn ( 8) can be used to estimate the diffusion layer thickness i n a CV
experirnenf.
Let us now return to the original observation of this section. namely that
diffusion rate is related to scan rate and competes with the reverse rate of
elwirun transfer.
The concentration grahents of the oxihzed species (at the cathodc peak) is
shown in Fi yre 2-18. The surface flux of both species is indicated, and by
conservation of material we have:
We can take the irreversible case to make an estimate of the diffusion rate
constant k:. Tile peak current is given by:
The terms multiplying C,, can be taken as the diffusion rate constant, which
has the same units as the heterogeneous rate constant kO(a = 0.5 and T = 25C).
For D = l O- kd/ s , we can estimate limiting cases of rcversibility, as when
one rate constant is two orders of magnitude larger than the other. In this way
we arrive at the 'quasi-reversible" region ranging from 0.5 vl t 2 (the reversible
1.2 '" t
/ Gradient = +
Figure 2-18 Concenlrarion gradient near the electrode. The tangent at a point
determines the direction and rate or diffusion.
case) to 5 x l oL5 vl/' (the irreversjble case), in good agreement with the regions
suggested earlier.
2.3.5 Competition between Heterogenous
and Homogenous Reactions
It is also useful to be able to compare heterogeneous nnd hamogeneous rate
constants. Irreversibility in the electrode reactjon can be induced by the
following chemical reaction by removing the reduced species at a rate faster than
the reverse electron transfer. The heterogeneous rate constant can be converted
to an equivalent homogeneous rate constant by introducing a third dimension,
which converts the surface reaction rate [mol cmP2 s-') to a volume reaction
(mol L- l s- I). A reasonable choice is the diffusion layer thickness at one second
(the time unit of the rate constant), shown in Figun 2-19. Thus, the eflective
volume for the surface reaction is 1 cm x 1 cm x (2D x 1 s) ' J2 crn. The heterog-
eneous rate can be converted to an equivalent homogeneous rate by multiplyin_e
by ( 20) - ' I 2. A factor of 1OOO takes the result from cubic centimeters to liters.
We have, finally.
For D = 10-'cm3/s, kVbi = 2.2 x 105k,,,.
Homogenecrul; reactions must be rathcc fast to compete with heterogeneous
reactions. Even though cyclic voltammograms may appear to be irreversible (no
reverse peak is apparent) the competition be~ween heterogeneous and homog-
eneous processes makes itself apparent in more subtle ways (see Chapter 6).
Figure t 1 9
Volume of a heterogeneous reaction.
-.. .
THE CYCLIC: VOLTAMMETRIC EXPElUMENT
55
The three components of an electrochemical mechanism (disregarding
adsorption) arc electrode reaction, diffusion, and chemical reaction. Thcse rates
of these processes can k compared in a semiquantitative manner.
As a consequence of the effect of scan rate on the CV result Tor both
homogeneous and heterogeneous processes, theoretical presentations often
employ dmensionless clusters. For instanm, for the E, mechanism, the factor:
controls the result, and for the E,C, mechanism the coritrolling factor is:
kch, mRT
Fv
As the mechanisms become more complicated, the number of dimensionless
factors needed to characterize the CV response also increases. Whle this
approach is powerful in showing the combined effect of all parameters at once, it
can become extremely abstract.
2.3.6 Visualizing the Meaning of Reversibility with Cprof
I
The program Cprof (provided on the diskette) simulates and graphs the
G : concentration profiles near the electrode for a reductive EC mechanism.
:
Ox + e- = Red E*', k" (n = 0.5)
Red * Product k,,,,,
In this way it is possible to vi su~l i u the effect of heterogeneous rate constants
and rates of following chemical reactions on the concentrations of the oxidized
t
s pi e s , the r e d u d species, and the product of the following chemical reaction.
E Cprof is for illustrative purposes only and has not been optimized. The scan
1 rate should be set to at least 1 volt/sec, and the rate constant of the following
i chemical rertction can be practically set from 0 to 500s- '. It is sugsested that the
reader simulate a reversible CV using the follo\l.jng parameters:
Initial Potential = 0.0 V
1 Final Potential = - 0.3 v
I '
Scan rate = 1Vs - I
Following this, simulations can be performed varying the k0 (making it
smaller) and k,, (making it larger) to visualize the meaning of reversible, quasi-
reversible, and irreversible.
2.4 Distortions of the Faradaic Response
There are several experimental realities that tend to distort the observed CV
waveshape. Through a combination of experimental and theoretical methods it
is often possible to alleviate these problems to the extent that a reliable analysis
becomes possible.
An electrical circuit model for the electrochemical a l l illustrates the origin of
these problems (Figure 2-20). The electrode-solution interface is modeled as a
capacitor in series with a resistance. The formation of the double layer as
potential is changed gives rise to an analogue of an elechical capacitor. So far we
have considered in detail only the "ideal" or faradaic current due to electrode
processes. A complete model of the CV experiment must indude the current due
to capacitive charging as the potential changes. A resistan= element models the
resistance between the working electrode and the reference electrode. The
potentiostat is controlling and monitoring the potential of the working electrode
with respect to the reference electrode. To the extent that there is an IR drop
across the solution, the potential of the WE will be misrepresented by the
monitored potential.
2.4.1 TR Drop
Theoretical treatments of cyclic voltammetry usually assume a cyclic linear
potential sweep at the working electrode. However, the solution resistance
causes a potential drop to exist across the working electrode and the reference
electrode. Thus, the potential at the working electrode is really the applied
potential plus the solution IR drop:
EWE = E,,, + IR,,l
(This equation is sometimes written with R, to represent "uncompensated"
resistance, indicating the possibility of partla1 instmental compensation of the
solution resistance).
Consider the effect on a typical CV. For positive (cathodic) current, the actual
WE potential is less negative than the applied [measured) potential, I be eBen is
Figure 220 Equivalent circuit for an electrochentical cell.
57
to shift peak potentials in a negative direction. For negative (anodic) current, the
shift is in the positive direction. Thus for a reversible eIectron transfer,
AE, > 58 mV in an experiment that has even a relatively small IR drop. Typical
experiments involving 5 pA of current in nonaqueous solution with resistance of
approximately 100052 can result in peak sepuatiou about 70mV.
Use of the equation
is a reasonable way to correct measured peak potentials in solution with
moderate resistance problems. Note that the correction for IR drop tracks the
current (the anodc and cathodic peak currents differ in sign and in magnitude).
The effect of IR drop can be included in simulation treatments.
It is best to make reasonable effort to minimize the solution IR drop by:
Optimizing the electrolyte concentration.
Placing WE and RE close together.
Using the feedback compensation method, available as a automated option in
some commercial units.
Using smaller electrodes.
--
2.4.2 Capacitive Current
Anvnher djsrorfion of the CV from the ideal waveshape arises because the
electrode-solution interface acts as a capacitor in series with the solution
res~stance. The most familiar capacitive current occurs in a potential step (to a
potential at which no faradaic current occurs). In this case, the current is given
by:
where the total capacitance is
, Cdl = C/cm2 x area
and AE is the size of the potential step (V), t is time, and R is resistance.
A plot of In(0 versus time has a slope of -(RC,,)-I and an intercept
In(AE/R). In this way the capacitance and resistance can be measured (Figure
2-21). The C/ ~r n- ~ (double layer capacitance) for most electrodes falls in t he
region 10-20 pF/crn2.
For a cyclic linear sweep, the situation is more complex. The double-layer
capacitance is in eneral a function of potential. However, the general features
ri can be described th constant capacitance. In t hs case, the capacitive current
rises (starting at E,), with a characteristic time that levels off. Upon the reverse in
scan direction, the capacitive current changes sign. The plateau current is equal
to the i , , = Cd, x v (Figure 2-22), while the faradaic current is proportional to
-the square root of the scan rate. Thus, the distorting effect of capacitive current is
largest at higher scan rates (Figure 2-23). The ratio of faradaic to capacitive
current is independent of electrode size.
4. 01 ' ' I I
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Tirne/mSec
Figure 2-21 Procedure for measuring resistance and capacitana by a potential step
experiment.
Figure 2-22 Capacitive response lor a cyclic sweep, assuming constant capacitance
- 4 5 0 1 , , , , , I
0.0 -0.1 -0.2 -0.3 - 0. 4 -,0.5
~ o t ~ n t i a l / V
Figure 2-23 CVs with capacitive current, assuming typical values for electrode area
and capacitance: solid curve, 100; open circles, 500; and solid circles, 850V/s.
Correcting for Capacitive Current
There are two approaches to correcting capacitive current: background sub-
traction and theoretical treatment.
In background subtraction, the current obtained from a CV collected in the
absence of electroactive species is subtracted from current collected in the
presence of electroactive species. Ths procedure assumes that the double layer
remains the same in the two experiments, which is generally true because the
double-layer properties are most strongly related to the excess electrolyte. , , - A
background subtraction also eliminates the distortion due 'to residual faracaic
current from electrolyte and solvent impurities.
Theoretical treatment is more difficult, since capacitance is a undetermined
(usually) function of potential.
The capacitive current and I R drop are interrelated. Since capacitive current
depends on sweep rate, and I R drop causes distortions in linearity of sweep, the
capacitance will not follow exactly from theory of linear potential sweep. Ths
effect can be incorporated into finite difference simulations.
2.5 Microelectrodes and Fast Scan Voltammetry
ElectrodEdiameter d is an important experimental variable. For a typical planar
disk WE and reference probe, solution resistance is proportional to 1/d,I6
whereas the current i s proportional to the area, or d2. As a consequence, I R drop
is proportional to d The capacitive rise time decreases as the electrode area is
made smaller. (This property is of particular consequence in potential step
1 experiments.) With the appearance of microelectrodes and fast potentiostatic
1 circuits, the time scale of CV has k e n extended into the submicrosecond
: range.'' As a consequence, faster following chemical reactions can be examined.
Note that for fast scan experiments to give useful results, electron transfer must
be rather facile. (See, e.g., Figure 2-24). If the heterogeneous rate constant is too
I
E (V)
'Figure 2 2 4 Example of last scan CV. The reduction of 9-bromoanthracene (IOmM) at
a scan rate of 113,000V/~. (Adapted from Reference 18.)
I
60 CYCLIC VOLTAMMTRY
small, the peak currents can be shifted out of the bounds of the potential window
at fast scan rates.
In using microelectrodcff one must take into accvu~lt the lower limit of scan
rate for which linear dinusion predorninatzs. As the sca~r rate becomes lower, the
predominant mode of diffusion changes over from linear to spherical (Figure 2-
17b). The current response is ddferent for spherjcai symmetry, because the rate
of diffusion increases. Microelectrode (slow scan) studies can take advantage of
this to measure fast heterogeneous rate constants.
The spherical diffusion-limiting current can be compared to the peak current
in CV to obtain a lower limit of useful scan rates for studies in the linear
diffusion regime. For a one-electron transfere we have:
The uppw and lower scan rate bounds for an electrode of a given diameter for
use in the linear diffusion regime are listed in Table 2-3, based on a I or 5%
current contribution from spherical diffusion, and a 0.005 or 0.01,* V I R drop.
As a consequence of the short time involved in gast scan experiments, total
electrolysjs is tnuch smaller at microelecirodes, and fouling of electrodes by
electrolysis products is minimized.
2.6 Potential Step Methods and Cyclic Voltammetry
Cyclic voltammetry is a powerful technique because the CV waveshape is
sensitive to dl the parameters of the electrochemical mechanism. For the same
reasons, however, a full quantitative analysis with CV can be dillicult, Tt is
usually helpful if qualitative or quantitative information can be obtained from
other sources. Potential step methods can play a complementary role to CV in
the analysis of electrochemical mechanisms. This is because they can be
performed under conditions of a fast and irreversible forward heterogeneous
rate constant.
2.6.1 Double Potential Step Chronoamperornetry
The potential waveform imposed at the working electrode for the double
potential step (DPS) is shown in Figure 2-25a. The characteristics of the
waveform are the initial potential E , the step potential Es, we step time z, and
the find potential E,. Here, we consider only the case of Ei = E,. Normally,
* Si ne we am looking for an estimte, i l wouldn't matter much if we took the reversible pe&
current.
61
able 2-3 Usable Scan Rates for EIeclmdes of Different Sizes (I mM solution)a
--
Diameter (crn) Lower limit (V/s) Upper limit (V/s)
icaplirsr
0.1
0.02-0.2 30-600
2.5
0.005 8-SO 1,350-15,000
14
0.001 200-2,000 8,ooo-s5,ooo
30
0.0005 800-8,000 16,000-175,000
45
- .
" The lower limit criterion is that ~ h e spherical Nusi on current is l as thao 5% of the iinear dausion curml
(val ue shown for D = IO-'- 10-6cm2/s. The upper limit criter~on 1s based on an IR drop of 10/100mV (assuming
R = I,000Q). The ratlo of capacitive to faradaic current is also given for the higher scan rate. Note that at rbe
highest scan rates it is advisable to use higher wncentrations, about 001 M.
Figure 2-25 (a) Wavefonn and (b) current response for a double potential step
experiment.
62 CYCLIC VOL T AMT RY
electrolysis occurs at the initial potential setting, and the potential is stepped to
a voltage well beyond the formal reduction potential of the principal electroact-
ive specles that undergoes reduction or oxidation. This arrangement ensures
that the electrode reaction will be fast and irreversible, as can be seen by
considering the effect on the Butler-Volmer equation and the Nernst equation.
The exact amount of voltage beyond the reduction potential necessary to obtain
t h s situation depends on k0 and a; usually 200mV will suf6ce. The DPS current
response (a current-time curve) for a simple electron transfer is shown in Figure
2-25b. For the first step, the current is given by:
and after the step the current is given by*:
The current response from singlerlpotentjal step is often used to determine
diffusion coefficients. In combination with cyclic voltammetry, both n and D can
be determined.
2.6.2 DPS Analysis of the EC Mechanism
The DPS response i s shown tor the case of a reduction with a following
irreversible first-order chemical reaction in Figure 2-26, for a step of 1 ms and
homogeneous rate constants ranging from 0 to lo4 s- ' . The current on the first
step is unaffected by the chemical reaction (so that the first step result can be
used to determine the diffusion coefficient of the electcoactive species). The
chemical reaction removes the reduced species, resulting in reverse current that
is diminished according to the rate constant of the followjng chemical reaction.
A solution for this problem is available in a series solutions involving modified
Rzssel ftmctionsi8; two or three terms are commonly taken:
where
and I, represents the modified Bessel functions.
Experimental DPS data can be analyzed by determining the diffusion
* Such large IR drops can be effmively dealt with by mulatian methods.
THE CYCLIC VOLTAMhfETRIC EXPERIMENT
Figure 2-26 DPS response for the EC mechanism, for values of the Following reaction
rate constant of 50, 100, and 500s-' . The reverse step current decays Faster as the rate
constant is increased.
coefficient on the first step, and the chemica1 reaction rate constant by fitting the
reverse step data to theory. Programs for the simulation of DPS experiments ase
included with this book and are described in the appendix.
t
2.6.3 Capacitive and Background Currents
'
S i d e potential step experiments are invariably performed with the goal of
h o mp l e t i n g some type d quantitative analysis, it is imperative that both
' capacitive current and background currents be taken into acmunt. Several
I
approaches are possible with regard to the capacitive current. Data points can
.: be ignored until the ratio of faradaic to capacitive current is targe. This is a
; common approach, particularly with microelectcodes, where the capacitive
$ decay can be very fast. Data can be taken in rapions where i x tl" is constant. It
is possible to try to improve time resolution by including the theoretical
1 capacitive current in the analysis. In DPS work the rninlfization of background
i currents is particularly important; background subtraction sllould bc used if
unavoidable background faradaic currents occur.
i
L
1
2.6.1 Time-Resolved Potential Step with Microelectrodes
: : Improved time resolution is possible with a combination of microelectrodes and
;
a fast potentiostat such as that described kl ow (Section 2.7). Figure 2-27 shows
'
the DPSexperiment for ferricyanide, utilizing~acornmercially availablepot-
entiostat with a time resolution of 0.1 ms. and the same experiment performed
with the "home-built" instrument which has a time resolution of about 0.25 ps.
CYCLIC VUL'TAMMETRY
Ti!,>c (~,-,?v<)
Figure 2-27 Increasing the time resolutio~l or DPS. Solid circles are with best time
resolution with BAS-100A (one point per 0.1 ms), dotted Iinr consists of theoretical
points, and the line represents data taken with a fast potmriosiat (one point per
0.004ms).
Fast potential step experiments have a great advantage over cyclic vol-
tarnmetric methods with regard to the analysis of the EC mechanism. Analysis
by CV is made difficult at high scan razes; data are distorted as a result of
separations due to IR drop and slow electrode kinetics. DPS has neither of these
problems.
2.7 Construction of a Fast Potentiostat
At the time of writing the available commercial instruments do not allow for the
Full range of time scales for CV or DPS experiments. In particular, they are
generally limited to less than 1000V/s or to time steps exceeding 1 ms. Most
likely this situation will soon change, as the utility of such experiments becomes
apparent. Electrochemical instrumentation that can perform high speed experi-
ments can k constructed rather simply and at relatively small cost.
Potentiostatic circuits make use of operutional urnpl$ers (0-4) to controi
voltage and to measure current. Operational amplifiers have a number of inputs,
but in circuit diagrams the power supply connections are understood and only
three connections are considered (Figure 2-28). Based upon their action, these
connections are the inverting input (-1, the noninverting input (+), and the
output. In normal use, OAs are used in a feedback mode; that is, feedback loop is
introduced from the output or from some other source to the inverting input.
The action of the OA in electrical currents can be understood largely on the
basis of a few characteristics.
THE CYCLIC VOLTAMhIETRIC EXPERLMENT
Figure 2-28 Operational amplifier.
I. V, = A(V+ - V-), where the open loop gain A i s usually greater than lo*. In
feedback mode, an immediate consequence of this condition is that V+ x V- .
Consider why this is so (refer to Figure 2-29). If there is a initial positive
difference in (I/+ - V-)= +1 V, a large positive output voltage will Appear and
feed back intv the inverting input. This feedback will decrease the value of
V+ - V- . The i dbacl i process ensures that the value of V- is very nearly
equal to V+. The particular feedback loop shown also ensures that the voltage
i
output will be equal to voltage input.
I 2. OAs have large input resistance. In other words, no current is allowed to flow
through the - or t inputs.
:
3. OAs have a low output resistance. Large currents can be drawn from the
b
S
output.
Besides the voltage follower configuration, which we have mentioned, the
i
current follower and voltage amplifier configurations are important in designjng
E a potentiostatic circuit.
i
In the current follower mode (Figure 2-30), the current flows around h e oop
/
amp through a resistance. The voltage monitored at the output is then, with
; respect to ground, V,,, = iR.
The voltage amplifier (Figure 2-31) has resistance elements at the inverting
1
input and in the feedback loop. Since the voltage at the inverting input is zero
:
with respect to ground, the incoming current is i,, = l,;,,,'R,,. The current in the
loop is - 1/,,,/RP Since there is no current flowing at the inverting input, the
I
Figure 2-29 Op amp in feedback mode (voltage follower).
CYCLIC VOLTAMMETRY
%s
Figure 2-30 Op amp in current follower modc.
incoming cwrent must flow around the loop, and i, = i,,,. The output voltage is
proportional to the ratio of the resistances:
A full potentiostatic circuit is shown in Figure 2-32. We assume that a voltage
input (a potential sweep or step) is available from a function generator. The
voltages measured versus ground in this circuit can be determined by con-
sideration ofthe action of the three OAs. The voltage at the inverting input of op
amp 1 can be calculated according to the constraint that no current may flow to
the imputs. This means that ii = - i,; and as a consequence, if R, = R,, then
V, = - V2. The output of op amp 1 is connected to the auxiliary electrode. Note
that the reference electrode can be considered in a feedback loop to opamp I ,
and a voltage follower is inserted between the reference and the inverting input
of op amp 1. This design allows the reference to maintain a stable potential by
ensuring that no current is drawn from it.
To complete the picture, we must examine the working electrode. It i s
connected in a current follower mode so that current through the working
electrode i s shunted around op amp 3. In a feedback mode, the inputs are equal,
Figure 231 Op amp used as voltage amplifier.
i axis
Figure 2-32 Complete potentiostatic circuit.
and the working electrode is pinned to the ground established by the control
amplifier.
Although by convention, voltages in a circuit are measured with respect to
ground (assigning the common ground = O.OV), it is also true that the working
electrode's Fermi level (and thus its potential) is changing with respect to
vacuum.
Finally, a voltage amplifier (op amp$) can be added to step up the output
voltage to an acceptable value for a recording instrument.
A quick check on the circuit operation can be made by inserting resistances
between the AE and WE and the RE and WE (to emulate an electrochemical
ce!l). Upon imposition of a voltage sweep, a linear output voltage can be
obtained that should agree with that calculnted from the circuit.
The time resolution of the circuit is Ijmited by the time response of the
operational amplifiers. Op amps with a time response of tens of voIks per
microsecond can be purchased at low cost. Noise can be mi ni nl i d by wrapping
CYCLIC VOLTAMMETRY
M @ d Waveform Generator
u
Figare 2-33 Construction of a tirneresolvd electrochemical instrument.
a11connections with shielding tape. Leads to the electrodes should be as short as
possible to minimize capacitan~, to achieve the best time response.
A fast rise time potentiostat system based on the circuit described is shown in
Figure 2-33. Tlus system features a progammable waveform generator board
for general simulation of waveforms and a waveform analyzer to digtize
and store the data. The present setup features cyclic staircase generation
(2.5mV/step) and double potential step experiments.
The effect of IR drop can also be ehminated by modifications of the
potentiostatic circuit. Performance of such a circuit under very high scan rates
has been discussed by Amatore et d.l0
2,8 Determination of the Number of Electrons
Several methods involving rnicmelsctrodes have been suggested for unarnbigu-
ously determining a, the number of electrons in an electrochemical mechanism
and D, the diffusion coefficient. While this information cannot be determined
from a cyclic voltammetric experiment alone, w and D can be found utilizing
experiments that combine li~lcar and nonlinear diffusion2'.
Using the standard inlaid disk electrode geometry that has been described,
the equations in the planar and nonlinear diffilsion limit are:
i , = n ~ ~ D ~ ~ ~ / ( . r r r ) ' ~ "
(a plot of i vs t-It' gives S = ~ F A D ' ' ~ C / ~ ' ~ ~ )
im = *nFDC . . . (at . . long -.
times2')
-..,A . >
THE CYCLlC VOLTAMMETR~C EXPERLMENT
69
Experiments can be performed in both regions with the same electrode by
using dimerent time scales or different sized electrodes. The equations for i, and
S can be solved to find n and D. For instance, Barallski et report thc
ColIowing for the reduction of 9.64 mM benzoquinone in DM SO:
in = 30.0 x Amp ( r = 8.8 pm)
Solving for n and D results in n = 1.05 and D = 8.7 x 10-bc~nZ s- I , in good
agreement with the values found by Baranski et al. using a slightly different
caIculation with a ferrocene reference.
References
1. Reichardt, R., Solvents und Solvent Effects in Organic Chmisiry. VCH Publishers: New York,
1%-
2 Fry, A.; Britton, W. E. In Lahorutory Echniques in EleciroanaIytical Chnnisrry, 1st ed.,
Kissenger, P. T.; Heineman, W. R., Eds. Marcel Dekker: New York, 1984, Chapter 13.
3. Rusling, J. Auc. Chem. Rex 1991,24, 75.
4. Gosser, D. K., Jr.: Huang, Q. J . Ebctruunub Chem. 1990,278,399.
5. Gosser, D. K., Jr.; Huang, Q.; Rieger, P. H. J. Electroanal. Chem. 19W, 136, 285.
6. Frat, U.; Iwasita, T.; Schmickler, W.; Stimming, U. J . Phys. Chm. 1985.89, 1059.
7. Bond, A. M.; Zongpeng L. J. Eleetrounal. Chem. 1989,259. 321.
8. Wightman, R. M., Wipl D. 0. Acc. Chcm. Rch. 1990.23,64
9. Wiedemann, D J.: Kawagw. K. T.; Kennedy, R. T.; Ciolowski. E. L.; Wightman, R. M. Anul.
Chem 1991,63, 2965.
10. Kissenger, P. T. In Lahoratorv Techniques i n E l e ~ ~ r u u n a ~ ~ t i c ~ l Ch&,tt~brry, 1st ed., Kissenger, P.
T.; Heineman, W. R . Eds. Marcel Dekker New York, 1984. Chapter 12
11. Bard, A. J.; Faulkner. L. R Elrrtmt.lu~riicul Mt'thodh 1st 4. John Wiley Sr Sons: New York,
1980.
12. Gosser, D. K., Jr.; Zhang. F. filunra 1991.39. 715.
13. Schwartq W. M.; Shain. I. I . Pl:,vs. Chcrrr. 19h5, 69, 30.
14. Parker, V.; Britton, W. E. und Fry. A. J. Edr Topics i n Orguttic El eur r wh~~mi s t r ~, I st ed. Plenum
Press: New York, 1986.
15. Klingr, R. J.; Kochi, J . K. J . Pl r ~s . Cllrm. 1981,86, 1731.
16. Greef, R.; Peat, R.; Peter. L. M.: Fletcher, D.; Robinson, J. lnsrrvmmtul Merhods i r ~ Elec-
trochemistry. Ellis Aorwod: Cllich~ter, 1985.
17. Andrieux, C. P.; Hapiot, P.; Saveant, J. M. Chem. Rev. 1990, 90, 723.
18. Rieger, P. H. Elcctrochemislry Prentice-Hall: Englewood Cliffs, NJ, 1987.
19. Schwarz, W. M.; Shain, I. J . Phys. 1981, 85, 1731.
20. Amatore, C.; Lefrou, C.; Pluger, F. J. EIecrroonuI. Chem. 1989, 43.
21. Aoki, K.; Osteryoung, J. J . Elcctrounrrl. Chem. 1981,122, 19.
22. Baranski, A. S.; Fawcett. W. R, and Giibert, C. M. Awl . Chm., 1985,57, 166.
C HAP T E R
3
A Survev of
Electrochemical ~echani sms
Certain zl~ctrochemical mechanisms reappear frequently, or arc of such pract-
icat or theore tical interest, that they have become recognizable "standards."
Often they are components of larger, more complex mechanisms. A reversible
chemical reaction can precede an electrode reaction, shfting the peak potential
and altering the waveshape. Electron transfer is often associated with a change
in motecular structure. An examination of the voltammetric response indicates
whether the structural change is concurrent with electron transfer or occurs in a
following, activated step. In aqueous solution, protonations can be at equilib-
rium with respect to the electrode processes. In recent years. such catalytic
mechanisms involving electron transfera~~lrctron transfer c h i # (EX7 catalysis
and homogeneous redox catalysis ( HRC) have gown in i tnportat~ce. Cyclic
voltammetric experiments have be11 pivot 33 in understanding and utilizing
these mechanisms.
This ckapter presents examples of CV analysis For more complex mechan-
isms. The examples illustrate not only the wide range of chemistry amenable ta a
CV study, but aIso the various ways in whi cl ~ sjnlulatjon methods have aided in
the analysis. The theoretical basis of simulation methods i s discussed in
Chapter 4. Chapter 5 uses several of the mechanisms discussed here to illustrate
the use of the simulation program CVSIM. In these cases, the mechanism
parameters obtain4 from simulation analysis are listed lor comparison with
the examples in Chapter 5.
72 CYCLIC VOLTAMMETRY A SURVEY OF ELECTROCHEMICAL MECHANISMS
3.1 The CE Mechanism
The reductive CE mechanism is formulated as follows:
k!
P e o x
k-,
o x + e - = Re d E O ' , ~ O , U
Experimentally, the initial solution contains the species P and Ox at
equilibrium concentrations. During the reductive sweep, Ox is reduced to Red,
and P starts to convert to Ox according to the chemical kinetic rate constants. If
the experiment is started with initial concentration of the species Red only, the
oxidative CV is an EC mechanism.
The cyclic voltammetric response for this system (with the electrode reaction
reversible, a CE, mechanism) is determined by Kc, and ( k , + k- , ) / v. The
limiting cases of the CE mechanism are ( I ) the chemical step is fast and at
equilibrium, and (2) the forward chemical reaction is slow with respect to the
time scale of the experiment. In case 1, the CV has an E, determined by the EO'
and K,,. Tn case 2, the cyclic voltammogram will be reversible and will reflect
only EO' and the initial concentration of species Ox.
Let us examine the transition from case 1 to case 2, which can be effected by a
change in scan rate. As the scan rate is increased, the kinetics of the chemical
reaction are apparent: the cathodic peak/Jv decreases because Ox does not
maintain equilibrium concentrations on the time scale of the experiment. The
cathodic peak potential also shifts negative relative to the peak in case 1. At
large scan rates, the reversible case 2 is achieved.
A quantitative study of the equilibrium and kinetics of an CE/EC-type
mechanism was recently reported by Lee et al.' This study utilized a com-
bination of potential step and cyclic voltammetric experiments in an examina-
tion of the reduction of the nitronium ion and the reverse process, the oxidation
of nitrogen dioxide.
As we have noted, potential step methods are particularly attractive for the
determination of chemical rate constants in electrochemical mechanisms
because the potential can be stepped to a potential at which the forward electron
transfer is fast and irreversible, so that the current response depends only on the
rates and mechanism of coupled chemical reactions. A complete quantitative
evaluation of the mechanism was achieved by combining the potential step
results with a series of simulations. The chemical reaction rate constants were
determined by single-step experiments (the oxidation of NO2). Early in the step,
the single-step response is determined by the equilibrium concentration of NO,.
At later times, the response reflects the rate of conversion of N,O, to NO,.
Simulated potential step response curves could be compared to experimental
data to extract the K, , and k , and k - , (see Figure 3-1).
Time (mScc)
Figure 31 Simulated single potential step response for the oxidation of NO, (CE
mechanism). Compare the response for an E mechanism (dashed line), with concentration
cqual to the (NO, + N,O,) concentration.
Cyclic voltammograms for the reduction of NO: and the oxidation of NO,
are shown in Figure 3-2. Since the chemical reaction rates were rather low, the
reduction potential could be obtained at modest scan rates by taking the
average of the cathohc and anodic peak potentials. At the lower scan rates, the
kinetics of the chemical reaction i nf l uen~s the voltammograms significantly.
Simulations of these experiments are shown in Figure 3-3. From CV simulations
of the faster scan rate experiments, the heterogeneous parameters k0 and cc were
determined. Figure 3-4 iltustrates the importance of scan rate as an experimental
variable. Several mechanisms may give similar current responses at a particular
scan rate. However, they arc less tikely to give similar current responses over a
wide range of scan rates (unless, of course, the mechanisms are kinetically
equivalent). The good match between simulated peak currents versus scan rate is
an important validation of the proposed mechanism.
This is our first encounter with the use of simulation to analyze CV results.
Through the theory of simulation (Chapters 4-6), a cyclic vollammetric or
potential step response can be calculated for any electrochemical mechanism,
given the parameters that describe the experiment (scan rate, scan range,
electrode area) and the mechanism (reduction potentials, electrode kinetics,
chemical reaction kinetics, and lffusion coefficients of all chemical species). The
unknown parameters of the electrochemical mechanism can be varied until a
simulation is obtained that closely resembles the experimental result.
The CV,'potential step analysis was carried out in a series of other solvents.
The variation in the reduction potential (measured against a ferrocene standard
in each solvent) was shown to be best correIated with the solvent donor number
(rather than the dielectric constant), indicating a specific interaction of the
solvent with the nitronium ion. The kinetics of the electrode process were much
. .. . , .A -.--.- I....... .. . . ---"-i
CYCLIC VOLTAMMETRY
- -
1.4 1.0
1.1 1.4 J .O
1.1
B V w m 6, VnSCE
Figure 3-2 Cyclic voltammograms of (a) NO: in acetonitrile at scan rates 0.1 and 7 V/s
and (b) N20, in acetonitrile at scan rates of 0.5 and 7 V/s. (Adapted from Reference 1.)
faster than could be expected on the basis of Marcus theory of electron transfer,
including both solvent reorganizatian and internal, molecular reorganization.
Lee et al. interpreted the unusually high electron transfer rate as being indicative
of an "~nner sphere" type of mechanism, whereby the nitraniurn ion can form a
complex with electrode surface and thereby lower the activation energy for
electron transfer. -.-
The simulation analysis resulted in the following parameters for the CE
mechanism (in acetonitrile):
C = chemical: kl = 5. 0s-I, kLi = 6 x 1 0 4 ~ - ' s - '
c
E = electrode: EO' = 1.32, k0 = 0.031,
= 0.48
A SURVEY OF ELECTROCHEMICAL MECHANISMS
-
I .e I .I 1. 0
E, V us SCE
Figure 3-3 Simulated cyclic voltammograms: (a) corresponds to Figure 3-2a; (b)
corresponds to Figure 3-Zb. (Adapted from Refcrence I.)
3.2 Multielectron Transfer
Formulas for AE,, and peak current include n, the total number of electrons
concurrently transferred. However, straightforward application of such for-
mulas may not be possible when pa exceeds 1. The second electron transfer might
take place akpotentials negative to the first, giving rise to two overlapped one-
electron peaks. Often there is a chemical reaction upon reduction or oxidation,
giving rise lo an ECE process with an apparent rnultielectron transfer. From
theoretical considerations, we expect concurrent two-electron transfer to be
rareU2
We start by considering a reversible two-electron transfer:
1 + e - ~ 2 E y
u
from the simulation analysis. The scan rate
dependence of the anodic peak current for
different concentrations of N,O, is compared
O - I o I to that predictd by the simulation analysis
l o g y , vs4 (smooth curves). (Adapted from ReFerence 1 .)
The shape of the cyclic voltammetric wave will depend on the relative values
of Ey' and ET (i.e., whether 2 is stable with respect to reduction at the reduction
potential of 1). Figure 3-5 shows the cyclic voltammetric result expected tor
different values of AE,-, = (ET - Ey ) . If the second reduction potential
exceeds 180 mV positive with respect to the first (AE,-, > 180mV), then the CV
takes on the characteristic n = 2 process, where the overall formal potential is
the average of the two reduction potentials and the AE, = 29 mV. Otherwise,
the CV will reflect two overlapped one-elsctron transfers, with the extent of
overlap depending on the relative peak potentials.
A recent report3 on the twodectron reduction of (tl-C6Me,),Ru2+ demon-
strated the resolution of two-electron processes even when the second is favored
thermodynamically. This is a possibility when the second electron transfer is
slower than the first. In this case an increase in the scan rate shifts the peak due
to the second electron transfer to more negative potentials, eventually resulting
in a peak splitting (Figure 3-6). The values of the reduction potentials and
electrode rate constants were estimated by simulation analysis:
TO obtain a good fit, it was necessary to include the kinetics of the
disproportionation reaction (3 + 1 9 2 + 2). Note that the equilibrium constant
IK,, = k,/k,) is constrained by the reduction potentials to be k,, = 0.5:
I
It appears that a change in hapticity (the character of arene bonding to the
(al
J0 r---.
- 2 0 1 h l 0.1 0.0 -0.1 -0.2 -0.3 - 0 4 - 0 5 -0 8 -0.7
Poiental ( V)
Potenlial ( V)
Figure $5 CVs lor two-electron transfer for (a) El > E,: and (b) El < E,.
metal) is concurrent with the second electron transfer (Figure 3-7), resulting in a
small heterogeneous rate constant. It is a little puzzling, however, that the
second is exactly 0.5; since a significant structural change is postulated, one
might expect the second electron transfer to show a transfer coefficient smaller
than 0.5.
: 3.3 Protonations at Equilibrium
Often protonations are coupled to electron translers. It is expected that in this
case the el~trochemical mechanism will be sensitive to the availability of
protons (pH and nature of solvent).
a - I
- 2
volt rs. PC / PC+
0 - 1
- 2
Vol t rr. PC / F C '
Figurr $6 Cyclic vultamn~ograrns of (qb - C,Me,),Ru: 0.2Vls (upper) and 10V/s
flower). (Adapted from Reference 3.1
Figure 3-7 Proposed change in bonding to ruthenium upon the second electron
transfer. (Adapted from Reference 3.)
A SURVEY OF ELECTROCHEMICAL MECHANISMS 79
The reduction pathways open to quinones and many other similar systems
(nitraso compounds. azobenzenes, etc.) can be represented by the "square
scheme" in Figure 3-8.
It has been known for a long time that pH affects the kinetics of the reduction
of the bznzoquinones. The reduction generally becomes more irreversible at
higher pH values. Otl this basis it has been proposed that the reduction pathway
of BQ is HeHe (proton-electron-proton-electron) at low pH and eHeH at
higher pH. The pK,, the EO', and the rates of the individual steps in the square
scheme will detern~inc the preferred pathway for reduction.
Lavjron has further developed the theory for quinonc-like systems.$ Assum-
ing that the protunations were at equilibrium (fast with respect to the electron
transfers), and that the transfer coefficients for the electrode reactions were all
0.5, he was able to show that such systems behaved exactly like two sequential
one-electron transfers, with apparent heterogeneous rate constants:
and apparent reduction gotentjals:
This approach has been utilized by Dznkjn and Wjphtman in analyzing the
pathway for the oxidation of catecIlvl to o- q~i nones. ~
1 Figure 3-8 The square scheme for benzoquinone reduction.
The cyclic voltammograms in Figure 3-9 are simulations of BQ reduction at
pH 0 and 6 based on Laviron's values for the apparent reduction potentiais and
apparent rate constants.
The quinone electrochemistry story becomes even more complex, and the
role of adsorption and solution chemical reactions are still being actively
investigated: this topic has been reviewed by Charnben6
3.4 Catalytic Mechanisms
Catalytic processes have k e n studied to great advantage by cyclic voltammetry.
These include catalysis of chemical reactions initiated by electron transfer at the
electrode and catalysis of redox processes by solution chemical reactions.
3.4.1 Electron Transfer Chain (ETC) Catalysis
Consider an ECE rncchanism where the product of the intervening chemical
reaction is itself part of a redox couple:
4 + e - = 3 Ey'
where
E;' < E?.
Pot e r l l i a l / V
Figure 3-9 Simulations of benzoquinone reduction at pH values ill 0 (solid) and 6
(dashed).
A SURVEY OF ELECTROCHEMICAL MECHANISMS 81
We can approach this mechanism by examinins the eflect on cyclic vol-
tammetry of increasing thc first-order rate constant k , (Figure 3-10). Of course,
when k, = 0, only the first reduction occurs, and the cyclic voltammogram
corresponding to a single electron transfer is ilhtaioed. As k, increases, several
characteristic changes occur. The lizight of the peak due to the reduction of 1
decreases. This is s result of the fornlatilsn of 3, which is immediately oxidized to
4 at po~entials where 1 is reduced. 4 is reduced back to 3 at a more negative
potential. The peak associated with this process increases with the rate of
production OF 3. Thc production of 4 occurs through a catalytic chain electron
transfer. For large rate constants k , , a stnall atriount of charge passed results in
con~plctc cnnversion of 1 to 4 near the electrode, The reverse peaks that
correspond to the reoxidation of 3 and 2, also are related to the
production/consumption of these species.
A similar catalysis can bc initiated in solution. I f a small amount of reducing
agent is added to a solution containing species I , a llornogeneous redox reaction:
kl
K = - = exp
Cq k-,
has the same net result as the electrode reactions. Many nucleophilic sub-
stitution reactions have been catalyzed by the electron transfer chain mechan-
ism; reviews have appeared of ETC applications in organic' and organometal-
lic8 chemistry, as well as in general.' OFcourse, there is nothing stopping the
homogeneous redox reaction from taking place during the electrochemicat
experiment. However, the effect is rather small as is illustrated for CVs simulated
with k, constant and tuning the homogeneous redox reactioi~ upward'' as
shown in Figure 3-11. The ETC mechanism is sometimes written in a
picturesque square scheme (Figure 3-12).
An early electrochemical study of the ETC catalysis of ligand suhsrituriun in
metal carbonyls is still one of the most thorough. In this work. Kochi et sl.
studied the oxidative catalysis of ligand substitution in manganese cyclo-
pentadienyl complexes. A typical reaction was the ETC reaction for trjph-
enylphosphine substitution:
g5 - MeCpMn(CO),L = KL
Me = MeCN, P = PPh,
- -
MnMe - e- =MnMct '
E y = 0.19, ky = 0.048, u , = 0.5
For every mde of charge passed, I013 moles of starting material was
-6
0.1 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7
Potential ( V)
Potcnt ial ( V)
Figure $10
Simulations of the ECE mechanism for increasing value of the rate
constant for the case E , < E,: {a) k, = OsL1, (b) k, = 10s-', and (c) k, = 1000s-'.
I'otcntial ( V)
Figure 311 Effect or the homogeneous redox reactinn on the ECE tti ecl ~at~i st~~:
k = 105111-'s-' (soIid line), compare with 3-10b (dashed line).
consumed, and the substitution reaction is complete in a manner of minutes. The
thermal reaction is not meawlreable on this time scale.
Cyclic vultammogran~s ilh~strafing various facets of this study Figure 3-13
shows the cyclic voltammo_eram for thc oxidation of the substrate cyclo-
pentad~enyl cclrnplex (3-13). The disappearance of the original peak and the
appearance of a new peak positive to the original are suggestive of an ETC
mccha~iism. Use of lower conce~ltra tions allows the observation of intermediate
results. In this case, the rate of product formation is reflected by the size of the
product peak. Cvmparjson with simulation permitted an estimate of the
thermodynamics and kinetic parameters of the entire mechanism (Figure 3-14)
for a variety of lipands.
Figure %12 The ECE mechanism written as a square scheme.
CYCLIC VOLTAMMETRY
P OT E N T I A L , V vs SCE
Figure 3-13 The reversible oxidation of MnMe in acetonitrile. (Adapted from Reference
11.)
P O T E N T I A L , V S S C E
Figure $14 Experimental and Grnulated CVr for the oxidation of 1.7 x l o- ' M MnMe
in the presenoe of various mt~lar ratios of phosphine ligand and maaganesz complex.
(Adapted from Reference I I .)
3.4.2 Homogeneous Redox Catalysis (HRC)
With the ETC mechanism, t he electrode reaction initiates a chain catalysis
reaction. It is also possible for a sequence of solution chcmical reactions to drive
an electrode reaction (e.g., to cause a reduction at a potential positive to its
formal reduction potential). Saveant and co-workers have developed the theory
of the eIectrochemical response for HRC schemes. '
In a reductive HRC (Figure 3-1 5) based on an EC mechanism, the mediator,
which has a reduction potential positive to the substrate, is reduced at the
electrode. The reduced mediator (species 2) diffuses into solution and reduces the
substrate, an uphill thermodynamic reaction. This unfavorable reaction is
driven by an irreversible reaction of the reduced substrate:
I + e - = 2 E!' (fast)
The llon~ogzrleous redox reaction recycles species 1 back to the electrode
according to the kinetics of the system and the relative concentration of 3 to 1
(Saveant terms this the excess factor, q = [3]/[l]). The HRC mechanisms arc
agnaled by two events:
1. An increase in current compared to the reduction of 1 alone, due to the
recycling of 1 to the electrode.
2, A decrease in the reverse peak (2 - e - = I), which occurs because of the
irreversibility of the overall process.
A steady state treatment of the solution chemical react ions results i n the
following expression for the observed rate of recycling of 1 :
,.*.<
Figure $15 Schematic representation of an HRC process.
This rate can be controlled by the homogeneous redox step or by the
irreversible chemical reaction, depending an the ratio of k, to k - , to k- , [I].
Case 1. k-,[I] <<kkz
The catalysis is controlled by the forward step of the homogeneous redox
reaction. 111 this case, thc rntto of the peak catalytic current to the current
obtained by reducing 1 alone, !,,,;ips,, can be analyzed to gi ve the rare constant
k, . This analysis can be done lusing published workirlg curves or by creating
curves by simulation. Figlire 3-16 shows simulated CVs indicating the effect clf
several values of the rate constant k , for an excess factor of 10.
The rate-determining step of the catalysis is the irreversible reaction. The value
afli,,k, can be f wnd from simulation analysis. IT, under the circumstances of the
experiment, k - , can be shown to be diffusion controlled (because of the very
large driving force for the revel st: reaction) thcn k, can bc estimated ( I ; , having
k e n determined from case 1). Rate constants up to lo9 s - ' can be measured in
this manner*
The reduction potential of the 3/4 couple, normally undetermined because of
the fast following reaction, can he estimated. If the rate constarlt k, for a series of
mediator coupIes PQ is measured by the HRC (case 1) method, an application of
"linearized" Marcus theory (simple LFER) Ieads to a plot of the measured rate
constant versus the driving force as shown in Figure 3-17. The plot has three
regions:
I . The diflusion-controlled region. Here, the driving force for the forward redox
~raction is largc. and the rate k , i s diffusion controlled. Nn experimental
points can be obtained in this region, but it can be estimated from rate theory.
2. The artiuation-controlled region. Here k, is determined by the following
LFER-type equation:
where P is a standard rate canstant referred to zero driving force and a is t h ~
transfer coefficient referred to the ho~nogeneou reaction.
3. The '.counterd~$usion" region. Here the rate of the reverse electron transfer
has reached the diffusion limit, and the forward rate is determined by this
value and the overall equiiibriunl cuostant.
The sylnmetry of t he graph requires that !he point of intersection of the two
diffusion lines (extrapolated) be at the reduction potential of the substrate.
The analysis of more complicated examples of HRC mechanisn~s is discussed
in Reference 12.
An example of an HRC-type mechanism involves a ferroceae carboxylic acid
yi.0
I
I'otcntial ( V)
Figure 3- 16 Simulations ui HRC lor u s e 1 ( h ,[PI x I,), illurtrat~ng the effect or a
L
change in the forward homogeneous electron transfer rat? constant. An excess facior
r ( 3 : 1 ) = l O . k , = 1 ~ . 2 . 5 ~ 1 0 ~ , d n d I O ~ M- ~ s - ~ .
!
{FEH) mediated rednetion of glucose oxidase (GO)." The mechanisn~ is
: expressed as follows:
I ki
I
GO,,, + 2 FEH+ = Gnu, + I FFH
r k..
GO,, f glucose -+ GO,,, + gluconate
: and is shown schemotieallyin Figure 3- 18 Tlre cyc11c voltammograms for the
I
P
r : I
Dffusion Activahon
\ - cou,,,
\ Diffusion
I
EO
Figure 3-17 The measured rate constant k , versus dr~ving force for the ARC scheme.
I
GO(red)
-2e-
/
C/
,'
J'
A, 2FeH' " * GO(ox) ++
/'
Gluconate
/'
/'
/'
Figure 318 A two-electron HRC schrtns: the fzrrircrm carboxylic acid catalyzed
reduction of glucose oxidse.
FEH alone and in the presence of glucose oxidase and glucosc are shown in
Figure 3-19. In this case GO was in large excess and the catalytic action was
cvntrolled by the homogeneous redox reaction. A simulation study using the full
description of a second-order reaction and actual diffusion coefficients resulted
in the determination of the rate constant for clectron transfer between FEH and
GO, k = 1.06 x I05LM-'s-'. The values obtained were further verified by
examining the scan rate dependence of the results (Figure 3-20).
In a more recent study, the mediating electron transfer reactions of glucose
oxidase have been reexamined in great detail using simulation methods. Several
outstandmg problerns wcre rcsolved regarding the pH dependence of the
Figure 3-19 CVs of ferrowne carbnxlyjc acid done (solid line) and din the presence or
glucose oxi da~c and gl uc~se (dottcd line). [Adapted from Reference 13.)
Figure 3-20 Working curve based on a simulation analysis of t he GO catalys~s. Tllr
simulations took account of the large difference in diffusion coeficients betweer1 fcrroacr~c.
carboxyhc acid and GO. (Adapted from Reference 14.)
reaction, and the mistaken assumption that the homogeneous redox reaction
obtains pseudo first conditions.14
3.5 The Reduction of Nitrobenzoic Acid
A study that coill bjned cyclic voltammet ry with a time-resolved, surface-
enhanced Rarnan spectroscopy ISERS) examination of the electroreduction of p-
nitrclbenzoic acid (PNBA) provided a more complete description of this complex
me~hani srn. ' ~ The redactive cyclic voltammogram to - 1.4 V is shown in Figure
3-21 (pH = 1 I), for smooth and roughened Ag electrodes.15 The use of
roughened dectrvdes is necessary for the SERS experiment. While an ad-
sorption prepeak was indicated on the roughened electrodes, the overall cyclic
voltammetric responses for both electrodes wcre remarkably similar. In such
cases, adsorption equilibrium is probabIy obtained, and qualitative com-
parisons between SERS studies on roughened electrodes and CV studies on
smooth electrodes are possi bie.
In Figure 3-21, the first peak (A), occurring at about -0.65 V, could be
assigned to a four-electron reduction of p-nitrobenzoic acid to the correspond-
ing hydroxyamine:
The second cathodic peak (B), assigned to the further reduction of the
hydroxyamine to p-aminobetlzoic acid, is not considered in more detail here.
On the reverse scan, the anodic pzak ( C) is due to the oxidation of the p-
(hydroxyamino)benzoate to nitrosobenzoate, a two-elsctron process. Direct
observation of the nitrosobenzoate proveded by SERS performed during the CV
,
experiment provided strong evidence for this assignment (Figures 3-22).
CYCLIC: VOLTAMMETRY
Potential, V vs. SCE
Figure 3-21 CV of 511m M paranitrobenzoic acid {PNBA) on smooth Ag electrodes.
Aqueous solution, 0.1 M Na,SO,; scan rate, 50rnV/s. (Adapted from Reference 15.)
Figure %22 Sequenoe of SERS spectra on a roughened Ag electrode, identifying the
nitroso intermedialc in the electrode process. (Adapted from Reference 15.)
91
On the third half-cycle of the CV experiment, the couple to C is observed,
peak D. However the peak is smaller than peak C, particularly at $low scan
rates. This result indicates a following chemical reaction which is thought to be
the coupling of the nitrosobenzoate with the hydroxyamine.
A careful consideration of the charac?cristics of the CV experiments,
including the dependencies of the peak currents and potentials on scan rate,
resulted in the detailed mechanism shown in Figure 3-23, with the following
values for the mechanistic parameters:
NOH W H
Figure 3-23 Proposed scheme for the mechanism of reduct~on uf PNBA.
As has been discussed. 3e-/2H+ PToCeSSCS can be modeled as two-electron
processes with transfer cueficients equal to 0.5. Values for the reduction
potentials, heterogeneous rate parameters, and chemical rate constants were
obtaind from the best fit obtained between simulation and experiment, a
process that required more than 500 simulations. The value of k,,,, - , is a lower
bound. Figure 3.24 shows a sinlulation of the CV with the experimental data.
The variation of sunulated and observed peak potentials and currents with scan
rate, shown in Figure 3-15, are in good agreement.
In this case 14 parameters have been obtained from a visual fit of the
simulation to the data. It is important to note that different sections of the CV
waveshape are sensitive to different parameters. For instance, the first cathodic
peak (A) and its scan rate dependency is related to 7 parameters (the first two
reductions and a following chemical reaction rate), The position and shape of
peaks C and D are sensitive t o the second two reduction potentials and
heterogeneous parameters, while their relative size is determined by k,,,-,.
In general, the 7 parameters obtained from the single first peak are less
credible and serve to allow a fit to be obtained. However, much more confidence
can be placed in the individual parameters obtained from the second and third
half-cycles of the CV.
3.6 Reduction of the Nitrosoniurn Cation
and Its Complexes
Lee et al. studed the reduction of the nitrosonium cation (NOt BF, ) to nirric
oxide." The CV OC nitrosonium cation in acetonitrile is shown in Figure 3-26.
A nearly reversible reduction is observed, from which thermodynamic
(EO' = - 1.18) and kinetic parameters (kO = 0.005 crnls, a = 0.5) were obtained.
I
Pctentlal, V us. SCE
Figure S24 Simulated versus experimental data for the reduction of PNBA. (Adapted
from Ref erace 15.)
Figure 3-25 Working curves based on paramelera arrived at by a simulation analysis.
I (Adapted from Reference 15.)
E, V vs SCE
Figure S26 CVs of NO'BF; in acetonitrile at 0.3. 0.5, and 0.7 V/s. (Adapted from
Reference 16.)
CYCLIC VOLTAMMETRY
v vs SCE v us SCE
Figure 3-27
CVs or IOmMNO'BF; with (A) 2.0,
methylbenzent. at a scan rate of 0.5 V/s.
-
t 6 \ I 0s
y us SCE
(B) 5.0, and (C) lOmM hexa-
In the presence of beramethylbenzene [Ar] a second wave appeared and was
assigned to the reduction of the char9e transfer complex [NO,AB, and the
thermodynamics and kinetics of the formation of this complex could also be
determined. (see Figure 3-27 lor the experimental CVs and Figure 3-28 for
simulations). The entire mechanism could hc formulated as follows:
NO+ +e - %NO E?'
k,
NO+ + Ar(Me), e [NO', ArIMe)bl
k -,
[ NOf , Ar( Me) , ] +e~[ NO, Ar( Me) , l Eq'
volt8 volts
Figure 528 Simulations of (Hj and (C) of Figure 3-27. (Adapted from Reference 16.)
A SURVEY OF ELECTROCHEMICAL MECHANlSMS
3,7 Reactivity of 17-, 18-, and 19-Electron
Tungsten Complexes
The oxidation of tricarbony l(rncsi tyleneltungsten was examined by 1R spectro-
electrochemical, NMR. and CV e upz r i mz ~~t s ~~ This study probed the reactivity
of the odd-electron species generated by oxidizing the 18-electron starting
material. The oxidative CV in acelonitrile (TBAPF,) is shown in Figure 3-29. A
superficial examination of the CV might lcad one to conclude that this CV is the
result of a one-electron oxidation and that the resulting 17-electron species is
being reduced on the reverse sweep, with the peaks separated because of a slow
heterogeneous charge transfer. However, a more detailed examination shows
that this cannot be the case. In particular, CVs such as those in Figure 3-39
displayed the following characteristics:
1. The oxidative current (peak A) corresponds to a two-electron process at scan
rates up to at least 10V/s at 228 K.
2. Both the observed waves are irreversible at scan rates 11p to 10,0B)V/s.
3. Wl~cn the switchng potential is 1.1 V, the B/A pcak curren? ratio i s collstatlt
and equal to 0.5.
4. The B/A current ratio increases as the switchins potential is made morc
positive.
1 Simulation analysis showcd that a mechanism consistent with all these
; observations is one in which the initial one-electron oxidation of W is followed
5 by a fast addition of solvenl (S), a 1 Pelectron adduct, which is further oxidized,
Figure 3-19 Experimental and simulated CYs of the oxidation of 1 rnM trisarbonyl-
1
(rncsitylenc~tungaten (W) in acetonitrile at 298 K. (Adapted from Reference 14.)
resulting in an overall two-electron process. Peak B then corresponds to the
one-electron reduction of the diuatjon:
k1
W+ + Sews + K1 =- K , = I k , = i o 5 s - '
k -
WS2+ + e - g WS' E q' = 0.08 V
The dependence of the peak currcnt ratio (B/A) could be matched by simulation
only if the equilibrium constant for the adduct formation was approximate1 y
unity and the rate constant k, % 105s-'.
The oxidation of W in the presence of mdlimolar concentrations of P(OBU)~
is shown in Figure 3-30. Peak B, the reduction of W2+, i s seen to decrease,
particularly at low scan ratcs. The new peak, C, which occurs at morc negative
potentials, was assigned to the one-electron reduction WPM. Two routes are
available to produce WP2 +: the addition of P to W, followed by oxidation and
the exchange of P with S in WSZ+. Only when all these steps were included
could simulations nlin~ic the experimental results, including the scan rate
dependence or thc peak currents. The complete mechanism, in the presence of
1 0.5 0 5 -1 -1.5
w vs. AdAgCl
Figure 3-30 CVs of 1 rnM W in the presence of 3.7 m M P(ORu),lP) at 228 K. (Adaptcd
horn Reference 14.)
A SmVEY OF ELECTROCHEMICAL MECHANISMS
I
Figure 3-31 Simulations or the experimental CVs ill Figure 3-30. (Adapted from
Reference 14.)
, the ligand, involves he following additior~al steps:
W+ t P+ WP* K , = 10, k , = 2 x ioJ
M- I S- '
wP" + e & WP* E"' 2 - - -0.74V
WS" + p=WP2 ' + S K , = 1 0 , k 3 = S MI S-'
Simulations of lhc CV oCW with added phosphite ligand are shown in Figure
3-31.
3.8 Mechanisms Involving Adsorption
I t often happens that an electroactive species h:~s significant interaction with the
electrode surface. I n such cases, the possibility exists an adsorbed species will
undergo electron transfer processes (Figure 3-32). While few quantitative
mechanistic studies involving adsorkd species have been attempted with CV.
several common characteristics of the CV response for redox processes invojv-
ing adsorbed species are readily recognizable.
The CV response involving only adsorbed species is characterized by sym-
metric cathodic and anodic waveshapes. The relative positions of the two
CY CLlC VOLTAMMETRY
Figure 3-32 An eiectrochemical rncchanistt~ can include participation of an adsorbed
species.
depend on the relative adsorption energies, af the oxiiii~ed and reduced species
(Figure 3-33). The equation for the current volts2e is:
exp - IE - E")] n2F2vA rox [&I [$
where the reduction poren tials refer to the unadsorbed species and
r,, = surface coverage (mol/cm2)
h,, = exp( - AG:ds}
The peak curretlt and potential are:
Note that rather than the aquare root dependence found for the diffusion-
controlled response. here we have the peak current proportional to the scan rate.
A lug-log plot of peak currcnt versus scan rate will give a slope = 0.3 for
diffusion and 1 for adsorption. This is the primary quantitativc method by which
simple adsorption peaks are distinguished from diffusion peaks. To avoid
misleading results, however, care must be taken to subtract capacitive and
Faradajc background currents.
Adsorption peaks can occur along with diffusion peaks. The extent of overlap
is determined by the relative strength of adsorption of the oxidized and reduced
species. For strong interactions, adsorption pre- or postwaves can be clearly
la)
Potential ( V )
Potential ( V)
Figure 333 CVs in which both the oxidized and reduced forms,are strongly adsorbsd:
(a) AGor.rda = AGrrdads. Ib) *Goa, , h < AGdad, , and (c) AGma, > AC,,,,.
L.. .
distinguished, depending on the relative strength of the interactions.la However,
diffusion and adsorption peaks may be overlapped and difficult to distinguish. A
superficial analysis may result in the adsorption component being overlooked.
Quantitative treatments of adsorption require a knowledge of the adsorption
isotherm, which may be potential dependent."
An electrochemical study of the mechanism of action of the naturally
occurjng antimalarial artemisinin, shown in (Figure 3-34a) illustrates how a
cyclic voltammetric diagran~ of a process involving adsorption was useful in
developing an understanding of a pharmacological mechanism."
Isolated in 1971, artemisinin has recently been widely used in Asia for the
treatment of malaria. I t has been suggested that intraparasitic hemin (Figure
3-34b) mediates the antimalarial activity of artemisinin. Malaria parasites
contain precipitated hemin, known as hemozoin. In vivo, a reaction between
hemin and artemisinin appears to generate free radicals, some of which appear
to alkylate hemin."
It is reasonable to suggest that hemin is involved in a reductive decom-
position of arternisinin, in analogy with known action of hemin on inorganic
peroxide. To test this idea, Zhang et al.19 examined the cyclic valtrzmmetric
responses of hemin and artemisinin separately and in the same solution. The
results supported the earlier models for the action of artemisinin and showed
that electron transfer is a viable mechanism Tor the interaction of hzmin and
artemisinin.
Artemisinin shows an irreversible, diffusi on-controlled reduction peak at
around -1 V at moderate scan rates (Figure 3-35) The cathodic transfer
coefficient, determined with Equation 2.5. is x .-- 0.35, indicating substantial
structural change upon reduction. This structural change is most likely the
cleavage of the U bond.
Hemin has an quasi-reversible reduction at -0.38V, resulting Cram the
reduction of an adsorbed species (Figure 3-36). The log-log plot of current
versus scan rate has unit slope (Figure 3-37).
Figure 134 (a) Artemisinin and (M hemin.
-10 --
-0.3 - 0 6 -0.9 -1. 2 - 1 j
Potential I V)
Figure 3-35 CV or 5 rnM concentration of artemisinin at 0.3 V/s.
When artemisj~lin is in thc presence of hemin concentrations abovc 0.01 mM.
the - 1 V arternisj~lin peak disappears completely and a new peak appears at
around -0.45 V (Figure 3-38]. This peak can be interpreted as resulting from the
catalytic reduction of artemisitlit1 mediated by the adsorbed hemin. The
mechanism is sketched in Figure 3-39. Presumably, the coordination of the iron
to the dioxygen acts as a kind of ir~ner sphere (conduit for reduction of
artemisinin.* I n the abscnce of the Fe, tlie reduction is extremely slow and takes
Poteritial ( V)
Figure 3-36 The reversible reduction of adsorbed hemin, 0.3 V/s.
* Iron compounds have long k n known to function as catalysts for hydrogen peroxide
decnmpo~ition.'~
1
CYCLIC VOLTAMMETRY
Log of Scan Rate in V/Sec
Figure 3 3 7 Test for adsorption: a log-log plot of the peak current versus swn rate lor
the reduction ol hemin is linear with a slope of 1.
place by an outer sphere electron transfer between the carbon electrode and Ihe
artemisinin.
The hcmin-mediated decomposition of artemisin in vivo can be understood
to take place via an inner sphere similar to that suggested by the CV results. In
the case of the CV exweriments, the electrode is the source of electrons, whereas - . - -- - - . . - .
the participation of thiols such as glutathione as electron donors is suspected jn
the physiological reacfion. The slow, outer sphere, reduction in the abance d
-.exposed" Fe also explains the low toxicity of artemisinin.
Poten0;rl I V )
Figure 3-38 The CV of I mM artemisinin and 0.W6mM hemin. 0.3 V/S.
Figure 3-39 The catalytic reduction of artemisinin mediated by adsorbed hemin.
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6. Chambers, J. Q. In The Chemistry uf thc Quinoid Compnunds; Val. 2: Patai, 3.. Rappoprt, Z.,
Eds., John Wiley & Sons: New York, 1988, pp. 719-756.
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7. Saveant,J. M. Acc. Chem. Rt7.r. IW, 13, 323.
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8. Astruc, D. Anqew. Chem., Int. Ed. E~rgl . 1988, 27, 643.
9. Channon, M.; Tobe, M. L. Ange~. . Chn~r.. I v ; . Ed. Engl. 1981, d l , 1 -86.
i
10. Gosser, D. K.,, Jr.; Rieger, P. H. .Jriul. Chrrrl. 1 9 s . 60. 1159.
I
11. Hershberger, J. W.; Klinger, R. J.; knchi. .I. K. J . Am. Clrrm .Yvc. 19W, 105. 71.
12. Andrieux, C. P.; Hapiot, P.; Savdani, J. M. ChtPnr. R ~ T . 1990. 90, 723.
13. Rusling. J. F.; Ito, K. Anul. Chim. Acru 1991.2.72. 23.
1
14. Bourdillon, C.; Dernaile, C.; Moiroux. J.: Snvbnt, J. M. J. Amer. Chem. Soc. 1W3, 115, 2.
15. Chi, C.; Zhang, W.; Birke, R. L.; Gosser, D K.. Jr.: Lombardi, J. R. J . Phyr Chrm. 1991, Q5,
F
6276.
I
16. k K. Y.; Kuch~nka, D. I. Kochi, J 1;. I m g Chin 1% 29,4196.
17. Zhang Y.; Gasser, D. K., Jr.; Rieger, P H , Swiegart, D. A. J . Am. Chem. Sot. 1991,113,4062
I
; 18. Bard, A. J.; Faulkner, L. R. Elecrroclrt~miral Merhdt , 151 ed. John Wiley & Sons: New York,
i 1980.
e
1. 19. Zhang, F.; Gosser, D. K, Jr.; Meshnick, S. R. Bio. Pharm. 1992.
1 20 ~ d n i c k ? S- R+;
A; R ~ W A.; X& c M.; Pan, n. Z. M d B i mh n Pormifo,. Im, 49,
C 181.
CHAPTER
The Simulation of
Electrochemical Experiments
There are many different approaches to solving the mathematical equations that
dcscribe electrochen~ici~l experiments. Because electrochemical mechanisms that
involve coupled chemical reactions can be quite complicated and varied, our
primary requirement 1.; that the method of solution be general. The method of
simulation by explicit finite differences (EFD)' lends itself to a quite general
i
trea~rnent.~ The EFD method can also be optimized to improve computational
speed without compromising its generality. The straightforward manner in
:
which the physical problem is translated into a numerical method also makes
the EFD method attractive to study. More detailed treatments than that
presented here can be found in the chapter by Maloy3 and the book by Britz?
1
' 1.1 The Discretized Di fi ri nn Equation
;
I
r
!
Figure 4-1 shows a generalized electrochemical experiment that includes
diffusion of compounds in solution, reduction or oxidation at the electrode, and
! chemical reactions in solution. Although adsorption processes can be included
1 in the framework of a simulation analysis, they are not considered here.
\ The fclllowing partial differential equation describes what is going on in
i solution:
CYCLIC VOLTAMMETRY
mur *-/ - ox,",,
~ e d -- Products
Re$,,.
k .-. Red,
Butler -Volmer DIffuslon Chemical Reaction
i?,quation ac/at=~a'c/ag ac/ at NRl
Figure 4 1 Model for the electrode process includes diffusion (Fick's laws), electrode
kinetics (the Butler-Volmer equation), and chemical reaction kinetics.
where
C, = concentration of s p e c k q
r = time
x = distance
kg = chemical rate constant for the nth solution chemical reaction C, ,,
(.,, = concentrations for the first and second species for the nth solution
chemical reaction rate expression
This is Fick's second law modified by a term to account for a generalized set
of first- and/or second-order chemical reactions. Because of the symmetry oft he
situation, we need consider urily drffusion that is normal to the electrode.
Near the electrode the concentrations will be determined in part by the
potential of the elect rode (through the Butler-Volmer equation). At a distance
beyond the diffusivn layer. the concentrations will he at bulk values. These are
the boundary conditions for Equation (1).
The Fjck's law part of Equalion ( 1 ) can be coriverted to hscrete form through
an application of Taylor serics apyrtlxi~nations of a function around a point.
The "forward" and "backward" series are given in Equations (2) and (3)
respectively.
Adding the two series, and regarding the variables y and z as concentration
and distance, respectivsly. we iirrive at:
a2C D[ Ci - , - 2 Ci + C, + t ]
- 5
-
axZ AX^
(4)
THE SIMULATION OF ELECTROCHEMICAL EXPEIUMENTS
107
Ths is the discrete version of the right-hand side of Fick's second law, where i i s
an index that keeps track of spatial points.
Considering only the first two terms of the forward series. and regarding the
variables y and z as concentration and time (and introducing the time index j).
we have:
the left-hand side of Fick's law.
Equations (4) and ( 5) can be rearranged to give the discrete version of Fick's
law:
where the concentration in the nest tune elzmetlt is giveti by the preceding
concentration and its neighbors.
Equation (6) is the framework of an explicit finite difference it-~ulation. The
e~ectrochemical experiment can be descrikd by a discrete time (of the cxperi-
ment) and space (distance from the electrode) grid (Figure 4-2), where t = 0 at
the beginning of the experiment and x = 0 at the electrode surface. If the
concentration of every species is known for every space and time grid point, then
the experiment is completely described. A point on the grid represents the
concentration for an entire volume element, the boundaries of whch are the
'
midpoints between the grid points.
i
Equation (6) can be said to describe the exchange of concentrations between
f
Figwe 4 2 The time (or experime~~t) and space {distance horn electrode surf=) grid
that is defined by the explicit finite diierence approach.
L
-. - . . . ----*--- ,,
neighboring volume elements. We can take a closer Look at how the space and
time grid i s related to the discretizd diffusion equation. In any one time
increment dt, diffusion propagates only to neighboring volume elements. This
brings in a constraint to Equation (6). that is:
The e x ~ r i mc o t takes place over a lotal time t,,, so that the value of 6t will
depend on the nur nbr of time increments nt:
For a
value of D, if nt is chosen, then Sx is fixed by the constraint of
equation (7).
In addition, t,, fixes the total size X of the space grid. A safe estimate to
include the entire-diffusion layer is:
X = qDi*xp)1/2
(about 4 Gmes thc mean square diffusion length).
Then the nurnkr of spatial elements ns is:
4.2 Evaluation of the Boundary CondiLiurm
Consider the spatial cells near thc electrode (Figure 4-3). The distance between
the center of the first spatial element (the first grid point) and the surface of the
electrode is fdx. The current flux, J = -f/nFA, is determined by the concen-
1 -3 A d ~ r look at the space gnd near the surface of the electrode.
-
--.
THE SIMULATION OF ELECTROCHEMICAL EXPEWENTS
109
tration gradients of the oxidized and reduced spenes by the Butler-Volmer
equation:
where the heterogeneous rate constants k are in centimeters per second. It is also
true that J, , = -J, , ,
Solving equations (1 1) and (12) for C,, and C,,, and substituting these values
into the heterogeneous rate equation results in the following expression for the
flux:
where the rate constants are given by:
from the Butler-Volmer equat ton.
This approach can k extended to two or more consscutive electron transfers.
The flux cxprcssion can be incorporated into an expression similar to
Equation (6). The flux (mol cmL2 s-l ) is converted to a concentration change by
multipiying through by the appropriate dimensional factors:
4.3 Dimensionless Units
The use of dimensionless units simplifies the construction of programs for
simulation. All the variables we have discussed can be made dimensionless by
normalizing them t o a standard value. For instance (denotitlg the dimensior~less
unit with a double dagger), we can write:
I10 CYCLIC VOLTAhfMETRY
where dx a d 6t are the time and space illcrerncnts of the simnlat,inn, C, is a
chosen normalizing concentration (typically the co~~centratinn of the principal
electroactive species), and 0, is a chosen normalizing diffusion coefficient.
The heterogeneous rate constant I S converted to dimensionless form hy
multiplying through by the appropriate simulation units.
The equation for diffusiol~ from the first spatial cell:
is written in dimensionless units as follows.
I f al l caIcdations are made in dimensionless units, how would one get back to
real units? With dimensional analysis. it can be swn that:
where J is needed in units of r n ~l c m- ~s - ' and C, is r nol / ~m- ~.
FinaIly flit current (A) is i = FA.1
4.4 Solution Chemical Kinetics
Homogeneous chemical kinetics can be treated in a number of ways in the
context of si mul a~i on. ~ Thc simplest way is to use a simple differential
approximation. For instance, the change in concentrati~n due to first-order
chemical kinetics, A 3 B, can be calculated as follows:
sc = - kf[C,]dt (25)
This approximation will be accurate for kdt i 0.1. This means that for large k,
we will be f o r d to use a small 6t and thus many time increments.
4.5 A Sample Simulatiun Program
A recipe for a Pascal program that will sinlulate cyclic voltammograms based on
the previous discussion is listed here.
Prwram Asimulation:
THE SIMULATION OF ELECTROCHEMICAL EXPERIhlENTS
111
Rocedure input.
{Input all the initial conditions, experimental parameters, a d electrochemical mechanisms.
Convert to dimensionless units when appropriate.)
Procedure Electrude,
{Calculare the flux due to electron rrander at the electrode, according to the Butkt-Vdrner
equation. Output the simulated current potential To a data file.)
Procedure DiRusron;
{Calculate the drffusion of each specles according to the discrete version of Fick's law. Modlfy
concentrations In each spatial element.)
Procedure Reaction;
[Calculate the extent of reamion for all species and modify accordrngly rhe concentrarrons
calculated earlier in the diffusion procedure.)
Main P?ogram
Begin
Input;
For I = 1 to nr do
Beg~n
E kctrode:
D~ffusion;
Reaction,
end;
End.
I, '-
I-,'
A program in Turbo Pascal to simulate a cyclic voltammogram for an EC
mechanism follows.
i Program C'J;
(A program t o illustrate simulation by expllcit fin~te differences-Simulates an EC mechan~sm)
'
(SN + ) {enables math c~processor)
Uses Crt;
nl, ns, k. a, b. r, s: longint;
Pol, ipot. spot, ipot. T, X: extended
delx. delp, delt, E, smnr, area .extended:
Current, khet, kf, kr, kchem :extended:
I C: arrayrl . .3,1 . .ZOO] of extended;
Ctemp: arrayrl . 3.1 . . 2001 of exrended;
J. array[l . . 3] of extended;
outfile : text;
Procedure Setup;
begin
write ('What 1s 1l1e reducliurl pulrrllial ill volts 7 :');
readln (E);
writein;
write { ' WM is the hefwwneous rate constant T ) ,
i
readln(khet); . ., . ,
wrifeln:
... . . . writelnl:
writeln;
write ('What i s the k (sec -1) of the following reaction ? :');
readln (kchsm);
writeln;
write {'What is the initial potential ? :'):
readln(ipo1):
writeln;
write ('What is the switching potential ? :');
readln (spot);
writeln;
writeln ('final potential = initial potent~al');
fpot : = ipof;
writeln;
write ('What is the scan rate ? :'I;
readln (scanr);
T - :2 abs(spot-inpot)/scanc (time of experiment)
X = 2 - sqrt(1 E-5 T); {assuming D = 1 E-51
nt : = 150, {A default number of time increments]
area : = 0.01 ;
delt : = T/nt;
if kc hen > 1 00 then
begin
dell . = 0,3/kchem:
nt : = trunc(T1delt);
end:
kchem : = kchem . delt: {make it dimensionless]
delx : = sqrt(1 E- 5 delt/0.45):
ns : = tiunc (X/delx).
khet : = khet deltldelx;
For a := 1 to ns + I do
Ctemp[l ,a] : = 1.00;
Ctemp [2.a] : = 0.00;
Ctemp[3,a] : = 0.00;
end;
for a : = 1 t 0 3 d 0
begin
j[a] := 0.0
end;
Delp := 2 (spot - ivot)/nt;
pot := ipot + delp;
THE SMULATION OF ELECTROCHEMICAL EXPERIMENTS
assign (outfile.'data.pas'):
rewrite (outfile);
end; {end of procedure setup)
Procedure Electrode;
Begin
kf := khet - exp ( - 19.46*(pot-E));
kr : = khet exp (1 9.46=(pot-E)):
Current : = J [I ] (delxldelt) . 96484 . 1 E-6 . area: {This is i/Area)
writeln(outf1le,pot~9:5,~ '.current: 1 2);
end: {end of procedure Electrode;
Procedure Diffus~on;
Beg~n
Fork: = 1 t o3do
begin
Ctemp[k.l! . = C[k.l ] + 0.45. (C[k,2] - C[k,l 1) - J [k];
For b := 2 tons do
Ctemp[k,b] := C[k.b] + 0.45 - (C[k,b-I] - 2.0
C[k.b1 +C[ kb+l ] );
end;
end;
end: {end of procdure Diffusionj
Procedure Chemreact;
If kchem > 0.00 then
begin
Fork := 1 to nsdo
begin
end;
end;
end; {end of procedure Chemreact]
begin
Writeln('CV Simulation of EC Mechanism');
writeln;
CYCLIC VOLTAMMETRY
setup:
begin
begin
for r : = 1 to ns do
begin
end;
end:
electrode:
diffusion:
chernreact;
if a -r nt12 then pot := got + delp;
if a > = nt12 then pot : = pot - delp;
end;
close(outfile);
writeln;
writeln('DATA FILE IN DATA.PAS');
writeln('H1T RETURN TO EXIT');
readln;
end.
References
1. Feldberg. S. W. A Generul Meihodl;,r Simulation, Vol. 3 in ~le&roanal~tical Chemistry Series.
Maml Dekkec New York, 1969.
2. Gosser, D. K.. Jr. ; Rieger, P. H. Aml . Chem. 1988,611, 1 159- 1 167.
3. Maloy, J . T. In Lnhorarury Techniques i n Electroanulyticnl Chemistry, 1st HI.; Kissenger, P. T.;
Heineman, W. R.. Eds Marcel Dekker: New York, 1984, pp. 417-461.
4. Brilz. D. Digitdl Sinitllutiurr i. Eluctruchrmistry. 2nd ed. Springer-Verlag: Berlin, 1988.
CHAPTER
5
CVSIM: A General Program
for the Simulation of
Cyclic Voltammetry
- -
Experiments
5.1 An Overview of CVSIM
Computer simulation by the explicit finite difference method has proven to be a
powerful tool for the analysis of cyclic voItammetric experiments. The shape of a
cyclic voltammetric curve reflects both electron transfer at the electrode and
solution chemical reactions that are coupled to the electron transfer. Thus,
through a cyclic voltammetric study, one can often deduce a great deal of
information regarding the electrode processes and chemical reactions in
solution that are initiated by electron transfer at the electrode. Simulations are
often helpful in the preliminary stages of a cyclic voltammetric study, assisting in
I predicting what possible mecbanism(s) can give rise to the cyclic voltnm-
mograms one observes. Once a particular mechanism has been decided on, rnte
and equilibrjum parameters of the chosen mechanism cat1 he extracted by
1
comparing expenmental results with successive simu1ations. Much attention has
been focused on ~mproving the explicit fimte d~fference method outlined in
Chapter 4. Notable advances have been t he description of an expanding space
grid to save computation t~me. the inclusion of the mutually interrelated effects
,
of IR drop and capacitive current,' and the development of general methods to
treat solution chemical reactions in the context of the explicit finite difference
method.'
This chapter describes the structure and use of the computer program
i
CVSIM.3 This general-purpose simulation program can simulate the CV
$
response or a great variety of electrode mechanisms. Also described is a graphics
I /
L - -_ 1- --
3 16 CYCLIC VOLTAMMETRY
program CVGRAF, for the visual comparison of two data sets (i.e., experimental
and simulated).
The executable codes for CVSIM and CVGRAF are included on a diskette
with this hook. Hardware required is a PC-compatible (80x86) computer. A
math coprocessor will speed up the calculations considerably. Chapter 6
describes another program, CVFIT, which incorporates a madified version of
CVSIM for the least-squares analysis of zxperu~~etitnl CV data. Finally, the
appendix describes DSTEP, a general program for the simulation of double
potential step experiments.
CVSIM is a PC-based program that enables the experimentalist to simulate
the CV for nearly any desired mechanism and to compare the result with
experiment. The desired mechanism is built up in a simple manner with a full
screen display, and there are options for varying the dflusion coefficients of
individual species.
The value of such an approach lies in the elimination of the need to solve by
analytiml or numerical means the partial differential equation I hat models each
new rrlechar~isrn. Thus, more timc i s available or the consideration of prnblems
of a chemical nature, and a large amount OF repetitious work is avoided. In
addition, by taking advantage of the irlcreasirig computational power OP
personal computers, a generalized program can be an accessible toot for thc
mechanistic analysis of cyclic voltammograrns.
Together, the programs CVSIM, CVFIT, and CVGRAF can be used for the
efficient analysis of CV and DPS data. The programs incorporate the following
qualities.
1. Mechariislic gener.a/ify. The program CVSIM mesa modular structure with a
general solution of the homogeneous chemical kinetics. This means that the
user can simulate virtually any electrochemical mechanism that crtn be
formulated as a combination of electron transfers at the electrode and
homogeneous chemical reactions. Diffusion coefficients for each species can
be specified.
2. Speed of computation. An expanhng space grid is used to minimize
computation time. In addition, the program is written in Turbo Pascal 6.0,
which can take advantage of the math coprocessors commonly used in
personal computers.
3. Ease d u e . A Cull screen display for input of mechanistic and experiaentai
parameters with options for corrections and changes is utilized. The para-
Ineters are entercd for thc most part in common experimental usage. not in
dimensionless units. A graphic analysis program is provided for on-screen
viewing of simulated or experimental files. Input is -error corrected"; that is, if
a "fatal" error is made in the input (such as entry of an real instead of an
integer), the program will re-request the information.
4. Inclusion of nonideul factors. The effects of 1R drop and capacitive current can
be incorporated in the simulation.
5 . Quanrlratiw cumpurison oJexpt~ri me~~ral and simulated dc~tir. A simplex routine
is used to optimize the fit between experimental and simulated cyclic
CVSIM: SIMULATING CYCr.IC VCI7.TAMMETRY EXFERMENTS
117
voltammograms (CVFIT). Experimental and simulated results can be
quickly compared visually (CVGR AF).
5.2 Extensions of the Simulation Method
The partial diflerential equation for linear diffusion and solution chemical
kinetics is:
The solution of this equation in terms of the EFD method wai described in
Chapter 4.
A discrete form of the diffusion term on the right-hand side of Equation
(1) is
where i i s spatial subscript and j is a time subscript.
Equation (2) is equivalent to the creation of a space and time grid (see Figure
4-2). Computation time can be decreased by utilizing an expanding space grid or
an expanding space-time grid. In this work, an expanding spatial grid was
utilized: an expanding time grid can cause inaccurate calculations of the solution
chemical kmetics.
The expanding grid was constructed such that the spatial increment doubles
111 size every fourth grid point. Near ihe electrode the wnc.t?ntrarions will be
determined by the potential (i.e., through the equations of electrochemical
kinetics) and diffusion, and at "infinite" &stance the concentrations will be the
same as the initial conditions. These facts constitute the boundary cnndition~ for
Equation (I). The Aux at the electrode was calculated according to the method
.
descritd in Chapter 4, which takes into account the flux of species at the surface
:
of the electrode due to both the heterogeneous kinetics (as described by the
Butler- Volmer equalion) and diffusion. The potential E In the Butler- Volrner
equation can be corrected far I R drop in a number of ways. Following the
method of Evans et a].,' the IR term is inclu&d by reading an experimental
current file and using a meissored tor estimated) resistance to calculate IR.
The capacitive cument is also calculated as in Reference f , using the I R drop
corrected potential in calculating the capacitive charging current at each time
step in the simulation.
~l t hough diffusion and chemical reaction arc concurrent p r w c s in the
explicit finite difference methad, they are calculated separately. This procedure,
118
CYCLlC VOLTAMMETRY
which is valid if the time increments are small enough, leads to the possibility of
cry general treatments of the chemical kinetic term in Equation (2). Simple
numerical methods such as an iterative modified Euler method can be used to
provide general solutions for the differential equations that model chemical
kinetics. Thus, a simple algorithm based on the following equation provides a
general solution chemical reaction kinetics:
where the changes in concentrations are obtained from a differential approxi-
mation for the kinetics using the initial concentration. For example, for the
kirletic scheme
the ~ t h concentrations for A and B are calculated as follows:
The inclusion of ali the features described above in a general program for the
simulation of cyciic voltammetric experiments is a matter of program structure.
In general, the solution of this problem involves assigning index numbers to
each species in the mechanism, to each electrode reaction, and to each solution
chemical reaction. The use of program loops to include all reactions for all
species is then implemented within the usual scheme for simulation by explicit
finite differences. This is illustrated by the following skeleton code of the Pascal
program.
VARIABLE DECLARATIONS {DECLARE ALL VARIABLES)
PROCEDURE SETUP
BEGlN
READ THE FOLLOWING INPUT INFORMATION
1. NUMBER OF SPEClES (NSPEC) AND CONCENTRATIONS OF EACH
2. NUMBER OF ELECTRODE COUPLES {NCOUPJ. AND THERMODYNAMIC AND
KINETIC PARAMETERS FOR EACH COUPLE
3. NUMBER OF CHEMICAL REACTIONS {NREACT) AND FORWARD AND
REVERSE RATE CONSTANTS FOR EACH REACTION
4. EXPERIMENTAL PARAMETERS {SCAN RANGES AND SCAN RATE]
CALCULATE: FROM MAXI MUM CHEMICAL RATE CONSTANT AND
EXPERIMENTAL PARAMETERS THE NUMBER OF TlME
INCREMENTS {NT] AND NUMBER OF SPACE INCREMENTS (MS)
CVSIM: sTMULATING' CYCLIC VOLTAWETRY EXPERIMENTS
OWI ON- CHANGE I . 2.3 OR 4 OR DEFAULT PARAMETERS
(TEMPERATURE OR DIFFUSION COEFFICIENT}
OPTION: READ PARAMETERS NECESSARY TO INCLUDE 1R DROP OR
CAPACITIVE CURRENT (RESISTANCE, AREA, AND CURRENT)
END
PROCEDURE ELECTRODE
BEGlN
FOR I = 1 TO NCOUP DO :LOOP OVER ELECTRODE COUPLES)
BEGIN
CALCULATE THE CURRENT FOR EACH ELECTRODE REACTION
END
OPTION, CALCULATE CAPACITIVE CURRENT
CALCULATE TOTAL CURRENT
OUTPUT POTENTIAL/CURRENT VALUES TO SCREEN AND 50 DATA FILES
END
PROCEDURE DIFFUSION
BEGlN
FOR I = 1 TO NSPEC DO {LOOP OVER SPECIES]
BEGIN
FOR I = J TO NS DO ;LOOP OVER SPATIAL INCREMENTS;
BEGIN
CALCULATE CONCENTRATION CHANGE DUE TO DIFFUSION
FOR SPECIES I
END
END
END
PROCf DURE CHEMREACT
BEGIN
1
FOR J = 1 TO NS DO (LOOP OVER SPATIAL INCREMENTS)
BEGlN
USE MODlFIED EULER METHOD TO CALCULATE CONCENTRATION
i CHANGES DUE TO SOLUTlON CHEMICAL REACTIONS.
END
: END
t
i m * * * - - * = * * * + * MAI N PROGRAM ==-====a*-=.*
k BEGIN
I
SETUP:
1
FOR I : = 1 TO NT {LOOP OVER Tl ME INCREMENTS)
INCREMENT THE ELECTRODE POTENT1AL ACCORDlNG TO SCAN RANGE, SCAN
RATE AND AS OPTION CURRENT AND RESISTANCE {IR DROP]
BEGlN
ELECTRODE;
DIFFUSION
CHEMREACT:
END;
WRITE OUT SIMULATION PARAMETERS TO DATA FILE
ANOTHER SIMULATION?
YES-GOT0 SETUP
NO (FINISH SIMULATION)
END.
120 CYCLIC: VULTAMMBTRY
5 3 Accuracy of Simulations
As discussed in Chapter 4, the number of space-time grid points (increments)
used in a simulation must be carefully considered. As with any numerical
procedure based on the construction of a grid, the mote grid points used, the
more accurate the results of the sunulation (assuming no roundoff errors).
However, the more grid points used, the longer the cornputation time. Thus, one
desires to find the least stringent criterion for number of grid points necessary to
result in accurate simulations. The Turbo Pascal variable type extended, used
throughout for all real numbers, has about 20 significant figures and a maximum
red number OF 1.1 x Errors due to roundoff error or linlitations of
magnitude do not commonly occur. Simulation of electrochemical experiments
by the finite difference method is a rather complicated numerical procedure: far
more than, say, the Runge-Kutta (R-K) method for solving ordinary dif-
ferential equations. In fact, the method (as presented here) is a coupling of the
finite difference method for solving the diffusion equation (using an expanding
spatial grid) with a second-order R-K method for solving homogeneous
chemical reaction equations. A formal error analysis has not been performed;
only ad hoc suggestions have been made. An approach taken by Feldberg, for
instance, suggests a criterion based on the size of the reaction layer4:
(For a first-order chemical reaction).
Fel dkrg has suggested that p = 56x; that is, the reaction layer should bc at
least 5 times the grid space size. In terms of the number of time increments, we
have:
and for f l = 0.45,
The number of time increments needed for a simulation then becomes
nt = time of experinlent x 50 x kc,,,.
However, our experience in using the program CVSl M is that the constraint:
nt = 4 x time of experiment x kc,,,
is sufficient to obtain desirable accuracy under most circumstances. The result is
a time savings of a little more than an order of magnitude. The reasons for this
particular constraint have been investigated in some detail,',' and it appears
that because of the complex, n~ul t i st e~ nature of the simulation, error estimates
cannot be ohtined by focusing on one asp& (i.e., the reaction layer).
CVSIM: SIMULATING CYCLIC VOLTAMMETRY EXPElUMENTS
121
Simulations of several mechanisms are shown t hat illust~atz the difference in
simulation time and the difference in the result when the two contrasting
constraints are used.
The simulation of an EC mechanism according to both the Feldberg criterion
and our criterion shows no visible difference (Figure 5-1). Indeed. the peak
currents d~ffer by less than 0.2%.
An ECE simulation is shown in Figure 5-2. Here again, there is nu sipnificanl
difference.
Finally, we consider a catalytic mechanism, where the electrode reactant is
regenerated by a second-order reaction (k = lob m - ' s- I), with a 20-[old excess
of the catalyst (Figure 5-3). This is considered to be a more severe test than the
others, because the reactant is generated at
the electrode surface. It is
important to relate the accuracy to the goals of the experiment. For instance,
this type of catalytic wave is usually used t o measure rate cot~stants by
comparing the diffusion wave (with only the substrate present) to the catalytic
wave. Invariably, this procedure itself is not accurate to more than a few
percent, and rate constants obtained ate usually reported to one or two
significant f i g~r es . ~ Tncidentally, as a consequence of the autocatalytic nature
of t he mechanism, pseudo-first-order conditions are not achieved until a large
excess of the ca~al ysi exists (200: 1).
: I
Potential (V)
Figure 5 1
Simulation or an EL' mechanism (R,,,, = 1000 s- ') with t k numhr or time
increments (NT) set to NT = 4 x time x k,,,, (c~rcles). and NT = 50 x time x kc,,,
(line).
CYCLIC VOLTAMMETRY
r
--I-
I
Potential (V)
Figure 5-2 Simulation OF an ECE mechanism, with the number of time iltcrenlenls set as
in Figure 5-1.
Figure 5-3 Simulation of a second-order catalytic reaction, with k,,,,, = 106M-'s
and 20-fold excess of reagent. Tune increments set as in Figure 5- 1.
CVSlM: SlMULATlNG CYCLIC VOLTAMMETRY EXPERIMENTS 123
Generally, highly accurate results for all mechanisms have been obtained
( ~ 0 . 5 % error). In any case, it is important to remember that the number or
time increments, which determines the accuracy, can be set b j the user. For any
new mechanism, a test simulation can be done using a more rigorous
constraint (use 10 times more time increments than the default) to check for
accuracy.
5.4 Installation and Use of CVSIM and CVGRAF
All the files on the diskette provided should be copied onto the bard disk to the
directory C:\SIMULATE. (First create the directory; then copy the files to the
directory.) All the programs should then be run from C:\SIMULATE.
CVSIM is initiated by typing CVSIM and hitting the enter key. The experiment
and the mechanism are described in response to a series of inquiries presented in
ii ti111 screen display.
Number of Species in the Mechanism
An integer equal to the total number of species in the mechanism is entered.
Although the screen input is designed for up to eight spccics, more can be
entered if necessary.*
I
I
i Concentrations of Each Species
The initial concentrativn of each species is entered in normalized units. That is,
the concentration oi each species is divided by a chosen narn~alizing concen-
;
tration (Cnorm), typicall) the species present with the highcst concentration
i (excluding of course the eleclrulyte). Each species is now associated with an
integer, in the order of entry. Su hsequent entries. which describe electrode
reactions and chemical react ions. utilize these number idznt ificatiotis.
i
Number and Description of Redox Couples
The number of redox couples in the mechanism is entered. Then the integer
index of the oxidized and reduced Forms of each redox couple are entered,
followed by the reduction potential ot each couple (in volts), I he heterogeneous
rate constant (cmjs), and the cathodic transfer coefficient a. For an electron
transfer that is considered to be reversible, a value of lOcm/s will ensure
reversibility under most circumstances. If a two-electron transfer (where one of
* If the enter key is accidentally fiit without first entering data, simply enter data on the next
line.
the redox species is shared by t wo couples) is among the electrode reactions,
these should be entered in sequence when written as sedudions. For instance:
l + e - - 2
2 + e - - 3
Solution Chemical Reactions
Each chemical reaction (first or second order) is described by entering two
indexes for the reactants and two for the products. (If the reaction is first order,
zero is entered in the space reserved for the second species of a second-order
reaction.) First-order rate constants are entered in reciprocal seconds. Second-
order rate constants are entered in units of M-' s-' *Cnorm.
Experimental Parameters
The number of half-cycles ( 1. 1 or 31, the initial potential. switching potential(s),
final potential (V) and scan rate (Vls) are entered. Asymmetric potential
waveforms, which are often useft~l, are possible in this schztne.
Changes in Input
At this point, the user can inspect the entire input screen and change selected
parameters. It is also possible to change the default temperature (298.1SK) or
the default diffusion coeficient for each species (1.00 x 10-5cm2/s). The
diffusion coefficients are changed by entering a multiplier of the default vduc
(e.g., enter 0.5 for a diffusion coefficient of 5.00 x l oz6 cm2/s). If it is desired to
simulate a mechanism with a diffusion coefficient larger than the default
coefficient, the default diffusion coefficient itself can be changed.
Nme s of Data and Record Files
The names of the simulated potential/current data file and file that saves the
entire simulation parameter set are requested. The current is output in amperes
and the potential in volts. This format is required of data sets to be graphed with
the CVGRAF program or to be used by the curve-fitting program CVFTT.
The Normalizing Concenim tion
The choice of normalizing concentration is entered in rnillimolar units (rnM).
Option for Capacitive Current
I f it is desired to include a capacitive current in the simulation, then the electrode
area (an2), double-layer capacitance (pF/cm2), and solution resistance (kQ)
must be entered.
CVSIM: SIMULATING CYCLIC VOLTAMMETRY EXPERIMENTS
125
Option for LR Drop
The effect of the 1R drop can be included as well. It i s necessary to provide an
experimental data file of current-potential values (1 point per millivolt) and to
enter the resistance and electrode area. The experimental current is read and the
simulation potentials are corrected accordingly.*
During the simulation, the potential-current values every f OOmV appear on
the screen. This provides a feeling for the time the simulation will take and aIso
serves as a guide to the progress of the simulation.
A simple graphics program for PC compatibles (CGA, VGA, and Hercules
graphics) is provided for the simultaneous examination of two data sets. It is
intended primarily for comparison of experimental and simulated data. The
input is quite simple: initial potential, final potential (V), current scale (pA), and
the names of the two data files are requested. Default values are provided. If only
one data file is to be examind, a blank file named tdata.pas should be created.
Movement of a crosshair cursor is controlled with the arrow keys, and
I
potential-current values are displayed at the top of the screen. A sample
, ,
CVGRAF display is shown in Figures 5-4.
I
5.5 Examples
Figures 5-5 through 5-1 1 show CVs that exhibit mechanisms discussed in
Chapters 2 and 3. Each figure is preceded by one or more exampIes that
illustrate thc use and capabilities of CVSIM.
Figure 5-4 Example of the CVGRAF graphic analysis program. Two data sets can b
superimposed (circles vs harsh for comparison.
I
c he format of the data fik is deshibed on page 138.
I
PoLential (")
Figure 5.5 Simulation of ferricyanide reduction.
!
i
-2
I
-1.0 -1.2 -1.4
-1.6
Fotential (V)
Figure 5-6 Simulation of the reduction of methylctrbalmin, a" EC
Cha~ter 6).
mechanism (see
Figure 5 8 NO; reduction, an EC mechanism.
-10 --
0 0 - U 4 -013 - I 2 - 1 6 - 2 U
Potctl l ~al ;L
Figure 19 SimuIat~on of a two-electron transfer (see Chapter 3).
Potential (V) 1
Figure 5-11
Example of slrnulation of
fast sweep voltammetric analysis or an
EC mrzhan~sm wi t h a fast lollowlng
reactidti.
EXAMPLE 1: Ferncyanide reduction.
r p
Number of Chemical Species: 2
Concentrations in normalized units:
1: 1-00 2: 0.00
Number of Electrode Reactions: 1
Ox + e- 9 Red E khet alpha
1 + e 9 2 0.253 0.044 0.5
1
Number of Chemical Reactions: 0
I
Number of half-cycles 1: 2
Initial potential : 0.5
Switching potential : 0.0
Final potential : 0.5
( Scan rate (v/s~L.) : 1.0
I Area of electrode (cm2) : 0.01
I Normalizing concentration (mM)
: 1
I
I IR option (YIN): N
I I
I Capacitive cllrrent (Y/N): N
I 1
1 Change # (Choose 0-8.0 = no change): 5
1
Enter normalized diffusion coefficients
1: 0.760 2: 0.630
I
I Change lnput or Default Value:
I (I ) Concentrations
(5) Diffusion coefficients ( = I )
( 2) Electrode reactions (6) Default diff. coeff. (D = 1 E - 5)
(3) Chemical reactions (7) Temperature (T = 298.1 5 )
(4) Exp. parameters (8) MT ( # of time increments)
I
. . A "1,
CVSM: SIMULATING CYCLIC VOLTAMMETRY EXPERIMENTS
129
EXAMPLE 2: Methylwbalaimin reduction (Chapter 6).
1 : 1 .oo 2: 0.00 3: 0.00
Ox + e- - Red E khet alpha
1 + e - 2 -1.529 0.012 0.78
RX1 + RX2 * PRt + PR2 k-forward k-reverse
2 + 0 - 3 + 0 580.0 0.0
Number of half-cycles ?: 2
Initial potential : -1.0
Switching potential : - 1.65
Final potential : -1.0
Scan rate (V/sec) : 0.300
Area of electrode (cm2) : 0.019
Normalizing concentration (mM) : 2.00
1 IR option (Y/N): N
I
1 Change # (Choose 1-8. 0 = no changes): 6
I
Enter the detault diffusion coefflc~ent
D = I .7E-6
I
Change l nput or Def aul t Vai u~s;
I
(1) Concentrations
(2) Electrode reactions
(6) Default diff. coeff. {D = 1 E-5)
(3) Chemical reactions
(7) Temperature (T = 298.1 5)
(4) Exp. parameters
( 8) NT I # of time increments)
I
EXAMPLE 3: CE mechanism (NO, oxidation).
7
Number of Chemicel Species: 3
Concentrations rn normalized units:
1: 1 .OO 2: 0.740 3: 0.00
Number of 8ect r ode Reactions: 1
Ox + e- * Red E khet alpha
1 + e - 2 1.32 0.03 0.48
RX1 + RX2 u PR1 + PR2 k-forward k-reverse
2 + 2 - 3 + 0 100.0 5.00
Initial porential 1: 1.10
Switching potential : 1.6
Final potential
: 1. 1
Scan rate ( Vl sec)
: 0.50
) Area of electrode (crn2) : 0.008
Normalir~ng concentratian (mMj : 1.6
1R aprion (Y/N): N
Capacitive current (Y/N): N
/ Change #f (Choose 1-8.0 = no changes): 6
I
1
Enter the default diffusion coefficient
I D = 1.8E-5
Change Input or Default Values:
(1 ) Concentrations
( 2) Electrode reactions
(6) Default diff. coeff. (D = 7 E-5)
(3) Chemical reactions (7) Temperature (T = 298.1 5)
(4) Exp, parameters
(8) NT ( # of time increments)
-
CVSIM: S M~ A T I N C CYCLIC VOLTAMMETRY EXPERIMENTS
131
EXAMPLE 4: NO; reduction.
r
Concentrztions b normalized units:
I : 1 .OO 2: 0.740 3; 0.00
Ox + e'c;. Red E khet alpha
1 + e s 2 1.32 0.03 0.48
Number of Chemical Reactions:
RX1 -t RX2 PRI I- PR2 k-forward k-reverse
2 + 2 - 3 + 0 120.0 2.50
Inilia1 potential . 1.60
Switching potential : 1 .I
Area of electrode (cm2) : 0.008
Norrnaliang concentration ( mM) : 2.0
IR option (Y/N): N
I
Change # (Choose 1-8,0 = no changes): 6
'I I
i
Enter the default diffusion coefficient
! D = 1.8E-5
I
(1) Conrentratians
(5) Diffusion coefficients ( = 1)
( 2) Electrode reactions (6) Default diff. coeff. (D = 1 E-5)
(4) EXP. parameters (81 NT ( # of time increments)
EXAMPLE 5: Two-electron transfer.
I
1: 1 .OO 2: 0.00 3 0.00
i
Ox + e - 9 Red E khet alpha
I
1 + e u 2 -1.421 0.50 0.5
2 + "-- - 3 - 1.403 0.0006 0.5
RX1 + R X 2 9 PRI + PR2 k-forward k-reverse
3 + 1 9 2 + 2 39.30 78.60
Final potential : -0.20
Scan rate (Vlsec) : 10.0
Area of electrode (cm2) : 1.8E-3
Normalizing concentration {mM) : f .3E-3
1 IR option (Y/N): N
I
( Capacitive current (YIN): N
I
Change # (Choose 1-8,0 = no changes): 6
D = 2E-5
Change # (Choose 1-8, 0 = no changes): 5
I
L
(1 ) Concentrations (5) Diffusion coefficients ( = 1 )
(2) Electrode reactions (6) Default diff. coeff. (0 = 1 E-5)
(3) Chemical reactions (7) Temperature (T = 298.1 5 )
(4) Exp. parameters (8) NT ( # of time increments)
CVSIM: SIMULATING CYCLIC VOLTAmETRY EXPERIMENTS
133
EXAMPLE 6: Protonations at equilibrium.
1
1: 1 .oo 2: 0.00 3: 0.00
Ox + e- - Red E khet alpha
1 + e 9 2 0.0980 503.0 0.5
2 + e- 9 3 0.5690 0.021 0.5
I
I
Initial potential : 0.700
Area of electrode (cmZ)
: 0.01
Normalizing concentration (mM) : 'I
I I R option (Y/NJ: N
I
I
I
1 Change # (Choose 1-8, 0 = no changes): 6
I
D = 5E-6
Change Input or Defaul t Values:
l ( 1) Concentrations (5) Diffusion coefhcients ( = 1)
(2) Electrode reactions (6) Default diff. coeH. (D = 1 E-5)
!
(3) Chemical reactions (7) Temperature (1 = 298.1 5)
(4) Exp. Parameters (8) NT ( # of time increments)
134 CYCWC VOLTAMMETRY
EXAMPLE 7: ETC mechanism.
-___ - _--
1: 0.330 2: 0.000 3: 1.000 4: 0.000
Ox -+ e- e Red E khet alpha
2 + e- - 1 0.190 0.048 0.50
4 + e- - 5 0.520 0.0230 0.50
RXZ + RX2 c7 PR1 -I- PR2 k-fonrvard k-reverse
2 + 3 G 4 4 0 39.000 0.000
4 + 1 - 2 + 5 1500.000 0.000
Number of half-cyclw 1: 2
Initial potential = 0.0000
Switching potential = 0.7000
Final potential = 0.0000
Scan rate = 0.8000
Area of electrode (cma) : 0.005
Normalizing concentration (mM) : 0-3
LR option ( YI N) : N
Chan~e # (Choose 1 -B.
= no changes): 7 T = 200
Change lnput or Default Values:
CVSIM: SIMULATING CYCLIC VOLTAMMETRY EXPERIMENTS
135
EXAMPLE 8: Fast sweep voltalnmetry.
Number of Chemical Species: 3 1
I
1: 1 .oo 2: 0.00 3: 0.00
I I
1 Or + e- o Red E khet alpha
1
1 + e s 2 -1.68 2.90 0.5
RX4 + RK2 + PR1 + PR2 k-forward k-reverse
2 + 0 a 3 + 0 8.OE+5 0.00
Number of half -cycles 7: 2
Switchirlg potential : - 2.0
F~nal potentiai : -1. 2
1 Scan rate (V/sec) : 2,28E+5
Area uf electrode (cmZ)
: 1. OE-2
Normalizing concentration ( mM) : 1
IR option (Y/N): N
Resistance (kohm : 1
Capacitive current {Y/N): Y
Double-layer capacitance ( f i F cm-2): 20
Resistance (kohm): 55
Change # (Choose 1-8, 0 = no changes): 6
D = 5E-6
I
1 Change lnput or Default Values:
1
1 (1 ) Concentrations
( 5) Diffusion coefficients ( = t )
(2) Electrode reactions (6) Default diff. coeff. (D = 1 E- 5 )
( 4) Exp. parameters 18) NT (# of time increments)
CYCLIC VOLTAMMETRY
References
1. Bowjrer, W. J.; Engelman, E. E.; Evans, D. H. J . Elcctrt.tt~nal. Chk,)~~. 1989, 241. 67.
2. Gosser. D. K.. Jr.. Rieger. P. H. Anal. Chum. 1988, 60, I 159.
3, Gomr. D. K.. Jr.: Zhang, F. Talanta 1991,38, 715.
4. Feldberg. S. W. J . Electruanal. Chem. 1W, 290, 49.
5. Britz. 0. Digital Sirnulotinn i n Eiedrochemistry, 2nd ed. Springer-Verlag: Derlin, 1981.
6. Andrieux, C. P.: Hapiot, P., Saveant, J. M. Chem. Reu. 1990, 90, 723.
CHAPTER
CVFIT: Si m~l ex Data
Analyisis w&h CVSIM
6.1 CVFIT: Simplex Data Analysis with CVSM
Simulation analysis of cyclic voltammograrns has typically been done by visual
comparison of experimental and simulated data. Many simulations are per-
formed, varying unknown parameters (reduction potentiab, rate constants, etc.),
untii a good visual fit is obtained. An alternative, more rigorous, approach is to
make a quantitative comparison of the entire cyclic voltammogram with t h a ~
predicted by theory.
The program CVFIT quantitatively compares cxpcrimental and simulated
data in a systematic manner.' It uses the Welder-Mead simplex algorit hm2 to
minimize the least-squares difference between the simulated and experimentnl
I
cyclic voltammograms. In prjnciplc, CVFTT permits the analyuis of any cyctic
I
; voltammogram that can be simulated with CVSTM. However, as with Any fitting
k
procedure, interpretation must be tempered with an understanding of the
i
method. The first requirement is the cullecrion of lugh quality data. Care *nust
be taken to avoid adsorption of electroactive species and to properly correct
background currents. Data analysis should be performed on independent data
sets to e nwe the reliability of the parameters obtained. In some cases the
computation time required will make the use of CVFIT impractical. However,
despite i t s limitations, data analysis with CVFIT can expand the horizons of
cyclic voltammetry.
This chapter provides instructions for the use of CVFIT, presents a prototype
i
analysis, and offers several suggestions regarding the analysis of cyclic
volt ammograms.
138
CYCLIC VOLTAMMETRY
6.2 Instru~tions for the use of CVFIT
6.2.1 Preparation of the Experimental Data File
The data file should be an ASCII file (with filename "data.pas") of potential (in
volts or millivolts) and current (in amps). Each voltage/current data point
should be separated by at least one space and should occupy one line.
Experiential notation is permissible. For example, Tor an initial potential of
0.000 V, a switching potential of -0.500V, and a final potential equal to 0.000 V,
the data file could Iook like the following.
Note that the potential starts at an jn~rement of 1 mV from the initihl
potential, and the last potential is exactly the final potential. Strictly adherence
to this form is necessary for the proper operation of CVFIT. The experimental
data fiks should follow the form of the simulated data files.
For comparison of experimental data wi th simulated data with the program
CVGRAF, the potential should be in units of volts.
6.2.2 Rudng the Program
The actual operation of CVFIT is quite similar to CVSIM, and the aspects that
are the same need not be repeated in detail. The mechanism is described and the
parameters entered as with CVSIM, except that each parameter must be
identified as a constant or as a parameter that will be optimized during the
fitting procedure. This is done by entering 0 or 1 when a parameter i s requested,
prior to entering thc parameter. Zero signifies that the parameter will remain
constant, and 1 signifies that the parameter will be optimized. The following
parameters must be identified iti this way: diffusion coefficients of individual
species. if different from the default value; reduction potentials, heterogeneous
rate constants and transfer coefficietlts, homogeneous rate constants, and
electrode area.
111 the program CVFlT a tolerance n~usl be stipulated. The tolerance is a
criterion fur ending t he fitting procedure. it is defined here as the largest
difference between the least-squares difference between any two simulations
based on t he Np -+ 1 parameter sets that are continually generated by the
simplex procedure (Np = the number of parameters to be fitted). The tolerance
is bnsed on the current data sets, which are in amperes. The tolerance required
for a reasonable fit is somewhat a matter of trial and error, and it depends on the
-. -. ,, , I ,.-.- _ .... _ . . .
- , .
CVFlT: SIMPLEX DATA ANALYSIS WITH WS[ M
l'otcntial ( V)
Figure 6 1
An example ul a fit (line) done on simutated data with added noise. The dat a
wcre originated from a simulation with E0 = -0.200V, ko = O.O2cm/s, 2 = 0.5, ;md
area = 0.1 cmZ. The fitted parameters were E0 = -0.1996 V, k0 = 0.02096cm/s, o: = 0.5.
and area = 0.0994cmz. The initial guesses were E = -0.25, k = 0.01, z = 0.3, and
area = 0.2. The four-parameter fit took I68 simplex iterations.
current scale of the experimental data. Typical values of tolerances range from
i E-8 to I E- 12. Finally, CVFIT asks for the total number of parameters to be fit.
The simplex procedure requires at least two parameters. In principle there is no
upper limit. However. a practical limit is about five or six.
A good way to bzcarne acquainted with CVFIT is to generate data with
CVSIM and fit the data with CVFIT. Such an example is shown in Figure 6-1,
where simulated data with noise added were fit for a reversible CV.*
6.3 A Prototype Analysis: The EC Mechanism
Reduction potentials are most commonly obtained by cyclic voltammetry for a
simple E mechanism. When a fast following chemical reaction occurs, no reverse
'
wave is observed and the peak potential and waveshape are both affectcd by
1 ,
both the heterogeneous and homogeneous rates. It is sometimes possible to
measure reduction potentials using fast scan rates. However, slow hctero-
I
geneous rate constants and growing distortions due to I R drop and capacitive
current work against this strategy. An alternative melhod is to combine double
,
potential step chronoamperometry with the CV simulation analysis. I n this way
a complete characterization of the EC mechanism is possib1ev3
1
The reduction of methylcobalamin is a typical EC mechanism in which an
electron transfer is foIIowed by a fast and irreversible chemical reaction.'' The
* See page 152 for more information on using CVFIT.
For a review of B,, electrochemistry see Reference 4. More m i work mn be found in
Referen= 5.
140 CYCLIC VOLTAbfmTRY
mechanism of the metbylcobalnmin reduction wus suggcstcd by Lexa and
Saveant using rapid sweep cyclic voltammetry in 1 : I ratio of DMF and 1 -
propanol.6 Based on these and other results, (7- lo), it appears that the chemical
reaction that follows reduction is a cobalt -carbon bond cleavage.
A working electrode that gives iacjle charge transfer is essential in the
characterization of thc electrochemical properties of a system by simulation and
fitting analysis. Methylcobalamin usually shows adsorption on common
electrode materials. After an exhaustive examination of electrode materials, it
was found that a silver amalgam electrode gives the best electrode response.
The proper solvent mixture also required some detailed consideration.
Methylcobalamin has limited solubility in DMF, which bas a higher freezing
point than methanol. On the other hand, methanol has a lower dielectric
constant than DMF, which causes higher resistance, particularly at Iow
temperatures. The optimum solvent mixture was 40: 60, DMFjmethanol.
The uncompensated resistance was analyzed by potential step chronoam-
perometry. The initial potential was set the same as the initial potential in cyclic
voltammetry experiments, and then a step of - 50 mV to the initial potential was
applied. The analysis of the RC decay curve was performed as described by He
and Faulkner" and in Chapter 2.
The rate coustant of the following chemical reaction was measured by doublc'
potential step cbronoamperometry. The double potential steps were carried out
with a time resolution 100 ps at a silver amalgam electrode with a diameter of
0.25 mm. The results were fitted to the theoretical curve developed by Schwarz
and Shain" and as discussed in Chapter 2. The first few points of data due to
double-layer charging current were ignored. The usable time window was
confim~zd by the Cottrell equation,13 where constancy of it1I2 was observed.
The catllodic current was fitted first within time 0 i t < z, where r is the period
of pulse applied. Then k,,,, was adjusted when thc parameters (n, A, C:, D,)
were kept constant within time z < t d 2.r until the anodic current could be
fitted by the double potential step relation for the EC mechanism. A general
experimental and fitting result is shown in Figure 6-Za, and Figure 6-2b gives the
detail, with the error range indicated. The results fall within 5-15% of an
average value.
Cyclic voltammogran~s (with background subtracted) at scan rates 50, 100,
and 300 mV/s are shown in Figure 6-3. These voltammograms are characterized
by a cathodic wave showing a well-defined current maximum but no anodic
wave on the reverse scan. The digital simulation and fitting results from the
CVFIT program are shown on the same voltammogcams. The input parameters
of the program included the diffusion coeficient Do, the number of electron
transfers n, the rate of the followin9 chemical reaction k,,,,, resistance R, and
experimental conditions. Then CVFlT gives an initial set OF guess paratneters
for the formal reduction potential EO', the heterogeneous charge transfer
constant kO, the charge transfer coefhcim~ a. and a proportionate cor~stant
(nominally the area) that includes small errors in concentration of methylcobu-
larnin, the electrode area, diffusion coefficients. and so on. The difFi~sion
coefficient used at -30C was measured by double potential step chrono-
CVFIT: SIMPLEX DATA ANALYSIS WITH CVSIM
Figure 6-2 Double potentiai step chronoamperometry experiment and htting result of
methylcobalarnin in mixed solvent (40% DMF, 60/, methanol) at - 301'C. Silver
amalgam electrode, 0.25 mm in diameter, methylcobalarnin = I I ~ M, TBAF = 0.30 M.
(a) Result fitted by kdcm = 5 9 0 s ' : solid points are experimental resulfr. (b) Detdil o l tho
fitting with error range, where the data close to noise background (at the end of the time
period) are ignord; open points are experimental results. Curve s wit11 = 590s- '. b
with 690s-', and c with 490sL'. (Adapted from Referenoe 3.)
amperametry in the time window ofconstancy i t 1I 2. The iR calcalntjon vption ul
I
CVFIT was utilized, which theoreticalfy corrects for iR drop effects on the CV
waveshipe.
The standard reduction potential, the heterogeneous rate constanr, and thc
transfer coefficient obtained from the CVFIT program are showll in Table 6-1.
For repetitive experiments, and for different scan rates, the fitted parameters
show only small variations. This is a good inlcation both that the mechanism is
correct and that the parameters obtained are meaningfd and not the result of
Iocal minima- Furthermqre, the reduction potential is consistent with that
measured under
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3

144 CYCLIC VOLTMMETRY
interesting to compare the reduction potential determined in this way to the
estimate obtained by assuming a reversible electron transfer (Equation 6,
Chapter 2). The difference is about 30mV at the lowest scan rate.
To estimate the EO' measurement error, which is caused by an error in the
measurement of the lolluwing chemical reaction k,,,,, a series of cyclic
voltammetry simulatjons was performed with different scan rate and k,,,,. It
was found that the deviation in k,,,, would not affect EO' measurement in our
electrochemical system. At a scan rate of 300mV/s, the peak potential shift is less
than 1 mV as k,,,, chatlgs from 490 s -' to 690 s-l; and the shift is 1 mV in the
same kchem change at a scan rate of 50 mV/s.
The rather large value of the cathodic transfer coefficient, a = 0.78, is
indicative of a transition state for electron transfer very close to the reactants.
This result supports t he proposed mechanism, where the transition state for
[BLJ reduction is expected to have the similar structure of the reactant B,,,.
Although the cyclic voltammograms appear to be irreversible, they should
not be. In the case of a totally irreversible system, we cannot expcct to determine
the reduction potential. To understand this apparent anon-laly more fully, a
study of the reversibility of the system was performed. The electrochemical
current corresponds to the difference between the rate of the forward electron
transfer kf [ B12J and its rate k,[B;,,] for the reverse process. The reversibility
factor f;12 for the methylcobalamin system is described as follows:
where [ El 2,]o and [B;2a], are the corresporthtlg concentrations on the
electrode surface. These concentrations can be obtained from thc digital
simulation for the first spatial grid ofthe system, where the concentration points
of the first several simulation grid points are extrapolated to the surface. Tllr
variation of the reversibility factor 1, as the function of the heterogeneous charge
transfer constant 1s shown in Figure 6-4. These reversibility factors are evaluated
at the peak potential of the first spatial grid in the digital simulation. The
simulations of the cyclic voltammetry for methylcobalamin at - 30C result in
reversibility factors f,. .- 0.18 at a scan rate of 300 mV/s and f, = 0.21 at 50 mVls.
Both factors are close to the root of the curve, but they are not completety
irreversible even tho ugh their cyclic voltammograms appear "irreversible."
For a totally irreversible system, a is given by
where E, is the peak potential and E,,, is the potential of half-peak. We expect
that E., obtained in this manner will be a reasonable value even though the
system 1s not totally irreversible. Kochi's results and the digital simulation data
also show the influence off, to asp, values by Equation (3). Tlre larger a,,, value
will have the smaller error if the system has similar irreversibility. Since a = 0.78
in this system, we expect a small error estimating a through relation (2) i f f , is in
the foot area of the curves shown in Figure 6-3a and b.
. - A , . . . .%., >, .., -. . . - .. . - _
I
CVFIT: SIMPLEX DATA ANALYSIS WITH CVSlM
Figure 6 4 The relationship of the rcversibiliry factor j; and the heterogeneous charge
transfer Constant kO. The concentrations of the electroactive species in the electrode
surface were evaluated a l the peaks or cyclic voltammogram by digital simulation with
E0 = - 1.529 V, 3 = 0.78. and Do = 1.8 x l O 6 mz/s at - 30C. The reversibility factor
fr wascdculrtcd through Eq~~a l ~o ~l ( I ). (a) 30OrnV/s, k,., = 590 s-l; (b) SOmV/s,
k c . . . = 5 9 0 s '; (c) 30On1Vls. kc... = 0 s '; and (d) SOmV/s, k c,em = 0 s ' . (Adapted
from Reference 3.)
I
The small error in potsntials used i n Equation (2) due to iR drop also results
in errors of a values. The potential was corrected for iR drop as suggested in
Chapter 2.
where i, is the peak current and i,,, is the half-wave-hdpht peak current. The
values of a,,,,,, from measurements in cyclic voltammc.pram are listed in Table
6-2. These results are consistent with the values of n obtained by simulation.
Figure 6-5 shows the influence of f , on o! values calculalrd by estimation from
simulation and through the graphical estimations ah,, and a,,,,,,rr. The error is
also consistent with the experimental measurements. Valucs in a,,,,,u, are
slightly larger than thaf in cqi, because the system is not complrtely irreversiMe.
6.4 Some Final Comments on Simulation Analysis
J
1. Ensure, as far as is possible, that the electrode
are diffusi n
controlled. , 2
-..y p
Y
CYCLIC VOLTAMMETRY
Table 6 2 The Various Measurements of x
-- -
R~tc
(mv$) a,,,.' ~,pp.cor: %: L
.,, - - . -
3M 0.72 0.80 0.76 0.18
0.7 1 u.80
0.7 1 0.90
0.71 Tc80
ICO 0.76 0.83 0.8(1 0.20
0.7s 0.84
0.75 0.84
0.78 a84
50 0.8 1 0.85 0.77 0.21
0.81 0.86
0.P1 0.P6
0.81 0.86
- . *- -
" Measured from experimwtal results.
Expwimmtal ]mulls conecld Ibrougb Eq~at i m (2).
~ c ~ ~ ~ ~ d rkuln a "l l u~ a r i u~ / f i ~ ~ ~ g uf the cyclic vul rarrl l l l ugvr~~a wi t h
input EO = - 1 . 5 3 V. kg = (I.01?cm/s. Do= 1.8 x : 0 - 6 ~ m2 ~ . and
k,,, = 590s-' at -30C.
SOIITCB: Adapted lrom Reference 3.
a
\
ml ' P
-.
F~&E 6 5 The relationship of the reverstbility factor jr and the apparent transfer
~ e ~ t a,,, The solid pbint rcprencnts tbesimdarion and fitting result, then esLim.trd
I l ~r ou Equation ( 2) . ( ~da pkd from Reference 3.)
I
CVFIT: SIMPLEX DATA ANALYSIS WITH CVSM
147
backgound or capantive current when the double-layer capacitance is a
function of potential.
3. Prepare correct data fiIcs, using 0.001 V per point, and start w~t h the initial
potential plus 0.001 V. End with the final potential. The units of current
should be amperes.
4. If computation time is an issue, use moderate to fast scan rates. Simulation
time 1s roughly proportional to experimental time. A simulation that take:: an
hour. with a scan rate of 0.1 V/s will take less than a rn~nute vcith a scan rate of
10 v/s.
5 Use the smallest scan range possible. Don't include lots of tlat baseline, which
absorbs much computation time without ylelding any meaningful
mformation.
6. ColIect data sets over several orders of magnitude of scan rates. The time
scale should correlate with the time scale of processes being investigated, for
instance, if chemical processes are involved.
7. For sol~itions with moderate resistance and moderate scan rates, don't use IR
compensation Rathcr, mzasurr: the resistance and use the I R calculation in
the fitting program.
8. FOT complex electrochemical mwhanisms, collect data on as mdny sub-
I
I
systems as possible. Tbe fits of these wilI give independent numbers and also
will reduce the overall fitting time. For an example, see Wandlowski et aLI4
I
I
1. Develop a reasonable mechanism using CVSIM. Try various ~nechanis~l~s
to see which one follows the experimental trcnds clo5ely.
1. Use CVFlT with as many independently determined parameters as possible
[e.g., diffusion coefkients, rate constants of following chemical steps as
measured by potenha1 step experiments).
3. Let the area of the electrode Roat in each fit. This can amount far small
errors in diffusioll coeficients or concentrations.
4. Fit the same methanism for data collected at dderent scan rates. This is a
very good indication of the correctness of the a.isurlied mechanism. It a
equivalent to a working curve approach. A divergence of a fitted parameter
indicates an incomplete or incorrect mechanism. On rhe other hand, fitted
I
parameters that are constant over scan rate indicate that the mechanism is
1
consistent with experiment. Error estimates on the parameters can be
obtnincd by standard deviation of parameters obtained for diKerent data,
i
sets {both at the same scan rate and varying scan rate).
5. Fit cxp.rimen~s done as a result d sumestion 8 in Section 6.4.1. TJ J wi l l
which take a long time and become less reliable.
, / provide independent parameter estimates, avoiding many pardter fits, ,
6. When first starti ng, choose a high value far the tokrro&rf.the pro-
to st art a ne
. .. -
148
CYCLIC VOLTAMMETRY
References
1. Gosser, D. K., Jr.; Zhang, F. Talunta 1991,38, 71 5-722.
2. Press, W. H.: Flannery, B. P.; Teukolsky, S. A,; Vetterling, W. T. Numrical Recipes The Art
of Scienrific Compurirrg: Cambridge Univemity Press: Cambridge, 1985.
3. Huang Q.; G e r , D. K.. Jr. Talanta IW2. 390, 1155.
4. Lexa, D.; Savant. J. M. Acc. Chern. Res. 1983,16,235.
5. Zhou, D. L; Tinernban, 0.; Scheffol4 R.; Wal&r, L. Hdv. Chim. Acta $994 71,2225.
6. LemD.; Saveant, J. M, J. Am. Chcm. Sw. 1978, I#, 3220.
7. Kenyhera T. M.; DeAngelis, T. P.; Norris. 6. J.; Heineman, W. R.; Mark, H. B. I. Am. Chem
Soc. 1976. 98,2469.
8. Lexa, D.: Saveanr, J. M.; Zickler, J. J . Am Chem. Soc. 1977,99, 2786.
9. Rubinson, K. A; habashi, E.; Mark, H. B. Inurg, Chem. 1482,21, 3571.
10. Kim, M. H.; Birke, R. L. I. Elecsroanal. Cbem. 1983, 144, 331.
1 I. He, P.; Faulkner, L. R. Anal. Ckm. 1986,58, 517.
12. Schwarz, W. M.; Shain, I. J. Phys. Chem. 1=, 69, 30.
L3. Klingler, R. J.; Kochi, J. K. 3. Phys. Chem. 1981, 85, 1731.
I 4 Wandlowski T.; Gosser, D. K., jr.; Akinele, E.; de Levle. R.: Horxk. V. Tulaotcl 1993,JU. 1789.
APPENDIX
Summary of Instructions
for CVSIM, CVGRAF, CVFIT,
and DSTEP
Installation CVSIM, CVFIT, and CVGRAF, and DSTEP
A11 the files on the diskette provided should be copied onto the hard disk to the
directory C:\SIMULATE (first create the directory; then copy the files to the
directory). All the programs should then be run from C:\SIMULATE.
CVSIM
The program is initiated by typing CVSIM and hitting the enter key. The
experi~nent ansthe mechanism are described in response to a series of inquiries
przserlted in a fuil screen display.
Number of Species in the Mechanism
An integer equal to the total number of species in the mechanism is entered. T h e
screen input is designed for up to eight species; mon: can b entered if necessary.
Concentrations of Each Species
, . : ,
,,.. "" . 2 - : > ,,&i,, / ,,.
150 CYCLIC VOLTAMTRY
(excluding of course the elsctrolylyte). Each species is now associated with an
integer, in the order of entry. Following entries, which describe electrode
reactions and chemical reactions. utilize these number identifications.
Number and Description of Redox Couples
The number of redox couples in the mechanism is entered. Next the integer
index is entered for tlic oxidized and reduced forms of each redox couple,
followed by the reduction potential of each couple (in volts), the heterogeneous
rate constant (cm/s), and the cntt~odic transfer coefficient u. For an electron
transfer that is considered to be reversible, a value of lOcm/s will ensure
reversibility under most circumstances. IFa two-electron transfer (where one of
the redox species is shared by two couples) is among the electrode reactions,
these should be entered in sequence when written as reductions. For instance:
Numbner and Description of Solution Chemical Reactions
The number of solution reactions in the mechanistn is entered. Each chemical
reaction (first or second order) is described by entering two indexes for the
reactants and two for the products. ( Ti the reaction is fi rst order. 0 is entered in
the space reserved fur the second species of a second-order reaction.) First-order
rate constants are elltered in units of reciprocal seconds. Second-order rate
constants arc entered in units of M- 's-l*Cnorm.
Experimental Parameters
The number of half-cycles (1,2, or 31, the initial potential, switching potential(s),
final potential (V). and scdn rate (Via) are entered. Asymmetric potential
waveforms, whch are often useful, are possible in this scheme.
Changes in Input
At this point, the user can inspect the entire input screen and change selected
parameters by entering the number associated with the parameters (ie-,
1 = concentrations, 2 = electrode reactions. etc.). It is also possible t o change
the default temperature (298.351(), the default diffusion coefficient
(1.00 x 10- 5c~2/ s) , or the individual diffusion coefficients. The individual
diffusion coefficients are changed by entering a multiplier of the default value
(e.g., enter 0.5 for a diffusion coefficient of 5.00 x lo-' crnz/s). If it is desired to
simulate a mechanism with a dlBvsion coefficient larger than the default
coefficient, the default diflusion mf i ci cnt itself can be changed. lt is always
APPENDIX
advised to make the default ddf~eion coefficient equal to the largest diffusion
coefficient of the nlechanism. It is also possible to increase the number of time
increments used in the aimulution, to check for convergence (and thus accuracy)
of the simulation.
Names of Data and Record Files
The names of the simulated potential-current data filc and a Ale that saves the
entire simulation parameter set are requested. The current is output in amperes
and the potential in volts. This format i s required of data sets to be graphed with
the CVGRAF program or to be used by the curve-fitting program CVFIT.
Normalizing Concentration
The choice of normalizing concentratjon is entered in millimular units (mM).
Option for Capacitive Current
Ifit is desired to include a capacitive current in the simulation, then the electrow
area (em2), double-layer capacitance (pF/cm2), solution resistance (kG) must
be entered.
Option for IR Drop
The effect of the I R drop can he included as well. It is necessary to provide an
experimental data file of current-potential values (A/V, 1 point per O.DOl V), and
to enter the resistance, electrode area. The experimental current is read and the
simulation potentials are corrected accordingly See texf fur detailed description
of the data file.
CVGRAF
A simple graphics program for PC con~patibles (CGA, VGA, and Hercules
graphics) is provided for the simultaneour examinntiotl of two d a h sets. It is
intended primarily for comparison of experinlcr~tul and simulated data.
CVGRAF is started by typing CVGRAF. The input is quite simple: initial
potential and find potential (V), current scale (pAmps), and the names of the
two data fiIes are requested. Default values are provided. If only one data file is
ro be exnmined, a blank file named tdata.pas should be created. Altemativd~,
the second file can have the same name as-the firdt. Movement: of a crosshair
cursor i s controlled with the arrow keys, ,and pokhti81-current v a l m am
:. displayedatthetopofthescreen. -
152
CYCLIC VOLTAMMETRY
CVFIT is similar to CVSIM. Lt i s necessary to identify parameters to be fitted,
provide an experimental data filc (data.pas), and input a tolerance. Parameters
capable of being fitted must be preceded by a 0 (constant) or 1 (fitted). The
history oi the fitting including the tstimitted parameters and the error term for
each simplex iteration i s in a filc irstdatxpas. The error term listed is actually
the sum of the least squares errors * lo6. The final fitted parameters are in a
file called paramtr.pas and a simulation using the fitted parameters in a ,file
segl.pas. An examplc of paramtr.pas is as follows:
n {no cap current)
n (no IR drop correction)
10 {program code)
2 {number of fitting parameters)
1 .OE-0005 {standard Diffusion Coefficient)
1.00000000000000E-0010 {tolerance)
0.00 {fixed) 0.01 0000000 (area] 0.000001 00 {normalizing concenlrat~on, rnol/mlj
298.1 50 {temperature)
3 {number of species)
1.000 (normalized cancentration of first species]
0.000 {normalized concentration of second species)
0.000 {norrnal~zed concentration of third species)
2 {two half cycles)
0.000 (init pot) -0.300 {switch pot) 0.000 {final pot) 1.0000 (scan rate;
0.000 {fixed) 1.000 {First diffusion coefficientj
0.000 {fixed) 1.000 {Second diffusion coefficient)
0.000 (fixed] 1.000 {Third diffusion coefficient)
1 {electrode &uple)
1 2 1.OE+0000 (fit] -0.1860 (Red Poi] 1.00 (ht) 0.0095 (khet) 0.00 (fixed] 0.50 (alihha)
1 {chemical reaction]
2 0 3 D 0.00 {fixed) I.OE+0.002 {kf) 0.000 {fixed) 0.OE +0000 (kr)
DSTEP i s a program that simulate single or double potential step experi-
ments. The entry mechanism is the same as CVStM. The experimental
parameters are initial potential, step potential, find potential, and time d step.
The output is lime in milliseconds, and current is in amperes.
Absolurt energy scale, 2
Adsorption. 43, 97-99
Acceptor number, 32
Artemisinin, 99- 102
Benzoquinone reduction. 7- 10, 1 1 - 12,
79-80
Boiling point, 32t
Born model of solvation. 9- I I
Index
Capacitive current, 57- 59
in double step experiments. 63
simulation of, 1 16- 17
Catalysis
of artemisinin reduction, 1M)- 2
electron transfer chain. 80-84
of glucose oxidase oxidation, 87-88
homogeneous redox, 85-89
Current follower, 65-66
Double layer, 23-23
Electrochemical e l l , 5, 28, 30-31
equivalent circuit for, 56
Electrodes
luggin aippilfary, 30-31
refercne, 34-35, 66-67
silver atnalgam, 33
work~ng. 32-34.66-67
Electrolytes, 33
Electron trnnsfer,
Butler-Voirner eqi~atiot~, 14,45, 109
free energy relationship. for, 19-21
inner sphere, 16.- 17. 19-2 1
Marcus theory, 17- 19
mullieleclron transfer, 75-77, 127, 132
ouler sphere, 16- 17
Entropy of reduction, 11
Faradaic current, 20
Dielectric constant, 18, 32r, 73
Fermi level energy, 1-3, 67
DiKusion, 51-53 Ferncyanide reduction, I
simulation of, 105-8
cyclic voitammetry, 30
visualization of, 55 simulation, 126, 128
Dimensionless units, 109-1 10
Fick's law. 51-52 105-7
Graphics, 125
Heterogeneous ratc constant. I?. 14, 45,
46
Hydrogen reference, 3-4
Inner sphere complex, 16, 14, 74, 10 1 - 2
1R drop. 56-57
simulation oT, 1 16-7
Koopman's theorem, 9
Linear free energy relationship, 12- 15
Mean square difiusion, 38
Melting point, 32t
Methylcobalamin reduction, 3447,
139- 146
simulation, 126, 129
M icroetectrodes, 59
used to determine electron number,
59-69
Nerna Equation, 3-445
Nitric oxidc, 92-94
Nitrobenzoic acid. 90- 92
Nitrogen dioxide. 72-75
simulation, 126- 117. 130- 13 1
Operational amplifiers, M- 66
Peak current
reversible one clectron transfer, 43,44
shifted r:itio. 43
Peak potcntial
Reversible one electron transfer, 42, 44
Potential
electrical, 3, 5
electrode, 3-5, 6-7, 27
window, 32, 35
of zero charge, 22, 24
Potential step chronoamperometry,
61-63
of methylcobalamin, I40-41
of nitrogen dioxide, 72-73
Potentiostat, 64-68
Protonations, 77-80, 133
Reduction potential, 1-6
Tor E,C mechanism, 139-46
lor E, mechanism, 43
for E,C mechanism, 49
Reversibility, 36: 35-46, 49-50, 14--45
Scan rate, 25
and diffi~siori. 5 1 - 52
Solvation. 2. 8, 9- 11
Solvatochromatic, j 2t
Solvents, 3 I - 32
properties, 32t
Tempo oxidation, I0
Transfer coefficient, 14-16,47, 1.15-46
Tricarbonyl(mesitylene)tungsten
oxidation. 95-97
Work function, 1
Voltage amplifier, 65-66
Voltage follower, 65

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