Cyclic voltammetry: a fingerprint of

electrochemically active species

Valentin Mirčeski
Institute of Chemistry
Faculty of Natural Sciences and Mathematics
“Ss Cyril and Methodius” University, Skopje
Republic of Macedonia

1
 Cyclic Voltammetry – a potentiodinamic transient voltammetry

1.2

0.05
1

0.8 0.04 RO+e

0.6 0.03

0.4
forward scan

Current / A
0.02
0.2
0.01
0
0 0.5
t / s1 1.5 2
0
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
reverse scan
Variation of the electrode potential in the course of the -0.01

experiment. The rate of potential variation in time is

called scan rate (v (V/s)), which represents the critical -0.02

R⇄O
time of the experiment.
+ e-
Cyclic voltammetry (CV) is the most
frequently used technique. Almost any
electrochemical study starts with
application of CV. From the features of the
cyclic voltammogram, one can deduce
thermodynamic, kinetic and
mechanistic characteristics of the
electrode reaction!
-0.03
O+eR
-0.04
Potential / V
The outcome of the experiment is presented as an I-E
curve, called cyclic voltammogram. By convention,
the positive current reflects oxidation, whereas the
negative current represents reduction reaction.
 Typical features of a cyclic voltammogram

•Anodic peak current 0.05

•Cathodic peak current 0.04

•Anodic peak potential Ip,a (anod.
•Cathodic peak potential 0.03
peak current)
Ep,a (anod.
peak potential)

Current / A
0.02
The peak-like shape of the voltammetric
curves of both forward and reverse scan 0.01
are consequence of the exhaustion of
the diffusion layer adjacent to the 0
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
electrode with the electroactive
-0.01
material. With time, the thickness of the
diffusion layer increases, thus the flux Ip,c (cathod.
-0.02
Ep,c (cathod.
(i.e., the current) decreases with time. peak current) peak
That is why the current commences -0.03
potential)
decreasing after reaching the peak of the
current. The expansion of the diffusion -0.04
Potential / V
layer with time is shown on a next slide.

3
 Concentration profiles of a Cottrell experiment (explanation of the
previous slide)

1 t =0

t = 0,1 s

t = 0,01 s The thickness of the

diffusion layer
cR / c*R

t = 0,001 s
increases with time!

t=1s

0,2

Concentration profiles. Variation of the concentration of electroactive

species with the distance x measured from the electrode surface at different
times of the chronoamperometric experiment.
4
 Electrode mechanism revealed by cyclic voltammetry:
Reversible electrode reaction
Reversible electrode reaction of R (R = O + ne) species dissolved in the electrolyte
solution undergoing oxidation at the electrode surface means that the voltammogram
is affected by the mass transfer regime only, and the redox species at the electrode
surface obey the Nernst equation: E = E0 +RT/nF ln (cO/cR). The peak current
Ip,a = (2,69  105) n3/2 AcD1/2 v1/2 Randles-Sevcik equation

n – number of electrons in the electrode

reaction 0.05

A – electrode surface area

c – concentration of redox active species 0.04

dissolved in the electrolyte solution

D – diffusion coefficient of the redox active 0.03

species

Current / A
v – scan rate (the speed of variation of the 0.02

potential with time

0.01
Emid
•The ratio of the peak currents is equal to 1;
Ip,c/Ip,a = 1 and it is independent on the scan 0
-0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
rate.
•Ep,a – Ep,c = RT/nF ( 59 mV/n) -0.01

•The peak potentials are independent on the -0.02

scan rate
•The mid-peak potential (Emid = (Ep,a – Ep,c)/2 -0.03

is equal to the formal (standard) potential E0 of

the redox couple R/O -0.04
Potential / V
Cyclic voltammograms of C60 and C70 in a toluene solution

6
 Cyclic voltammograms of ferrocenedimethanol: reversible
electrode reaction

0.400 Ip = const.  v1/2

Ip,a/Ip,c = 0.095  0.019
Ep,a – Ep,c = 0.057 V
0.300

1,2
0.200
1

Ip,a/ mA
0,8
I / mA

0.100 0,6

0,4

0 0,2

0
0 5 10 15 20
-0.100 1/2
v / (mV/s)

-0.100 0 0.100 0.200 0.300 0.400 0.500 0.600 0.700

E/V

7
 Totally irreversible electrode reaction

R  O + ne- electrochemically
0.468
0.5
reversible irreversible
electrode electrode
The plot compares CV of a reversible 0.4 reaction reaction
(blue) with a very slow (irreversible)
electrode reaction. For a very slow
0.3
irreversible electrode reaction, the peak
potential and current of the forward
scan are deffined with the eqs below. In 0.2

some cases, the reverse peak cannot be

even observed, and the voltammogram  k  1 0.1
of a irreversible electrode reaction
 k 2
contains only one CV peak. 0

0.1

0.2

0.3

 0.379 0.4
k0 is the standard rate constant and a is 0.4 0.2 0 0.2 0.4

the electron transfer coefficient.  0.5 Ek 0.5

 Quasireversible electrode reaction

Quasireversible electrode reaction 0.468

0.5
The rate decreases
is controlled by both mass
transfer regime and the 0.4

kinetics of the electrode

reaction. The critical parameter
0.3

that controls voltammetric

0.2
characteristics, is defined as  k 1

k = к/( D)1/2, where  k 2

0.1
 = nFv/RT . Hence, the  k 3

dimensionless kinetic parameter k  k 4 0

unifies the diffusion coefficient (D)  k 5

as a parameter representing the 0.1

mass transfer, the standard rate

constant (к), as a parameter 0.2

controlling the rate of the electrode

reaction, and the scan rate (v), as a 0.3

parameter controlling the time The rate decreases

 0.379 0.4
available for the electrode reaction. 0.4 0.2 0 0.2 0.4
 0.5 Ek 0.5

Dimensionless cyclic voltammograms, obtained by the simulation of the experiment. The dimensionless current
function  is defined as  = I (nFA)-1 (D)-1/2. The plot displays a comparison of the dimensionless current function 
for electrode reactions characterized with different rate.
 Dimensionless current function vs. real current

In cyclic voltammetry, the current of any electrode mechanism can be defined as

I = (nFA) (v)1/2(nF/RT)1/2 D 1/2 

The product (nFA) (v)1/2(nF/RT)1/2 D 1/2 contains only constants for given electrode reaction and
experimental conditions, and it could be considered as amperometric constant kamp. Hence,

I = kamp 

The function , could be reviled by simulations (mathematical modeling) only. It is specific for
each electrode mechanism. Usually, it is a function of many other parameters, as electrode
potential, rate constants, electron transfer coefficient, diffusion coefficients etc.:

 = f(E, k0, a, D…)

Care must be taken in reading the literature in regard whether particular discussion refers to the
properties of the real current I, or to the dimensionless current function , or to both. For
instance, for a quasireversible electrode reaction, the dimensionless current function  decreases
by increasing the scan rate, however, the real current increases with the scan rate, as the scan rate
affects both kamp and . Obviously, the effect of the scan rate on the kamp prevails compared to the
simultaneous effect of the scan rate to . This is illustrated on the next slide.

10
 Dimensionless vs. real cyclic voltammograms: variation of the
scan rate

20
15.735 0.367

scan rate increases scan rate

15
0.3
increases

0.2
Real current Dimensionless
Ik 1 10  k 1
current function
Ik 2  k  2 0.1

Ik 3 5  k 3

Ik 4  k 4 0

Ik 5  k 5
0
0.1

5 scan rate increase

0.2

scan rate increase

 7.013 10  0.214 0.3
0.4 0.2 0 0.2 0.4 0.4 0.2 0 0.2 0.4
 0.5 Ek 0.5  0.5 Ek 0.5

Cyclic voltammograms obtained by the simulation of the experiment at a planar electode of a

dissolved redox couple. The dimensionless current function  is defined as  = I (nFA)-1 (D)-1/2.
11
 Decamethylferrocene: Quasireversible electrode reaction

Variation of the electrode kinetic scan rate increase

parameter k = к/(D)1/2 by altering
the scan rate of the experiment.
Increasing the scan rate, the
parameter k decreases. As a
consequence, the peak potential
separation increases, indicating a
quasirevrsible electrode reaction.
Let us recall that for a reversible
electrode reaction the peak scan rate increase
potential separation should be
independent on the scan rate.

12
Revealing complex electrode mechanisms: electrochemistry of
cyclic hydroxylamine

CH3
O
CMH PB pH 7.8 O
0.000045
10 mV/s
0.000040 25 mV/s
CH3
0.000035 50 mV/s H3C
100 mV/s N
0.000030 H3C CH3
200 mV/s OH
0.000025
350 mV/s
0.000020 500 mV/s
0.000015
quasireversible
I (A)

0.000010
electrode reaction
0.000005
0.000000
reversible
-0.000005 electrode reaction
-0.000010
-0.000015
-0.000020

-1.5 -1.0 -0.5 0.0 0.5 1.0

E (V)

1-hydroxy-3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine (CMH): redox probe

used for detection of superoxide formation in living cells.
13
 pH-dependency of CMH voltammetry

pH 4.2 v = 100 mV/s

0.025
pH 5.1
pH 6.2
0.020
pH 7
0.015
pH 7.8
pH 9
0.000010 pH 9.8
pH 11
0.000005 pH 12
pH 4 ~ 12
0.000000

-0.000005

-0.000010

-0.000015
-1.0 -0.5 0.0 0.5 1.0 1.5

14
 Consecutive electron transfer: EE mechanism

R R R

-H+ -e - -e -
N +H+ N +e - N +e - N+
OH O– O· O
CMH CM-
CM
. CMox

CMH PB pH7.8
0.000020

100 mV/s
0.000015

0.000010

0.000005

0.000000

-0.000005

-0.000010

-1.0 -0.5 0.0 0.5 1.0

15
Electrode reaction coupled with a following irreversible chemical
reaction - EC mechanism

Cyclic voltammetryu is an excellent method for studying chemical reactions coupled with the
electrode reaction. If the chemical reaction follows the electrode reaction, then the mechanism is
termed as an EC mechanism, where the symbol E refers to the electrode reaction, while the
symbol C refers to the follow up chemical reaction.
k
R ⇄ ne- + O  P
In the scheme above, initially, in the solution, R species are present only. At the electrode surface,
the reversible electrode reaction R = O +ne- is taking place. However, the product of the
electrode reaction. i.e., the O species, are additionally involved in the chemical reaction leading to
the electrochemically inactive final product P. The latter chemical reaction is attributed with a
rate constant k. The latter chemical reaction takes place only in the vicinity of the electrode
surface, i.e., in the thin diffusion layer close to the electrode in which O species are present due to
previous electrode reaction. As O species are lost in the chemical reaction, in the reverse scan of
the cyclic voltammogram, the reverse current is diminishing proportional to the rate of the
chemical reaction. The shape of the cyclic voltammograms depends on the kinetic parameter
kchem = k/ , which unifies the rate of the chemical reaction (k) and the available time of the
voltammetric experiment represented by the scan rate  = nFv/RT
Typical voltammetric response of an EC mechanism observed for different values of the ratio kchem
= k/ . When kchem is big value (kchem = 500), the rate of the follow-up chemical reaction is big,
almost the complete amount of O species are consumed in the chemical reaction, thus, in the
reverse scan of the cyclic voltammogram, no reduction current could be seen, as no O species
remained to be reduced back to R species. When the chemical parameter is moderate (e.g., kchem =
0.01), the reverse scan is still formed, as significant fraction of O species are still present in the
diffusion layer as the follow-up chemical reaction is significantly slow. Obviously, for given k, the
parameter kchem could be made big or small depending on the scan rate of the experiment (i.e., the
available time for the chemical reaction), which is an excellent tool for studying and estimating the
kinetics of the chemical reaction.

kchem =
EC mechanism of dopamine: predicting the evolution of the
consecutive cyclic voltammograms

•Dopamine/dopamine o-quinone is a reversible redox couple;

•Dopamine o- quinone is chemically unstable and undergoes intra-

molecular reorganization to leucochrome;

•Leucochore is also electroactive compund. It can be oxidized at less

positive potentials than dopamine;
18
Electrochemical mechanism preceded by a chemical reaction: and CE
mechanism. Redox chemistry of 2-palmitoylhydroquinone – an artificial cellular
membrane calcium transporter
OH O O OH

C15H31 C15H31

OH 1 OH 2
O O
OH O O O O OH
C15H31
C15H31 C15H31
C15H31
⇆ + 2H+ + 2e ⇆ + 2H+ + 2e

OH 1 O OH 2 O

0.125x10-5

0.075x10-5
1
I/A

0.025x10-5

-0.025x10-5

-0.075x10 -5

-0.100 0 0.100 0.200 0.300 0.400 0.500 0.600 0.700

E vs Ag/AgCl (3 M KCl) / V
19
 Revealing the mechanism by varying the scan rate

v = 10 mV s-1 v = 50 mV s-1 v = 100 mV s-1

-4
0.150x10

-5
0.200x10 0.100x10 -4

0.007
-4
0.050x10
-5
0.100x10 0.005
0.0025 0

I/mA
I/A

i/A
0 0 -0.050x10 -4

-0.0025 -0.100x10 -4

-5
-0.100x10
-0.005 -4
-0.150x10
-0.0075
-5
-0.200x10 -0.200x10 -4

-0.010
-4
-0.250x10
-0.300 -0.050 0.200 0.450 0.700
-5
-0.300x10 -0.300 -0.050 0.200 0.450 0.700
-0.300 -0.050 0.200 0.450 0.700 E/V
E/V E/V

v = 1 mV s-1
-6
0.500x10
-6
0.400x10
-6
0.300x10
-6
0.200x10
-6
0.100x10
i/A

0
-6
-0.100x10
-6
-0.200x10
-6
-0.300x10
-6
-0.400x10
-6
-0.500x10
-0.300 -0.050 0.200 0.450 0.700
E/V

20
 Voltammetry of an a surface confined redox couple: Reversible
electrode reaction

Reversible electrode reaction of a thin

film:

This is typical, idealized response of a

reversible electrode reaction of a thin film
immobilized on the electrode surface. The
shape of the voltammogram dislikes
strongly from the typical wave-shaped
voltammogram of a dissolved redox
couple. For a thin film, there is no mass
transfer and the exhaustion of the redox
active material in the course of the
potential scan causes a peak like shape of
voltammetric branches of the cyclic
voltammogram.

21
The current of a reversible surface (thin-film) electrode reaction is defined as

Here Go, and GR are surface concentration of O and R species, GT = Go + GR is the total
surface concentration, E’ is the formal potential, and bo and bR are adsorption
constants related with the Gibbs free energy of adsorption.

Peak current is defined as:

Peak potential is defined as:

In addition, the following is valid: Ip,c = Ip,a, and Ep,c = Ep,a and the half-peak width is

The charge consumed in a course of a single potential scan (calculated as a surface

under the single voltammetric peak) is

22
 Interactions between particles of the immobilized polymer
on the electrode surface

If there are interactions between

immobilized species on the electrode
surface, the shape of the voltammogram
change as shown below. The
interactions are quantified by the
numerical interaction parameter a
linked with the Frumkin adsorption
isotherm. The values on the plot refer to
the interaction parameter. When a = 0,
there are no interactions. For a > 0 and
a < 0, the interactions are attractive or
repulsive between immobilized species
on the electrode surface. Obviously the
broadening and narrowing of the
voltammetric peaks are linked to the
repulsive and attractive interactions,
respectively.

23
 Guasireversible electrode reaction of a surface confined
redox couple

If the charge transfer within the film is

slow, the redox equilibrium does not
prevail, hence instead of having so called
reversible electrochemical behaviour, the
system behaves as a quasireversible
electrode process. Thus, the rate of the
charge transfer controls the
voltammetric response, which is
obviously seen from the shape of the
voltammograms. The numbers on the
plots correspond to the surface standard
rate constant k0 (s-1). Thus, as the rate of
the charge transport within the film is
becoming slower, the separation
between the cathodic and anodic CV
peaks increases proportionally together
with the decrease of the peak currents.

24
25
26