First, the electrode must reduce the nearby anthracene to the stable anion radical:

ns must often be understood as applying to intermediates, rather than to starting species

final products. An + e —> An* (5.1.1)

For example, Co#rell

This eventconsider
requires aan
veryEqua,on
overall and
process
large current, inChronoamperometry
which
because and R are
it occurs instantly. coupled
Current flowsin an overall
subse
quently
ultielectron to maintain the fully reduced condition at the electrode surface. The initial reduc
process
tion has created a concentration gradient that in turn produces a continuing flux of
anthracene to the electrode surface. Since
+ nethis
*± arriving
R material cannot coexist with the (3.5.7)
electrode at E 2, it must be eliminated by reduction. The flux of anthracene, hence the cur
a mechanism having the following general character:
+ n'e +± O' (net result of steps preceding RD S) (3.5.8)

O'+ e^R' (RD S) (3.5.9)

R' + ri'e <± R (net result oft steps

> t > f >following
3 2 0
1
RD S) (3.5.10)
j_
bviously ' +n" + 1 = . 1 0 t
0 0 x 0 t

The current potential

(a) characteristic can be written
(b) as (c)
Figure 5.1.2 (a) Waveform for a step experiment in which species is electroinactive at E\, but
(a) Waveform for a step experiment in which species is electroinac6ve
af(E E (1 (
is reduced at a diffusion[C
limited
'( 0,rate
t)eat Ei (b)^ Concentration
C profiles
/ (0, )for
^ various
" times
" ^ )into
] the (3.5.11)
O R
experiment, (c) Current flow vs. time.
a at E1,a butl vist reduced
0 t h e R D Sat Tahdiffusion
i s limited rate at E2
ere £°ds> >(b)
& Concentra6on
%& P P profiles for variousrelation is (3.3.11)
6mes written for the RDS and
intothe experiment,
ultiplied by(c)
n, because
Current each
flow vs. net6me conversion of O' to R' results in the flow of n electrons,
just one electron, across the interface. The concentrations CQ>(0, t) and C R '(0, i) are
ntrolled not only by the interplay between mass transfer and the kinetics of heteroge
step takes place. As shown in F igures 5.1.3b and 5.1.3c, the current potential curve has
a wave shape much like that encountered in earlier considerations of steady state
voltammetry under convective conditions (Section 1.4.2). This kind of experiment is
Co#rell Equa,on and Sampled Chronoamperometry
called sampled current voltammetry, several forms of which are in common practice.
The simplest, usually operating exactly as described above, is called normal pulse
voltammetry. In this chapter, we will consider sampled current voltammetry in a gen
eral way, with the aim of establishing concepts that apply across a broad range of par

\
4 5

(a) (b) (c)

F igure 5.1.3 Sampled current voltammetry. (a) Step waveforms applied in a series of
experiments, (b) Current time curves observed in response to the steps, (c) Sampled current
Sampled current voltammetry.
voltammogram.

(a) Step waveforms applied in a series of experiments;

(b) Current time curves observed in response to the steps;
(c) Sampled current voltammogram
 c*
exponential line
(fully activation-
controlled reaction)

cR
jL
0
0 dN
x
c*

j / a.u.

cR
0
0 dN
x
c*

cR
E / a.u.
0
0 dN
x
Le#: Current
Fig.vs2.6
E curve for single-step
Left: Polarization electrochemical
curve for reac6onreaction
single-step electrochemical underunderthe influence
the influenceofofmass transport
control on mass
a macroscopic electrode
transport control (one-dimensional
on a macroscopic mass transport).
electrode (one-dimensional The dashed
mass transport). line shows the
The dashed
exponen6al line shows the
current exponential
increase current
for the caseincrease
whenforthethesurface
case when the surface concentration
concentra6on of the is equal to the
of the reactant
reactant is equal to the bulk one, regardless of the current density. Right: Concentration profile
bulk one, regardless of the current density.
curves of the reactant in a solution under hydrodynamic control for three characteristic sections of
Right: Concentra6on
the polarization profile curves
curve. From of the
bottom reactant
to top: incontrol,
activation a solu6on
mixedfor threeand
activation characteris6c
mass transportsec6ons of the
polariza6on curve.
control, fullFrom boIomcontrol
mass transport to top:(atac6va6on
the diffusioncontrol, mixed
limited current ac6va6on
density). and
Symbols: X:mass
distancetransport control -
from the electrode, cR : reactant concentration, c*: bulk concentration of the reactant, d N : thickness
full diffusion control (at the limited current). Symbols: X: distance from the electrode, cR: reactant
of the Nernstian diffusion layer
concentra6on, c*: bulk concentra6on of the reactant, dN: thickness of the Nerns6an diffusion layer
 voltammetry. In this chapter, we will consider sampled current voltammetry in a gen
eral way, with the aim of establishing concepts that apply across a broad range of par
Sampled Chronoamperometry
E

\
4 5

trode Kinetics 27
(a) (b) (c)
Potentiostatic polarization
Galvanostatic
F igure 5.1.3 Sampled current voltammetry. (a) Step waveforms applied in a series of
polarization Mixed
experiments, (b)activation and curves
Current time Diffusion-limited
observed in response to the steps, (c) Sampled current
diffusion control conditions Sampled
voltammogram.
current
voltammetry
 with UMEs. In this experiment, it is customary to reco
tential, which is obviously equivalent to recording curr
for theChronoamperometry
Tridimensional method is linear potential sweep chronoamperom
data
as linear sweep voltammetry (LSV).1

(*) (

Figure 6.1.1 (a) A portion of the i-t-E surface for a nernstian

60//I mV. (b) Linear potential sweep across this surface. [Re
sed in 100 s) to about 1000 V/s with conventional electrodes and up to 10 V/s
s. In this experiment, it is customary to record the current as a function of po-
ich is obviouslyChronoamperometry
equivalent to recording current
withversus time.
a linear The formal
varia,on ofname
E
hod is linear potential sweep chronoamperometry, but most workers refer to it
weep voltammetry (LSV).1

E= vt

(*) (b)

1 (a) A portion of the i-t-E surface for a nernstian reaction. Potential axis is in units of
b) Linear potential sweep across this surface. [Reprinted with permission from W. H.
Anal. Chem., 32, 1509 (1960). Copyright 1960, American Chemical Society.]
 Tridimensional representa,on of i vs E and t
II.1 Cyclic Voltammetry 61

Fig. II.1.3a, b Schematic drawing of a 3D plot with characteristic current–potential–time rela-

E= vt
tionships for chronoamperometric and steady-state responses. The trace following the intersecting
plane shows approximately the peak characteristics of a linear sweep voltammogram

Schematic drawing of a 3D plot with characteristic current–potential–time

experiment, the diffusion layer thickness continuously moves into the solution
relationships for chronoamperometric
phase. During and
the initial course of a cyclic steady-state
voltammetric responses.
experiment, the diffusion
The trace
layerfollowing
also moves the intersecting
into the plane
solution phase. shows
However, thisapproximately thebypeak
is of course followed a
characteristics of a linear sweep voltammogram
 Linear Sweep Voltammetry (LSV)

6.2 N emstian (Reversi

6.1 Introd
> 0.4

Js .

0.2

0.1

F igure 6.2.1 Line

sweep voltammogra
0 t Et E° E(ort) dimensionless curre
on the potential axi
(a) (b) (c)

Figure 6.1.2 (a) Linear potential sweep or ramp starting at EL (b) Resulting i-E
(c) Concentration profiles of A6.2.2 A1 for
and Peak Current and Potential
potentials beyond the peak.
The function TT^xicrt), and hence the current, reaches a maximum
0.4463. From (6.2.17) the peak current, / p, is

A typical LSV response curve for the anthracene system considered in

ip = n3/ 2
 Reversible systems
Randles-Sevcik equation

12
i p = 0.4463nFAC (nFvD RT )

ip = ( 2.687 ×10 5 ) An 3 2 v1 2 D1 2C

• n = number of electrons in the redox reac6on

• v = scan rate in Vs-1
• A = the electrode area cm2
• T = the temperature K
• D = diffusion coefficient cm2 s-1
Cyclic Voltammetry
 Journal of Chemical Education Article

Figure 3. (A−G): Concentration profiles (mM) for Fc+ (blue) and Fc (green) as a function of the distance from the electrode (d, from the electrode
surface to the bulk solution, e.g. 0.5 mm) at various points during the voltammogram. Adapted from Reference 4. Copyright © 2011, Imperial College
Press.
Figure: (H):(A−G):
VoltammogramConcentration profiles
of the reversible reduction of a 1 mM(mM) for
Fc+ solution Fc+
to Fc, (blue)
at a scan rate of and
100 mVFc (green)
s−1. (I): as a asfunction
Applied potential
time for a generic cyclic voltammetry experiment, with the initial, switching, and end potentials represented (A, D, and G, respectively).
of
a function of

the distance from the electrode (d, from the electrode surface to the bulk solution, e.g.
cell (E) to the standard potential of a species (E0) and the relative from the surface of the electrode are dependent on the potential
0.5 mm) 16 at various points during the voltammogram. (H): Voltammogram of the reversible
activities of the oxidized (Ox) and reduced (Red) analyte in the applied and how species move between the surface of the
reduction of a 1 mM Fc+ solution to Fc, at a scan
system at equilibrium. In the equation, F is Faraday’s constant,
R is the universal gas constant, n is the number of electrons, and T
rate of 100 mV s . (I): Applied potential
electrode and the bulk solution−1(see below). These factors all
contribute to the “duck”-shaped voltammograms.
asis the
a temperature
function of time for a generic cyclic voltammetry As the potential isexperiment,
scanned negatively with
+
the initial,
(cathodically) from
point A to point D (Figure 3), [Fc ] is steadily depleted near the
switching,
E=E + 0 and
RT end
ln
(Ox) potentials
0
= E + 2.3026 represented
RT
log
(Ox) (A, D, and G, respectively).
electrode as it is reduced to Fc. At point C, where the peak
10
nF (Red) nF (Red) cathodic current (ip,c) is observed, the current is dictated by the
(1) delivery of additional Fc+ via diffusion from the bulk solution.
In application of the Nernst Equation to the one-electron The volume of solution at the surface of the electrode con-
reduction of Fc+ to Fc, the activities are replaced with their taining the reduced Fc, called the diffusion layer, continues to grow
concentrations, which are more experimentally accessible, the throughout the scan. This slows down mass transport of Fc+ to the
0 0
Cyclic Voltammetry of a Reversible System

REVERSIBLE means that the species formed by the electron transfer process
does NOT undergo any further process. In other words, the reduced or
oxidized species thus formed is stable and no chemical reaction occurs.

|ipa|/|ipc| = 1

Peak-peak separation, at room T (25 °C), is 59 mV

ip = ( 2.687 ×10 5 ) An 3 2 v1 2 D1 2C
1…5 mV s−1 ). If the metal deposition process is reversible and the deposition takes

e
C

current / a.u.
ip,a

ip,c Ep,a
Ep,c

electrode potential /a.u.

Fig. 2.8 Cyclic voltammogram for a solute that undergoes a simple electrochemical transformation.
Arrows indicate the sweep direction. e exponential current rise corresponding to a fully activation-
Cyclic voltammogram
controlled for a solute
reaction; C: current decay that undergoes
corresponding to athe
reversible electrochemical
Cottrell equation; b: baseline for the
transforma6on.
negative-going scan. Indices indicate the anodic (a), cathodic (c) and peak (p) values of the electrode
Arrows
potentialindicate the sweep direc6on. e exponen6al current rise corresponding to a fully
and the current
ac6va6on-controlled reac6on; C: current decay corresponding to the CoIrell equa6on;
b: baseline for the backward scan. Indices indicate the anodic (a), cathodic (c) and peak
(p) values of the electrode poten6al and the current
 phase. During the initial course of a cyclic voltammetric experiment, the diffusion
layer also moves into the solution phase. However, this is of course followed by a

Fig. II.1.4 Plots of the potential stimulation applied in steady-state, chronoamperometric, and
Plots of the potential stimulation applied in steady-state, chronoamperometric, and cyclic
cyclic voltammetric experiments together with the resulting current response and the concentration
voltammetric
profile inexperiments together
the vicinity of the electrodewith the resulting current response and the
surface
concentration profile in the proximity of the electrode surface
 Cyclic Voltammetry of a Chemical Reaction
Following up the Electron Transfer

Journal of Chemical Education Arti

this tutorial, we have aimed to provide these researchers

an approachable and comprehensive guide to utilizing c
voltammetry in research and education endeavors. By integra
the theoretical underpinnings of electrochemical analysis
practical experimental details, highlighting experimental pit
and providing introductory training modules, this text refl
current best practices in learning and utilizing cyclic voltamm

■
*
ASSOCIATED CONTENT
S Supporting Information

The Supporting Information is available on the ACS Publicat

website at DOI: 10.1021/acs.jchemed.7b00361.
All modules mentioned in the text (PDF, DOCX)
1 V/s
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: dempseyj@email.unc.edu.