Fundamentals of Electrochemistry

CHEM*7234 CHEM 720

Section 5: Voltammetric Methods

 Voltammetric Methods
Historical
Electrolysis at DME -1920s
Usually 3-electrode cells

Measurement of current that results from the

application of potential.

Different voltammetric techniques are

distinguished primarily by the potential function
that is applied to the working electrode and by
the material used as the working electrode.
 Types of Voltammetry
Polarography
Linear sweep and Cyclic Voltammetry
Hydrodynamic Voltammetry
Pulsed methods
AC Voltammetry (not here)
ip = 2.69 x 105 n3/2 A DO1/2 v1/2 CO

It is instructive to start with Polarography

Voltammetry at a dropping mercury electrode

Polarography uses mercury
droplet electrode that is
regularly renewed during
analysis.
Applications:
Metal ions (especially
heavy metal
pollutants) - high
sensitivity.
Organic species able
to be oxidized or
reduced at electrodes:
quinones, reducing
sugars and derivatives,
thiol and disulphide
compounds, oxidation
cofactors (coenzymes
etc), vitamins,
pharmaceuticals.
Alternative when
spectroscopic methods
fail.
 History

Jaroslav Heyrovsk was the inventor

of the polarographic method, and the
father of electroanalytical chemistry,
for which he was the recipient of the
Nobel Prize. His contribution to
electroanalytical chemistry can not
be overestimated. All modern
voltammetric methods used now in
electroanalytical chemistry originate
from polarography.

On February 10, 1922, the "polarograph" was born as Heyrovsk recorded

the current-voltage curve for a solution of 1 M NaOH. Heyrovsk
correctly interpreted the current increase between -1.9 and -2.0 V as being
due to deposition of Na+ ions, forming an amalgam.
Typical polarographic curves (dependence of current I on the
voltage E applied to the electrodes; the small oscillations
indicate the slow dropping of mercury): lower curve - the
supporting solution of ammonium chloride and hydroxide
containing small amounts of cadmium, zinc and manganese,
upper curve - the same after addition of small amount of
thallium.

Swedish king Gustav Adolf VI awards the

Nobel Prize to Heyrovsk
in Stockholm on 10.12.1959
Potential Ramps

Linear sweep Polarography

In order to derive the the current response
one must account for the variation of drop
area with time:

A = 4(3mt/4d)2/3 = 0.85(mt)2/3
Density of Mass flow rate of drop
drop

We can substitute this into Cottrell

Equation (see Mass Transport Notes)

i(t) = nFACD1/2/ 1/2t1/2

We also replace D by 7/3D to account for the
compression of the diffusion layer by the expanding
drop

Giving the Ilkovich Equation:

id = 708nD1/2m2/3t1/6C
I has units of Amps when D is in cm2s-1,m is
in g/s and t is in seconds. C is in mol/cm3

This expression gives the current at the end of the drop life.

The average current is obtained by integrating the current

over this time period

iav = 607nD1/2m2/3t1/6C
The diffusion current is determined by subtracting away
the residual current
Further improvements can be made by reducing charging
currents (see Pulse methods later)

E1/2 = E0 + RT/nF log (DR/Do)1/2 (reversible couple)

Usually Ds are similar so half wave potential is similar

to formal potential. Also potential is independent of
concentration and can therefore be used as a diagnostic
of identity of analytes. For example
Class Functional Group E1/2 (v
SCE)
Azo -N=N- -0.4
carbonyl >C=O -2.2
Nitro NO2 -0.9
Quinone C=O -0.1
 Organic reductions often involve hydrogen ions

R + nH+ + ne RHn

Good buffering reqd in organic polarography

Metal Complexes
MLp + ne + Hg M(Hg) + pL

Difference between half-wave potential for

complexed and uncomplexed metal ion is given
by:
E1/2(c) - E1/2(free) =

RT/nF ln Kd - RT/nF p ln [L] +RT/nF ln (D free/D (c))1/2

Stoichiometry can thus be determined by

plotting
E1/2 versus [L]
Also possible to improve resolution between
Heyrovsky-Ilkovich Equation
Describes wave shape for reversible systems (with
fast electron transfer kinetics)
E = E1/2 + RT/nF ln((id - i)/i)
Plot E vs log((id - i)/i) gives straight line of slope
0.059/n
Convenient way to get n
Intercept is half wave potential

Irreversible systems
The waves are more drawn out than for
reversible systems
Limiting currents still show a linear function of
concentration
Shape of polarogram is given by:

E = E0 + RT/nF ln (1.35kf((id - i)/i)(t/D)1/2)

transfer coefficient forward rate constant

Charging Currents : first look

Drop acts as capacitor

Double layer
Since potential change during drop life is very
small we can neglect charging changing with
potential
charging thus depends on time and electrode
area

ic = dq/dt = (E-Epzc)Cdl dA/dt

but A = 4(3mt/4d)2/3 = 0.85(mt)2/3

ic = 0.00567 (E-Epzc) Cdl m2/3t-1/3

so I(total) = id + ic = kt1/6 + kt-1/3

Charging current sets limit of detection
Various ways of reducing it
e.g., Sample current at end of drop life
(TAST polarography)
Other methods involve Pulse voltammetry
-see later
 Voltammetry
The supporting electrolyte
Ensures diffusion control of limiting
currents by eliminating migration
currents
Table: Limiting currents observed for
9.5 x 10-4 M PbCl2 as a function of
the concentration of KNO3
supporting electrolyte

Molarity Il
of KNO3 A
0 17.6
0.001 12.0
0.005 9.8
0.10 8.45
1.0 8.45

At low inert electrolyte concentration, a large

fraction of the total current is due to
migration current - currents due to electrostatic
attraction of ion for electrode
For soln 1, Imigration = 17.6 - 8.45 = 9.2 A;
Idiffusion = 8.45 A
 Cyclic Voltammetry

potential is continuously changed as a linear

function of time. The rate of change of potential
with time is referred to as the scan rate (v).
cyclic voltammetry, in which the direction of the
potential is reversed at the end of the first scan.
Thus, the waveform is usually of the form of an
isosceles triangle.
advantage that the product of the electron
transfer reaction that occurred in the forward
scan can be probed again in the reverse scan.
powerful tool for the determination of formal
redox potentials, detection of chemical reactions
that precede or follow the electrochemical
reaction and evaluation of electron transfer
kinetics.
Potential Sweep

Gives:

Why
I-E-t surface revisited (see Chronoamp notes)

Polarography -constant time E-I

Chronamp - i -t
CV -I-E-t (diagonal cut) -notice wave
shape
Diffusional tails- governed by mass
transport
You can simulate this: for example
using the ensemble method of finite
differences. See Bard and Faulkner (old
edition) Appendix B p675 et seq.
Sign Conventions:
2 conventions in the literature:
American - plot cathodic current positive, plot negative
potentials decreasing to the right.
IUPAC - plot anodic currents positive, plot positive
potentials increasing to the right.
The slightly illogical American convention arose for
historical reasons.
IUPAC stands for International Union of Pure & Applied
Chemistry.

anodic

cathodic

IUPAC Style
 The Randles-Sevcik equation
Reversible systems

ip = 0.4463 n F A C (n F v D / R T)1/2
n : number of electrons, v scan rate (V / sec),
F :Faradays constant (96485 C / mol), A : electrode area (cm2),
R is the universal gas constant (8.314 J / mol K), T is the
absolute temperature (K), and D is the analytes diffusion
coefficient (cm2/sec). Note that if the temperature is assumed to
be 25C (298.15 K), the Randles-Sevcik equation can be
written in a more concise form,
ip = (2.687x105) n3/2 v1/2 D1/2 A C
where the constant is understood to have units (i.e., 2.687x10 5
C mol1 V1/2).
 ipa= ipc for a reversible couple
Peak ratios are often strongly
affected by chemical reactions
coupled to the redox process
See later and also Organic
Electrochemistry (Prof. Houmam)

Peak positions are related to formal potential of

redox process
E0 = (Epa + Epc ) /2
Separation of peaks fr a reversible couple is
0.059/n V
1-e fast electron transfer thus gives 59mV
separation
Peak potentials are then independent of scan rate
(see previous page)
Half-peak potential Ep/2 = E1/2 0.028/n
sign is + for a reduction
 shape of voltammogram depends on transfer
coefficient () and on a dimensionless
parameter
= k0 [RT/DF]1/2
is the scan rate
for >7 votammogram is reversible
when deviates from 0.5 the voltammograms
become asymmetric -cathodic peak sharper as
expected from Butler Volmer eqn.

= 0.25, 0.5 .75

= 0.5
=10,1.0.1,0.01
Microelectrodes

wave shape is different

Ferrocene redox at a 10 m diameter glassy

carbon electrode.
-why?
This steady-state current is explained by envisioning that the
microelectrode is a "dot" with the diffusion layer being
hemispherical in shape extending out into the solution. The amount
of ferrocene diffusing to the electrode surface is defined by the
volume enclosed by an expanding hemisphere, not a plane
projecting into the solution as in the case of a planar electrode.
One salient feature of the microelectrode is the small current
magnitude, which means that iR loss is negligible even at high scan
rates. This allows the determination of kinetic rates of electron
transfer that are very fast by going to high scan rates.
Also time constant RC is small (see Lecture One) -fast electron
transfer can be studied

The fundamental reason you have met before in

the Mass Transport lectures
recall that diffusional properties depend on the
geometry (and size) of the electrode
we now have a brief look at microelectrodes
 Voltammetry at microelectrodes

microelectrodes have at least one dimension of the order of

microns
In a strict sense, a microelectrode can be defined as an
electrode that has a characteristic surface dimension smaller
than the thickness of the diffusion layer on the timescale of
the electrochemical experiment
small size facilitates their use in very small sample volumes.
- opened up the possibility of in vivo electrochemistry. This
has been a major driving force in the development of
microelectrodes and has received considerable attention ..
 Mass Transport

at small electrodes, growth of diffusion layer is initially similar

to that at larger electrodes;
at longer times, it slows significantly. Thus the size of the
diffusion layer at t > 0 is smaller at small electrodes, and the
concentration gradient and therefore the rate of (diffusional) mass
transport are considerably greater at microelectrodes.
At short times size of the diffusion layer is smaller than
that of the electrode, and planar diffusion dominates--even
at microelectrodes.
at very short time scale experiments (e.g., fast-scan cyclic
voltammetry) a microelectrode will exhibit macroelectrode
(planar diffusion) behavior.
at longer times, the dimensions of the diffusion layer
exceed those of the microelectrode, and the diffusion
becomes hemispherical. The molecules diffusing to the
electrode surface then come from the hemispherical
volume (of the reactant-depleted region) that increases
with time; this is not the case at macroelectrodes, where
planar diffusion dominates
 so current at microelectrode is a sum of both
planar and spherical diffusion
magnitude of each will depend on time and
size of microelectrode

id = nFADC [ ( 1/Dt)1/2 + 1/r]

so:

id = C(1/ + 1/r)

planar diffusion spherical

diffusion

The first term predominates at short times

(<<r ),while the second at a sufficiently
long time (>>r ).

is the diffusion layer thickness,.This

quantity is defined,for planar semi-
infinite diffusion.
= (Dt)1/2
Irreversible and Quasi-Reversible Systems: Macroelectrodes

Fast

Slow
For 'slow reactions (so called quasi-reversible or
irreversible electron transfer reactions) the voltage
applied will not result in the generation of the
concentrations at the electrode surface predicted by
the Nernst equation.
kinetics of the reaction are 'slow' and thus the
equilibria are not established rapidly (in
comparison to the voltage scan rate).
position of the current maximum, Ep) shifts
depending upon the reduction rate constant (and
also the voltage scan rate). This occurs because the
current takes more time to respond to the the
applied voltage than the reversible case.
For irreversible processes (those with sluggish
electron exchange), the individual peaks are reduced
in size and widely separated. Totally irreversible
systems are characterized by a shift of the peak
potential with scan rate:
Ep = E - (RT/nF)[lnkDlnnFR

is the transfer coefficient and na is the number

of electrons involved in the charge-transfer step.
Thus, Ep occurs at potentials higher than E,
with the overpotential related to k and .
Independent of the value k, such peak
displacement can be compensated by an
appropriate change of the scan rate.
peak potential and the half-peak potential (at
25C) will differ by 48/n mV.
Hence, the voltammogram becomes more
drawn-out as n decreases.
The peak current, given by:
ip = (2.99x105)n(na2ACD1/2n1/2
ip is still proportional to the bulk concentration,
but will be lower in height (depending upon the
value of
Assuming = 0.5, the ratio of the reversible-
to-irreversible current peaks is 1.27 (i.e. the
peak current for the irreversible process is about
80% of the peak for a reversible one).
For quasi-reversible systems (with 10-1 > k >
10-5 cm/s) the current is controlled by both the
charge transfer and mass transport.
Shape of the cyclic voltammogram is a
function of the ratio k/(nFDRT
As ratio increases, the process approaches the
reversible case. For small values of it, the
system exhibits an irreversible behavior.
Overall, the voltammograms of a quasi-
reversible system are more drawn out and
exhibit a larger separation in peak potentials
compared to a reversible system.
Reaction mechanisms

Cyclic voltammetry can be used to

diagnose presence of reactions that precede
or follow electron transfer
Classified by EC
affects surface concentrations of
electroactive species
changes in shape of voltammogram
info on intermediates

Introduction
Cyclic voltammetry can be used to
investigate the chemical reactivity of
species. To illustrate this let us consider a
few possible reactions.
First we consider the EC reaction:
 The voltammogram will exhibit a smaller reverse
peak because the product (R) is chemically
removed from the electrode surface.
The mass transport equations for this reaction
when diffusional transport is dominant are:

mass transport equation for (O) is identical to

the case when no chemical reaction occurs
species (R) however has an additional term to
account for the fact that it is destroyed
chemically by a first order reaction.
It is possible to gain information about the
chemical rate constant kEC by studying the
reaction via cyclic voltammetry.
EC reaction for reversible electron transfer reaction and rate constant
kEC is extremely large.

back peak height kEC.

wave shifts as kEC increases
results from the desire of the
electrochemical system to set up an
equilibrium controlled by the applied voltage.
for reversible electron transfer reactions the
ratio of (O) and (R) at the surface can be
predicted by the Nernst equation at any
particular value of applied voltage.
chemical reaction removes (R) so when this
happens the applied voltage forces more (O)
to convert to (R) electrochemically to
restablish the required ratio.
As more (O) is converted to (R) this results
in the flow of more current and the wave
begins to shift anodically (for a reduction).

E = E0 +RT/nF ln [O]/[R]
CE Reaction: Scan rate dependence

fast

slow
Many other (endless) possibilities - too many
to discuss here
e.g., ECE

Here S is more difficult to reduce than O

ECE:product easier to reduce

First cathodic scan is normal -then you see S

EC (catalytic)

O is regenerated -re-reduced etc

Adsorption in cyclic voltammetry

Repetitive voltammograms for micromolar

riboflavin at a HMDE

note peak separation is smaller than for solution

phase couple
if it is ideal then separation = 0
peak half-width = 90.6/n mV
peak current is directly proportional to surface
coverage () and scan rate
ip = (n2F2A)/4RT

Peak area also gives coverage

Q =nFA can be used to determine area
occupied by molecule - can give orientational
information
 Rotating Disk Voltammetry

important advance in voltammetry

rotating disk electrode (RDE)
and later the rotating ring-disk electrode (RRDE) by
Levich and co-workers in the former Union of Soviet
Socialist Republics. Although steady-state
voltammograms had previously been obtained for
stirred solutions most of these voltammograms were
not amenable to rigorous mathematical treatments.
RDE shows hydrodynamic behavior that could be
treated mathematically
allowed the RDE to be applied to solution and
kinetic studies. and rapid homogeneous reactions
under steady-state conditions

RDE is constructed from a disk of electrode material (e.g. gold,

glassy carbon or platinum) imbedded in a rod of insulating material
(e.g. Teflon). The electrode is attached to a motor and rotated at a
certain frequency. The movement of rotation leads to a very well
defined solution flow pattern. The rotating device acts as a pump,
pulling the solution upward and then throwing it outward.
 The Levich Equation

Veniamin Grigorievich (Benjamin) Levich

was a leading scientist in electrochemical
hydrodynamics, - invented and developed
by him. The famous Levich equation
describing a current at a rotating disk
electrode is named after him.

It is important to note that the layer of solution immediately

adjacent to the surface of the electrode behaves as if it were
stuck to the electrode. While the bulk of the solution is being
stirred vigorously by the rotating electrode, this thin layer of
solution manages to cling to the surface of the electrode and
appears (from the perspective of the rotating electrode) to be
motionless. This layer is called the stagnant layer in order to
distinguish it from the remaining bulk of the solution.
Analyte is conveyed to the electrode surface by a
combination of two types of transport.
vortex flow in the bulk solution continuously brings fresh
analyte to the outer edge of the stagnant layer.
analyte diffuses across stagnant layer. The thinner the
stagnant layer, the faster the analyte can diffuse across it
and reach the electrode surface.
Faster electrode rotation makes the stagnant layer thinner.
faster rotation rates permit the analyte to diffuse to the
electrode faster, resulting in a higher current being
measured at the electrode.

The act of rotation drags material to the electrode surface where it can react.
Providing the rotation speed is kept within the limits that laminar flow is
maintained then the mass transport equation is given by

where the x dimension is the distance normal to the electrode surface. It is

apparent that the mass transport equation is now dominated by both
diffusion and convection and both these terms effect the concentration of
reagent close to the electrode surface. Therefore to predict the current for
this type of electrode we must solve this subject to the reactions occurring
at the electrode.
 Rotated disk voltammetry is similar to cyclic
voltammetry in that the working electrode potential is
(slowly) swept back and forth across the formal potential
of analyte.

The Levich equation This equation takes into

account both the rate of diffusion across the
stagnant layer and the complex solution flow
pattern. In particular, the Levich equation gives
the height of the sigmoidal wave observed in
rotated disk voltammetry. The sigmoid wave
height is often called the Levich current, iL, and it
is directly proportional to the analyte
concentration, C. The Levich equation is written
as:
iL = (0.620) n F A D2/3 w1/2 v1/6 C
where w is the angular rotation rate of the
electrode (radians/sec) and v is the kinematic
viscosity of the solution (cm2/sec). The kinematic
viscosity is the ratio of the solution's viscosity to
its density.
results for a series of rotated disk voltammograms
taken at different scan rates.
a Levich study. The limiting current (or Levich
current) is measured and plotted against the square
root of the rotation rate, producing a Levich plot.
Note that the experimental rotation rate, f , is
measured in RPM and must be converted to the
angular rotation rate, w, so that it has units of
radians per second
in experiment shown the electrode area, A, was
0.1963 cm2, the analyte concentration, C, was
2.55x106 mol/cm3, and the solution had a kinematic
viscosity, v, equal to 0.00916 cm2/sec. After careful
substitution and unit analysis, you can solve for the
diffusion coefficient, D, and obtain a value equal to
4.75x106 cm2/s.
The kinematic viscosity is the ratio of
the absolute viscosity of a solution to its
density. Absolute viscosity is measured
in poises (1 poise = gram cm1 sec1).
Kinematic viscosity is measured in
stokes (1 stoke = cm2 sec1). Extensive
tables of solution viscosity and more
information about viscosity units can be
found in the CRC Handbook of
Chemistry and Physics.
Rotating Ring Disk Voltammetry

Rotating-ring-disk electrode: A
variant of the rotating-disk electrode
which includes a second electrode - a
concentric ring electrode - that is
placed outside the disk and used to
analyze the species generated on the
disk. The ring is electrically insulated
from the disk so that their potentials
can be controlled independently.
Abbreviated as RRDE

convenient way to measure post-electron

transfer reactions of products
relationship between disk current and ring
current depends on rate of movement of product
from the disk
 only a fraction of disc products will reach ring
each ring-disk electrode must be calibrated with a
well-behaved reversible couple to determine the
collection efficiency (N)
N= iR / iD
couples used - ferri/ferocynadide,
quinone/hydroquinone
efficiency depends on electrode geometry (radii of
disk and ring)

Example: peroxide- study of post electron transfer

rapid disproportionation

electrochem HOOH - e HOO

followed by HOO + HOO HOOH + O2

we now look at cyclic voltammetry and RRDE study

 CV in MeCN
disk

Ring

CV: ipa increases with [HOOH] (A to D)

ipa proportional to square root of scan rate
note plateau in wave after peak - indicative
of secondary redox process
 b: Ring currents
RHS: cathodic scan
A ED is disconnected: B ED is at +2.6V vs SCE
products can be characterized by scanning ring
from +1 to -2V
first wave at 0.4V is indicative of HOO
 If 1/ N (collection efficiency) is
plotted against [HOOH] then:

HOO disproportionation rate constant can

be calculated if:
1. Oxidation of HOOH is diffusion
controlled (seescan rate dependence of ipa

2 the only decay path for HOO is

disproportionation while moving from disk
to ring
 disproportionation of HOO follows
simple second order rate law:
1/[HOO ]t - 1/[HOO ]0 =kt

conc on inner conc at disk: zero

edge of ring time

experimental collection efficiencies

when compared to theoretical N make it
possible to relate the two HOO
concentrations
[HOO ]t = N(exp)/N [HOO ]0
and so:
1/N(exp) = 1/N + kt/N [HOOH]

plot 1/N vs [HOOH] gives k

 Pulse Methods: as promised

Examples below refer to polarography but

are applicable to other votammetric methods
as well
all attempt to improve signal to noise
usually by removing capacitive currents

Normal Pulse
Polarography

current measured at a single instant in the lifetime of each

drop.
higher signal because there is more electroactive species
around each drop of mercury.
somewhat more sensitive than sampled DC and regular
polarography.
data obtained have the same shape as a regular LSV.
 A modification on NPP is Differential
Pulse Polarography (DPP)

current measured twice during the lifetime of each drop

difference in current is plotted.
Results in a peak-shaped feature, where the top of the
peak corresponds to E1/2, and the height gives
concentration
This shape is the derivative of the regular LSV data. DPP
has the advantage of sensitive detection limits and
discrimination against background currents. Traditionally,
metals in the ppm range can be determined with DPP.
 note -small currents but almost devoid of
capacitive contribution
derivative improves contrast between
overlapping waves
 Square Wave Voltammetry

advantage of square wave voltammetry is that the entire

scan can be performed on a single mercury drop in about 10
seconds, as opposed to about 5 minutes for the techniques
described previously. SWV saves time, reduces the amount of
mercury used per scan by a factor of 100. If used with a pre-
reduction step, detection limits of 1-10 ppb can be achieved,
which rivals graphite furnace AA in sensitivity.
data for SWV similar to DPP
height and width of the wave depends on the exact
combination of experimental parameters (i.e. scan rate
and pulse height