10

Introduction to Voltammetry
Voltammetry refers to the group of electroanalytical
techniques that are generally based on the application of
potential to a small working electrode that causes a redox Voltammogram

reaction, resulting in a current which is measured. Fig:1

Here the current is measured under complete
polarization. i passes between
WE and CE
The rate of oxidation or reduction of the analyte is limited
by the rate of mass transport (diffusion, migration and
convection) of the analyte to the working electrode
surface.
To enhance polarization, the working electrodes have
surface areas of few square millimeters or even micro
meters. E at WE is vs. RE
Applications: electrochemical sensors to quantify
Fig:2 3 Electrode system
[analyte].
 Comparing with other methods

• In voltammetry the current that develops in an electrochemical cell is measured

under conditions of complete concentration polarization.
• In contrast potentiometry measurements are made at currents that approach
zero and where polarization is absent.
• In coulometry measures are taken to minimize the effects of concentration
polarization. Further more in voltammetry there is minimal consumption of
analyte while in coulometry essentially all of the analyte is converted to another
state.
• When current proportional to analyte concentration is monitored at a fixed
potential, the technique is called amperometry.
 Excitation Signals
In voltammetry, a variable potential excitation signal is impressed on a working electrode
in an electrochemical cell. This produces a characteristic current response that can be
measured. The wave forms of four common excitation signals (potential vs time plots)
used in voltammetry are shown here.

Fig:3
4
 Voltammetry Instrumentation
Dc voltage source
• Three electrode system for carrying out linear sweep
voltammetry measurements is shown here.
• The electrodes are immersed in a solution containing the Variable resistor

analyte and supporting electrolyte.

• Supporting electrolyte is the alkali metal salt solution. This is
non reactive at the working electrode with the potentials
used. This solution reduces the effects of migration and
lowers the resistance of the solution.
• Working electrode: Its potential versus a reference electrode
is varied linearly with time.
• Reference electrode: Its potential remains constant through
out the experiment
• Counter electrode: usually either a coil of platinum
wire or a pool of mercury. The current passes between Fig:4
the counter electrode and working electrode.
 Voltammetry Instrumentation

• The digital volt meter has high electrical resistance (>1011 Ω) that there is
essentially no current in the circuit containing the reference electrode.

• A voltammogram is recorded by moving the contact C and recording the resulting

current as a function of the potential between the working electrode and the
reference electrode.
 Ideal polarized electrode (IPE) The potential range Pt, Hg and C
WEs depends on the electrode
Potential Range material and the composition of the
immersed solution.
The positive potential limits are
caused by the large currents that
develop due to the oxidation of
WE water to give O2. The negative limits
arise from the reduction of water to
produce H2.
Relatively large potentials are
tolerated with Hg electrodes
because of high overvoltage of
hydrogen on this metal.
2H2O → O2 + 4H+ + 4𝑒 − 2H+ + 2𝑒 − → H2 With Hg electrodes many metal ions
are reversibly reduced to amalgams
Fig:5 at the surface of a mercury
electrode.
 Working electrodes
• Disk electrode: They are small flat disks of a conductor (platinum
or gold) that are press fitted into a rod of an inert material such
as Teflon with the wire contact.
Fig:6
• Hanging mercury drop electrode (HMDE): consists of a fine
capillary tube connected to a mercury reservoir. The micrometer
connected to the capillary permits formation of drops having
surface areas that are reproducible.
▪ they have a relatively large negative potential range.
▪ many metal ions are reversibly reduced to amalgams at their
surfaces, simplifying the chemistry.
Fig:7
 Working electrodes

• Microelectrode: consists of metal wires (carbon

fiber, gold, platinum or silver) sealed within
tempered glass bodies.
• Sandwich type flow electrode: The block is made
of poly ether ether ketone(PEEK). The glassy
carbon or noble metals make up the working
electrode. Fig:8
• Dropping mercury electrode: Used in
polarography. Consists of capillary tubing through
which mercury is forced by a mercury head.

Fig:9
 Linear Scan Voltammograms
• Appearance of a typical linear scan voltammogram for
an electrolysis involving the reduction of an analyte species
A to give a product P at a mercury film electrode is
illustrated here. The solution is about 10-4 M in A and 0.0 M
in P and 0.1 M in KCl (supporting electrolyte).

• Here the working electrode is assumed to be connected

to the negative terminal of the linear scan generator so
that the applied potentials are given a negative sign.
By U.S. (Imperial) convention, cathodic (reduction) currents
are positive and anodic currents are given negative sign.
Fig:10
• Linear scan voltammograms generally have a sigmoidal
The half reaction at the working
shape and are called voltammetry waves.
electrode is
A + n𝑒 − ⇌ P E0 = −0.26 V
 Linear Scan Voltammograms

• The constant current beyond the steep rise is called limiting current ;
• Limiting current is proportional to [A], used for quantitative analysis.
• Plateaus as mass-transport of A to the electrode surface is at the maximum,
maintains a steady state.
• Peak would indicate depletion of A or complete concentration polarization.
• The potential at which the current is equal to one half the limiting current is called
half wave potential and is given symbol E½
• Half-wave potential is closely related to the standard reduction potential, used for
identification of analyte (qualitative analysis).
 Hydrodynamic Voltammetry

• Reproducible limiting currents can be achieved rapidly

when either the analyte solution or the working
electrode is constant motion. This is called
hydrodynamic voltammetry.
• This is achieved by the following ways
1. With an ordinary magnetic stirrer
2. Rotating the working electrode
3. Pass the analyte solution through a tube fitted with
a working electrode.

Fig:11
 Concentration profiles at electrode surfaces
• Consider the reaction: A + n𝑒 − ⇌ P 𝐸 ° = −0.26 V
• The initial concentration of A is CA while that of the product P is zero.
°
0.0592 𝑐𝑃
• Eappl = 𝐸𝐴° – log ° − Eref
𝑛 𝑐𝐴
• Eappl is the potential between the WE and RE.
• CP å nd CA ̊are the molar concentrations of P(product) and A(analyte) in a thin layer
of solution at the electrode surface only.
• Electrolysis at a small voltammetry electrode does not significantly change the bulk
concentration of the analyte solution (cA) during the course of a voltammetry
experiment.
• As a result, the concentration of A in the bulk solution remains unchanged and
concentration of P in the bulk is negligible or zero.
 Profiles for planar electrodes in Unstirred solutions

Fig 12 shows current response to a

stepped potential in an unstirred
solution.
(a) Excitation potential.
(b) Current response.
Fig:12

• For unstirred solutions, mass transport of analyte to electrode surface occurs only by
diffusion.
• A pulsed excitation potential Eappl is applied to the working electrode for a period of time t
seconds, the current reaches a peak value. It decays due to slow diffusion of bulk analyte
towards the electrode surface.
• We also assume that Eappl is large enough so that 𝑐𝑃o /𝑐𝐴o in the equation is 1000 or greater.
• The concentration of A at the electrode 𝑐𝐴o is reduced to zero.
 Concentration distance profiles during diffusion controlled reduction

Before the application of potential

the concentration of A remains
constant with distance from the
electrode.

When potential is applied, the

concentration of A increases linearly
from the surface over time and
concentration of P decrease with
Fig:13
time.
Concentration profiles for A and P after
0,1,5 and 10 ms
Eappl = point Z in
Eappl = 0 V the figure 10
 Voltammetric currents
The current i required to produce these gradients is proportional to the slopes of the
straight line portions of the solid lines shown in Figure 13b

nFADA([analyte]bulk − [analyte]x=0 )
Where i=
δ
i= current in amperes,
n is the number of moles of electrons transferred in the redox reaction.
F is Faraday’s constant.
A is the area of the electrode (cm2)
D is the diffusion coefficient for the analyte (cm2/s)
[analyte] = concentration (mol/cm3);
x=0 is at the electrode surface;
δ is the thickness of the diffusion layer (cm).

In stirred solutions, convection and migration occur together with diffusion. However the
current required can be approximated by using the same expression for unstirred solutions.
 Current voltage relationships for Reversible and irreversible reactions

• An electrochemical process such as A + n𝑒 − ⇌ P is said to be reversible if it obeys

the Nernst equation under the conditions of the experiment.

• In totally irreversible system either the forward or the reverse reaction is so slow
as to be completely negligible.

• In a partially reversible system the reaction in one direction is much slower than
the other although not totally insignificant.

• A process that appears reversible when the potential is changed slowly may show
signs of irreversibility when a faster rate of change of potential is applied.
 Polarography
• Voltammetry conducted with dropping
mercury electrode is called polarography.

• Polarographic currents are controlled by

diffusion alone, not by convection or
migration.

• The dispenser in the figure suspends one drop

of mercury from the bottom of the capillary.
After current and voltage are measured, the
drop is mechanically dislodged.

• Freshly exposed Hg yields reproducible current

potential behavior.

Fig:14
 Polarography
• Most reaction studied with the Hg electrode are reductions. At a Pt surface reductions
of H+ competes with reduction of many analytes.
2H+(aq) + 2𝑒 − ⇌ H2(g) E˚= 0 V
• For Hg surface the large overpotential for reduction of H+ at the Hg surface, allows
reactions that are thermodynamically less favorable than reduction of H+ can be
carried out without competitive reduction of H+
• In neutral or basic solutions, even alkali metal cations are reduced more easily than H+.
Further more reduction of a metal into a mercury amalgam is more favorable than
reduction to the solid state:
K+ + 𝑒 − ⇌ K(s) E˚ = −2.936 V
K+ + 𝑒 − + Hg ⇌ K(Hg) E˚ = − 1.975 V
• Mercury is not useful for studying oxidation because Hg is oxidized in non complexing
media near +0.25V (vs SCE)
 Polarogram
Qualitative analysis: E½ is the potential at which half the maximum
current is reached. It is characteristic of a given analyte.
Quantitative analysis: The diffusion current in the plateau region is
proportional to the concentration of the analyte.

( i d )max = 708 nD1/2m 2/3t 1/6c Id in 𝜇A; D = cm2/s

m is Hg flow rate, mg/s; t in s; concentration C in mM

Residual current, measured in the absence of analyte, is due to
the reduction of impurities in solution and on the surface of the
electrodes
For quantitative analysis the limiting current should be controlled Fig:15

by the rate at which analyte can diffuse to the electrode. So Sampled current polarogram of
a. Cd2+ in 1M HCl and
minimize convection by using an unstirred solution and minimize b. 1M HCl alone
migration by using a high concentration of supporting electrolyte
such as 1 M HCl Cd2+ + 2𝑒 − + Hg ⇌ Cd(Hg)
 Faradaic and Charging currents
The current we seek to measure in voltammetry is faradaic current due
to reduction or oxidation of analyte at the working electrode.

When we step the working electrode to a more negative potential by

forcing electrons into the electrode from the potentio stat, the cations
in solution flow toward the electrode and anions flow away from the
electrode. This flow of ions and electrons is called charging current.

➢ Charging current is also called capacitor current or condenser

current.
➢ Charging current should be kept to the minimum as it obscures the
faradaic current.
➢ Charging current controls the detection limit in voltammetry.

Fig:16
 Cyclic Voltammetry (CV)

• In cyclic voltammetry , we apply the triangular wave form to

the working electrode.
• After the application of a linear voltage ramp between times
t0 and t1, the ramp is reversed to bring the potential back to
Fig:17
its initial value at time t0.
• The excitation cycle might be repeated many times.
• The voltage extrema at which the reversal takes place are called switching potentials.
• The range of switching potentials chosen for a given experiment is one in which a
diffusion-controlled oxidation or reduction of one or more analytes occurs.
• The direction of the initial scan may be negative (as shown in Figure) or positive,
depending on the composition of the sample. A forward scan is a scan in the direction
of more negative potentials and a reverse scan is the opposite.
 Cyclic Voltammogram
t2 Figure a shows a potential versus time waveform.
Figure b shows a cyclic voltammogram for a solution that is 6.0
t1
mM in K3Fe(CN)6 and 1M in KNO3
t0 The upper portion from time t0 to time t1 exhibits a cathodic wave.
Instead of leveling off at the top of the wave, current decreases at
more negative potential because analyte becomes depleted near
the electrode.

Diffusion is too slow to replenish analyte near the electrode.

At the time of peak voltage cathode current has decayed below
the peak value.

After the peak potential, the applied potential is reversed and

eventually the reduced product near the electrode is oxidized. This
reaction produces an anodic wave between t1 and t2. As reduced
product is depleted, current approaches its initial value at t2
Fig:18
 Cyclic Voltammogram
1. There is a tiny anodic current at the initial potential of +0.8 V due to the oxidation of
water to give oxygen; this immediately decreases to zero.

2. No current is observed between a potential of +0.7 V and +0.4 V because no

reducible or oxidizable species is present in this potential range.

3. When the potential becomes less positive than approximately +0.4 V, a cathodic
current begins to develop (point B) due to the reduction of hexacyanoferrate(III) ion
to hexacyanoferrate(II) ion.

4. A rapid increase in the current occurs in the region of B to D as the surface

concentration of Fe(CN)63- becomes smaller and smaller

5. Note that the current at the peak consists of (1) the initial current surge, to adjust
the surface concentration to its equilibrium concentration and (2) the normal
diffusion-controlled current.
 Cyclic Voltammogram…

6. The first curret decays rapidly (points D to F) as the diffusion layer is extended
farther and farther away from the electrode surface.
7. At point F (−0.15 V), the scan direction is switched but the current continues to be
cathodic because the potentials are still negative enough to cause reduction of
Fe(CN)63- to Fe(CN)64-
8. As the potential sweeps in the positive direction, reduction of Fe(CN)63- ceases.
The current goes to zero, then becomes anodic due to the re-oxidation of
Fe(CN)64- that has accumulated near the surface during the forward scan.
9. This anodic current peaks and then decreases as the accumulated Fe(CN)64- is
used up by the anodic reaction.
 CV for Reversible reactions
• The cyclic voltammograms of reversible (figure a) and
irreversible (figure b) reactions are given in the figure.
• A reversible reaction is fast enough to maintain
equilibrium concentrations of reactants and products at
the electrode surface. Peak anodic and peak cathodic
currents (ipa and ipc)have equal magnitudes in a
reversible process and are separated by

2.303 𝑅𝑇 59.0
Δ𝐸𝑝 = 𝐸𝑝𝑎 – 𝐸𝑝𝑐 = = mV at 25℃
𝑛𝐹 𝑛

Where 𝐸𝑝𝑎 and 𝐸𝑝𝑐 are the potentials at which the

peak anodic and peak cathodic currents are observed
and n is the number of electrons in the half reaction.
• The half wave potential 𝐸1/2 lies midway between the
two peak potentials.
Fig:19
 CV for Irreversible reactions
• In an irreversible reaction cyclic voltammogram the reaction too slow to
maintain equilibrium concentrations of reactant and product at the
electrode surface.
• Cathodic and anodic peaks are broader and more separated.
• ∆Ep will exceed its expected value.
• If the oxidation were very slow no anodic peak would appear.
 Randles-Sevcik Equation
For a reversible reaction the peak current ipc for the forward scan of the first cycle is
proportional to the concentration of analyte and the square root of the scan rate.
ip = 2.686  105 n 3/2 AcD1/2 1/2
ip is peak current in A (= C / s)
2.686 × 105 has units of C mol-1 V-½
n is the number of moles of electrons transferred in the redox reaction
A is the area of the electrode in cm2
c is the concentration of analyte in mol/cm3
D is the diffusion coefficient for the analyte in cm2/s
v is the scan rate in V/s

Magnitude of the peak current can be increased

when:
- a larger electrode is used
- a higher concentration of analyte is used
- a faster scan rate is used Fig:20
 Effect of Scan Rate on Peak Current

ip α v1/2
Fig:22

For a reversible process, the peak current

increases linearly as a function of the
square root of scan rate (v).

Fig:21 E1/2 and ∆Ep are not affected by scan rate.

3+
Ferrocenium
2+
Ferrocene http://nuschem.wixsite.com/videogaller
y/delta-ep-and-scan-rate
 Applications of voltammetry

• It is applicable to the analysis of many inorganic metal ions anions such as

bromate, iodate, dichromate, vanadate selenite and nitrite.

• Used in the study of organic functional groups such as carbonyl group, carboxylic

acid group, peroxides epoxides, hydroquinone and mercaptans.

• Used to characterize the redox behavior of compounds (C60, Fe3+) and to

elucidate the kinetics of electrode reactions.