Voltammetry

UNIT 7 VOLTAMMETRY
Structure
7.1 Introduction
Objectives
7.2 Electrodes and Processes
7.3 Common Voltammetric Methods
7.4 Direct Methods
Linear Sweep Voltammetry
Sampled DC Polarography
Hydrodynamic Voltammetry
7.5 Pulse Methods
Normal Pulse Voltammetry
Differential Pulse Voltammetry
Square Wave Voltammetry
Cyclic Voltammetry
7.6 Stripping Methods
Anodic Stripping Voltammetry
Cathodic Stripping Voltammetry
Adsorptive Stripping Voltammetry
7.7 Alternating Current Methods
Voltammetry-Instrument
7.8 Summary
7.9 Terminal Questions
7.10 Answers

7.1 INTRODUCTION
This is the first unit of the electroanalytical methods course. We will start our
discussion by defining what is voltammetry and then continue our discussion with the
different methods of voltammetry. We will discuss the sampled DC polarography and
hydrodynamic voltammetry. We will also discuss in detail the pulse methods viz.
Normal pulse polarography, Differential pulse polarography and Square wave
polarography/voltammetry.

Then cyclic voltammetry (CV) will be discussed along with a diagnostic test to decide
reversibility of a redox reaction. Finally the instrumentation involving CV will be
explained.

Objectives
After studying this unit, you should be able to:
• define voltammetry,
• discuss the electrodes and processes of voltammetry,
• discuss the dc methods in voltammetry,
• explain the pulse methods of voltammetry,
• explain anodic, cathodic and adsorptive stripping methods in voltammetry,
• discuss the alternating current methods in voltammetry,
• name the instruments involved in voltammetry, and
• select a suitable method of voltammetry for the analysis of a particular sample.

5
Electroanalytical
Methods-III 7.2 ELECTRODES AND PROCESSES
Voltammetry is the general name given to a group of electroanalytical methods in
which the current is measured as a function of applied potential wherein the
polarization of the indicator or working electrode is enhanced. For this, the working
electrodes used in voltammetry are generally microelectrodes having surface area of
Microelectrodes are
few square micrometers to square millimeters. This field has been developed from
working electrodes that Polarography (developed by Heyrovsky); which is a particular type of voltammetry,
have surface areas smaller which used a dropping mercury electrode as the working micro-electrode.
than a few square Voltammetry includes all techniques in which the current potential measurements are
millimeters. made at stationary and fixed electrodes. After studying this unit, you will be in a
position to understand different voltammetric techniques.

The measurement of a current is done when the complete concentration polarization

takes place in an electrochemical cell. Voltammetry has developed from polarography.
Polarography, as will be discussed in Unit 8, uses the DME as the working electrode.
In voltammetry, the process of polarization is enhanced by using ‘microelectrodes’ as
the working electrodes.

Thus, we can say that the electrochemical method in which the current is measured as
a function of the potential applied to a microelectrode is known as voltammetry. These
electrodes may be solid like gold, platinum and glassy carbon or mercury. If the
electrode is formed by a drop of mercury dropping from a fine glass capillary, the
technique is called “Polarography” (discussed in detail in Unit 8).

Other forms of working electrodes used are hanging mercury dropping electrode
(HMDE), static mercury drop electrode (SMDE), thin mercury film electrode (TMFE),
glassy carbon electrode (GCE), carbon paste electrode (CPE), etc. Working electrodes
made of noble metals are used less frequently. Some electrodes are given in Fig. 7.1.

Processes
Various methods are assigned to the terms voltammetry and polarography which differ
in the measuring techniques and the type of electric potential used to excite the
determination process.

Voltammetry is widely used for the quantitative analysis of trace metal ions at micro
level. This study of redox processes lead to the qualitative and quantitative analysis of
heavy metals and some organic substances in solution. In addition to this aspect this
technique is quite versatile for research purpose in the fields of

i) redox processes

ii) electron transfer mechanisms at chemically modified electrode surfaces

iii) adsorption processes

iv) corrosion proof materials

Voltammetry: Volt- v) new electronic processes for chemical industries

ampere-metry means
measurement of current- vi) production of new types of batteries that can store large quantities of energy
voltage relationship.
More recently this technique is gaining more importance in the technique of
production of pharmaceutical materials with the introduction of principles of green
chemistry.

6
Voltammetry

7
Electroanalytical
Methods-III 7.3 COMMON VOLTAMMETRIC METHODS
The most widely used voltammetric methods are

A) Direct current methods

i) D.C. Polarography (discussed in detail in Unit 8).
ii) Linear sweep voltammetry
iii) Sampled D.C. Polarography
iv) Hydrodynamic voltammetry

B) Pulse methods
v) Normal Pulse voltammetry
vi) Differential Pulse voltammetry
vii) Square wave voltammetry
viii) Cyclic voltammetry

C) Stripping voltammetry
ix) Anodic stripping voltammetry
x) Cathodic stripping voltammetry
xi) Adsorptive stripping voltammetry

D) Alternating current methods

7.4 DIRECT METHODS

Under this category linear sweep voltammetry and hydrodynamic voltammetry will be
discussed in addition to the sampled D.C. polarography.
Polarography is a
particular type of
voltammetry in which the 7.4.1 Linear Sweep Voltammetry
working micro electrode The simplest type of voltammetry is called Linear Sweep Voltammetry (LSV). In this
is a D.M.E.
technique, the potential of the working electrode is varied linearly as a function of
time and the current response is recorded. The scan rates are relatively slow, i.e. less
than 5 mV/sec, which allows the movement of fresh analyte to reach the electrode
surface, so that the electrode is always in equilibrium with the bulk solution. Consider
a one electron reduction reaction.

A + e− = B E o = 0.00V
which obeys Nernst equation.

Here, E is the potential of the working electrode, E˚ is the standard reduction potential
of A.

If a solution containing only A is taken in a cell and an applied potential of about

200 mV is applied, then a miniscule amount of current will flow to convert a small
amount of A to B so that Nernst equation is obeyed at the electrode surface. The
amount of current increases as the potential approached the E˚, when E becomes equal
to E˚, [B] = [A] at the electrode surface or in other words, at E˚, half of the total A
reaching the electrode is converted to B, so that the current is half way to its limiting
current.

8
As E is lowered further, all the A is converted to B, as soon as it reaches the electrode. Voltammetry

Fig. 7.2: Normal DC polarography

An important feature of this technique is that largest change in slope occurs around E˚.
The value of the potential corresponding to the point where the current is exactly half
of the total current is known as half wave potential (E½) and this value is used to
identify the unknown species (qualitative analysis) and the difference in the value of
the current from the start to the maximum value is known as limiting current, i.e. sum
of migration current + residual current and diffusion current, but after elimination of
the first two the diffusion current (id) that is directly proportional to the concentration
of the analyte and is used for its analytical determination (quantitative analysis)
id = KcA … (7.1)
where cA is the analyte concentration and K is a constant

Fig. 7.3: Linear Sweep Voltammogram

Polarographic determinations with higher sensitivity can be achieved if the ratio of
iF/iC is improved by other measuring techniques by increasing the Faradaic current or
reducing the condenser current. These modifications gave rise to sampled DC
polarography and pulse methods.

In normal DC polarography, the electrode area is not constant and hence the current
fluctuates with the life time of each drop within some range as shown in Fig.7.3. This
problem can be alleviated by measuring the current once at the end of the life time of
each drop and this method is called Sampled DC Polarography or Tast Polarography.

7.4.2 Sampled DC Polarography

In this technique instead of recording the current continuously, it was sampled for a
5 millisecond period just before the drop falls. Between the sampling periods, the
recorder was maintained at its last current level by means of a sample and hold circuit.

9
Electroanalytical The major advantage of this current sampling is that it substantially reduces large
Methods-III current fluctuations due to continuous growth and fall of the drops at dropping
electrode.
From Fig. 7.3, it can be seen that the current near the end of the life of a drop is nearly
constant and it is this current only that is measured in the current sampled technique
resulting in a smooth curve with very little current fluctuations.

Fig. 7.4: Sampled DC Polarogram

LSV in which the solution or the electrode is kept in motion is called hydrodynamic
voltammetry.

SAQ 1
a) Why does the current fluctuate with the life time of each drop as shown in
Faradaic Current: Fig.7.3?
Current due to
electrochemical reaction …………………………………………………………………………………………...
in a cell.
…………………………………………………………………………………………..
Cathodic Current: A
faradaic current due to a b) What do you mean by Tast Polarography?
reduction reaction.
…………………………………………………………………………………………...
Anodic Current: A
faradaic current due to an …………………………………………………………………………………………..
oxidation reaction.
SAQ 2
What are the major advantages of current sampling in Sampled DC polarography?

…………………………………………………………………………………………...
…………………………………………………………………………………………..

7.4.3 Hydrodynamic Voltammetry

In hydrodynamic voltammetry current is measured as a function of the potential
applied to a solid working electrode kept in stirring solution. Linear scan profiles are
used while the solution is in motion towards the electrode.
The cell has three electrodes, the working electrode (usually mercury coated
electrodes); a reference electrode (SCE) and a counter electrode (Pt coil). The current
in the cell passes between the working electrode and counter electrode.
The electroactive substance undergoing electrode reactions at micro electrode is
brought to the electrode by three modes:
i) migration of charged ions under the influence of an electric field due to
attraction of the electrode that has a positive or negative charge.

10
ii) convection resulting from stirring or vibration. Voltammetry

iii) diffusion due to concentration gradient established near electrode during the
reaction.
This is the current that is proportional to the concentration of electroactive substance
and is given by
nFAD
il = ca … (7.2)
δ
where
ca = Concentration of analyte, n = number of electrons, F = Faraday constant,
A = Area of the electrode surface, D = Diffusion coefficient of the analyte,
il = Limiting current, δ = thickness of Nernst layer

Hydrodynamic
voltammetry:
Voltammetry in which the
Fig. 7.5: A three electrode cell for hydrodynamic voltammetry
solution is mechanically
Here, stirring is accomplished using a magnetic stirrer but in some other cases the stirred.
electrode is rotated at a constant high speed in the solution thus providing a stirring
action. The obtained voltammogram is a wave and the current voltage plot is
characterized by an initial residual current that grows up with increasing potential till
the E½ and then slowly increases till a stationary level is reached. At this value of
potential the ions reaching the electrode discharge immediately thus the concentration
of the analyte in the diffusion layer is almost nil. The continuous flowing of ions into
the diffusion layer due to stirring maintain a constant current.

Another way of carrying out this technique involves the flowing of analyte solution
through a tube in which the microelectrode is fixed. This technique has been used as a
voltammetric detector in HPLC.
Some important applications of this technique include the detection and determination
of oxygen and chemical species like glucose, lactose and sucrose. This detector has
also been used in fundamental studies in electrochemistry and detection of end points
in electrometric and volumetric titrations.

11
Electroanalytical SAQ 3
Methods-III
a) What do you mean by Hydrodynamic voltammetry?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
b) In Hydrodynamic voltammetry, how the flow of analyte solution is carried out?

…………………………………………………………………………………………...
…………………………………………………………………………………………...

7.5 PULSE METHODS

The sensitivity of linear scan voltammetry or polarography is limited by charging
current which is large initially in the drop life. The slowness, inconvenient apparatus
and poor detection limits of linear scan voltammetry or polarography were the reasons
for its decline. The sensitivity of these two methods is improved by pulse methods by
about 6.5 times by eliminating charging current. The current in these methods is
measured at a time when the difference between the Faradaic current and the
interfering charging current is large. There are four important pulse methods namely

i) Normal pulse voltammetry/polarography

ii) Differential pulse voltammetry/polarography

iii) Square wave voltammetry

iv) Cyclic voltammetry

The potential excitation signals used in different voltammetric methods are given in
Fig.7.6 and the individual methods are discussed in the following sections.

7.5.1 Normal Pulse Polarography (NPP)

In this technique, the potential is altered by using square wave potential pulses and is
applied only briefly for about 50 ms before each current measurement. The data
obtained have the same shape as LSV and the sensitivity is increased. The dropping
mercury electrode is held at the initial potential until there are only about 60 ms left in
the life time of the drop. Thus very little electrolysis and depletion occurs. During the
last 15 ms, before the expiration of the pulse time, the current is measured. Each new
drop is stepped upto a greater potential and is measured after about a 40 ms delay, a
sensitivity improvement of approximately three times is observed.

7.5.2 Differential Pulse Polarography (DPP)

A still greater improvement is reached by using the programming wave form as shown
in Fig. 7.6. In this technique a 50 mv pulse is applied during the last 50 ms of the life
time of the mercury drop. The current is measured twice during the life time of each
drop, firstly just before the pulse and second one just before the drop falls. The
difference in the current is plotted resulting a peak shaped curve. The top of the peak
corresponds to E½ and the height of the peak depends on the concentration.

The peak current in differential pulse voltammetry increases linearly with the
concentration of the analyte. It also increases with the pulse amplitude but in a
complicated linear fashion. In practice amplitudes greater than 100 mv are not used,
since the peaks broaden and the resolution is significantly inhibited.

12
 Voltammetry

Fig. 7.6: Some basic parameters in different voltammetric/polarographic techniques

13
Electroanalytical
Methods-III

Fig. 7.7: Pulse application measuring procedure and current potential curves for
(a) Normal pulse voltammetry; and (b) Differential pulse voltammetry

The higher detection limit in this technique is due to superior discrimination against
charging current and impurity Faradaic current.

The peak current in differential pulse polarography is given by

n2 F 2 D
ip = A.C a ∆EA tp … (7.3)
4 RT π
where, ip = Peak current, n = Number of exchanged electrons, F = Faraday constant,
R = Gas constant, T = Temp. in Abs. Scale, A = Electrode surface area,
Ca = Concentration of the analyte, ∆ EA = Pulse amplitude, D = Diffusion coefficient
of the analyte, and tp = Pulse duration.

The detection limit for the determination by this technique is similar to square wave
polarography at 10–7 – 10–8 mol/dm3. But for irreversible reaction it is lowered.

7.5.3 Square Wave Polarography/Voltammetry

This is a type of pulse polarography that offers the advantages of high sensitivity,
great speed and low detection limit. The entire voltammogram is obtained in less than
10 ms. It uses a potential wave form similar to one used in DPP and the entire
potential sequence is applied during the life time of a single drop. This can be used
with DME and HMDE. The excitation signal in this technique is obtained by
superimposing the pulse shown on to the stair case signal. The length of each step in
stair case signal is synchronized with the pulse period (τ) and is about 5 ms. The
potential step is 10 mv (∆Es). The magnitude of the pulse is often 50 mv. Under these
conditions corresponding to a pulse frequency of 200 Hz, a 1-V scan require 0.5 s.

For reversible reactions, a larger pulse is used so that its size is great enough for the
oxidation of the product formed in the forward reaction occurs during the reverse
phase. The forward pulse gives the cathodic current i1, while the reverse phase gives
the anodic current i2 and the difference between these two ∆i = i2 – i1 is plotted to give
the voltammograms. This difference is directly proportional to the concentration, the
potential at the peak corresponds to the E½. It is possible to increase the precision of

14
the analysis by signal averaging data from several voltammetric scans. Detection Voltammetry
limits for square wave voltammetry are reported to be 10–7 to 10–8 M.

The peak current in this technique is given by

1
ip = kn 2 D 2 ∆EA Ca … (7.4)

where, ip = peak current, k = constant, n = number of exchanged electrons,

D = diffusion coefficient of analyte, ∆EA = Pulse amplitude, and ca = concentration of
the analyte.

SAQ 4
i) Distinguish between
a) Linear-scan polarography and pulse polarography.
b) Differential-pulse polarography and square-wave polarography.

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...
ii) Which one is better and why? NPP(NPV) or DPP(DPV) ?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

7.5.4 Cyclic Voltammetry

Cyclic Voltammetry (CV) is an attractive method for the teaching of a number of
concepts in electrochemistry. In brief, it is perhaps the most versatile electrochemical
technique for the study of electroactive species. The effectiveness of CV results from
its capability for rapidly observing the redox behaviour over a wide range of potential.
The resulting voltammogram is similar to a conventional spectrum in that it conveys
information as a function of an energy scan. In spite of its wide applications, this
technique is not generally well understood as compared to other instrumental
techniques such as spectroscopy and chromatography.

Fig. 7.8: Typical cyclic voltammogram

Fundamentals of Cyclic Voltammetry: It consists of cycling the potential of an
electrode that is immersed in an unstirred solution of the electroactive species and then
measuring the resulting current. The potential of this working electrode is controlled
versus a reference electrode such as a saturated calomel electrode (SCE) or a

15
Electroanalytical silver/silver chloride electrode (Ag/AgCl).The controlling potential which is applied
Methods-III across these two electrodes can be considered as excitation signal. The excitation
signal for CV is a linear potential scan with a triangular waveform as given in Fig. 7.9.
This triangular potential excitation signal sweeps the potential of the electrode
between two values, sometimes called the switching potentials. The excitation signal
in Fig. 7.9 causes the potential first to scan negatively from +0.80 (initial potential) to
– 0.20 V (EF final potential) versus SCE at which point the scan direction is reversed,
resulting a positive scan back to the original potential of +0.80 V (Ei). The scan rate as
reflected by the slope is 50 mV per second as shown in Fig. 7.9. A second cycle is
indicated by the darked line. Single or multiple cycles can be used.

Fig. 7.9: Typical excitation signal for cyclic voltammetry-a triangular potential
waveform with switching potentials at 0.8 and –0.2 V versus SCE

Fig. 7.10: Cyclic voltammogram of 6mM K3Fe(CN)6 in 1M KNO3, Scan initiated at 0.8 V
versus SCE in negative direction at 50 mV/s. Platinum electrode area=2.54 mm2.
A cyclic voltammogram is obtained by measuring the current at the working electrode
during the potential scan. The current can be considered the response signal to the
potential excitation signal. The voltammogram is a display of current (vertical axis)
versus potential (horizontal axis). Since the potential varies linearly with time, the
horizontal axis can also be thought of as a time axis. This will be helpful in
understanding the basic principle of the technique.

A typical cyclic voltammogram is given in Fig. 7.10. In a platinum working electrode

is a solution containing 6.0 mm of K3Fe (CN)6 as the electroactive species in 1.0 M
KNO3 in water as the supporting electrolyte. The potential excitation signal used to

16
obtain this voltammogram is shown in Fig. 7.9 but with the negative switching Voltammetry
potential of –0.15V. Thus, the vertical axis in Fig.7.9 is now the horizontal axis of
Fig.7.10. The initial potential (Ei) of 0.80 V applied at (a) is chosen to avoid any
electrolysis of [Fe(CN)6]3– when the electrode is switched on. The potential is then
scanned negatively, forward scan, as indicated by the arrow. When the potential is
sufficiently negative to reduce [FeIII(CN)6]3– cathodic current is indicated by (b) due to
electrode process

[Fe III (CN 6 )3− + e → [ FeII (CN) 6 ]4 − … (7.5)

The electrode is now sufficiently strong reductant to reduce [FeIII(CN)6]3– to
FeII(CN)6]4–

The cathodic current increases rapidly (b → d) until the concentration of [FeIII(CN)6]3–

at the electrode surface is substantially diminished, resulting the current to peak (d).
The current then decays ( d → g) as the solution surrounding the electrode is depleted
of [FeIII(CN)6]3– due to electrolytic conversion to [FeII(CN)6 ]4– . The scan direction is
then switched to positive at –0.15 V (t) for the reverse scan. The potential is still
sufficiently negative to reduce [FeIII(CN)6]3– , so the cathodic current continues even
though the potential is now scanning in the positive direction. When the electrode
becomes sufficiently strong oxidant, [FeII (CN)6]4– , which has been accumulating
adjacent to the working electrode, can now be oxidized by the electrode process:
[FeII (CN 6 )4 − → [FeIII (CN)6 ]3− + e … (7.6)
This causes anodic current (i → k). The anodic current rapidly increases until the
surface concentration of [FeII(CN)6]4– is diminished, resulting the current to peak (j).
The current then decays (j → k) as the solution around the electrode is depleted of
[FeII(CN)6]4– . The first cycle is completed when the potential reaches back to + 0.80
V. Now the cyclic voltammogram is obtained. It is clear that any potential positive of
~0.40 V would be suitable as the initial potential in the reduction of [FeIII(CN)6]3–
would not occur when the potential is applied. This procedure avoids inadvertent
electrolysis as a result of applying the initial potential. In the forward scan
[FeII(CN)6]4– is electrochemically generated from [FeIII(CN)6]3– as indicated by the
cathodic current while in the reverse scan [FeII (CN)6]4– is oxidized back to
[FeIII(CN)6]3– as indicated by the anodic current. A more detailed understanding can
be obtained by considering the Nernst equation and the changes in concentration that
occur in solution adjacent to the electrode during electrolysis. The potential excitation
signal depends on the ratio of [FeIII(CN)6]3– /[FeII(CN)6]4– at the electrode surface as
described by Nernst equation for a reversible system:
0.0595 [Fe III (CN ) 6 ]3−
E = E o([Fe II (CN)6 ]4- ,[Fe III (CN)6 ]3- ) + log … (7.7)
1 [Fe II (CN ) 6 ]4 −

where E0′ is the formal reduction potential of the sample. An initial value of E which is
sufficiently positive of E0 ′ maintains a ratio in which [FeIII(CN)6]3– greatly
predominates. Thus, application of +0.80 V at the initial potential causes negligible
current. However, as E is scanned negatively, conversion of [FeIII(CN)6]3– to
[FeII(CN)6]4– by reduction is mandatory for satisfaction of the Nernst equation. The
ratio of iron redox states that must exist at the electrode surface at several potentials
during the scan is shown on the lower horizontal axis in Fig.7.10. The logarithmic
relationship between E and [FeIII(CN)6]3– /[FeII(CN)6]4– is reflected by a rapid rate of
change in the region where E = Eo i.e., [FeIII(CN)6]3– /[FeII(CN)6]4– = 1. This causes
the diametric rise in cathodic current (b → d) during the forward scan.

The important parameters of a cyclic voltammogram are the magnitudes of the anodic
peak current ( I p a ) and cathodic peak current ( I p c ), and anodic peak potential ( Ep a )

17
Electroanalytical and cathodic peak potential ( Ep ). These parameters are labeled in Fig.7.10. One
Methods-III c
method of measuring Ip involves extrapolation of a baseline current as shown in
Fig.7.10. The establishment of correct baseline is essential for the accurate
measurement of peak currents. It is generally difficult for more complicated systems.
The peak current for a reversible system is described by the Randles-Sevcik equation
for the forward sweep of the first cycle.
ip = ( 2.686 × 105 ) n 3 2 AD1 2C0v1 2 … (7.8)

where ip is peak current in ampere, n is electron stoichiometry, A is area of the

electrode (cm2), D is diffusion coefficient (cm2/second), Co is the concentration
(mol/cm3), and v is scan rate (v/second)

ip α Co if all the parameters are kept constant. The relationship to concentration is

particularly important in analytical applications and in studies of electrode mechanism.
The value of I p and I p c should be identical for a simple reversible (fast) couple i.e.
a

Ip
c
= 1 … (7.9)
Ip
a

According to Eq. (7.8), Ip increases with v1/2. . However, the ratio of peak currents can
be significantly effected by chemical reactions coupled to the electrode process.
A redox couple in which both species rapidly exchange electrons with the working
electrode is called an electrochemically reversible couple. The formal reduction
potential (E0′) for a reversible couple is centered between Ep a and Ep c .

Ep + Ep
E 0′ = a c
… (7.10)
2
The number of electrons transferred in the electrode reaction (n) for a reversible
couple can be determined from the separation between peak potentials.

∆Ep = Ep − Ep = 0.059 … (7.11)

a c n
Thus, for a one-electron process, such as the reduction of [FeIII(CN)6]3– to [FeII(CN)6 ]4–
, exhibited ∆ Ep of 0.059 V. Slow electron transfer at the electrode surface,
“irreversibility” causes the peak separation ( ∆ E) to increase.

The electrochemical irreversibility is caused by slow electron exchange of the redox

species with the working electrode. In this case Eqs. (7.8), (7.9), (7.10) and (7.11) are
not applicable. The electrochemical irreversibility is characterized by a separation of
peak potential greater than indicated by Eq. (7.11).

The electrochemical irreversibility is caused by slow electron exchange of the redox

species with the working electrode. The process is said to be quasi-reversible if it is
reversible at low sweep rates but becomes irreversible at higher ones after having
passed through a region known as quasi-reversible at intermediate values. This
transition from reversibility occurs when the relative rate of electron transfer with
respect to that of mass transport is insufficient to maintain Nernstian equilibrium at the
electrode surface. In the quasi-reversible region, both forward and backward reactions
make a contribution to the observed current.

Peak separation greater than the predicted theoretical value (59/n mV) is typically
caused by IR drop due to high resistance between working and reference electrodes.
This is especially a problem at fast scan rates where ‘I’ can be large and in non-

18
aqueous solvent where ‘R’ can be large. Also, slow heterogeneous electron exchange Voltammetry
with the electrode can increase Ep .

The various criteria applied for the diagnosis of reversibility, irreversibility or quasi-
reversibility are summarized in Table 7.1.

Table 7.1: Diagnostic test to decide the reversibility of a redox reaction by cyclic
voltammetry
Criteria for Criteria for quasi–reversible Criteria for total
reversible system system irreversible system
(i) E = Epa– Epc (i) Ip increases with v1/2 (i) No reverse peak.
= (0.0591/n) V but is not proportional to
it.
(ii) [Ep –Ep/2] = (ii) [ I p a / I p c ] = 1 provided (ii) I p c ∝ v1/2
(0.0591/n) V
αc = αa = 0.5 * .
(iii) [ I p a / I p c ] = 1 (iii) Ep is greater than 0.059/n (iii) Ep c shift -30/ αc nα *
V and increases with
mV for each decade
increasing v.
increase in v.
(iv) Ip ∝ v1/2 (iv) Ep c shifts negatively with (iv) (Ep–Ep/2) = 48/ αc nα
increasing v. mV.
(v) EP is dependent
of v
(vi) At potential
beyond Ep, I– 2 ∝
time.

* The notations have their usual meaning as described in the text

αc and αa are transport numbers of cation and anion respectively
nα is the number of electrons transferred upto, and including, the rate determining step

Probably the most marked feature of a cyclic voltammogram of a total irreversible

system is the total absence of a reverse peak. However, such a feature on its own does
not necessarily imply an irreversible electron transfer process, but could be due to a
fast following chemical reaction. Hence, other tests must therefore be made.

In some cases, the anodic current is low as compared to the cathodic current. This is
because throughout most of the experiment there is a concentration difference which
drives back the reduced species away from the electrode, most of the reduced species
produced in forward reduction process, therefore, diffuse into the bulk solution and
cannot be re-oxidized on the time scale of a cyclic voltammetric experiment during
reverse direction, i.e. anodic process. Hence, it gives reduced anodic peak current as
compared to cathodic peak current.

Instrumentation
Cyclic voltammetry requires a waveform generator to produce the excitation signal, a
potentiostat to apply this signal to an electrochemical cell, similar to a polarographic
cell, a current to voltage converter to measure the resulting current and an X-Y
recorder or oscilloscope to display the voltammogram. The first three items are
normally incorporated into a single electronic device, though modular instruments

19
Electroanalytical may also be used. The potentiostat ensures that the working electrode potential will
Methods-III not be influenced by the reactions which take place. Data may be obtained with X-Y
recorder at slow scan i.e. less than 500 mV/second while storage oscilloscope at faster
rates having scan rate upto 20,000 V/second have been used, however ratio faster than
100 V/second are rarely practical because of IR Drop and changing current.

Waveform
Generator Potentiostat
Cell

Current to
X Y voltage
converter

Fig .7.11: Instrumentation for Cyclic Voltammetry

O: Working electrode, Reference electrode, Auxiliary electrode

Modern potentiostat utilize a three-electrode system as shown in Fig.7.11. The

potentiostat applies the desired potential between a working electrode and a reference
electrode. The working electrode is the electrode on which the electrolysis of interest
takes place. The current required to sustain the electrolysis at the working electrode is
provided with the help of an auxiliary electrode. This arrangement prevents large
current from passing through the reference electrode that could change its potential. A
normal polarographic cell may be used in this technique. Such cells usually consist of
glass container with a cap having holes for introducing electrodes and for the passage
of pure nitrogen gas for the removal of oxygen from the test solution similar to
polarography. The reference electrode is typically a SCE in a Ag/AgCl electrode
which is often isolated from the solution with a salt bridge to prevent contamination
by leakage from the reference electrode. The auxiliary electrode is usually a platinum
wire that is placed directly into the solution. Since the limiting (peak) current in all the
voltammetric techniques is temperature dependent, the cell should be thermostated.
Cells are commercially available that may require as little as 1-2 ml of the test
solution. Thin-layer cells enable voltammograms to be recorded on down to 60 µl.

A large variety of working electrodes have been used in voltammetry. The dropping
mercury electrode is used especially in polarography and the hanging mercury drop
electrode (HMDE) in cyclic voltammetry. A thin coat of mercury can be deposited on
a substrate such as graphite to form a mercury film electrode (MFE). A significant
advantage of mercury is its good negative potential range. Solid electrode such as
platinum, gold, glossy carbon, wax impregnated graphite and carbon-paste are also
used in cyclic voltammetry. Such electrodes have a better positive potential range than
mercury.

In conclusion CV has become increasingly popular in all fields of chemistry as a

means of studying of redox states. The technique enables a wide potential range to be
scanned rapidly for reducible or oxidizable substances. This capability together with
its variable time scale and good sensitivity make this the most versatile
electrochemical technique. At the same time it must be emphasized that its merits are
mainly in the realm of qualitative or diagnostic purpose. Quantitative measurements
(rate or concentration) are best obtained via other techniques e.g. pulse technique. Due
to the kinetic control of many cyclic voltammetry experiments, some caution is
advisable when evaluating the results in term of thermodynamic parameters like
measurements of E0´.

20
SAQ 5 Voltammetry

i) How are pulse methods better than the direct methods?

…………………………………………………………………………………………...
ii) What is the difference between voltammetry and polarography?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
iii) What is the advantage of solid electrode (like platinum) over mercury electrode
in CV?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
iv) Why CV has been recognized as the most versatile electrochemical technique?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
v) In a system that uses a three electrode potentiostat, between which two electrode
is the potential measured?

…………………………………………………………………………………………...
…………………………………………………………………………………………...

7.6 STRIPPING METHODS

Stripping voltammetry is the most sensitive electrochemical technique for the
quantitative analysis of microquantitative electroactive analytes which oxidize or
reduce reversibly at solid electrodes or form insoluble species at the electrode surface
that can be subsequently removed electrochemically and analysed.

Basically two steps are involved in this technique

1. The analyte of interest is electrolytically deposited on the working electrode by
controlled potential electrolysis.
2. A reverse potential seal or stripping step is applied in which the deposited
analyte is removed from the electrode.

The first step is basically preconcentration or electrodeposition while the second one is
the stripping step. Three different types of this technique are available.

7.6.1 Anodic Stripping Voltammetry

This technique is used to determine trace amounts of metal ions that can be
preconcentrated at an electrode by reduction to the metallic state. The microelectrode
behaves as a cathode during the deposition step and as an anode during the stripping
step with the analyte being oxidized to the original form:

This may be explained in detail taking the example of Cu+2, the deposition reaction at
HMDE (Hanging Mercury Drop Electrode) held at a cathodic potential sufficient to
deposit the metal ion on the electrode
Cu 2 + (aq ) + 2e − = Cu (Hg ) … (7.12)

21
Electroanalytical where Cu(Hg) is copper amalgamated with mercury. This step is basically a
Methods-III preconcentration step where the metal ion from a large volume of the solution is
concentrated on a small volume of the electrode. The solution is stirred during the
electrolysis to increase the rate of deposition. Near the end of the deposition time
stirring is stopped and usually 1-30 mins are used for deposition. In the second step,
the potential is scanned anodically towards more positive potential. When the potential
becomes positive, the analyte is stripped from the electrode returning to its oxidized
form

Cu ( Hg) = Cu 2+ (aq ) + 2 e − … (7.13)

And the current during this step is monitored as a function of potential giving rise to
the voltammogram, the peak current of which is proportional to the analyte
concentration in the solution. This technique is sensitive to experimental conditions
like area of mercury film electrode or size of the Hg drop, deposition time, rest time,
rate of stirring and scan rate during the stripping step. If properly controlled this
method will be quite sensitive and accurate and is best used for metals that form
amalgams.

Stripping voltammetry:
A voltammetric
technique in which the
analyte is first deposited
on the electrode from a
large volume of the
analyte and then stripped
electrochemically
monitoring the current as
a function of the
potential. Fig. 7.12: Details of stripping voltammetry

22
In anodic stripping voltammetry the determination of the analyte is based on the Voltammetry
anodic dissolution. This process is followed voltammetrically and the peak current
thus obtained is proportional to the potential scan rate and radius of mercury drop
(HMDE) or scan rate and surface area of the mercury film (TMFE). In both the cases
the peak current ip is given by

ip = K . n3 2 . D1 2cM 0 (Hg )υ1 2 r 2 .tace

… (7.14)
ip = K .n 2 . AFc 0 ( Hg) υ tace
M

Where, ip = peak current, n = electron transfer during the oxidation of the analyte,
D = diffusion coefficient, K = constant, CM˚ = concentration of metal in the amalgam,
AF = surface area, υ = scan rate, and tace = accumulation time.

However in both the cases the peak current depends on the accumulation time tace and
therefore, is proportional to the concentration of analyte cM˚(Hg) in the amalgam and
indirectly proportional to the concentration of the analyte in the sample solution.

Peak currents in this technique are a linear function of concentration and hence this
technique can be used for the determination of many metal ions in trace quantities in
environmental samples.

7.6.2 Cathodic Stripping Voltammetry

It is used for the determination of anions that form insoluble mercury (I) salts at the
mercury surface or insoluble silver salts on a silver electrode. The experimental design
is similar to that for A.S.V. with two modifications. The decomposition step involves
the oxidation of the Hg electrode to Hg2+ which then reacts with the analyte to form an
insoluble film at the surface. The decomposition step with Cl– is
2Hg (l) + 2Cl− (aq ) = Hg 2 Cl 2 (s) + 2 e − … (7.15)
The second step, i.e. stripping, is followed by scanning cathodically towards a more
negative potential reducing Hg2+ back to Hg and returning the analyte to the solution.
Hg 2 Cl 2 (s) + 2 e − = 2Hg (l) + 2Cl − (aq ) … (7.16)
(Some analytes analysed are halides, sulphides, mercaptan.)

7.6.3 Adsorptive Stripping Voltammetry

In this technique analyte is adsorbed on the electrode surface and there is no
electrolysis step and after complete deposition the potential is scanned in anodic or
cathodic direction depending on whether the analyte is to be oxidized or reduced.

The deposition step in this method amounts to an electrochemical pre-concentration of

the analyte, i.e. the concentration of the analyte on the surface of the microelectrode is
greater than the bulk of solution and hence these methods are extremely sensitive and
the detection limit can be improved by factors of 106 for selected species. Some
analytes analysed by this method are cocaine and testosterone.

SAQ 6
i) Which of the following is better and why?
a) Linear sweep voltammetry and cyclic voltammetry.
b) Anodic stripping voltammetry and Adsorptive stripping voltammetry.

…………………………………………………………………………………….
……...……………………………………………………………………………..

23
Electroanalytical ii) What are the two basic steps involved in stripping voltammetry?
Methods-III
…………………………………………………………………………………….
……...……………………………………………………………………………..

iii) What is so special about the peak currents in Anodic stripping voltammetry?

…………………………………………………………………………………….
……...……………………………………………………………………………..
……...……………………………………………………………………………..
……...……………………………………………………………………………..

7.7 ALTERNATING CURRENT METHODS

In this technique the linear potential is modulated by a sine wave voltage of a small
amplitude. This produces an alternate current, whose size is determined by the direct
potential applied and which is greatest at the half wave potential. The plot of
selectively measured AC against the potential gives a peak shaped alternative current
polarogram as shown in Fig.7.13.

Fig. 7.13: Principle of AC voltammetry

A simplified expression for peak current

ip = K .n2 .E~ f 2 . ca … (7.17)

where, ip = peak current, K = constant, E~ = amplitude of superimposed AC,

ca = concentration of the analyte, n = number of electrons, and F = frequency

Thus, the height of AC polarographic peak can be used to determine the concentration
in a way similar to DC polarographic method. AC polarographic peak currents are
widely dependent on the kinetics of charge transfer reaction and the signals of strongly
irreversible processes are suppressed. For reversible processes the half width of the
90
peak b½ = (mv) depends on the electron exchange as a result of which, for large
n
value of n, b will be narrower and with slow processes, b will be broader.

24
AC polarographic determinations are limited to a sensitivity of about 10–5 mol/dm3 Voltammetry
because of high capacitance current contribution which is the main source for periodic
charging and discharging of double layer.

The above sensitivity for reversible redox processes can be improved to about (5-10)–7
mol/dm3 if the AC is measured at a particular phase shift with reference to the
excitation signal in order to separate the Faradaic and capacitive current. This is the 1st
harmonic AC polarography (AC-1, polarography). The measurement of the harmonic
of the AC resulting from the nonlinearity of the Faradaic resistance, e.g. 2nd harmonic
with the aid of phase selective rectification (AC - 2 polarography) reduces the
capacitance current contribution thus increasing the sensitivity and the selectivity of
the determination. The market available instruments are equipped to measure both the
types of currents.

SAQ 7
How can the height of AC polarographic peak be utilized?

…………………………………………………………………………………………...
…………………………………………………………………………………………...
…………………………………………………………………………………………...

7.7.1 Voltammetry – Instrument

The basic instrument consist of two important components

Computer

Fig 7.14: Basic instrument for voltammetry

1. Normal three electrode polarograph.
2. Linear scan voltage generator to give different type of signals.
The polarographic cell is made up of a three electrodes dipped in a solution
containing the eletroactive species and excess of inert electrolyte usually called
supporting electrolyte.
i) Working electrode, usually a microelectrode whose potential is varied linearly
with time.

25
Electroanalytical ii) Reference electrode: Normally a standard electrode is used whose potential is
Methods-III constant throughout the experiment (saturated calomel electrode or Ag/AgCl
electrode).
iii) Counter electrode, which is a coil of platinum wire or a pool of mercury that
simply serves to conduct electricity from the signal source through the solution
to the microelectrode.
The potentiostat allow to impose the potential scanning between the working and
reference electrodes while the current flowing through the circuit is recorded between
the working and auxiliary electrodes.
The computer CVA Trace analyzer from Metrohm Ltd. can be used as an integrated
instrument with keyboard or a commercially available personal computer interface to
measuring system with software can be used:
i) to send the scanning parameters to the potentiostatic analyzer and check its
correctness and accuracy,
ii) handle the current potential output data.

7.8 SUMMARY
In this unit, you learnt about voltammetry. Various electrodes, especially the common
microelectrodes used in voltammetry were discussed. Then we discussed the common
voltammetry methods. The linear sweep voltammetry, sampled D.C. polarography and
hydrodynamic voltammetry were discussed under the direct current methods. A
detailed discussion of the different pulse methods was done including normal pulse
voltammetry, differential pulse voltammetry, square wave voltammetry and cyclic
voltammetry. Also you have learnt about the various stripping methods including
anodic, cathodic and adsorptive stripping voltammetry. Alternating current methods
were also discussed. In the last section of the unit we learnt about the instrumental
details and steps involved in practical voltammetry.

7.9 TERMINAL QUESTIONS

1. Why is it not necessary to remove dissolved oxygen from the solution before
recording voltammogram in case of anodic current?

2. Discuss the advantages and disadvantages of stripping techniques.

3. Why are the residual currents less with current sampled polarography?

4. Indium and Cadmium ions in 0.1 M HCl give peaks at potentials – 0.557 V and
– 0.597 V by differential pulse polarographic analysis. When a standard solution
containing 0.4 ppm of indium is analyed, it gave peak current (in arbitrary units)
corresponding to 100.25 at – 0.557 V and 43.75 at – 0.597 V. A standard
solution containing 0.4 ppm of Cd gave ips 29.52 at – 0.557 V and 64.8 at –
0.597 V. What is the concentration of indium and cadmium in a sample if the
peak current is 190 at & 0.557 V and 120 at & 0.597V.

5. Anodic stripping voltammetry is used for the analysis of copper in a sea water
sample using standard addition method. When a 50 ml sample is analysed it
gave a peak current of 0.886 µA. A 5.00 µdm3 spike of 10 ppm Cu++ is added to
the sample and the resulting peak current is 3.52 µA. Calculate the
concentration of Cu++ in ppm in the given sample of sea water.

6. Suggest how Eq. (7.11) could be employed to determine the number of electrons
n involved in a reversible reaction at a microelectrode.

26
7. Draw the DME and label its parts. Voltammetry

8. Why are stripping methods more sensitive than other voltammetric procedures?

9. What is the purpose of the electrodeposition step in stripping analysis?

10. How can the reversibility of an electrode process be investigated in cycle

voltammetry?

11. Why must the electrode surface be regularly polished?

12. What is the equivalent equation for classical DC polarography?

13. What are the different pulse methods in voltammetry?

14. Why would the HMDE and the DME be unsuitable for use in flow systems?

15. What is usually meant by the terms anodic and cathodic and when is an
electrode an anode or a cathode?

16. Why would an unstirred solution offer greater reproducibility?

17. Why can stripping voltammetry be applied to only a very small number of
organic compounds?

18. What are the three most important roles played by the separation step?

7.10 ANSWERS
Self Assessment Questions

1. a) This is because in normal DC polarography, the electrode area is not

constant.
b) Tast polarography is also known as sampled DC polarography. In this
technique instead of recording the current continuously, it is sampled for
say a 5 millisecond period just before the drop falls. Between the
sampling periods, the recorder is maintained at its last current level by
means of a sample and hold circuit.

2. The major advantage of current sampling is that it substantially reduces large

current fluctuations due to continuous growth and fall of the drops at dropping
electrode.

3. a) Hydrodynamic voltammetry is the voltammetric method in which the

current is measured as a function of the potential applied to a solid
working electrode kept in stirring solution.
b) In hydrodynamic voltammetry the flow of analyte solution may be done
through a tube in which the microelectrode is fixed.

27
Electroanalytical 4. i) a)
Methods-III
Linear Scan Polarography Pulse Polarography

i) In this technique, the potential of i) The current is measured at a time

the working electrode is varied when the difference between the
linearly as a function of time of Faradaic current of the interfering
the current response is recorded charging current is large
ii) Limited by charging current which ii) The charging current is
is large initially in the drop life. eliminated
iii) Slow, inconvenient apparatus & iii) Sensitivity improved by 6.5 times
poor detection limit

b)

Differential Pulse Polarography Square Wave Polarography

i) In this technique a 50 mv pulse is i) It uses a potential wave form
applied during the last 50ms of the similar to one used in DPP.
life time of the mercury drop. The entire potential sequence is
applied during the life time of a
single drop.
ii) The peak current increases linearly
with the concentration of the
analyte.

ii) The differential pulse polarography is better than normal pulse

polarography as a greater improvement is reached by using the
programming wave. In this technique a 50 mV pulse is applied during the
last 50 ms of the life time of the mercury drop. The current is measured
twice during the life time of each drop, firstly just before the pulse and
second one just before the drop falls. The difference in the current is
plotted resulting a peak shaped curve. The top of the peak corresponds to
E½ and the height of the peak depends on the concentration.

5. i) The pulse methods are better than the direct methods as the sensitivity is
improved by about 6.5 times by eliminating charging current. The current
in these methods is measured at a time when the difference between the
Faradaic current and the interfering charging current is large.
ii) Polarography is voltammetry at controlled potential using a DME as the
working electrode.
iii) Solid electrode (like platinum) is advantageous over mercury electrode in
CV as they have a better positive potential range than mercury.
iv) CV has become increasingly popular in all fields of chemistry as a means
of studying of redox states. The technique enables a wide potential range
to be scanned rapidly for reducible or oxidizable substances. This
capability together with its variable time scale and good sensitivity make
this the most versatile electrochemical technique.
v) The potential is measured between a working electrode and reference
electrode.

28
 Voltammetry
6. i) a) The cyclic voltammetry is better than linear sweep voltammetry as
CV has the capability for rapidly observing the redox behaviour
over a wide range of potential. The resulting voltammogram is
similar to a conventional spectrum in that it conveys information as
a function of an energy scan.
b) The Adsorptive stripping voltammetry is better than the Anodic
stripping voltammetry. In Adsorptive stripping voltammetry
technique analyte is adsorbed on the electrode surface and there is
no electrolysis step and after complete deposition the potential is
scanned in anodic or cathodic direction depending on whether the
analyte is to be oxidized or reduced. The deposition step in this
method amounts to an electrochemical pre-concentration of the
analyte, i.e. the concentration of the analyte on the surface of the
microelectrode is greater than the bulk of solution and hence these
methods are extremely sensitive and the detection limit can be
improved by factors of 106 for selected species.

ii) The two basic steps involved in stripping voltammetry are

1. The analyte of interest is electrolytically deposited on the working
electrode by controlled potential electrolysis.
2. A reverse potential seal or stripping step is applied in which the
deposited analyte is removed from the electrode.
The first step is basically preconcentration or electrodeposition while the
second one is the stripping step.

iii) In Anodic stripping voltammetry the peak current thus obtained is

proportional to the potential scan rate and radius of mercury drop
(HMDE) or scan rate and surface area of the mercury film (TMFE). In
both the cases the peak current depends on the accumulation time tace and,
therefore, is proportional to the concentration of analyte CM˚ (Hg) in the
amalgam and indirectly proportional to the concentration of the analyte in
the sample solution. Peak currents in this technique are a linear function
of concentration and hence this technique can be used for the
determination of many metal ions in trace quantities in environmental
samples.

7. The height of AC polarographic peak can be used to determine the concentration

in a way similar to DC polarographic method. AC polarographic peak currents
are widely dependent on the kinetics of charge transfer reaction and the signals
of strongly irreversible processes are suppressed. For reversible processes the
90
half width of the peak b½ = (mV) depends on the electron exchange as a
n
result of which, for large value of n, b will be narrower and with slow processes,
b will be broader.

Terminal Questions

1. O2 interferes at zero potential and while scanning towards negative potential. If

scanning is towards more positive potentials generating anodic current,
dissolved oxygen will not interfere and hence need not be removed.

2. Advantages of stripping techniques: The sensitivity is more because of

preconcentration step. Disadvantages of stripping techniques: These

29
Electroanalytical techniques are quite sensitive to experimental conditions which are to be
Methods-III carefully controlled to get accurate and precise results.

3. The residual currents are less with current sampled polarography as current is
measured near the end of the drop.

4. Peak currents in differential pulse polarography are directly proportional to the

analytes concentration
ip = k (analyte ppm)
where k is a constant depending on the analyte and applied potential.
The values of k at potentials –0.557 (E1) and –0.597 (E2) for both the metals are
given by
100.25
KIn.E1 = = 250.62 ppm–1
0.4
43.75
KIn.E2 = = 109.4 ppm–1
0.4
29.52
Kcd.E1 = = 73.8 ppm–1
0.4
64.8
Kcd.E2 = = 162.0 ppm–1
0.4
Writing the simultaneous equations for the current at the two potentials

iE1 = 250.62 (Con In) + 73.8 (Con Cd) = 190

iE2 = 109.4 (Con In) + 162.0 (Con Cd) = 120

On solving these two equations we get the

ConIn = 0.674 ppm
ConCd = 0.285 ppm in the given sample.

5. Peak current in anodic stripping voltammetry is proportional to the analyte

concentration
ip α Cu++ (ppm)
ip = k (Con. Cu++)

where k is a constant
Thus for the sample 0.886 = k (con. Cu++) … (1)
and for the standard solution

3.52 = k
 0.05 dm3 5.00×10−6 dm3 
 3 −6 3
(Con . Cu )
++
+ 3 −6 3
(10 ppm ) …(2)
 0.05 dm + 5 x 10 dm 0.05 dm + 5×10 dm 
Solving the Eq. (1) for k and substituting in Eq. (2) the concentration of Cu++ in
the given sample of sea water comes out to 3.36 × 10– 4 ppm.

6. The number of electrons transferred in the electrode reaction (n) for a reversible
couple can be determined from the separation between peak potentials.

∆Ep = Ep − Ep = 0.059
a c n

Thus, for a one-electron process such as the reduction of [FeIII(CN)6]3– to

[FeII(CN)6]4– exhibits ∆ Ep of 0.059 V. So, by knowing ∆ Ep the number of

30
 electrons n involved in a reversible reaction at a microelectrode can be Voltammetry
determined.

7. Fig. 7.1 c

8. It is the most sensitive because it includes a preconcentration step in which the

analyte is collected over a long period from a large volume and reoxidized (or
re-reduced) in a short ‘burst’ creating an enhanced current signal.

9. The analyte of interest is electrolytically deposited on the working electrode by

controlled potential electrolysis.

10. Refer to Table 7.1

11. Electrode products can often build up on the surface of a solid or stationary
electrode. Species from the solution may adsorb on the surface. Some solid
electrode materials may even develop oxide layers on the surface. All of these
produce changes in the nature of the electrode and often completely distort the
electrochemical response. By regular polishing back to a clean metal or graphite
surface, some attempt can be made to achieve a reproducible surface. Better
results are usually obtained from a smooth rather than a rough surface.

12. The Ilkovic equation: id = 708 nD1/2 m2/3 t1/6c

13. Pulse methods

i) Normal Pulse voltammetry
ii) Differential Pulse voltammetry
iii) Square wave voltammetry
iv) Cyclic voltammetry

14. They are much too mechanically unstable. The drop can be knocked off far too
easily. They have in fact been used in flow systems but great care and much
patience is needed. Further it is difficult to construct very small cells to hold a
mercury drop electrode − a major disadvantage.

15. An anodic reaction is an oxidation. A cathodic reaction is a reduction. An anode

is an electrode at which an oxidation reaction is taking place. Its potential need
not have a positive value but oxidation occurs more easily the more positive the
potential. Thus, the anodic direction is to more positive potentials. Similarly a
cathodic or reduction process could occur at a positive potential but as the
electrode becomes more negative it becomes more cathodic.

16. Simple undisturbed diffusion is a highly reproducible phenomenon and highly

suitable for an analytical application. In a stirred solution the movement of the
solution can be highly complex and not always predictable. If eddies form in the
stirred solution they are very unreproducible and must be avoided.

Even in a very evenly stirred solution a slight displacement of the electrode can
change the flow pattern. Reproducible stirring requires careful cell design and
experimentation. The best stirring is a rotating electrode in a reproducible
position in the cell.

31
Electroanalytical 17. Most organic compounds do not form insoluble electrode products. Most
Methods-III organic compounds are soluble at these high dilution trace levels. Many of those
organic electrode products that are insoluble cannot be reoxidised or reduced to
form a stripping peak, or the insoluble layer is insufficiently coherent. The most
common type of organic compound to which stripping analysis can be applied
are those containing a thiol group.

18. i) To separate the analyte from a medium in which it cannot be determined.

ii) To remove potential interfering species.
iii) To separate and allow individual determination of electrochemically
similar analytes.

32