Further Physical Chemistry:

Electrochemistry session 10
https://www.youtube.com/watch?v=LiRqWcgJkb4Controlled Potential Techniques
It is the measurement of the current response to an applied potential. There are different techniques
involving controlled potential.

Voltammetry

History
This field has been developed from Polarography. Voltammetry was developed by Czech chemist
Jaroslav Heyrovsky in the year 1992. He received the noble prize in chemistry for this work. Early
voltammetric methods experienced a number of difficulties. Then significant advances were made
in all areas of voltammetry (theory, methodology, and instrumentation). This enhanced the
sensitivity and expanded the variety of analytical methods. The introduction of low-cost
operational amplifiers in this also facilitated the rapid commercial development of relatively
inexpensive instrumentation.

Theory

1
In voltammetry, the effects of the applied potential and the behavior of the redox current are
described by several well-known laws. The applied potential controls the concentrations of the
redox species at the electrode surface and the rate of the reaction (k), as described by the Nernst
or Butler– Volmer equations, respectively. The interplay between these processes is responsible
for the characteristic features observed in the voltammograms of the various techniques.

Nernst equation:

Butler–Volmer equation:

2
Electrode Setup
It consists of two or three electrodes; the working, counter, and reference electrode.

Working (indicator) electrode:

It provides the interface across which a charge can be transferred or its effects felt. The reduction
or oxidation of a substance at the surface of a working electrode, at the appropriate applied
potential, results in the mass transport of new material to the electrode surface and the generation
of a current. Working electrodes are of various geometries and materials, ranging from small Hg
drops to flat Pt disks. Commonly used electrode materials are gold, platinum, and glassy carbon.
Mercury is useful because: 1. It displays a wide negative potential range 2. It’s surface is readily
regenerated by producing a new drop or film 3. Many metal ions can be reversibly reduced into it.
Reference Electrodes:
Normally a standard electrode is used whose potential is constant throughout the experiment. They
are easy to assemble and maintain. The most commonly used reference electrodes for aqueous
solutions are the calomel electrode and the silver/silver chloride electrode (Ag/AgCl). Electrodes
are commercially available in a variety of sizes and shapes. In most cases the reference electrode
should be as close as possible to the working electrode. Sometimes to avoid contamination, it may
be necessary to place the reference electrode in a separate compartment.

Counter (Auxiliary) electrode:

It consists of 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. In most voltammetric techniques
the analytical reactions at the electrode surfaces occur over very short time periods. Thus, isolation
of the counter electrode from the sample is not normally necessary. Most often the counter
electrode consists of a thin Pt wire, although Au and sometimes graphite have also been used.

Cell:
Cells or sample holders come in a variety of sizes, shapes, and materials. Type used depends on
the amount and type of sample, the technique, and the analytical data to be obtained. The material
of the cell (glass, Teflon, polyethylene) is selected to minimize reaction with the sample.

Types of Voltammetry:
• Linear sweep voltammetry
• Cyclic voltammetry
• Square-wave voltammetry
• Cathodic stripping voltammetry
• Alternating current voltammetry
• Rotated electrode voltammetry
• Staircase voltammetry
• Anodic stripping voltammetry
• Adsorptive stripping voltammetry
• Polarography

3
• Normal pulse voltammetry • Differential pulse voltammetry
• Chronoamperometry
Uses
 Quantitative determination of organic and inorganic (pharmaceutical compounds and
metal ions) in aqueous and non-aqueous solutions
 Measurement of kinetic rates and constants
 Determination of adsorption processes on surfaces
 Determination of electron transfer and reaction mechanisms
 Determination of thermodynamic properties of solvated species
 Fundamental studies of oxidation and reduction processes in various media
 Making of corrosion proof materials
 Production of new types of batteries that can store large quantities of energy
 Determination of redox potentials
 Detection of eluted analytes in high- performance liquid chromatography (HPLC) and
flow injection analysis

Advantages
 Excellent sensitivity with a very large useful linear concentration range for both inorganic
and organic species (10–12 to 10–1 M)
 A large number of useful solvents and electrolytes, a wide range of temperatures, rapid
analysis times (seconds)
 Simultaneous determination of several analytes, the ability to determine kinetic and
mechanistic parameters
 A well-developed theory and thus the ability to reasonably estimate the values of
unknown parameters

Polarography:
Polarography is a subclass of voltammetry where the working electrode is a dropping mercury
electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their wide
cathodic ranges and renewable surfaces. It was invented in 1922 by Jaroslav Heyrovský, for which
he won the Nobel Prize in 1959.
There are three types of mercury electrodes; Hanging mercury drop electrode (HMDE), Dropping
mercury electrode (DME), and Static mercury drop electrode (SMDE). In the hanging mercury
drop electrode, or HMDE, we extrude the drop of Hg by rotating a micrometer screw that pushes
the mercury from a reservoir through a narrow capillary tube. In the dropping mercury electrode,
or DME, mercury drops form at the end of the capillary tube as a result of gravity. Unlike the
HMDE, the mercury drop of a DME grows continuously—as mercury flows from the reservoir

4
under the influence of gravity—and has a finite lifetime of several seconds. At the end of its
lifetime the mercury drop is dislodged, either manually or on its own, and replaced by a new drop.
The static mercury drop electrode, or SMDE, uses a solenoid driven plunger to control the flow
of mercury. Activation of the solenoid momentarily lifts the plunger, allowing mercury to flow
through the capillary and forming a single, hanging Hg drop. Repeatedly activating the solenoid
produces a series of Hg drops. In this way the SMDE may be used as either a HMDE or a DME.

Fig. 2. (a) Hanging mercury drop electrode, or HMDE; (b) dropping mercury electrode, or DME;
and (c) static mercury drop electrode, or SMDE.
The simple principle of polarography is the study of solutions or of electrode processes by means
of electrolysis with two electrodes, one polarizable and one non-polarizable (see Figure below).
Polarography is a specific type of measurement that falls into the general category of linear-sweep
voltammetry where the electrode potential is altered in a linear fashion from the initial potential to
the final potential. Polarography differs from other linear sweep voltammetry measurement is that
polarography makes use of the dropping mercury electrode (DME) or the static mercury drop
electrode.

5
Although polarography takes place in an unstirred solution, we obtain a limiting current instead of
a peak current. When an Hg drop separates from the glass capillary and falls to the bottom of the
electrochemical cell, it mixes the solution and produces oscillations. Each new Hg drop, therefore,
grows into a solution whose composition is identical to the bulk solution. The limiting current—
which is also called the diffusion current—is measured using either the maximum current, imax, or
from the average current, iavg. The relationship between the analyte’s concentration, C A, and the
limiting current is given by the Ilkovic equation.

(il)max=706nD1/2m2/3t1/6CA=KmaxCA
(il)avg=607nD1/2m2/3t1/6CA=KavgCA
where n is the number of electrons in the redox reaction, D is the analyte’s diffusion coefficient,
m is the flow rate of the Hg, t is the drop’s lifetime and Kmax and Kavg are constants. The half-
wave potential, E1/2, provides qualitative information about the redox reaction.
A plot of the current vs. potential in a polarography experiment shows the current oscillations
corresponding to the drops of Hg falling from the capillary. If one connected the maximum current
of each drop, a sigmoidal shape would result. The limiting current (the plateau on the sigmoid),
called the diffusion current because diffusion is the principal contribution to the flux of
electroactive material at this point of the Hg drop life.

6
 Fig.3 Polarography
Linear Sweep Voltammetry (LSV):
In this method where the current at a working electrode is measured while the potential between
the working electrode and a reference electrode is swept linearly in time. In this technique a fixed
potential (voltage) range is used. A signal generator produces a potential sweep from Ei to Ef and
a potentiostate applies this potential wave to the electrode under study. The potential scan direction
may be positive or negative. For instance, as in Fig 4, the scan begins from left hand side of the
voltammogram where no current flows. As the potential is swept further to the right (more
reductive values) a current begins to flow and eventually reaches a peak before dropping.
Oxidation or reduction of species is registered as a peak or trough in the current signal at the
potential at which the species begins to be oxidized or reduced. The current response is plotted as
a function of voltage rather than time. The sensitivity of current changes vs. voltage can be
increased by increasing the scan rate. Higher potentials per second result in more
oxidation/reduction of a species at the surface of the working electrode.
Scan rate=Sweep rate = dE/dt

7
 Fig. 4
Application of Linear Sweep Voltammetry
Linear sweep voltammetry is used to identify unknown species and determine the concentration
of solutions. E1/2 can be used to identify the unknown species while the height of the limiting
current can determine the concentration.

In cases where the reaction is irreversible cyclic voltammetry is not applicable, linear sweep
voltammetry is employed.
Staircase Voltammetry (SCV):

It is derived from linear sweep voltammetry. In staircase voltammetry the potential sweep is a
series of stair steps. The current is measured at the end of each potential change, right before the
next so that the contribution to the current signal from the capacitive charging current is reduced.
The potential-time waveform involves successive potential steps of ~10mV height and about 50ms
duration. See Fig. 5.

The staircase voltammetry can be Linear Staircase Voltammetry (LSCV) or Cyclic Staircase
Voltammetry (CSCV). In LSCV, after the induction period, the potential of the working electrode
is stepped from the Initial Potential to the Final Potential in Step amplitude increments. The period
of each step is controlled by the Step period increment. In CSCV, using a two segment experiment
as an example, the electrode potential is swept from the Initial potential to the Upper potential or
Lower potential, then reversed and swept to the Final potential.

8
 Fig. 5
Cyclic Voltammetry: In a cyclic voltammetry experiment the working electrode potential is
scanned linearly versus time like linear sweep voltammetry. Cyclic voltammetry takes the
experiment a step further than linear sweep voltammetry which ends when it reaches a set potential.
The current at the working electrode is plotted versus the applied voltage to give the cyclic
voltammogram trace (Fig 6). It is generally used to study the electrochemical properties of an
analyte in solution. Common materials used as electrodes include glassy carbon, platinum, and
gold. Electrodes are generally encased in a rod of inert insulator with a disk exposed at one end.
In this example, first scan the potential to more positive values, resulting in the following oxidation
reaction for the species R.

9
 R⇋O+ne−

When the potential reaches a predetermined switching potential, the direction of the scan is reverse
and it goes toward more negative potentials. As the oxidized specie is generated on the forward
scan, during the reverse scan it is reduced back to R.

O+ne−⇋R

Because the cyclic voltammetry is carried out in an unstirred solution, the resulting cyclic
voltammogram, as shown in Figure, has peak currents instead of limiting currents. The
voltammogram has separate peaks for the oxidation reaction and the reduction reaction, each
characterized by a peak potential and a peak current.

Fig. 6
The peak current in cyclic voltammetry is given by the Randles-Sevcik equation
ip=(2.69×105)n3/2AD1/2ν1/2C=KC

where n is the number of electrons in the redox reaction, A is the area of the working electrode, D
is the diffusion coefficient for the electroactive species, ν is the scan rate, and C is the concentration
of the electroactive species at the electrode.

Applications of CV:
Cyclic voltammetry (CV) has become an important and widely used electroanalytical technique in
many areas of chemistry. It is often used to study a variety of redox processes, to determine the
stability of reaction products, the presence of intermediates in redox reactions, electron transfer
kinetics, and the reversibility of a reaction. CV can also be used to determine the electron
stoichiometry of a system, the diffusion coefficient of an analyte, and the formal reduction
potential of an analyte, which can be used as an identification tool.

10
Square Wave Voltammetry:
This technique was invented by Ramaley and Krause, and developed extensively by the
Osteryoungs and their co-workers. It is a differential technique in which potential waveform
composed of a symmetrical square wave of constant amplitude is superimposed on a base staircase
potential as in Fig. 7. It is the plot of the difference in the current measured in forward (if) and
reverse cycle (ir), plotted against the average potential of each waveform cycle. In this technique,
the peak potential occurs at the Em of the redox couple because the current function is symmetrical
around the potential. The main advantages of SWV are excellent peak separation and high
sensitivity.

Fig. 7.

Rotated Electrode Voltammetry:

Rotated electrode voltammetry, a subclass of voltammetry, is technique in which the working
electrode usually a rotating disk electrode (RDE) or rotating ring-disk electrode (RRDE) is rotated
at a very high rate (2000 to 10,000 RPM). This asserts some control over the mass transport process
which brings the analyte to the electrode surface. This technique was made popular through the
work of the Russian electrochemist, Benjamin Levich. This technique is useful for studying the
kinetics and electrochemical reaction mechanism for a half reaction.

Chronoamperometery:
Chronoamperometry is an electrochemical technique in which the potential of the working
electrode is stepped and the resulting current from faradaic processes occurring at the electrode
(caused by the potential step) is monitored as a function of time. It involves stepping the potential
of the working electrode from a value at which no faradaic reaction occurs to a potential at which
the surface concentration of the electroactive species is effectively zero.

11