ARBAMINCH UNIVERSITY

SCHOOL OF POST GRADUATE STUDIES

COLLEGE OF NATURAL SCIENCES

DEPARTMENT OF CHEMISTRY

MSc PROGRAM IN INORGANIC CHEMISTRY

ADVANCED INSRUMENTAL ANALYSIS

SEMINAR ON

VOLTAMMETRIC TECHNIQUES

BY

NARDOS TESFALEM

ADVISOR DR.TOLERA S.

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 TABLE OF CONTENTS
ACKRONYM--------------------------------------------------------------------------------------------------------------- iii
1. INTRODUCTION------------------------------------------------------------------------------------------------------ 1
1.1 Voltammetry--------------------------------------------------------------------------------------------------------- 2
1.2 Working principle of voltammetry-----------------------------------------------------------------------------3
1.3 Current in Voltammetry------------------------------------------------------------------------------------------- 4
1.4 Instrumentation----------------------------------------------------------------------------------------------------- 6
1.5 Shape of Voltammograms---------------------------------------------------------------------------------------- 8
1.6 Quantitative and Qualitative Aspects of Voltammetry-----------------------------------------------------9
1.6.1 Qualitative-------------------------------------------------------------------------------------------------------9

1.6.2 Quantitative-----------------------------------------------------------------------------------------------------9

1.7 Characteristics----------------------------------------------------------------------------------------------------- 10
2. VOLTAMMETRIC TECHNIQUES---------------------------------------------------------------------------12
2.1 Polarography------------------------------------------------------------------------------------------------------- 12
2.2 Pulse Methods----------------------------------------------------------------------------------------------------- 13
2.2.1. Normal Pulse Voltammetry (NPV)---------------------------------------------------------------------13
2.2.2 Differential Pulse Voltammetry (DPV)------------------------------------------------------------------13
2.2.3 Square-Wave Voltammetry (SWV)---------------------------------------------------------------------13
2.3 Stripping Voltammetry------------------------------------------------------------------------------------- 14
2.3.1 Anodic stripping voltammetry(ASV)-------------------------------------------------------------14
2.3.2 Cathodic stripping voltammetry (CSV)----------------------------------------------------------15
2.3.3 Adsorptive stripping voltammetry (ASV)--------------------------------------------------------15
2.3.4 Potentiometric stripping voltammetry (PSV)---------------------------------------------------15
2.3.5 Rapid Scans Voltammetry – Linear Sweep Voltammetry, LSV----------------------------16
2.4 Cyclic Voltammetry, CV----------------------------------------------------------------------------------- 16
3. STEPS OF VOLTAMMETRIC ANALYSIS-------------------------------------------------------------------18
Reference------------------------------------------------------------------------------------------------------------------- 20

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Table of figures

Figure 1: Voltametry------------------------------------------------------------------------------------------
Figure 2: Voltammetric Measurements--------------------------------------------------------------------
Figure 3 : three common shapes of voltammograms-----------------------------------------------------
Figure 4:Polarography set up------------------------------------------------------------------------------
Figure 5: Anodic stripping voltammetry-----------------------------------------------------------------
Figure 6: Cyclic voltammetry------------------------------------------------------------------------------

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 ACKRONYM

WE………………………………..........................................................Working Electrode
AE…………………………………………………………….……......Auxiliary Electrode
RE…………………………………………………………….………..Reference electrode
HMDE………………………………………………...Hanging Mercury Drop Electrode
DME……………………………………………..…………..Dropping Mercury Electrode
SMDE…………………………………………...…………Static Mercury Drop Electrode
EDL…………………………………………………………….…...Electrical Double Layer
NPV……………………………………………….…………..Normal Pulse Voltammetry
DPV………………………………………….……………Differential Pulse Voltammetry
SWV........................................................................................…..Square Wave Voltammetry
HPLC……………………………………………..High Pressure Liquid Chromatography
ASV………………………………………………………...Anodic Stripping Voltammetry
CSV………………………………………………………Cathodic Stripping Voltammetry
ASV……………………………………………………Adsorptive Stripping Voltammetry
PSV………………………………………………..Potentiometric Stripping Voltammetry
LSV…………………………………………………………….Linear Sweap Voltammetry
CV……………………………………………………………………..Cyclic Voltammetry

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1. INTRODUCTION

Earlier the voltammetry was known as electrochemistry. In 1922 voltammetry was

established from the invention of polarography by Jaroslav Heyrovsky, a Czech chemist got
Noble Prize in chemistry in 1959. In 1960’s and 1970’s, many advancements were made in
voltammetry. The advancements improved the sensitivity and range of analytical techniques.
All voltammetric techniques apply potential (E) to an electrode and the resultant current (i) is
observed. In many cases the applied potential is varied or the current is monitored over a
period of time (t). Thus, all voltammetric techniques can be described as some function of E,
i, and t. They are considered active techniques (as opposed to passive techniques such as
potentiometric) because the applied potential forces a change in the concentration of an
electroactive species at the electrode surface by electrochemically reducing or oxidizing it[1].
The analytical advantages of the various voltammetric techniques include 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, and the
ease with which different potential waveforms can be generated and small currents
measured[2]. Analytical chemists routinely use voltammetric techniques for the quantitative
determination of a variety of dissolved inorganic and organic substances. Inorganic, physical,
and biological chemists widely use voltammetric techniques for a variety of purposes,
including fundamental studies of oxidation and reduction processes in various media,
adsorption processes on surfaces, electron transfer and reaction mechanisms, kinetics of
electron transfer processes, and transport, speciation, and thermodynamic properties of
solvated species. Voltammetric methods are also applied to the determination of compounds
of pharmaceutical interest and, when coupled with HPLC, they are effective tools for the
analysis of complex mixture.[3]

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1.1 Voltammetry
Voltammetry is the study of the current response of a chemical under an applied potential
difference. Voltammetry encompasses a number of different methods, each of which can tell
us about the kinetics and thermodynamics of electron addition (reduction) and electron loss
(oxidation). In addition, voltammetry can be used to test for the presence of an electroactive
substance.In voltammetry a time-dependent potential is applied to an electrochemical cell,
and the current flowing through the cell is measured as a function of that potential. A plot of
current as a function of applied potential is called a voltammogram and is the electrochemical
equivalent of a spectrum in spectroscopy, providing quantitative and qualitative information
about the species involved in the oxidation or reduction reaction.
The voltammetry method relies on the fact that the current measured reflects rate determining
diffusion of the analytic species from the bulk solution to the surface of the indicator
electrode where it is readily oxidized or reduced.
As an applied potential is changed over time a current is measured
Reduces ions in the electrode commonly use three electrodes
Working Electrode (WE)
Auxiliary Electrode (AE)
Reference Electrode (RE

Figure 1: Voltammetry

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1.2. Working principle of voltammetry
The electrochemical cell, where the voltammetric experiment is carried out, consists of a
working (indicator) electrode, a reference electrode, and usually a counter (auxiliary)
electrode. In general, an electrode provides the interface across which a charge can be
transferred or its effects felt. Because the working electrode is where the reaction or transfer
of interest is taking place, whenever we refer to the electrode, we always mean the working
electrode. 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. Even though the various types of
voltammetric techniques may appear to be very different at first glance, their fundamental
principles and applications derive from the same electrochemical theory.
Several different materials have been used as working electrodes, including mercury,
platinum, gold, silver, and carbon. The earliest voltammetric techniques, including
polarography, used mercury for the working electrode. Since mercury is a liquid, the working
electrode often consists of a drop suspended from the end of a capillary tube.
In the hanging mercury drop electrode, or HMDE, a drop of the desired size is formed by
the action of a micrometer screw that pushes the mercury 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 and has a finite lifetime of several seconds. At the end of its lifetime the
mercury drop is dislodged, either manually or by gravity, and replaced by a new drop.
The static mercury drop electrode, or SMDE, uses a solenoid-driven plunger to control the
flow of mercury. The SMDE can be used as either a hanging mercury drop electrode or as a
dropping mercury electrode. A single activation of the solenoid momentarily lifts the
plunger, allowing enough mercury to flow through the capillary to form a single drop. To
obtain a dropping mercury electrode the solenoid is activated repeatedly. A mercury film
electrode consists of a thin layer of mercury deposited on the surface of a solid carbon,

platinum, or gold electrodes. The solid electrode is placed in a solution of Hg2+ and held at

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a potential at which the reduction of Hg2+ to Hg is favorable, forming a thin mercury

film.
Figure 2: Voltammetric Measurements

Mercury electrodes: (a) hanging mercury drop electrode; (b) dropping mercury electrode; (c)
static mercury drop electrode

1.3 Current in Voltammetry

When an analyte is oxidized at the working electrode, a current passes electrons through the
external electric circuitry to the auxiliary electrode, where reduction of the solvent or other
components of the solution matrix occurs. Reducing an analyte at the working electrode
requires a source of electrons, generating a current that flows from the auxiliary electrode to
the cathode. In either case, a current resulting from redox reactions at the working and
auxiliary electrodes is called a faradaic current. In this section we consider the factors
affecting the magnitude of this faradaic current, as well as the source of any non-faradaic
currents.

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Sign Conventions 

Since the reaction of interest occurs at the working electrode,the classification of current is b
ased on this reaction. A current due to the analyte’sReduction is called a cathodic current an
d, by convention, is considered positive. Anodic currents are due to oxidation reactions and 
carry a negative value.

Influence of Mass Transport on the Faradaic Current

There are three modes of mass transport that influence the rate at which reactants and
products are transported to and from the electrode surface: diffusion, migration, and
convection.
Diffusion from a region of high concentration to a region of low concentration occurs
whenever the concentration of an ion or molecule at the surface of the electrode is different
from that in bulk solution. The volume of solution in which the concentration gradient exists
is called the diffusion layer. Without other modes of mass transport, the width of the
diffusion layer, d, increases with time as the concentration of reactants near the electrode
surface decreases.
The contribution of diffusion to the rate of mass transport, therefore, is time-dependent.
Influence of the Kinetics of Electron Transfer on the Faradaic Current
The rate of mass transport is one factor influencing the current in a voltammetric experiment.
The ease with which electrons are transferred between the electrode and the reactants and
products in solution also affects the current. When electron transfer kinetics is fast, the redox
reaction is at equilibrium, and the concentrations of reactants and products at the electrode
are those specified. Such systems are considered electrochemically reversible. In other
systems, when electron transfer kinetics is sufficiently slow, the concentration of reactants
and products at the electrode surface, and thus the current, differ from that predicted. In this
case the system is electrochemically irreversible.

Non-faradaic Currents Faradaic currents result from a redox reaction at the electrode
surface. Other currents may also exist in an electrochemical cell that is unrelated to any redox
reaction. These currents are called non faradaic currents and must be accounted for if the
faradaic component of the measured current is to be determined.

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The most important example of a non-faradaic current occurs whenever the electrode’s
potential is changed. In discussing migration as a means of mass transport, we noted that
negatively charged particles in solution migrate toward a positively charged electrode, and
positively charged particles move away from the same electrode.
When an inert electrolyte is responsible for migration, the result is a structured electrode–
surface interface called the electrical double layer, or EDL, the exact structure of which is of
no concern in the context of this text. The movement of charged particles in solution,
however, gives rise to a short-lived, non-faradaic charging current. Changing the potential of
an electrode causes a change in the structure of the EDL, producing a small charging current.
Residual Current Even in the absence of analyte, a small current inevitably flows through
an electrochemical cell. This current, which is called the residual current consists of two
components: a faradaic current due to the oxidation or reduction of trace impurities, and the
charging current.

1.4 Instrumentation
The basic components of a modern electroanalytical system for voltammetry are a
potentiostat, computer, and the electrochemical cell. In some cases the potentiostat and
computer are bundled into one package, whereas in other systems the computer and the A/D
and D/A converters and microcontroller are separate, and the potentiostat can operate
independently. The Potentiostat The task of applying a known potential and monitoring the
current falls to the potentiostat. The most widely used potentiostats today are assembled from
discrete integrated-circuit operational amplifiers and other digital modules. In many cases,
especially in the larger instruments, the potentiostat package also includes electrometer
circuits, A/D and D/A converters, and dedicated microprocessors with memory. The output
of OA-1 is connected to the counter electrode with feedback to its own inverting input
through the reference electrode. This feedback decreases the difference between the inverting
and noninverting inputs of OA-1 and causes the reference electrode to assume the same
potential as Ein of OA-1. Because the potential difference between the working electrode and
the reference electrode is zero the working electrode is set to the same potential as applied to
the OA-1 input. With the reference electrode connected to E in through the high impedance
of OA-3, the current must flow through the counter electrode. Current flow through the
reference not only is undesirable because of its higher resistance but also would eventually

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cause its potential to become unreliable. A three-electrode system is normally used in
voltammetry for currents in the range of microamperes to milliamperes. With the use of
micron-sized electrodes, currents are in the pico- to nanoampere range, and thus two
electrodes are often used (that is, the counter and reference are tied together). An OA acting
as a current-to-voltage converter (OA-2) provides the output signal for the A/D converter.
Most voltammetric techniques are dynamic (that is, they require a potential modulated
according to some predefined waveform). Accurate and flexible control of the applied
potential is a critical function of the potentiostat. In early analog instruments, a linear scan
meant just that, a continuous linear change in potential from one preset value to another.
Since the advent of digital electronics almost all potentiostats operate in a digital
(incremental) fashion. Thus, the application of a linear scan is actually the application of a
“staircase” modulated potential with small enough steps to be equivalent to the analog case.
Not surprisingly, digital fabrication of the applied potential has opened up a whole new area
of pulsed voltammetry, which gives fast experiments and increased sensitivity. In the simpler
standalone potentiostats the excitation signal used to modulate the applied potential is usually
provided by an externally adjustable waveform generator. In the computer-controlled
instruments, the properties of the modulation and the waveform are under software control
and can be specified by the operator. The most commonly used waveforms are linear scan,
differential pulse, and triangular and square wave. The use of micro- and nanometer-size
electrodes has made it necessary to build potentiostats with very low current capabilities.
Microelectrodes routinely give current responses in the pico- to nanoampere range. High-
speed scanning techniques such as square-wave voltammetry require very fast response times
from the electronics. These diverse and exacting demands have pushed potentiostat
manufacturers into providing a wide spectrum of potentiostats tailored to specific
applications. The Electrodes and Cell a typical electrochemical cell consists of the sample
dissolved in a solvent, an ionic electrolyte, and three (or sometimes two) electrodes. Cells
(that is, sample holders) come in a variety of sizes, shapes, and materials. The 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. In most cases the reference electrode should be as close as possible
to the working electrode; in some cases, to avoid contamination, it may be necessary to place

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the reference electrode in a separate compartment. The unique requirements for each of the
voltammetry techniques are described under the individual techniques. Reference Electrodes
The reference electrode should provide a reversible half-reaction with Nernstian behavior, be
constant over time, and be easy to assemble and maintain. The most commonly used
reference electrodes for aqueous solutions are the calomel electrode, with potential
determined by the reaction Hg2Cl2 (s) + 2e– = 2Hg (l) + 2Cl– and the silver/silver chloride
electrode (Ag/AgCl), with potential determined by the reaction AgCl(s) + e– = Ag(s) + Cl– .
Table 37.1 shows the potentials of the commonly used calomel electrodes, along with those
of some other reference electrodes. These electrodes are commercially available in a variety
of sizes and shapes. Counter Electrodes In most voltammetric techniques the analytical
reactions at the electrode surfaces occur over very short time periods and rarely produce any
appreciable changes in bulk concentrations of R or O. 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. Working Electrodes The
working electrodes are of various geometries and materials, ranging from small Hg drops to
flat Pt disks. Mercury is useful because it displays a wide negative potential range (because it
is difficult to reduce hydrogen ion or water at the mercury surface), its surface is readily
regenerated by producing a new drop or film, and many metal ions can be reversibly reduced
into it. Other commonly used electrode materials are gold, platinum, and glass

1.5. Shape of Voltammograms

The shape of a voltammogram is determined by several experimental factors, the most
important of which are how the current is measured and whether convection is included as a
means of mass transport. Despite an abundance of different voltammetric techniques, several
of which are discussed in this chapter, only three shapes are common for voltammograms.
The voltammogram is characterized by a current that increases from the background residual
current to a limiting current at potentials at which the analyte is oxidized or reduced. Since
the magnitude of a faradaic current is inversely proportional to, a limiting current implies that
the thickness of the diffusion layer remains constant. The simplest method for obtaining a
limiting current is to stir the solution, which can be accomplished with a magnetic stir bar, or
by rotating the electrode.

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Voltammetric techniques that include convection by stirring are called hydrodynamic
voltammetry. When convection is absent, the thickness of the diffusion layer increases with
time, resulting in a peak current in place of a limiting current.

Alternatively, the change in current following a change in potential may be measured.

Figure 3 : three common shapes of voltammograms

1.6 Quantitative and Qualitative Aspects of Voltammetry

1.6.1 Qualitative

voltammetric techniques give rise to current signals that appear at a characteristic position on
the potential scale. The potential at which the signal appears gives qualitative information
about the reactant. However, the ability of the potential of the signal to identify the reactant is
not very large because the position of the signal depends on the reactant conditions and the
resolution is poor. Thus, a characteristic potential excludes many possibilities for the identity
of the reactant; in particular, the voltammetric response absolutely excludes all non-
electroactive substances. If the response is the same as that of a known substance, obtained
under exactly the same conditions, then the known substance is a good hypothesis for the
identity. However, in general voltammetric techniques are not good tools for qualitative
identification of analytes.

1.6.2 Quantitative

Virtue of voltammetric techniques is their good accuracy, excellent precision (<1%),

sensitivity, and wide dynamic range. In the special case of stripping voltammetry, detection
limits routinely are lower than the amount of signal due to contamination of sample.

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1.7 Characteristics
Voltammetry is based upon the measurement of a current that develops in an electrochemical
cell under conditions of complete concentration polarization.
Potentiometric measurements are made at currents that approach zero and where polarization
is absent. Furthermore, in voltammetry a minimal consumption of analyte takes place,
whereas in electro gravimeter and coulometer essentially all of the analyte is converted to
another state. Voltammetry (particularly classical polarography) was an important tool used
by chemists for the determination of inorganic ions and certain organic species in aqueous
solutions.

The common characteristic of all voltammetry techniques is that they involve the application
of a potential (E) to an electrode and the monitoring of the resulting current (i) flowing
through the electrochemical cell. In many cases the applied potential is varied or the current
is monitored over a period of time (t). Thus, all voltammetry techniques can be described as
some function of E, i, and t. They are considered active techniques (as opposed to passive
techniques such as potentiometric) because the applied potential forces a change in the
concentration of an electro active species at the electrode surface by electrochemically
reducing or oxidizing it.

The analytical advantages of the various voltammetric techniques include excellent

sensitivity with a very large useful linear concentration range for both inorganic and organic
species (10–12 to 10–1M),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, and the ease with which
different potential waveforms can be generated and small currents measured.

Analytical chemists routinely use voltammetric techniques for the quantitative determination
of a variety of dissolved inorganic and organic substances. Inorganic, physical, and
biological chemists widely use voltammetric techniques for a variety of purposes, including
fundamental studies of oxidation and reduction processes in various media, adsorption
processes on surfaces, electron transfer and reaction mechanisms, kinetics of electron transfer

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processes, and transport, speciation, and thermodynamic properties of solvated species.
Voltammetric methods are also applied to the determination of compounds of pharmaceutical
interest and, when coupled with HPLC, they are effective tools for the analysis of complex
mixtures.
1.8. Application of voltammetry
• Quantitative determination of organic and inorganic compounds in aqueous and non-
aqueous solutions
• Measurement of kinetic rates and constants
• Determination adsorption processes on surfaces
• Determination electron transfer and reaction mechanisms
• Determination of thermodynamic properties of solvated species
• Fundamental studies of oxidation and reduction processes in various media
• Determination of complexation and coordination values
• Quantitative determination of pharmaceutical compounds
• Determination of metal ion concentrations in water to sub–parts-per-billion levels
• Determination of redox potentials
• Detection of eluted analytes in high-performance liquid chromatography (HPLC) and flow
injection analysis
• Determination of number of electrons in redox reactions

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2. VOLTAMMETRIC TECHNIQUES
This section discusses in more detail some of the more common forms of voltammetry
currently in use for a variety of analytical purposes. The uniqueness of each rests on subtle
differences in the manner and timing in which the potential is applied and the current
measured. These differences can also provide very diverse chemical, electrochemical, and
physical information, such as highly quantitative analyses, rate constants for chemical
reactions, electrons involved on redox reactions, and diffusion constants.

2.1 Polarography
The earliest voltammetric experiment was normal polarography at a dropping mercury
electrode. In normal polarography the potential is linearly scanned, producing
voltammogram. Although polarography takes place in an unstirred solution, a limiting
current is obtained because the falling Hg drops mix the solution. Each new Hg drop,
therefore, grows in a solution whose composition is identical to that of the initial bulk
solution. Oscillations in the current are due to the growth of the Hg drop, which leads to a
time-dependent change in the area of the working electrode.

 Figure 4: Polarography set up

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2.2. Pulse Methods
In order to increase speed and sensitivity, many forms of potential modulation (other than
just a simple staircase ramp) have been tried over the years.

2.2.1. Normal Pulse Voltammetry (NPV)

This technique uses a series of potential pulses of increasing amplitude. The current
measurement is made near the end of each pulse, which allows time for the charging current
to decay. It is usually carried out in an unstirred solution at either DME (called normal pulse
polarography) or solid electrodes. The potential is pulsed from an initial potential Ei . The
duration of the pulse, t, is usually 1 to 100 msec and the interval between pulses typically 0.1
to 5 sec. The resulting voltammogram displays the sampled current on the vertical axis and
the potential to which the pulse is stepped on the horizontal axis.

2.2.2 Differential Pulse Voltammetry (DPV)

This technique is comparable to normal pulse voltammetry in that the potential is also
scanned with a series of pulses. However, it differs from NPV because each potential pulse is
fixed, of small amplitude (10 to 100 mV), and is superimposed on a slowly changing base
potential. Current is measured at two points for each pulse, the first point (1) just before the
application of the pulse and the second (2) at the end of the pulse. These sampling points are
selected to allow for the decay of the nonfaradaic (charging) current. The difference between
current measurements at these points for each pulse is determined and plotted against the
base potential.

2.2.3 Square-Wave Voltammetry (SWV)

The excitation signal in SWV consists of a symmetrical square-wave pulse of amplitude Esw
superimposed on a staircase waveform of step height DE, where the forward pulse of the
square wave coincides with the staircase step. The net current, inet, is obtained by taking the
difference between the forward and reverse currents (ifor – irev) and is centered on the redox
potential. The peak height is directly proportional to the concentration of the electroactive
species and direct detection limits as low as 10–8 M are possible.
Square-wave voltammetry has several advantages. Among these are its excellent sensitivity
and the rejection of background currents. Another is the speed (for example, its ability to

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scan the voltage range over one drop during polarography with the DME). This speed,
coupled with computer control and signal averaging, allows for experiments to be performed
repetitively and increases the signal to-noise ratio. Applications of square-wave voltammetry
include the study of electrode kinetics with regard to preceding, following, or catalytic
homogeneous chemical reactions, determination of some species at trace levels, and its use
with electrochemical detection in HPLC.

2.3. Stripping Voltammetry

A form of voltammetry in which the analyte is first deposited on the electrode and then
removed or stripped electrochemically while monitoring the current as a function of the
applied potential. One of the most important quantitative voltammetric techniques is
stripping voltammetry, which is composed of three related techniques: anodic, cathodic, and
adsorptive stripping voltammetry.

Since anodic stripping voltammetry has found the widest application, we consider it in the
greatest detail.
The first is a controlled potential electrolysis in which the working electrode, usually a
hanging mercury drop or mercury film, is held at a cathodic potential sufficient to deposit the
metal ion on the electrode.

2.3.1 Anodic stripping voltammetry (ASV)

ASV is one of the most widely used forms of stripping voltammetric analysis. It is an
extremely sensitive technique available for determination of trace metals in water samples
and has the advantage of simultaneous determination of metals at concentrations as low as
10-10 M. In this technique as shown in Figure (a), the metal is preconcentrated onto the
electrode surface which is done by cathodic deposition at a controlled time and potential.
After resting period, the potential is scanned anodically by using a more sensitive potential-
time (pulse) waveform, called SWASV which discriminates against the charging background
current. During the stripping step, as can be seen in Figure (b), the metal is re-oxidized,
stripped out from the electrode surface. The voltammetric response shown in Figure (c),
provides analytical information of interest. Ep serves to identify the analyte in the sample.
The ip depends upon various parameters of the pre concentration and stripping steps; as well

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as on the characteristics of the analyte and the electrode geometry; and it is proportional to
the analyte concentration in the sample.

Figure 4: Anodic stripping voltammetry

(a) Pre concentration step, (b) stripping step and (c) the voltammetric result of anodic striping
voltammetry.

2.3.2 Cathodic stripping voltammetry (CSV)

CSV is used to determine many of organic and inorganic compounds that form insoluble salts
with the electrode material. It can be considered as mirror image of ASV. It involves
deposition of the analyte on the electrode when anodic potential is applied to the working
electrode followed by stripping in a negative-going (cathodic) potential to reduce the
deposited analyte back into the solution.

2.3.3 Adsorptive stripping voltammetry (ASV)

ASV is quite similar to ASV and CSV methods. The primary difference could be explained
as using adsorption in the preconcentration step. The adsorption process plays an important
role in the accumulation step. ASV can be employed in trace analysis of organic and
inorganic analyte species. In this method a metal ion reacts with a suitable ligand and forms a
complex by being adsorbed on the electrode surface. Then the deposited complex form of the
analyte is stripped by reduction or oxidation potential.

2.3.4 Potentiometric stripping voltammetry (PSV)

PSV is a technique where potentiostatic control is disconnected following preconcentration,
and the preconcentrated analytes are reoxidized by an oxidizing agent present in the solution
or an oxidizing current. A stirred solution during the stripping step is used in order to
facilitate the transport of oxidant.

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2.3.5 Rapid Scans Voltammetry – Linear Sweep Voltammetry, LSV
Rapid scan Voltammetry is the simplest technique. At the working electrode is applied a
rapid potential scanning that varies linearly (20 –100 mV/s). The scanning starts before the
discharging potential and stops afterwards,
The phenomena involved during the potential scanning have been yet described capacitive
current increases when the velocity of scanning is increased and cannot be electronically
compensated. Thus the performances of this technique are strongly restricted. Detection
limits range at mg/l levels.

2.4. Cyclic Voltammetry, CV

Cyclic voltammetry is the most commonly used electroanalytical technique for obtaining
rapid quantitative data about an electrochemical reaction. The importance of cyclic
voltammetry is that it provides a quick result concerning the kinetics of a heterogeneous
electron-transfer, diffusion coefficients, and thermodynamic information for a process.
Cyclic voltammetry also can give data on subsequent chemical reactions or adsorption
processes. Cyclic voltammetry is usually the first experiment performed on an electroactive
analyte because of its ability to provide the redox potential of that analyte. This technique
also allows fast evaluation of the effect that a particular matrix may have on a redox process.
During a typical cyclic voltammetry experiment, a component of the solution is electrolyzed
(oxidized or reduced) by placing the solution in contact with an electrode, and then applying
a potential to that electrode that is sufficiently positive or negative with respect to a reference
half-cell (e.g., calomel or Ag|AgCl). The electrode’s voltage is adjusted higher or lower
linearly, and finally, the voltage is returned to the original value at same linear rate.

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Figure 6: Cyclic voltammetry

When the electrode becomes sufficiently negative or positive, a species in solution may gain
electrons from the electrode’s surface, or transfer electrons to that surface. As the potential is
swept back and forth past the formal potential, E°, of an analyte, a current flows through the
electrode that either oxidizes or reduces the analyte. Electron-transfer is a measurable current
in the electrode’s circuitry. The magnitude of this current is proportional to the concentration
of the analyte in solution, which allows cyclic voltammetry to be used in an analytical
determination of concentration.[4]

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3. STEPS OF VOLTAMMETRIC ANALYSIS
a. Sample treatment
For a voltammetric analysis the sample has to be a solution. If the sample is solid, it has to be
dissolved in a proper way. Liquids with complex matrix and low soluble solids are to be
digested or extracted. Rarely, it is not necessary to digest complex matrices, i.e. the analysis
of ascorbic acid in fruit juice can be performed without any treatment.
At the end of any treatment the obtained solution has to have the following characteristics:
No suspended solids. If present they have to be eliminated by filtering or
centrifuging. The separate solid can be analyzed separately.
No colloids. Colloids compete with electrochemical processes, sometime stopping
them or keeping them not reproducible. Often a simple oxidizing treatment with UV
lamp is sufficient to overcome this interference.
No surfactants, because they also can stop the electrochemical processes or
decreasing the sensitivity of the method. Also in this case a simple oxidizing
treatment with UV lamp is sufficient to overcome this interference.
PH between 1 and 10 and atmosphere neither too much oxidizing nor too much
reducing, otherwise the mercury electrode can react or give raise to a very noisy
signal. This latter phenomena effect also solids electrode..
If the analysis is performed in a solvent different from water, when possible, an
electrolyte has to be added increasing the electrical conductivity of the solution
b. Addition of the supporting electrolyte
Every analysis has to be performed using a typical supporting electrolyte. The
characteristics of this solution is described in the manual or reported in literature.
c. Bubbling of the solution with nitrogen
Oxygen is always present in solution and gives rise to 2 voltammetric peaks; the first at 0 V
and the other one at 1 V. This gas has to be eliminated from the solution before the analysis,
by a prolonged bubbling of nitrogen. Lower is the analyte concentration to be found, greater
has to be the bubbling time.
d. Pause (delay)
Solution has to be leave quiescent stopping after the bubbling.

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e. Electrode cleaning
 Mercury electrode: some drops are discharged
 Solid electrode: an inverse scanning has to be performed
f. Scanning and registration of the sample voltammogram
 Addition of standard solution of analyte
 Scanning and registration of the voltammogram after the addition (the process is
repeated 2-8times)
 Measure of the all peak (or wave) heights
 Drawing the graph
 Reading of the unknown concentration

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Reference
[1] V. Instrumentation, H. Voltammetry, C. Voltammetry, P. Voltammetry, and S.
Methods, “Voltammetry,” pp. 1–13, 1967.

[2] E. Apparatus, “Cyclic Voltammetry,” pp. 43–54.

[3] S. P. Kounaves, “Voltammetric Techniques,” pp. 709–726.

[4] F. Scholz, “Voltammetric techniques of analysis : the essentials,” ChemTexts, vol. 1,

no. 4, pp. 1–24, 2015, doi: 10.1007/s40828-015-0016

[5] S. Mendoza, E. Bustos, J. Manriquez, and L. Godinez, “Volumetric techniques,”

Agricultural and food electroanalysis. pp. 23–48, 2015.

[6] A. H. Alghamdi, “Applications of stripping voltammetric techniques in food analysis,”

Arab. J. Chem., vol. 3, no. 1, pp. 1–7, 2010, doi: 10.1016/j.arabjc.2009.12.001.

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