Republic of the Philippines

BATANGAS STATE UNIVERSITY

The National Engineering University
Alangilan Campus
Golden Country Homes, Alangilan, Batangas City, Batangas, Philippines 4200
Tel Nos.: (+63 43) 425-0139 loc. 2121 / 2221
E-mail Address: ceafa@g.batstate-u.edu.ph | Website Address: http://www.batstate-u.edu.ph

College of Engineering
Department of Electronics

SUMMARY OF REPORT
“VOLTAMMETRY”

Presented to:
Engr. Apryll Joy A. Hernandez
Batangas State University
Alangilan, Batangas City

In Partial Fulfillment
of the Requirements for
Che 437 – Analytical Instrumentation
Bachelor of Science in Instrumentation and Control Engineering

By:

GROUP NO.3

Atienza, Kim Andrew B. / 20-01195

Cadacio, Krizlene Kyla V. / 20-05951

ICE - 3205

April 2023

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ELECTROANALYTICAL METHODS: VOLTAMMETRY
Objectives

By the end of the discussion, the students are expected to:

1. Understand the concepts of voltammetry.

2. The instrumentation and principle of operation of voltammetry.

Basic Concepts
 a redox reaction transfers electrons between the reactant species and the Electrode
 produces a measurable current
 the greater concentration of reactive species, the greater the current
 measurement of currents can be used to determine concentrations
 voltammetry - an electrical current is measured as a function of applied potential
 used to identify and quantify
 the study of current as a function of applied potential

Introduction
Most of the electroanalytical methods rely on the flow of electrons between one or more
of the electrodes and the analyte. One common electroanalytical method is voltammetry.

Voltammetry is based on the measurement of the current that develops in an

electrochemical cell under conditions where concentration polarization exists. A polarized
electrode is one to which we have applied a voltage in excess of that predicted by the Nernst
equation to cause oxidation or reduction to occur. In contrast, potentiometric measurements are
made at currents that approach zero and where polarization is absent.

Voltammetry differs from coulometry in that, with coulometry, measures are taken to
minimize or compensate for the effects of concentration polarization. Furthermore, in voltammetry
there is minimal consumption of the analyte, whereas in coulometry essentially all of the analyte
is converted to another state.

Figure 1. Jaroslav Heyrovsky

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 Historically, the field of voltammetry developed from polarography, which is a particular
type of voltammetry that was invented by the Czechoslovakian chemist Jaroslav Heyrovsky in the
early 1920s. Polarography differs from other types of voltammetry in that the working electrode is
the unique dropping mercury electrode. At one time, polarography was an important tool used by
chemists for the determination of inorganic ions and certain organicspecies in aqueous solutions.

Instrumentation of Voltammetry
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 Potentionstat

A potentiostat is an analytical instrument designed to control the working electrode's

potential in a multiple electrode electrochemical cell. The potentiostat contains many internal
circuits that allow it to function in this capacity. The circuits generate and measure potentials and
currents.

 Signal generator
The signal generator determines the applied voltage resolution of the
potentiostat. It outputs variable DC (direct current) voltages via a digital-to-analogue
converter (DAC), which converts a computer-generated signal into a voltage. This allows
the user to be able to accurately control the output voltage of the potentiostat via a
computer.

 Feedback amplifier
The voltage feedback amplifier is perhaps the most important part of the
potentiostat circuit. It measures the voltage between the working reference and the
reference electrode, passing it to the signal converter to be sent to the computer. However,
it also feeds this voltage to the negative terminal of the control amplifier. This enables the
potentiostat, via the control amplifier, to keep the set voltage stable relative to the
reference electrode.

It is important that the feedback amplifier does not overload the electrode voltage
and disturb the electrochemical reaction, so a high input impedance with very low input
current (pA) is used. The feedback amplifier also needs to be fast enough to allow the
potentiostat to keep up with the rapid changes that can occur in electrochemical reactions
and provide the feedback voltage to the output amplifier.

 Control amplifier
The control amplifier takes the voltage output of the signal generator and the
feedback amplifier and outputs the voltage that will be passed between the working and
counter electrodes. This is where the potentiostat accounts for any loss of voltage due to
electrochemical reactions taking place in the cell. By using the output of the feedback
amplifier as an input of the control amplifier, the signal is increased or decreased, allowing
the device to keep the voltage between the working and reference electrodes stable.

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 The specifications of the control amplifier will determine the maximum voltage and
current that the potentiostat system can output.

 Current amplifier and current ranges

This section of the circuit is for measuring the current passing through the working
electrode and counter electrode. It consists of a single resistor or a set of resistors (the
current ranges) and an amplifier. Each resistor corresponds to a different current range
and can be toggled on or off to select the desired current range. Therefore, the number
and resistances of these resistors will determine the currents that can be measured by a
potentiostat.

When the current passes through a resistor it generates a voltage. The voltage is
increased by the amplifier according to the selected current range and passed into the
signal converter where it is converted to a current measurement.

 Signal converter
The signal converter uses an analogue-to-digital converter (ADC) to convert the
output of the voltage feedback amplifier and the current amplifier into a digital signal that
can be interpreted by a computer connected to the potentiostat.

Potentiostats can be used to control two, three or four electrode configurations

(and as discussed above, multi-channel bipotentiostats or polypotentiostats can control
rotating ring-disk electrode systems).

The Electrodes and Cell

The working electrode, along with a reference electrode and a counter electrode are
commonly placed in an eIectrochemical cell, with a fill solution containing an inert electrolyte
and the analyte. Cell designs can be quite simple to quite complex, with solution volumes ranging
from a few microliters to many milliliters.

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 the reference electrode in a separate compartment.
The unique requirements for each of the voltammetric 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.

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 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 glassy carbon.

TYPES OF VOLTAMMETRY
1. Linear Sweep Voltammetry
2. Staircase Voltammetry
3. Cyclic Voltammetry
4. Squarewave Voltammetry
5. Anodic Stripping Voltammetry
6. Hydrodynamic Voltammetry
7. Cathodic Stripping Voltammetry
8. Absorptive Stripping Voltammetry
9. Alternating Current Voltammetry
10. Polarography
11. Rotated Electrode Voltammetry
12. Normal Pulse Voltammetry
13. Differential Pulse Voltammetry
14. Chronoamperometry

TYPES OF VOLTAMMETRY
 Cyclic Voltammetry

Figure 2. Cyclic Voltammetry

Source: Dickinson (2013)

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  Cyclic voltammetry is a method for investigating the electrochemical behavior of a
system and is the most widely used technique for acquiring qualitative information
about electrochemical reactions. The power of cyclic voltammetry results from its
ability to rapidly provide considerable information on the thermodynamics of redox
processes, on the kinetics of heterogeneous electron-transfer reactions, and on
coupled chemical reactions or adsorption processes.
 Cyclic voltammetry is often the first experimental approach performed in an
electroanalytical study, since it offers rapid location of redox potentials of the
electroactive species and convenient evaluation of the effect of media upon the
redox process. In other words it provides a fundamental electron-transfer
properties of the chemical compounds in solution
 Provides a fundamental electron-transfer properties of the chemical compounds in
solution.

 Differential Pulse Voltammetry

Figure 3. Differential Pulse Voltammetry

Source: Peroff (2023)
 A series of pulses is applied to the electrode with sequential increasing baseline
voltage.
 Increases the sensitivity of voltammetry.
 Differential-pulse voltammetry provides well-defined peaks at a concentration level
that is at least 1000 times lower than that needed for a classical voltammetric wave.
 Become one of the most widely used analytical voltammetric procedures and is
especially useful for determining trace concentrations of heavy metal ions.

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 Square Wave Voltammetry

Figure 4. Square Wave Voltammetry

Source: Peroff (2023)

 Potentiostatic method that offers some advantages to common techniques like Cyclic
Voltammetry.
 Used for both quantitative chemical analysis and study of the mechanism, kinetics,
and thermodynamics of chemical reactions.
 Square wave voltammetry can be used to perform an experiment much faster than
normal and
 differential pulse techniques, which typically run at scan rates of 1 to 10 mV/sec.

 Hydrodynamic Voltammetry

Figure 5. Hydrodynamic Voltammetry

Source: Principles of Instrumental Analysis, Seventh Edition (2018)

 An electrochemical technique where the cell current flowing during convective mass
transfer (the movement of material by the action of a fluid) is measured as a function
of time and as a function of the potential between the indicator and reference
electrodes.

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  Hydrodynamic voltammetry is a type of voltammetry technique in which the solution
containing the analyte flows with respect to the electrode being used for the purpose
of measurement.

Advantages of Voltammetry
Among several analytical methods, voltammetric methods have distinct advantages over other
existing ones. Some of this are:

 high selectivity and sensitivity,

 use of low quantity of sample,
 little or without sample treatment,
 low waste generation,
 which contributes to reduced environmental impact,
 applicability to biological samples without any pretreatment,
 and time saving

REAL LIFE APPLICATION

 FOOD INDUSTRY

Figure 6. Food Safety Analysis

Source: Alghamdi (2009)
The science of food and nutritional analysis has developed rapidly in recent years.
Measuring the quality, safety, nutrition and stability of food products is the primary concern
of analytical chemists who are working within food processing industry and in academic
and governmental food analytical laboratories. In fact, food scientists obtained this
valuable information via the application of various modern instrumental techniques which
analyzed the foodstuffs composition, appearance, texture, flavor and shelf life. The
importance and awareness of nutrition in the public health issues has resulted in increased
demands for knowledge of the nutrient content of the foods.

Voltammetry is used in determination of food contaminants (toxic metals, pesticide,

fertilizers and veterinary drugs residuals), trace essential elements, food additive dyes and
other organic compounds of biological significance from environmental pollutants and
industrial chemicals during food processing and packaging.

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 PHARMACEUTICAL INDUSTRY

Figure 7. Pharmaceutical Industry

Source: Silver Pines Treatment Center (2018)

Electrochemical behavior of several chemically interesting pharmaceuticals on

different carbon electrodes was investigated with the help of cyclic voltammetry.
Voltammetry is also applied in investigation of the electrochemical behavior of
paracetamol and direct determination of paracetamol in pharmaceutical tablet samples.

 ENVIRONMENTAL SCIENCE

Figure 8. Environmental Science for Anodic Stripping Voltammetry

Source: Borrill (2019)

Voltammetry is used in monitoring trace metals in the environment used in analysis

of environmental samples and other materials such as environmental pollutant and
organic compounds in the air and soils.

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 VOLTAMMETRIC SENSORS

Figure 9. Voltammetric Sensors

Source: Baig and Numan (2020)

In voltammetric sensors, the current response is measured as a function of applied

potential. The potential is varied either step by step or continuously in order to determine the
current as a function of the cells potential I = f (E), which is called a voltammogram.

A number of voltammetric systems are produced commercially for the determination

of species that are of interest in industry and research. These devices are sometimes
called electrodes but are actually complete voltammetric cells, which are better referred to
as sensors. These sensors can be employed for the analysis of organic and inorganic analytes
in various matrices.

 THE OXYGEN ELECTRODE

Figure 10. The Oxygen Electrode

Source: Gonzalez (2017)

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 The determination of dissolved oxygen in a variety of aqueous environments, such as
sea water, blood, sewage, effluents from chemical plants, and soils is of tremendous
importance to industry, biomedical and environmental research, and clinical medicine. One of
the most common and convenient methods for making such measurements is with the Clark
oxygen sensor, which was patented by L.C. Clark, Jr. in 1956.

RECENT ADVANCEMENT
Early voltammetric techniques had many problems, limiting their viability for everyday use
in analytical chemistry such problems in using mercury, residual currents, and the data are harder
to analyze. With intensive studies and technological advancement, voltammetry has developed
very rapidly, and several types have been introduced with high efficiency, sensitivity, and
selectivity.

Recent developments focused on data analysis which include preprocessing by digital

filtering, principal components analysis for distinguishing analytes, and developing automated
algorithms to detect peaks. Future challenges include multisite measurements, machine learning,
and integration with other techniques

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