CYCLIC VOLTAMMETRY

PRESENTED TO: DR MUHAMMAD NADEEM BADANI

PRESENTED BY: ANEEQA BIBI(2K-22-PHY-MS-11)
CONTENTS:
 Voltammetry and its types
 History of Voltammetry
 Cyclic Voltammetry
 Introduction
 Physics Behind
 Working Principle
 Instrumentation
 Results and discussions
 Advantages and disadvantages
 Applications
VOLTAMMETRY:
 DEFINITION:
Voltammetry is defined as the measurement of current which flows at an electrode as a
function of the potential applied to the electrode.
 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.
HISTORY:
 The earliest voltammetric technique to be introduced was polarography, which was
developed by Jaroslav Heyrovsky (1890– 1967) in the early 1920s, for which he was awarded
the Nobel Prize in chemistry in 1959.
 The earlier voltammetric methods experienced a number of difficulties, but after in the
1960s and 1970s significant advances were made in all areas of voltammetry (theory,
methodology, and instrumentation), which enhanced the sensitivity of analytical methods.
TYPES OF VOLTAMMETRY:
Following are the various types of voltammetry:
 Linear sweep voltammetry
 Staircase voltammetry
 Square wave voltammetry
 Anodic stripping voltammetry
 Cathodic stripping voltammetry
 Adsorptive stripping voltammetry
 Alternating current voltammetry
TYPES OF VOLTAMMETRY:
 Normal pulse voltammetry
 Differential pulse voltammetry
 Chronoamperometry
 Cyclic voltammetry (CV) Types
CYCLIC VOLTAMMETRY:
 INTRODUCTION:
Cyclic voltammetry is an electrochemical technique used to study the redox
behavior of chemical species in a solution.
It involves applying a linearly varying potential to an electrode while measuring the
resulting current.
By analyzing the current-potential relationship, valuable information about the
electrochemical processes occurring at the electrode surface can be obtained.
PHYSICS BEHIND CYCLIC VOLTAMMETRY:
 Certainly! The physics behind cyclic voltammetry involves understanding the behavior of electrons and
charged species in an electrolyte solution during electrochemical reactions. Here's a simplified
explanation:
1. Redox Reactions: Cyclic voltammetry focuses on studying the electron transfer between molecules or
ions in the solution and the electrode. This transfer occurs through oxidation (loss of electrons) and
reduction (gain of electrons) processes. The applied potential in cyclic voltammetry drives these redox
reactions, causing the species to undergo changes in their charge states.
2. Electrochemical Cells: Cyclic voltammetry uses an electrochemical cell with three main parts: the
working electrode, reference electrode, and counter electrode. The working electrode is where the redox
reactions take place, the reference electrode provides a stable reference potential, and the counter
electrode balances the electrical flow. Together, these electrodes create an electrochemical system where
the reactions occur.
Continued..
3. Charged Species and Movement: Charged species, such as ions, move in the electrolyte
solution. During cyclic voltammetry, they must travel between the electrode surface and the
solution. This movement happens through two processes: diffusion and migration. Diffusion
refers to the random motion of species due to differences in concentration, while migration is
the directed movement of charged species influenced by an electric field.
4. Double Layer Capacitance: At the electrode surface, a double layer forms due to the
separation of charges. This double layer consists of ions that stick to the electrode surface and
counter ions in the solution. The double layer has a capacitance, which is a measure of its
ability to store electrical charge. This capacitance affects the current response during the
potential sweep in cyclic voltammetry.
CONTINUED..
5. Current-Potential Relationship: The current flowing through the electrode is measured
as the potential is varied in cyclic voltammetry. The resulting current-potential relationship,
known as the voltammogram, provides information about the redox processes and the
behavior of the electrochemical system. The shape of the voltammogram can indicate
factors like the reversibility of the reactions and the rate at which they occur.
By analyzing the voltammogram, scientists can understand the kinetics, reversibility, and
diffusion behavior of electrochemical processes. This knowledge helps in studying the
behavior of molecules, materials, and systems, leading to advancements in fields such as
electrochemistry, materials science, and analytical chemistry
INSTRUMENTATION(EXPERIMENTAL SETUP)
Continued..
Cyclic Voltammetry (CV) is basically consisted of three-electrode system which are:
 Working electrode
 Counter electrode
 Reference electrode
In addition, we have:
 Potentiostat
 Computing system
Continued..
 CV consists of a three-electrode system containing working electrode, counter electrode and a
reference electrode. The working electrode is the electrode under investigation while counter
electrode consists of platinum wire.
 In standard electrochemistry cells, the counter electrodes are used to complete the circuit with
potentiostat. They are mainly made up of platinum wires because they are low in cost, resistive to
oxidation, do not react and are merely damaged when put in acids or electrolytes. Reference
electrode is composed of Ag/AgCl also called the third electrode of the system. The potential at
reference electrode is already known and stable which remains unaffected and retain its well-
defined potential throughout the electrochemical measurements. Reference electrode consistently
controls the regulation of voltage at working electrode by providing a stable potential and
simultaneously measures the voltage at the working electrode without creating any instability in
the system as ideal reference electrode must possess zero impedance.
CONTINUED..
 The three-electrode system is dipped in an electrolyte usually a molar solution of potassium
hydroxide (KOH). This agency is connected to a potentiostat which reads the signals and then
converts them into data containing information regarding the activity on the electrode-
electrolyte interface. The information is then received by a computer system that displays the CV
voltammogram along-with all the data values.
Continued..
ELEMENTS OF CV:

INPUT EQUIPMENT OUTPUT

Setting up the Controlling the voltage using
electrode+electrolyte the Potentiostat. Recording the Cyclic
solution in the cell. Voltammogram.
WORKING MECHANISM:
 Working electrode containing the electrode material under investigation is given a potential that is
varied periodically and systematically. The transfer of electrons starts between the redox active
material present on the working electrode and the counter electrode, which is assisted by the
electrolyte for flow purpose. The counter electrode balances the current at the working electrode.
When reduction occurs at working electrode then it is balanced by oxidation phenomena that occurs
on the counter electrode surface. There is absolutely no charge transfer between reference electrode
and working electrode.
 Reference electrode plays a pivotal role in measuring the current flow at the working electrode-
electrolyte interface. The current flows as a consequence of redox reactions occurring at working
electrode and is measured and recorded as the current flows between the counter electrode and
working electrode through ions of electrolyte. The current response is, therefore, mainly dependent
upon the redox material that is being used as working electrode. Moreover, as explained earlier, the
applied voltage is used in order to control the redox reactions that occur on the electrode-electrolyte
interface.
RESULTS AND DISCUSSIONS:
 You control the potential (energy of electrons at the working electrode surface), and
measure the current. In a CV, you change the energy of electrons at a constant scan
rate to a vertex potential, and then reverse.
 Current is the flow of electrons
• When you see a current peak in a CV, that indicates electron transfer is happening
• Oxidation happens at more positive potentials, reduction happens at more negative
potentials
Continued..
Continued..

 The CV below is an example of a redox reaction that is kinetically very fast:

• No overpotential, so no additional energy beyond thermodynamics required to
drive oxidation and reduction
• The shape of the CV is determined only by thermodynamics (Eo and the Nernst
equation)
Continued..
 Nernst equation: E = Eo – (0.059/n)ln([reduced species]/[oxidized species])

E1/2 = potential that is halfway in between oxidation and

reduction peaks

If the CV is a ferrocene/ferrocenium redox couple, then if

the concentration of ferrocene (Fe2+) is the same as
ferrocenium (Fe3+), then E1/2 = Eo
WHAT IS HAPPENING IN SOLUTION NEAR THE ELECTRODE
SURFACE?

Example for an oxidation reaction:

Continued..

• As an oxidizing potential is applied, positive charge builds up on electrode.

• Anions attracted to electrode, cations are repelled.
• Once enough oxidizing potential is applied, the redox active molecule will transfer
an electron to the electrode.
• The resulting oxidized species will diffuse away from electrode.
 ADVANTAGES:
 Cyclic voltammetry provides valuable information about the electrochemical processes
occurring at the electrode surface.
 CV is used to determine specific capacitance of the active material, current responses and
cycle life.
 The resulting voltammogram, which represents the current-potential relationship, offers
insights into the redox behavior, reversibility, kinetics, and capacitive behavior of the
analyte or species of interest.
 It can also provide information about electron transfer rates, reaction mechanisms, and
the stability of the electrochemical system.
 Continued..
 Cyclic voltammetry requires only a small amount of sample, making it suitable for cases
where sample availability is limited or precious.
 It is particularly advantageous in situations where obtaining large quantities of the analyte
may be challenging or expensive.
DISADVANTAGES:
 In some cases, cyclic voltammetry can lead to electrode fouling, where unwanted
deposits or films accumulate on the electrode surface during the experiment.
 This fouling can alter the electrode behavior, hinder the accurate interpretation of
experimental results, and require frequent cleaning or electrode replacement.
 While cyclic voltammetry provides information about the overall kinetics of redox
reactions, it may not provide a complete understanding of the specific reaction rates and
pathways involved.
 More advanced techniques, such as impedance spectroscopy or rotating disk electrode
voltammetry, may be necessary to obtain more detailed kinetic information.
 Continued..
 Determination of redox potentials and kinetics of electrochemical reactions.
 Characterization of electroactive species and their behavior in solution.
 Study of electrode processes and surface reactions
 Investigation of electron transfer mechanisms and mechanisms of electrochemical reactions
 Analysis of electrochemical properties and stability of materials and coatings
 Quantitative analysis of analytes in complex matrices (e.g., determination of trace metals in
environmental samples)
 Evaluation of electrocatalytic activity and efficiency of catalysts
APPLICATIONS:
 It is possible to estimate the capacitance of an electrode or an electrochemical system
using cyclic voltammetry.
 Capacitance is a measure of the ability of a system to store electrical charge, and in the
context of cyclic voltammetry, it refers to the double-layer capacitance that forms at the
electrode-electrolyte interface.
 Cyclic voltammetry has a wide range of applications in various scientific fields. Here are
some key applications of cyclic voltammetry:
 Electrochemical Analysis: Cyclic voltammetry is used for qualitative and quantitative
analysis of electroactive species. It can determine redox potentials, oxidation/reduction
mechanisms, and concentration levels of analytes in solution.
 Continued..
 Electrode Kinetics: Cyclic voltammetry provides information about the kinetics of electrode
processes, including electron transfer rates, reaction mechanisms, and charge transfer
coefficients. It is used to study the kinetics of electrochemical reactions and understand
reaction mechanisms.
 Material Characterization: Cyclic voltammetry is employed to characterize the electrochemical
properties and stability of materials. It helps assess the performance of materials for energy
storage devices (batteries, supercapacitors), corrosion resistance, and catalytic activity.
 Sensor Development: Cyclic voltammetry is used in the development of electrochemical
sensors and biosensors. By studying the electrochemical response of analytes, it enables the
design of sensitive and selective sensors for detecting various substances, such as pollutants,
biomarkers, and pharmaceuticals.
 Continued..
 Environmental Analysis: Cyclic voltammetry plays a vital role in environmental analysis. It
is used to determine trace levels of metals, pollutants, and organic compounds in
environmental samples, helping assess water quality, monitor pollution levels, and study
environmental processes.
 Pharmaceutical Analysis: Cyclic voltammetry is applied in pharmaceutical analysis to
investigate drug interactions, determine drug stability, and assess the quality and purity of
pharmaceutical compounds. It aids in drug discovery and development processes.
 Bioelectrochemistry: Cyclic voltammetry is used in bioelectrochemical studies to
investigate electron transfer processes in biological systems. It helps understand
enzymatic reactions, redox-active biomolecules, and electron transfer in proteins and
DNA.
Continued..
 Surface Science and Electrode Modification: Cyclic voltammetry is employed to study surface
reactions, electrode modification, and electrochemical deposition processes. It helps in
understanding surface phenomena, electroplating, thin film growth, and surface modification
for various applications.
 Teaching and Research: Cyclic voltammetry is extensively used in academic research and
teaching laboratories to demonstrate fundamental electrochemical principles, investigate
electrochemical phenomena, and train students in electrochemical techniques.
These are just a few examples of the broad range of applications of cyclic voltammetry. The
versatility and analytical capabilities of cyclic voltammetry make it a valuable tool in numerous
scientific and technological disciplines.
REFRENCES:
 Frank A.Settle Handbook of Instrumental Techniques for Analytical Chemistry,pearson education, 2004.
 Douglas A.skoog, F. James Holler, Stanley R.Crouch, Instrumental Analysis,Brooks/cole lengage
learning,2007
 Gary D.Christian, Analytical chemistry,Wiley student edition,sixth edition.
 Geiger, W. E. Organometallics 2008, 26, 5738.
 Mabbott, G. A. J. Chem. Educ. 1983, 60, 697.
 Van Benschoten, J. J.; Lewis, J. Y.; Heineman, W. R.; Roston, D. A.; Kissinger, P. T. J. Chem. Educ. 1983, 60,
772.
 Geiger, W. E. in Laboratory Techniques in Electroanalytical Chemistry, 2nd Ed., Kissinger, P. T., Heineman,
W. R. Eds.; Marcel Dekker, Inc.: New York, 1996, 683