Electrochemical Sensing and

Applications
Presented by
PRAGATI JOSHI
I.D. No.- 51092
Ph.D. Chemistry (4thsem)
LAYOUT
 Electrochemical Sensors
 Introduction
 Fundamentals and theory of CV
 Triple electrode assembly
 Randles - Sevcik equation
 Applications of CV
 Principle of square wave voltammetry
 Applications of SWV
 References
 Electrochemical Sensors
 Electrochemical sensor is a powerful diagnostic device with

high sensitivity and selectivity

 A class of sensors in which electrode is the sensing element

They have wide commercial applications as

 No generation of waste
 Miniaturization in portable devices
 Fast analysis
 Low production cost

Principle :
The fundamental principle of any electrochemical sensor is
the recognition of the analyte through the active layer of the
material that composes it to the recording equipment
Assosciated with nanotechnology electrochemical sensors are becoming
increasingly precise, selective, sensitive and portable
Classification
They convert information assosciated with EC reactions into
an applicable qualitative and quantitative analysis

Potentiometric

Electrochemical Conductometric
Sensors

Voltammetric
Cyclic
Voltammetry SquareWave
Voltammetry

Redox Behaviour
Quantification
and Calibration
 CYCLIC VOLTAMMETRY (CV)
Cyclic voltammetry was first reported in 1938 and
described by J.B. Randles.

J.B. Randles CV instrument developed by Randles

 CV is a potential sweep technique
 It involves sweeping the electrode potential at a know

sweep rate
 CV investigates electrochemical behaviour of a system
 It is first experimental approach in electroanalytical

studies
It gives information about:
 Adsorption Processes
 Thermodynamics of redox processes
 Kinetics of electron transfer reactions
 Instrumentation

Electrochemical Workstation
Triple electrode assembly

Potentiostat
 The molecules which are electrochemically active are
considered.
 The important parameters are the magnitudes of anodic peak

current (ipa), the cathodic peak current (ipc), the anodic peak
potential (Epa) and cathodic peak potential (Epc).

Cyclic voltammogram
 Basic Principle of CV
 In a CV experiment the current at WE is plotted versus the applied
voltage to give a cyclic voltammogram
 The potential is applied between WE and RE, current is measured
between WE and AE
 Peak width and height depends upon nature of electrolyte, electrode
material and scan rate

CV evaluates thermodynamic and kinetic parameters

 Number of electron change
 Gibbs free energy
 Entropy

The Nernst Equation gives the relationship between the potential and the
concentrations of the oxidized and reduced form of the redox couple

In CV, Randles-Sevcik equation describes the effect of scan rate on the

peak current ip
For simple redox events, ip depends on scan rate
The diffusion coefficient of an electroactive species can be determined
by this equation
 A. Initial negative current
B. At 0.4V, current begins because of
reduction at cathode
B-D. Rapid increase in current as the
surface concenteration decreases
D. Represents Epc and ipc
D-F Current decay

J. Represents Epa and ipa

Applications

Study of reaction mechanisms

Change in shape of cyclic voltammograms can elucidate reaction pathways
Quantitative Determination
Concentration of analyte, Number of electrons per molecule in analyte and
Diffusion coefficient
Electrochemical studies
To evaluate electrochemical reversibility by looking at the difference
between the peak potentials for the anodic and the cathodic scans.
Characterization Studies
Any process that includes electron transfer can be characterized using CV
 Corrosion studies in CV
CV is used to measure corrosion that proceeds at same rate at
metal surface
 Study of adsorption processes
 Glucose detectors for diabetics
Electrodes coated with special polymers find use as glucose
detectors
 Square Wave Voltammetry (SWV)
 SWV is a powerful electrochemical technique suitable for analytical
application, mechanistic study of electrode processes and electro
kinetic measurement
 In a SWV experiment, the current at a working electrode is measured
while the potential between the working electrode and a reference
electrode is swept linearly in time
 The potential waveform can be viewed as a superposition of a regular
square wave onto an underlying staircase; in this sense, SWV can be
considered a modification of staircase voltammetry
 Because of the minimal contributions from non- faradaic currents, the
use of a differential current plot instead of separate forward and
reverse current plots, and significant time evolution between potential
reversal and current sampling, high sensitivity screening can be
obtained utilizing SWV
 For this reason, square wave voltammetry has been utilized in
numerous electrochemical measurements and can be viewed as an
improvement to other electroanalytical techniques
 The effectiveness of a sensor is directly proportional to how
sensitive and selective it is as relates to its analyte. This
responsiveness may be increased by applying more sensitive
electrochemical technique such as SWV
Applications of SWV
 1- SWV in diagnostic biosensors
Electrochemical sensors and biosensors based on SWV for diagnostic
applications

Analyte Electrodes Analytical parameters

E.coli MWCNT coated GCE Linearity range: 2× 102 to 2× 10-8

Glucose Photosensitive modified Linearity range: 5.0 to 120µM. LOD:

gold electrode 0.2µgL-1

Guanine Pt modified GCE Linearity range: 0.1-500µM

 2- Food analysis
The efficiency and sensitivity of SWV are used in the detection of
food contaminants (bacteria, viruses, and parasites) and to verify the
therapeutic ingredients of dietary supplements.

Analyte Electrodes Analytical parameters

Aspartame BDDE Linearity range: 5× 106 to 4× 105 molL-

1
LOD: 3.5 × 10-7

Biotin Graphite epoxy composite Linearity range: 1.4 to × 108 to 3.5 ×

electrode 107 molL-1 . LOD: 20mgL-1
3- Environmental Monitoring
 4- Pesticide Analysis
 Pesticides when sprayed on target crops get mixed into the soil
and ground water only 0.1% reaches the specific target which is a
matter of concern
 EC methods like SWV helps in trace level quantification of
pesticides
The cyclic voltammogram (A) and square wave voltammogram (B)
before (blue) and after (red) a 50 mM injection of 4-nitrophenol into
pH 7.4, 0.1 M phosphate buffer solution

 SWV is more sensitive than CV

 References
 F. Scholz, 2010, Electroanalytical Methods. Guide to
Experiments and Applications, ed. 2nd, Springer, p.138-149
 https://en.wikipedia.org/.
 G. P. Jin, Q. Z. Chen, Y.F.Ding, J.B.He, ElectrochimActa, 52
(2007) 2535.
 W. Cheng, G. Jin, Y. Zhang, Russ. J. Electrochem., 41 (2005)
940.
 W. Ma, D. M. Sun, Russ. J. Electrochem., 43 (2007) 1382.
 H. Zhao, Y. Zhang, Z. Yuan, Anal. Chim. Acta, 441 (2001) 11.