CHAPTER THREE

SENSORS
3.1.Introduction

Sensors are a small device used for direct measurement of a physical quantity of an analyte in a
sample matrix and the response is continuous and reversible.Sensors (detectors/transducers)
covers a wide category of devices used to monitor, measure, test, analyse data as generated due
to changes in a measured norm (usually concentration for chemical sensors). Chemical sensors
are devices that convert chemical information (concentration, activity or partial pressure of the
analyte) into a measurable signal. Any chemical sensor contains two basic components:
a receptor which is a chemical recognition unit and a transducer.
Chemical sensors function on the interaction of a receptor with the analyte and transformation of
chemical information into a form of energy that will be later converted by the transducer into a
useful analytical signal. Chemical sensors can be classified into various groups according to the
operating principle of the transducer. On the basis of the transducing element, they are
categorized as electrochemical sensors, optical sensors, piezoelectric sensors and thermal
sensors. Among all chemical sensors, electrochemical sensors present an important subclass in
which an electrode is used as a transducer.

Electrochemical sensors have more advantage over the others due to the electrodes of
electrochemical can sense the materials which are present within the host without doing any
damage to the host system and produces an electrical signal that is related to the concentration of
an analyte.

Thus, the simplest electrochemical cell is composed of two electrodes: a test or working
electrode, and a reference electrode. However, two-electrode systems are only suitable for
equilibrium measurements, and in dynamic electrochemistry experiments a third electrode needs
to be introduced. Dynamic electrochemical experiments involve the departure from the system
equilibrium position, bringing about the passage of current. The potential at the working
electrode is measured against the reference electrode, through which no current flows. The
working electrode is that at which the process under study takes place.
Figure 3. 1. Schematic representation of an electrochemical cell consisting of three Electrodes

Thus, the third electrode, also known as auxiliary or counter electrode, facilitates the passage of
the current, closing the circuit. The potential of this auxiliary electrode normally neither known
nor important, as the primary function of this electrode is to support the current passing through
the working electrode.
The cell potential is calculated as

Figure 3.2. Major components of the electrochemical system used for thee ectrochemical
measurements.
3.2. Some Important Terms

Analyte: the target molecular species. This is the molecule we wish to identify and quantify.
Matrix: everything else present in our sample apart from the analyte. Matrix interference, where
sensor response is inadvertently elicited by so-called spectator species present in the sample, is a
major problem in bioanalysis due to the complexity of biological systems.
Matrix interference can usefully be divided into two categories:
(i) signal caused by non-target molecules, e.g., ascorbic acid or paracetamol, both of
which are oxidized at potentials used for the measurement of glucose.
(ii) (ii) sensor inactivation or ‘poisoning’ due to adsorption of proteins or other surface-
active material. For example, albumin is typically present at around 4 % (w/v) in
plasma. Adsorption of albumin can occlude or scatter light transmission from fibre
optic sensors or prevent electrocatalysis on amperometric or voltammetric sensors
(vide infra).
Sensitivity: the change in sensor output per unit change in analyte concentration.
Limit of Detection (LOD): the level of analyte that leads to a sensor signal which is statistically
significantly different from the background signal obtained in the absence of analyte.
A frequently used definition of LOD is a concentration that gives a signal greater than three
times the standard deviation of a blank sample consisting entirely of matrix.
Selectivity: the ability of the analytical method to respond only to the target analyte.
3.3. Electrochemical sensing principles

Depending on the exact mode of signal transduction, electrochemical sensors can use a range of
modes of detection such as
 potentiometric,
 voltammetric and
 conductimetric.

3.3.1. Potentiometric
Potentiometric sensors are very attractive for field operations because of their high selectivity,
simplicity and low cost.
They are, however, less sensitive and often slower than their voltammetric counterparts. In the
past, potentiometric devices have been most widely used, but there is an increasing amount of
research being carried out on amperometric sensors that has tipped this balance.
In potentiometric sensors, the analytical information is obtained by converting the recognition
process into a potential signal, which is logarithmically proportional to the concentration
(activity) of species generated or consumed in the recognition event. The Nernst equation
logarithmically relates the measured electrode potential, E, to the relative activities of the redox
species of interest.

The most representative potentiometric sensor is the ion selective electrode (ISE). The ISE uses
an indicator electrode which selectively measures the activity of a particular analyte ion. An ion-
selective membrane, placed at the tip of the electrode, is designed to yield a potential signal that
is selective for the target ion. This potential signal is generated by a charge separation at the
interface between the ion-selective membrane and the solution due to selective partitioning of the
ionic species between these two phases. The response is measured under conditions of essentially
zero current. The response of the indicator electrode should be fast, reversible and governed by
the Nernst equation.
3.3.2. Voltammetric Sensors

The root of the word voltammetry, “voltam-”, refers to both potential (“volt-”) and current (“am-
”). During the voltammetric experiment some applied potential at a working electrode is varied
at some scan rate in both forward and reverse directions while the current is simultaneously
monitored. The basic instrumentation for the cyclic voltammetry analysis requires controlled
potential equipment (potentiostat) and an electrochemical cell consisting of three electrodes. The
analysis is normally carried out using an electrochemical analyser connected to a three electrode
cell, containing the working electrode, reference electrode and auxiliary electrode.

Voltammetry provides an electroanalytical techniques, the premise of which is that current is

linearly dependent upon the concentration of the electroactive species (analyte) involved in a
chemical or biological recognition process (at a scanned or fixed potential). Voltammetry implies
a varying voltage. Cyclic voltammetry, squarewave and stripping voltammetry are some of the
more common techniques.

Cyclic Voltammetry

In voltammetry the word root “voltam-” refers to both potential (“volt-”) and current (“am-”).
During any voltammetry experiment the potential of an electrode is varied while we
simultaneously monitor the induced current. When cyclic voltammetry is performed, a solid
electrode called the working electrode (WE) is employed. During an experiment the potential of
the WE is ramped at a scan rate (v), and the resultant trace of current against potential is plotted
in what is called a voltammogram.

CV techniques are widely used as powerful technique for the study of reversible, irreversible and
quasi-reversible redox reaction and also it gives useful information regarding mechanism of
electrochemical studies. In cyclic voltammetry the potential is ramped from an initial potential
(Ei) and at the end of its linear sweep, the direction of the potential scan is reversed, usually
stopping at the initial potential.
Figure 3.2. A typical cyclic voltammogram showing the basic peak parameters, Epa, Epc,
Ipa and Ipc

Differential Pulse Voltammetry

The basis of all pulse techniques is the difference in the rate of decay of back ground and
faradaic currents following a potential step. The background current decays exponentially,
whereas the faradaic current decays as a function of 1/ (time)1/2; that is, the rate of decay of the
background current is considerably faster than the decay of the faradaic current.
The background current is negligible at a time which is constant for a given electrochemical cell,
and ranges from μs to ms). Therefore, after this time, the measured current consists solely of the
faradaic current; that is, measuring the current at the end of the potential pulse allows
discrimination between the faradaic and charging current.

Square wave voltammetry (SWV)

Square wave voltammetry is a type of pulse voltammetry that offers the advantage of speed and
high sensitivity. An entire voltammogram is obtained in a few seconds or less. In addition,
square wave voltammetry (SWV) has proved to be a suitable method to investigate redox
reactions with overlapping waves. The excitation signal in SWV consists of a symmetrical
square wave pulse of amplitude superimposed on staircase wave form of step height ΔE. The
forward pulse coincides with the staircase step.

Figure 3.3. Excitation waveform of square wave voltammetry (Curve a) and response
obtained by square wave voltammetry (Curve b).

Amperometry is strictly a sub-class of voltammetry in which the electrode is held at constant

potentials for various lengths of time. The distinction between amperometry and voltammetry is
mostly historic as there was a time when it was difficult to switch between "holding" and
"scanning" a potential.
Stripping analysis is one of the most sensitive voltammetric methods. Such techniques enjoy the
advantages that there is no need for derivatization and that these methods are less sensitive to
matrix effects than other analytical techniques. It is mostly used for trace analysis of heavy
metals for environmental analysis.
 Anodic Stripping Voltammetry (ASV)
 If the current to be detected is anodic, the method is called ASV
 ASV involves three basic Mechanisms
i) Accumulation (Equilibration) step:
(M2+) solution + (E) surface → (M2+- E) adsorb)
ii) Reduction step: M2+ + 2e- → M
iii) Stripping (detection) step: M → M2+ +2e- (M is Pb, Cd, Zn ,Cu )
In amperometry, the working electrode is held at a constant potential while the current is
monitored. The current is then related to the concentration of the analyte present. This sensing
method is commonly employed in both biosensors and immunosensors. The first amperometric
sensor was the oxygen electrode developed by L.C. Clark. Oxygen entering the system through a
gas-permeable membrane is reduced to water at a noble metal cathode.
 Amperometric and voltammetric methods however, involve applying a non-equilibrium
electrical potential and measuring the resulting current or current–voltage relationship to
obtain quantitative (in the case of amperometry) or qualitative information.
3.3.3. Conductimetric

Conductimetric sensors are based on the measurement of electrolyte conductivity, which varies
when the cell is exposed to different environments. The sensing effect is based on the change of
the number of mobile charge carriers in the electrolyte. If the electrodes are prevented from
polarizing, the electrolyte shows ohmic behavior. The conductivity is a linear function of the ion
concentration; therefore, it can be used for sensor applications.
Conductimetric methods are fundamentally non-selective. Only with the advent of modified
surfaces for selectivity and much improved instrumentation have these become more viable
methods. There are some very practical considerations that make conductimetric methods
attractive, such as low cost and simplicity, since no reference electrodes are needed.
Improved instrumentation has contributed to rapid and easy determination of analytes, based
only on the measurement of conductivity. The most predominant materials used in these sensors
will be examined first. The methods of numerical processing of the analytical signal will then be
discussed, followed by certain phenomena or properties which lend themselves to the purpose of
sensing. Thin films are used mostly as gas sensors, due to their conductivity changes following
surface chemisorption. For example, due to oxygen chemisorption, CdS films can be used as
oxygen sensors.
Porous films of MnWO4 Can work as a humidity sensor, oxides doped with copper or copper
oxide can be very sensitive to gases containing H2S and semiconducting Ga2O3 thin films can
detect CH4 Polymers, either conductive themselves or with a modifier, are also often used.
Polypyrrole can detect volatile amines, or when doped with ClO4- and tosylate, it can be made
into a sensor for NH3.
3.4. Electrochemical Biosensors

A biosensor contains a recognition layers which combines a biological components such as

enzymes, tissue, microorganism, nucleic acid, cellular structure etc. A biosensor tool converts
the signal of the interaction between the analyte and the biological element into an easily
detectable signal such as light, voltage, current, mass, etc. The catalytic activity of AChE is
inhibited by trace amounts of organophosphorus and carbamate pesticides. The combination of
enzymatic reactions with the electrochemical method of monitoring electroactive enzymatic
products allowed to develop enzyme based electrochemical biosensors for sensitive and rapid
determination of pesticides. Biosensors have attractive applications in human care, food industry,
controlling the environment and for genetic applications. The greatest advantage of such
biosensors are in their application being user friendly, having a fast response, high sensitivity,
strong selectivity, and their practical use for real sampling. See the following chemical reaction
mechanism of enzymes with organophosphorus.

O
O
P OR
AChE-Ser-OH + P OR SR
AChE-Ser-OH
SR

P OR

O-Ser-AChE

Biosensor and Its Working Principles

The principle of electrochemical sensors is that when an electro-active analyte is subjected to

fixed or varying potential of some predefined patterns causes oxidation or reduction of analyte
on the working electrode surface, which leads to the generation of an electrochemically
measurable signal by the variation on electron fluxes. This signal can be measured by the
electrochemical detector. The working of electrochemical biosensors is mainly based on the use
of bio-receptor element retained in direct contact with an electrochemically active transducer
(electrode) to obtain an analytically useful signal by coupling biochemical and electro-chemical
interactions.

Figure 3.4. working principle for biosensor

3.5. Gas Sensors

There are different types of gas sensor like Catalytic sensors, electrochemical gas sensor,
thermoelectric gas sensor, optical gas sensors …..Etc
Electrochemical Gas Sensors
These types of sensors allow gases to diffuse through a porous membrane to an electrode where
it is either reduced or oxidized at the electrode. Electrochemical sensors operate by reacting with
a target gas and producing an electrical signal that is proportional to the gas concentration. A
typical electrochemical gas sensor consists of a sensing electrode or working electrode and a
counter electrode which are separated by a thin layer of electrolyte. Before the gas comes in
contact with the sensor, it goes through a thin capillary-type opening and then diffuses through a
hydrophobic barrier before finally reaching the electrode surface. The function of this membrane
is to prevent liquid electrolyte from leaking out and generate enough electrical signal at the
sensing electrode. It also consists of a reference electrode whose function is to maintain a stable
and constant potential at the sensing electrode due to the continuous electrochemical reactions
occurring on the electrode surface. The electrochemical reaction with the target gas generates a
flow of current flow between the sensing and counter electrodes. The electrolyte is responsible
for carrying the ionic charges across the electrode.

An electrochemical sensor can be used for measuring carbon monoxide by undergoing a

chemical reaction as follows:

As shown in equation (1), Oxidation reaction takes place at the sensing electrode, CO2 diffuses
into the air and the positively charged ions migrate into the electrolyte.

The oxidation reaction is balanced by a corresponding reduction reaction at the counter electrode
as shown in equation (2). At one electrode, water is consumed while electrons are generated and
at the other electrode water is created while electrons are consumed. The carbon monoxide
generated diffuses in the air and the positively charged hydrogen ions travel down to the
electrolyte.
Similarly, for hydrogen the electrochemical reaction is as shown in equation 3, Hydrogen gas
diffuses and becomes oxidized at the sensing electrode. This reaction causes a change in the
potential of the sensing electrode and thus reduction of oxygen takes place as shown in equation
4.

Performance Indicators and Gas Sensor’s Stability

To evaluate the performance of gas sensing methods or gas sensors, several indicators should be
considered:
(1) sensitivity: the minimum value of target gases’ volume concentration when they could
be detected;
(2) selectivity: the ability of gas sensors to identify a specific gas among a gas mixture;
(3) response time: the period from the time when gas concentration reaches a specific value to
that when sensor generates a warning signal;
(4) energy consumption;
(5) reversibility: whether the sensing materials could return to its original state after detection;
(6) adsorptive capacity (also affects sensitivity and selectivity);
(7) fabrication cost.