Chapter three

Sensors and analytical systems

By Tassew Alemayehu (Assistance professor)

 Introduction
A sensor (also called detector) is a converter that measures a
physical quantity and converts it into a signal which can be read by
an observer or by an (today mostly electronic instrument).
Is a device which is able to detect a change in physical/ chemical
quantity and produce an electrical signal suitable for a computer.

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 A chemical sensor can be defined as a device that
provides continuous information about its environment.
Provides a certain type of response directly related to the
quantity of a specific chemical species.
All chemical sensors consist of a transducer, which
transforms the response into a detectable signal on
modern instrumentation, and a chemically selective layer,
which isolates the response of the analyte from its
immediate environment.
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 Chemical sensors contain two basic functional units: a receptor
part and a transducer part.
Some sensors may include a separator, for example, a membrane.

In the receptor part of a sensor the chemical information is

transformed into a form of energy which may be measured by the
transducer.
The transducer part is a device capable of transforming the energy
carrying the chemical information about the sample into a useful
analytical signal.

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Cont.

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 Electrochemical sensors
The oldest electrochemical sensors date back to the 1950s and
were used for oxygen monitoring.
More recently, as the Occupational Safety and Health
Administration (OSHA) began requiring the monitoring of toxic
and combustible gases in confined space applications, new and
better electrochemical sensors have been developed.
Currently, a variety of electrochemical sensors are being used
extensively in many stationary and portable applications for
personal safety.

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Figure 1 shows a small collection of such electrochemical sensors.

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 The physical size, geometry, selection of various components, and
the construction of an electrochemical sensor usually depends on its
intended use.
The most common misconception about electrochemical sensors is
that they are all the same.
In fact, the appearance of the electrochemical sensors used to detect
various gases may be similar, but their functions are markedly
different.
Consequently, one can expect varying performance from each of
these sensors, in terms of sensitivity, selectivity, response time, and
operating life.
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 For example, a low concentration gas sensor with very high sensitivity uses a
coarse-porosity hydrophobic membrane and less restricted capillary to allow
more gas molecules to pass through to produce enough signal for better
sensitivity.
However, this design also allows more of the electrolytes water molecules to
escape out to the environment.
In other words, an electrochemical sensor with high sensitivity would have a
relatively short operating life due to evaporation of moisture through the porous
membrane.
Similarly, the electrolyte composition and the sensing electrode material is
selected based on the chemical reactivity of the target gas.
By careful selection of the electrolyte and/or the sensing electrode, one can
achieve the selectivity towards the target gas, but the sensitivity may be reduced.
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 In summary, different electrochemical sensors may appear very
similar, but are constructed with different materials including such
critical elements as sensing electrodes,

electrolyte composition, and

porosity of hydrophobic barriers.

Additionally, some electrochemical sensors use external electrical

energy to make them reactive to the target gas.
All components of the sensors play a crucial role in determining
the overall characteristics of the sensors.

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Cont

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 Principle of Operation
Electrochemical sensors operate by reacting with the gas of interest and
producing an electrical signal proportional to the gas concentration.

A typical electrochemical sensor consists of a sensing electrode(or working

electrode), and a counter electrode separated by a thin layer of electrolyte
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 Gas that comes in contact with the sensor first passes through a
small capillary-type opening and then diffuses through a
hydrophobic barrier, and eventually reaches the electrode surface.
This approach is adopted to allow the proper amount of gas to react
at the sensing electrode to produce a sufficient electrical signal
while preventing the electrolyte from leaking out of the sensor,
Figure 4.
The gas that diffuses through the barrier reacts at the surface of the
sensing electrode involving either an oxidation or reduction
mechanism.

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Cont..

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 These reactions are catalyzed by the electrode materials
specifically developed for the gas of interest.
With a resistor connected across the electrodes, a current
proportional to the gas concentration flows between the anode and
the cathode.
The current can be measured to determine the gas concentration.

Because a current is generated in the process, the electrochemical

sensor is often described as an amperometric gas sensor or a
micro fuel cell.

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 Importance of a Reference Electrode
For a sensor requiring an external driving voltage, it is important to
have a stable and constant potential at the sensing electrode.
In reality, the sensing electrode potential does not remain constant
due to the continuous electrochemical reaction taking place on the
surface of the electrode.
It causes deterioration of the performance of the sensor over
extended periods of time.
To improve the performance of the sensor, a reference electrode is
introduced.

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 This reference electrode is placed within the electrolyte in
close proximity to the sensing electrode.
A fixed stable constant potential is applied to the sensing
electrode.
The reference electrode maintains the value of this fixed
voltage at the sensing electrode.
No current flows to or from the reference electrode

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 The gas molecules react at the sensing electrode and the current
flow between the sensing and the counter electrode is measured and
is typically related directly to the gas concentration.
The value of the voltage applied to the sensing electrode makes the
sensor specific to the target gas.
The micro fuel cell-type electrochemical sensors do not require an
external driving voltage.
For example, an electrochemical sensor specific to oxygen has an
anode, either Pb or Cd, that supplies electrons for the reduction of
oxygen at the cathode.

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 During the oxidation of the anode, the electrons are released and travel via an
external circuit to the cathode where oxygen molecules consume the electrons
as follows:

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 Major Components

A. Gas Permeable Membrane (also called hydrophobic membrane):

used to cover the sensors sensing (catalyst) electrode and,

to control the amount of gas molecules reaching the electrode

surface.
Such barriers are typically made of thin, low-porosity Teflon
membranes. Such sensors are called membrane clad sensors.
Alternatively, the sensing electrode is covered with a high-porosity
Teflon and the amount of gas molecules reaching the electrode
surface is controlled by a capillary. Such sensors are referred to as
capillary-type sensors
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 Besides offering a mechanical protection to the sensor, the
membrane performs the additional function of filtering out
unwanted particulates.
Selecting the correct pore size of the membrane and capillary
is necessary to transfer the proper amount of gas molecules.
the pore/hole size should be such as to allow enough gas molecules
to reach the sensing electrode and also prevent liquid electrolyte
from leaking out or drying out the sensor too quickly.

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 B. Electrode:
It is a catalyzed material which performs the half cell reaction over a long
period of time.
Typically, the electrode is made from a noble metal, such as platinum or gold,
and catalyzed for an effective reaction with gas molecules. Depending on the
design of the sensor, all three electrodes can be made of different materials to
complete the cell reaction.

C. Electrolyte:
It must facilitate the cell reaction and carry the ionic charge

It must also form a stable reference potential with the reference electrode and
be compatible with materials used within the sensor.
If the electrolyte evaporates too quickly, the sensors signal will deteriorate.

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 D. Filter:
Sometimes a scrubber filter is installed in front of the sensor to
filter out unwanted gases.
There is a limited selection of filters, each with different degrees of
effectiveness.
The most commonly used filter medium is activated charcoal,

The activated charcoal filters out most chemicals with the exception
of carbon monoxide and hydrogen gases.
By properly selecting the filter medium, an electrochemical sensor
can be made more selective to its target gases.

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 Fig. 5 Filtering with Activated Charcoal
Minor variations in the details of the sensor design can have a profound influence
on the sensors accuracy, response time, sensitivity, selectivity, and life
expectancy. 24
 Importance of Oxygen
The reactions at the sensing electrode(anode) for some gases are as
follows:

Simultaneously, the reactions at the counter electrode (cathode)

need oxygen molecules to complete the process:

O2 + 4H+ + 4e- 2H2O

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 Characteristics
There are many different ways that electrochemical sensors are constructed,
depending both on the gas to be detected as well as the manufacturer. However,
the main characteristics of the sensors are essentially very similar.

common characteristics of electrochemical sensors:

1. Are three-electrode sensors, there is normally a jumper which connects the

working and reference electrodes.

2. Most of the toxic gas sensors require a small amount of oxygen to function
properly. It is wise to double-check with the manufacturer in applications that
use non oxygen background gas

3. Electrolyte within the sensor cell is an aqueous solution separated by a

hydrophobic barrier which will not allow the aqueous solution to leak out.

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 Summary
Electrochemical sensors require very little power to operate.

In fact, their power consumption is the lowest among all sensor

types available for gas monitoring.
For this reason, the sensors are widely used in portable instruments
that contain multiple sensors.
A sensors life expectancy is predicted by its manufacturer under
conditions that are considered normal.
However, the life expectancy of the sensor is highly dependent on
the environmental contaminants, temperature, and humidity to
which it is exposed.
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 Types of Electrochemical sensors

1. Potentiometric sensors
Electrochemical measurements for analytical purposes are carried
out under conditions of equilibrium (zero current).
The equilibrium potential, Eeq, results from the sum of the partial
anodic and cathodic currents due to the various electrode reactions
being equal to zero.
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.
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 Nernst equation logarithmically relates the measured electrode
potential, E, to the relativeactivities of the redox species of interest:

Where is the standard electrode potential and

And are the activities of the oxidised and reduced species,

R is the universal gas constant;

T is the absolute temperature; F is the Faraday constant;

n is the number of moles of electrons exchanged in the electrochemical reaction.

The most representative potentiometric sensor is the ion selective electrode
(ISE).
It uses an indicator electrode which selectively measures the activity of a
particular analyte ion.
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 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.
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Classical ISEs, the arrangement is symmetrical which means that the
membrane separates two solutions, the test solution and the inner
solution with a constant concentration of ionic species.
The electrical contact to an ISE is provided by a reference electrode
(usually Ag/AgCl) in contact with the internal solution that contains
chloride ions at constant concentration.
The measured ISE potential is the sum of the two reference
electrode potentials,
the membrane potential constituted by boundary potentials at each
membrane/solution interface, and
a possible diffusion potential caused by an ion concentration gradient within
the ion-selective membrane phase. 31
ISEs with solid inner contacts (asymmetrical)
potentials generated at each membrane interface are included in the overall
sensor signal response
to obtain a solid-contact ISE with a stable electrode potential, a fast and
thermodynamically reversible ion-to-electron transduction in the solid state is
required.
These ion-selective electrodes have nowadays similar performance
characteristics to inner-solution ion-selective electrodes and offer new and
advantageous technical possibilities such as

- miniaturization to the m scale,

- cost-effective fabrication,

- no need for maintenance,

- flexibility, and multiple shape configurations.

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 Among the electroactive materials available today, conducting
polymers have emerged as a promising ion-to-electron transducers
for solid-contact ISEs.
In this type of solid contact ISE, the conducting polymer is coated
with a conventional ion-selective membrane, and the ion-selectivity
is determined mainly by the ion-selective membrane.

For example, potentiometric sensors based on a glassy carbon

electrode covered with polyaniline have been developed and
applied for the successful determination of Ag+ ions.

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2. Voltammetric and Amperometric sensors
An amperometric sensor measures a current flow between two
electrodes at a fixed applied potential, while
A voltammetric sensor measures a current flow between two
electrodes as a function of applied potential (variable voltage).
Thus an amperometric sensor is a fixed-potential voltammetric
Sensor
voltammetric Sensor is linearly dependent upon the concentration
of the electroactive species (analyte) involved in a chemical or
biological recognition process

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 Cyclic, square wave and stripping voltammetry are common
techniques.

Cyclic : determine he concentration of the electroactive species

quantitatively by the measurement of limiting current as;

Where
Ip is the peak current in Ampere,

n the number of electrons transfer,

A the surface area in cm2,

Ci the concentration of species

Di the diffusion coefficient of species and

v the scan rate in V s-1. 35

Voltamogramm

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Square wave voltammogram

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3. Conductimetric and impedimetric sensors
Conductimetric sensors are based on the measurement of electrolyte
conductivity
The sensing effect is based on the change of the number of mobile charge
carriers in the electrolyte.
Conductivity measurements are generally performed with an AC supply.

The conductivity is a linear function of the ion concentration; therefore, it

can be used for sensor applications.
Conductivity measurements in general, are non-specific for a given ion type.

Also, the polarization and the limiting current operation mode need to be avoided
as these can damage the electrode interface.
Thus, a small amplitude alternating bias can be used for sensor measurements
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 Impedance-based sensors have a similar design as mixed potential
type sensors.
Instead of measuring the voltage, a sinusoidal voltage is applied
and the resulting current is measured.
Electrical impedance is the measure of the opposition that a circuit
presents to a current when a voltage is applied.
In quantitative terms, it is the complex ratio of the voltage to the
current in an alternating current (AC) circuit.
Impedance extends the concept of resistance to AC circuits, and
possesses both magnitude and phase, unlike resistance, which has
only magnitude.
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 Physical and analytical properties of electroanalytical
sensors
1. Cost
Electrochemical sensors provide a low cost analytical tool

the ability to produce electrochemical sensors in large numbers at a

low cost is a major requirement for many applications.
Thus, the ability to mass manufacture sensors, with minimal
production costs facilitates the potential of sensors as low-cost
disposable platforms.

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2. Miniaturisation

is the trend to manufacture ever smaller mechanical, optical and

electronic products and devices

Through the reduction in size of both the functionally critical

components of sensing devices and the sensors themselves,
miniaturisation is used for the reduction of:
- transport times and volumes

- dead volumes

- sample preparation

- reagent consumption

- energy consumption

- time expenditure and monetary cost. 41

3. Selectivity
Selectivity is defined as the ability of a sensor to detect one specific species even
in the presence of other chemical species / interferon's.

4. Stability
The most desirable sensors are those that retain their characteristics when tested
or used under varying conditions and environments,
i.e. are those which can function in a harsh condition.

nanocomposites sensor fabrication, possess enhanced physical and chemical

properties.
This interaction depends strongly on characteristics of each component, i.e.
interface, size, shape and structure.
In extreme cases, where there is no or little interaction between the components,
the composites properties should be equivalent to a simple sum of the properties
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of the individual elements
5. Multi-analyte detection
Is the Simultaneous detection of multiple analytes by any sensor.

Current research is endeavouring to exploit the capability of voltammetric

analysis to sensitively, selectively rapidly differentiate between numerous
compounds.
This is particularly evident in recent developments in biosensors.

A biosensor is an analytical device, used for the detection of an analyte,

that combines a biological component with a physicochemical detector.
The sensitive biological element (e.g. tissue, microorganisms, organelles,
cell receptors, enzymes, antibodies, nucleic acids, etc.) is a biologically
derived material or biomimetic component that interacts with the analyte
under study
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 4. Electroplating and corrosion
Electro plating
Electroplating is a procedure that uses electrolysis to apply a thin
layer of a metal over the surface of another metal.

Electrolysis is the process of making a non-spontaneous chemical

redox reaction to occur by passing electricity through a substance.

In electroplating, the anode is made up of the metal you want to

coat the surface of another metal with.

There is also a salt solution present of the anode metal.

While electrolysis is taking place, the anode metal is oxidized and

goes into solution as positive ions.
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 These positive ions are then reduced on the surface of the cathode
(the metal you wish to coat).

The aim of metal plating through electrolysis includes:

making the metal more resistant to corrosion

making the metal appear more attractive

Examples of electroplating

Coating jewelry with thin layer of expensive metal.

Coating chromium over steel to make rust resistant

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Cont.

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Example
1. A spoon is to be plated with silver, Ag.
Identify the anode and cathode.
Write an equation electrode reactions at the anode and cathode
What electrolyte is used?

Answer: Cathode = spoon (metal to be coated),

Anode = silver

silver anode is oxidized,

Ag(s) Ag+(aq) + 1e-

Ag+ (aq) ions are reduced.

Ag+ (aq) + 1e- Ag(s)

Electrolyte solution is made of AgNO3 47
 Corrosion
is defined as the deterioration of a material, usually a metal,
because of a reaction with its environment. or
Process of Distruction of the material through chemical or
electrochemical attack by its environment
Happens at different rates with different metals and in different
environments.
If we expose iron or steel to air and water we can expect to see rust
form in a short time, showing the color of red-brown iron oxide.
Depending on the environment the rust may develop in minutes.

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 Classification:

1. Dry or Chemical Corrosion

2. Wet or Electrochemical corrosion

1.Dry or Chemical Corrosion

- Occurs due to chemical attack of by the environment

- Occurs due to high temperature and without liquid phase.

- It is of two types: a) Oxidation corrosion b) Corrosion by gases

(a)Oxidation Corrosion:
- It is due to direct attack of oxygen on metals.

- Oxygen molecules are attracted to the surface by Vander Wall Force

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Mechanism:-

1. When temp increases the metal undergoes oxidation and losses e-

2M 2M+n + 2ne-

2. Electron are gained by the oxygen molecules and forms oxide ions

nO2 + 4ne- 2n O2- Oxide Ion

3. Scale of metal oxide formed

2M + nO2 2M + 2n O2- Metal Oxide

(b)Corrosion by Gases
Carbon di-oxide, Chlorine, Hydrogen Sulphide, Sulphur di-oxide, Flourine

- Depends on chemical affinity b/w metal and the gas.

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2. Wet or Electrochemical Corrosion
Occurs when aqueous solution or liquid electrolytes are present
Wet corrosion takes place in environments where the relative
humidity exceeds 60 %.
It is most efficient in waters containing salts, such as NaCl (e.g., due
to the high conductivity of the solution.

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 It is generally accepted that the usual cause of corrosion of metals
involves electrochemistry.
A flow of electricity occurs from one area of the metal to another
area through an electrolyte, i.e. any solution capable of conducting
electricity such as seawater, hard water, or other moisture on the
substrate.
We refer to the corrosion process as an electrochemical reaction,
sometimes referred to as a galvanic action.
For galvanic corrosion to occur we must have four things:
---Anode
Cathode
Metallic Pathway
Electrolyte
The steel itself contains anodes and cathodes (areas on the surface
that have different electrical potentials) and it is its own metallic
pathway.
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Anodic Reaction:
Dissolution of metal takes place.
As result metal ions are formed with the liberation of free
electrons.
M M+n + e-
Metal Ion
Cathodic Reaction
(i) Hydrogen Evolution :- Occurs usually in acidic medium
2H+ + 2e- H2 (g)
(ii) Oxygen Absorption :- occurs when solution is aerated sufficiently.
O2+ 4H+ + 4e- 2H2O (In acidic medium)
O2+ 4H+ + 4e- 4OH- (In basic medium)

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Galvanic Corrosion:- When two different metals are
present in contact with each other in conducting medium
e.g. Electrolyte

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 Factors Affecting Corrosion

1. Nature of the Metal

(i) Position in Galvanic Series:

If two metals are present in in electrolyte, the metal with less reduction
potential undergoes corrosion.
- Greater the difference faster the corrosion.

(ii) Over Voltage:

Due to high evolution of hydrogen, the rate is slow

(iii) Area and Distance:

When anodic metal area is smaller than cathodic area, rate of corrosion
at anode is higher because of demand of electron by cathodic area.
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IV. Physical and Mechanical properties of Metal:

(a) Pure metals are more corrosion resistant.

(b) Smaller grain size metal have high solubility and corrosion.

(c) Uniform distribution of stress on metal reduces rate of corrosion.

(d) Passive metals shows higher corrosion resistance ( form protective oxide film)

(e) Polycrystalline forms are more sensitive.

2. Nature of Environment

(i) Temperature: directly proportional

(ii) Humidity: faster in humid conditions

(iii)pH : If less than 7 rate is high.

Impurities and Suspended Particles: provides electrolyte for conductivity and

hence corrosion increases

(i) Oxygen: directly proportional 56

 ways of corrosion control :

1. Selection of metal and alloy:

- Using pure and noble metals

- Practically not possible because of low strength of pure metal

- Use of metal alloys which are homogeneous

2. Proper Design of metal

Minimal contact with medium
Prevention from moisture
Adequate ventilation and drainage
Bend should be smooth
Bimetallic contacts should be avoided
Paint cathodic portion
Prevent uneven stress

Allows access for surface preparation and coating operations. 57

3. Inhibitors

Inhibitors are materials that may be injected into the system .

They plate out on the surface and inhibit the formation of corrosion cells.

They are commonly used in pipelines and other vessels that will contain materials
that are corrosive.

4. Cathodic Protection:

Force the metal to be protected to behave like cathode.

(i) Sacrificial anodic protection:

- Metal to be protected from corrosion connected to more anodic metal

- Commonly used metals Mg, Zn, Al and their alloys

(ii) Impressed current method:

- Direct current is applied in opposite direction to nullify the corrosion current

- Converts the corroding metal from anode to cathode 58

5. Protective Coatings
The coatings we apply may be inhibitive , barrier, or sacrificial.

surface preparation.: clean and suitably roughened surface .

Adhesion is the most important attribute of a coating.

- Coating material should be chemically inert under particular temp and pressure.

6. Modifying Environment

(i) Eliminating dissolved oxygen:

- De-aeration and Deactivation

(ii) Reducing Moisture:

- Dehumidification by using silica gels

(iii)Reducing Acidity:

- Neutralizing the acidic environment by adding lime, NaOH, Ammonia

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Summary

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