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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.
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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,
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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.
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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.
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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
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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:
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
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Summary
Electrochemical sensors require very little power to operate.
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:
- cost-effective fabrication,
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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.
Where
Ip is the peak current in Ampere,
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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.
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
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2. Miniaturisation
- dead volumes
- sample preparation
- reagent consumption
- energy consumption
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.
Examples of electroplating
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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?
Anode = silver
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Classification:
(a)Oxidation Corrosion:
- It is due to direct attack of oxygen on metals.
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Mechanism:-
2M 2M+n + 2ne-
2. Electron are gained by the oxygen molecules and forms oxide ions
(b)Corrosion by Gases
Carbon di-oxide, Chlorine, Hydrogen Sulphide, Sulphur di-oxide, Flourine
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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
If two metals are present in in electrolyte, the metal with less reduction
potential undergoes corrosion.
- Greater the difference faster the corrosion.
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:
(b) Smaller grain size metal have high solubility and corrosion.
(d) Passive metals shows higher corrosion resistance ( form protective oxide film)
2. Nature of Environment
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:
- Coating material should be chemically inert under particular temp and pressure.
6. Modifying Environment
(iii)Reducing Acidity:
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