ELECTROCHEMICAL SENSOR

Cyclic Voltammetry

Cyclic voltammetry is the most widely used technique for acquiring

qualitative information about electrochemical reactions.The power of
cyclic voltammetry results from its ability to rapidly provide
considerable information on the thermodynamics of redox processes
and the kinetics of heterogeneous electron transfer reactions and on
coupled chemical reactions or adsorption processes. Cyclic
voltammetry is often the first experiment performed in an
electroanalytical study. In particular, it offers a rapid location of redox
potentials of the electroactive species, and convenient evaluation of
the effect of media on the redox process.
Cyclic voltammetry consists of scanning linearly the potential of a stationary
working electrode (in an unstirred solution), using a triangular potential
waveform (Fig. 1). Depending on the information sought, single or multiple
cycles can be used. During the potential sweep, the potentiostat measures
the current resulting from the applied potential. The resulting current–
potential plot is termed a cyclic voltammogram. The cyclic voltammogram is a
complicated, time-dependent function of a large number of physical and
chemical parameters.
Figure 2 illustrates the expected response of a reversible redox couple during a
single potential cycle. It is assumed that only the oxidized form O is present
initially. Thus, a negative-going potential scan is chosen for the first half-cycle,
starting from a value where no reduction occurs. As the applied potential
approaches the characteristic E° for the redox process, a cathodic current
begins to increase, until a peak is reached. After traversing the potential
region in which the reduction process takes place (at least 90/n mV beyond the
peak), the direction of the potential sweep is reversed. During the reverse
scan, R molecules (generated in the forward half-cycle, and accumulated near
the surface) are reoxidized back to O, resulting in an anodic peak.
The characteristic peaks in the cycle voltammogram are caused by the
formation of the diffusion layer near the electrode surface. These can be best
understood by carefully examining the concentration–distance profiles during
the potential sweep. For example, Figure 3 illustrates four concentration
gradients for the reactant and product at different times corresponding to (a)
the initial potential value, (b,d) the formal potential of the couple (during the
forward and reversed scans, respectively), and (c) the achievement of a zero-
reactant surface concentration. Note that the continuous change in the surface
concentration is coupled with an expansion of the diffusion-layer thickness (as
expected in quiescent solutions). The resulting current peaks thus reflect the
continuous change of the concentration gradient with time. Hence, the
increase in the peak current corresponds to the achievement of diffusion
control, while the current drop (beyond the peak) exhibits a t−1/2 dependence
(independent of the applied potential). For these reasons, the reversal current
has the same shape as does the forward one
(a) Concentration distribution of
the oxidized and reduced forms of
the redox couple at different times
during a cyclic voltammetric
experiment corresponding to the
initial potential, (b, d) to the formal potential of
the couple during the forward
and reversed scans

(c) to the achievement of a zero-

reactant surface concentration.
 Data Interpretation
The cyclic voltammogram is characterized by several important parameters.
Four of these observables, the two peak currents and two peak potentials,
Reversible Systems The peak current for a reversible couple (at 25°C) is given by
the Randles–Sevcik equation

where n is the number of electrons, A the electrode area (in cm2), C the
concentration (in mol/cm3),D the diffusion coefficient (in cm2/s), and v the
potential scan rate (in V/s). Accordingly, the current is directly proportional to
concentration and increases with the square root of the scan rate. Such
dependence on the scan rate is indicative of electrode reaction controlled by
mass transport
The reverse-to-forward peak current ratio, ip,r/ip,f, is unity for a simple
reversible couple.
The position of the peaks on the potential axis (Ep) is related to the formal
potential of the redox process. The formal potential for a reversible couple is
centered between Ep,a and Ep,c:

The separation between the peak potentials (for a reversible couple) is

given by
 GAS SENSORS

Real-time monitoring of gases, such as carbon dioxide, oxygen, and ammonia,

is of great importance in many practical environmental, clinical, or industrial
situations. Gas-sensing electrodes are highly selective devices for measuring
dissolved gases. They are reliable and simple, exhibit excellent selectivity, but
tend to have relatively slow response times (particularly as the limit of
detection is approached).
Gas sensors usually incorporate a conventional ion-selective electrode
surrounded by a thin film of an intermediate electrolyte solution and enclosed
by a gas-permeable membrane.
An internal reference electrode is usually included, so that the sensor
represents a complete electrochemical cell.
The gas (of interest) in the sample solution diffuses through the membrane
and comes to equilibrium with the internal electrolyte solution.
In the internal compartment, between the membrane and the ion-selective
electrode, the gas undergoes a chemical reaction, consuming or forming an ion
to be detected by the ion-selective electrode.
Since the local activity of this ion is proportional to the amount of gas
dissolved in the sample, the electrode response is directly related to the
concentration of the gas in the sample.
The response is usually linear over a range of typically four orders of
magnitude; the upper limit is determined by the concentration of the inner
electrolyte solution.
The permeable membrane is the key to the electrode’s gas selectivity.
 Carbon Dioxide Sensors
Carbon dioxide devices were originally developed by Severinghaus and
Bradley to measure the partial pressure of carbon dioxide in blood. This
electrode, still in use today (in various automated systems for blood gas
analysis), consists of an ordinary glass pH electrode covered by a carbon
dioxide membrane, usually silicone, with an electrolyte (sodium
bicarbonate–sodium chloride) solution entrapped between. When
carbon dioxide from the outer sample diffuses through the
semipermeable membrane, it lowers the pH of the inner solution:
Such changes in pH are sensed by the inner glass electrode. The
overall cell potential is thus determined by the carbon dioxide
concentration in the sample:

Schematic representation of the potentiometric sensor for carbon

dioxide.
 Oxygen Electrodes
While most gas sensors rely on potentiometric detection, the important
oxygen probe is based on amperometric measurements.
In particular, membrane covered oxygen probes based on the design have
found acceptance for many applications.
The sensor is based on a pair of electrodes immersed in an electrolyte
solution and separated from the test solution by a gas-permeable hydrophobic
membrane.
The membrane is usually made of Teflon, silicon rubber, or polyethylene,
while the electrolyte is a solution of potassium chloride and buffer.
Oxygen diffuses through the membrane and is reduced at the surface of the
sensing electrode.
The resulting electrolytic current is proportional to the rate of diffusion of
oxygen to the cathode, and hence to the partial pressure of oxygen in the
sample.
 Membrane-covered oxygen probe

The actual potential applied at the cathode (with respect to the

anode/reference electrode) depends on the particular design. Cathodes
made of platinum, gold, or silver are commonly incorporated in different
commercial probes.
 Corrosion
Corrosion slowly coats the surfaces of metallic objects with oxides or
other salts of the metal. The rusting of iron, tarnishing of silver,
development of green coating on copper and bronze are some of the
examples of corrosion. It causes enormous damage to buildings,
bridges, ships and to all objects made of metals especially that of iron.
In corrosion, a metal is oxidised by loss of electrons to oxygen and
formation of oxides. Corrosion of iron (commonly known as rusting)
occurs in presence of water and air. The chemistry of corrosion is quite
complex but it may be considered essentially as an electrochemical
phenomenon.