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Electrode kinetics and Polarization phenomena
P. Bhanu Prakash, 16005A0805, IV B.Tech Chemical Engineering, JNTUA CEA
 The electrochemical reaction differs from a chemical
Abstract-- An electrode is an ideal catalyst in reaction in that at least one of the partial reactions of
that the potential difference at electrode solution
interface controls both the thermodynamics and the
kinetics of electro chemical reactions. The electrode
kinetics play an important role to understand the
corrosion behavior of the metals in different
environment. Here the possible to transfer of
electrons between the electrode and electrolyte. This
process is results in a reactant undergoing an
oxidation and reduction reaction. The electrolysis
results in flow of current around the electrical circuit.
The rate of current can be controlled between the
metal and species of solution. Polarization is
collective term for certain mechanical side effects (of
a electrochemical process) by which isolating barrier
developing the interface between the electrode and
electrolyte. This polarization influence the reaction
mechanism chemical kinetics of electrode which
leads to corrosion. It is decreases the potential of
electrode.
. electrolysis, when the anode’s potential becomes
I. INTRODUCTION
1.Electrode kinetics:
Electrode reactions are heterogeneous processes
involving a number of steps whose kinetics depend
on the rate of charge transfer and mass transfer and
the rate of chemical reactions coupled with charge
transfer. The reaction kinetics of an electrochemical
reaction depend not only on the concentration of the
reactants, the temperature and the material of the
catalyst but also on the electrode potential. Since the
electrode potential depends on the concentration of
the reactants, temperature etc., it is possible to
calculate the various thermodynamic parameters
from the study of electrode potential as a function of
temperature or concentration.
the overall electrode reaction must be a charge
transfer reaction which involves the transfer of
charge across the double layer. The rate of electrode
reaction is proportional to the current density which
in turn depends on the electrode potential,
concentration of the reactants and temperature. As in
the case of chemical reaction kinetics, the slowest
reaction in the overall reaction is the rate determining
step in electrode kinetics also. Since the electrode
process is heterogenous in nature, its reaction rate is
considerably influenced by the double layer
structure, adsorption of reactants, products,
supporting electrolyte and other addition agents.
2. Polarization:
Polarization is a mechanism that typically results
in a change in the potential of an electrode during
nobler than that of the cathode. It has the effect
(based on conditions) of decreasing the output
voltage of batteries, and increasing the voltage
required for electrolysis cells or lowering currents.
Polarization can also be described as a kinetic
deviation from equilibrium due to an electric current
passing through a galvanic cell. Polarization may
occur at the cathode (cathodic polarization) or at the
anode (anodic polarization). Cathodic polarization is
more common.
II. EXPLANATION
Electrode kinetics:
In this section we will develop a quantitative current
flowing in either the reductive or oxidative steps can
be predicted using the following expressions for the
influence of the electrode voltage on the rate of
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electron transfer. For simplicity we will consider a

single electron transfer reaction between two species where the term in the exponential is the free energy
(O) and (R) change in taking the reactant from its initial value to
the transition state divided by the temperature and
The current flowing in either the reductive or gas constant. This free energy plot is also
oxidative steps can be predicted using the following qualitatively valid for electrode reactions
expressions

ic = -FAKred(O)

ia = FAKox(R)

For the reduction reaction the current (ic) is related to

the electrode area (A), the surface concentration of
the reactant [O]o, the rate constant for the electron
transfer (kRed or kOx) and Faraday's constant (F). A
similar expression is valid for the oxidation, now the
current is labelled (ia), with the surface concentration
that of the species Similarly the rate constant for
electron transfer corresponds to that of the oxidation
process. Note that by definition the reductive current
is negative and the oxidative positive, the difference
in sign simply tells us that current flows in opposite
directions across the interface depending upon
whether we are studying an oxidation or reduction.
To establish how the rate constants kox and kred are
Polarization:
influenced by the applied voltage we will use
Polarization as an electrochemical phenomenon is
transition state theory from chemical kinetics. You
will recall that in this theory the reaction is of importance in the corrosion process. For all
considered to proceed via an energy barrier. The metals and alloys in any aqueous environment,
summit of this barrier is referred to as the transition cathodic polarization always reduces the corrosion
state. rate. Cathodic protection refers to the application of
a cathodic polarization to a corroding system.
The rate of reaction for a chemical process(eg)
Polarization can occur in three ways:
 Concentration polarization
 Resistance polarization
 Activation polarization
Concentration polarization of an electrode is the
result of the formation of a diffusion layer adjacent
to the surface of the electrode where there is a
gradient of ion concentration. Diffusion of the ions
through the layers controls the electrochemical
reaction and is important for processes such as
electroplating and corrosion. Concentration
polarization may be reduced by increasing agitation
or raising the temperature of the electrolyte.
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Resistance polarization describes the potential drop
due to the high resistivity of the electrolyte
surrounding the electrode. It may also be a result of
the insulation effect of the film on the electrode
surface formed by the reaction products. Resistance
polarization is expressed by the Ohm's law.
Activation polarization occurs when the
electrochemical reaction proceeds through several
successive steps. The speed of the overall reaction
is determined by the slowest step (known as the
rate-determining step) of the process. For example,
in a hydrogen reduction reaction, the reaction may
proceed as follows
 1. Hydrogen ions are absorbed from the
solution onto the anode surface.
2. Electron transfer occurs from the anode to
the hydrogen ions to form hydrogen.
3. The hydrogen atoms form hydrogen gas
molecules.
4. Hydrogen gas bubbles are formed
Applications:
1.It has a number of different uses, particularly in
industry. The principles of cells are used to
make electrical batteries. In science and technology,
a battery is a device that stores chemical energy and
makes it available in an electrical form
the electrolysis of the raw material brine. Brine is a
saturated solution of sodium chloride (Nacl) that is
obtained from natural salt deposits.
7.Polarization has the capacity to inhibitcertain und
esirable corrosive processes.
Conclusion:
Based on these electrode kinetics can determine the
corrosion kinetics and it would be understand about
the current density it is how depend upon the
electrode area and surface of concentration.
Polarization is resistance to corrosion. Concentration
polarization is common in all.
REFERENCE:
1.M G. Fontana, corrosion engineering (third
edition) McGrow Hill company.
2.BY W. J. Albery, department of chemistry,
imperical college, London.
3.J.OM.Bockris and S.Srinivasarao, fuel cells:
electrochemistery,New York (1970).

2.It can be used for electroplating. Electroplating

occurs when an electrically conductive object is
coated with a layer of metal using electrical current.
Sometimes, electroplating is used to give a metal
particular properties or for aesthetic reasons.

3.Corrosion protection

4.Abrasion and wear resistance

5.The production of jewellery

6.The chlorine-alkali (chloralkali) industry is an

important part of the chemical industry, which
produces chlorine and sodium hydroxide through