Electrode Process

1. Mass transfer

2. Charge transfer
Electrode processes are influenced by various factors

a. Mass transfer from electrode to solution or vice versa

b. Electron transfer at the electrode surface

c. Chemical reactions

d. Adsorption and desorption phenomena

e. Nature of electrode material

f. Composition of electrolyte

g. Temperature

h. Applied voltage
 vvvvv

Electrode-electrolyte interface picture

consists of following plane

i. Inner Helmholtz plane (IHP)

ii. Outer Helmholtz plane (OHP)

iii. Diffuse layer

iv. Solvated ions

Mass transfer Charge transfer

a. Migration Charge transfer reaction involves the transfer of electrons

from one chemical species to another resulting into the
b. Convection formation of new chemical species on the surface of
electrode.
c. Diffusion

Migration Convection
 Electrode-Electrolyte interface
Current density; The amount of electric current
Reduction traveling per unit cross-section area
r1, ic

At equilibrium.
r1 = r2 and ia = ic = i0
Oxidation
M Mn+ r2, ia

If ia > ic
E’-E0Mn+/Mn = +ve
Anodic Polarization
X

If ic > ia
E’’-E0Mn+/Mn = -ve
G# Cathodic polarization
G
 Polarization
Deviation of potential from the equilibrium potential because of current flow or net charge flow
is called polarization. M n+ + ne M(s)

Explanation I;
The electrolysis process is reversible. If the condition of the reversibility is not maintained, the
energy required will be greater than that required by Nernst equation.

The energy required to run the non-spontaneous electrochemical reaction is equal to the
theoretical (demanded by Nernst equation) plus the energy necessary to overcome the
irreversibility. The cell which demands additional voltage than the theoretical value is said to be
polarized and the process is called polarization.
Explanation II;
Ohms law , E = IR or I = E/R
E = emf of external source, R = resistance of the circuit and I = current

In actual practice, it is found that the current I is not equal in magnitude of E/R but
may be less. It is because, the chemical changes occurring at electrode converts the
electrolytic cell into Galvanic cell with an emf (e). The direction of emf (e) is
opposite to that of applied EMF (E). In this condition, the current in the circuit is I =
(E-e)/R. Here, the emf (e) is called counter emf or back emf of the electrolytic cell.
The phenomenon of back emf brought about by the products of electrolysis is
called polarization. The reverse current is called polarization current.
Illustration
Let us consider an electrolysis of dilute sulphuric acid using two platinum
electrodes. At the beginning, when an external emf is applied, hydrogen gas
evolves at cathode and oxygen gas evolves at anode. After sometimes, the
evolution of gas gets stopped though the current flows through the cell. This
is due to the hydrogen and oxygen evolved at electrode get adsorbed on the
electrode surfaces thereby giving rise to back emf which opposes the external
emf applied. The back emf is called polarization emf. When the back emf is
equal to the external EMF, no current flows at all and cell is completely said
to be polarized.
The polarization is also called electrolytic polarization and the electrode is
said to be polarized.
Polarization occurs by either of the following phenomenon (types):

i. Concentration polarization
When concentration of ions at electrode is greater than at the bulk, polarization occurs. This type of
polarization is called concentration polarization. This occurs when the rate of electrochemical reaction is
faster than the rate of diffusion of ions to the bulk.

ii. Activation polarization

Polarization caused by the additional activation energy required at the rate determining step as
demanded theoretically during electrochemical process is termed as activation polarization.

iii. Resistant polarization (IR drop)

Potential drop is observed due to high resistivity of the electrolyte surrounding the electrode or due to
insulation effect of the adjacent layer of liquid to the electrode. This type of polarization is termed as
resistant polarization.
 Overpotential or overvoltage

The overvoltage of an electrochemical reaction is defined as the difference between the working
potential of electrode (practically observed potential) and potential at equilibrium ( i.e. theorical
potential). The term ‘overpotential’ is initially given by Caspari (1899) and later on it was
developed by Julius Tafel (1905). In the hydrogen evolution reaction, Tafel measured the excess
potential over the theoretical value (thermodynamic value) at cathode at a definite current
density. This excess of potential is termed as overvoltage or overpotential. The voltage at which
bubble formation starts is called bubble overvoltage. Therefore, overvoltage is the excess voltage
which must be applied to a cell or electrode to initiate an electrochemical reaction as compared to
the theoretical value.

 = E - Eeq
Illustration
Let us consider the electrolysis of acidified water which involves the production of hydrogen gas at
cathode and oxygen gas at anode.
H2O ⎯→ 2H+ + OH-
Cations go to cathode and anions go to anode.
At anode: 4 OH- ⎯→ 2H2O + O2 + 4e- (oxidation reaction), E° = +1.23 V
At cathode: 4H+ + 4e- ⎯→ 2H2 (reduction reaction), E° = 0.00 V

Total cell potential = E°cathode – E°anode = 0.0–1.23 = –1.23 V

Theoretically, -1.23 V is required for the electrolysis of water. However, in actual practice, the
electrolysis is not possible under that potential. The actual required potential for the electrolysis of
water is found to be higher than the theoretical value due to various factors such as electrode surface
condition, presence of impurities or need to overcome kinetic barrier.
 Overvoltage (η)= Practically observed potential (Epr) – Theoretical potential (Eth)

Let us consider the practically observed potential for the electrolysis of water be 1.49 V
then;
(η) = (Epr) – (Eth)
= (–1.49 V) – (-1.23 V)
= –0.26 V

Therefore, an overvoltage of 0.26 V is required in excess for the electrolysis of water

under a given condition. For anodic reaction, overvoltage (η) is positive and for cathodic
reaction, overvoltage (η) is negative. Overvoltage is affected by temperature, surface
area of electrode, applied current density, presence of impurities and pressure.
 Polarization and Corrosion
Polarization is the change of potential from a stable state (open circuit electrode potential) as
a result of passage of current. Open circuit potential (OCP) is the potential across the positive
and negative terminal of a cell when it is not discharging any current to a load. Open circuit
potential is also termed as open circuit voltage or zero current potential or rest potential or
equilibrium potential.
In corrosion, OCP refers to the free corroding potential of a system. In the corrosion study or
electro-catalysis study, the potential of working electrode is adjusted with respect to the OCP
value to control the electrochemical conditions during the experiment.

The polarization is the change in the potential of an electrode during electrolysis, where
potential of anode and cathode get changed from their respective reversible potential.
Polarization means, the potential shift away from OCP. If the potential shifts in the positive
direction (above Ecorr), it is called anodic polarization. If the potential shifts in the negative
direction (below Ecorr), it is called cathodic polarization. In aqueous environment, cathodic
polarization always reduces the corrosion rate. Therefore, cathodic protection is essentially
the application of cathodic polarization to a corroding system. Anodic polarization always
increases the rate of corrosion.
 Butler-Volmer equation and Tafel plots

Butler-Volmer equation describe the relationship between current passing through an

electrode and the potential difference across the electrode in an electrochemical process.

The Butler-Volmer equation considering the both anodic and cathodic reaction occurs
on the same electrode.

𝛂𝐚𝐧𝐅 𝛂𝐜𝐧𝐅
i = 𝒊𝟎 𝐞𝐱𝐩 (𝐄 − 𝐄𝐞𝐪 ) − 𝐞𝐱𝐩 − (𝐄 − 𝐄𝐞𝐪 )
𝐑𝐓 𝐑𝐓

𝛂𝐚𝐧𝐅 𝛂𝐜𝐧𝐅
i = 𝒊𝟎 𝐞𝐱𝐩 Ƞ − 𝐞𝐱𝐩 − Ƞ
𝐑𝐓 𝐑𝐓
 i = electrode current density (A/m2)
io = exchange current density: It is current density at zero over potential.
a = Anodic charge transfer coefficient. It is dimensionless quantity.
c = Cathodic charge transfer coefficient. It is dimensionless quantity.
a+ c = 1
n = number of electrons involved in electrode reaction
F = Faraday constant (96500 coulomb/mol)
η = Overpotential. Here, η = E-Eeq. E is actual or practically observed potential and Eeq is
equilibrium (or theoretical) potential. Overpotnetial could be positive or negative depending upon
the direction of half-cell reaction.
R = Universal gas constant, R = 8.314 J mol-1 K-1.
T = Temperature in Kelvin

In this equation, i0 is the pre-exponential factor (exchange current density) which is an equilibrium
property and dictates the shape of I-V curve (or, current density versus potential curve) of the half-
cell reaction at non-equilibrium condition. According to Butler-Volmer equation, current has an
exponential dependency on potential.
Current density versus potential according to Butler-Volmer equation
(Ja = anodic current density, Jc = cathodic current density)
Butler-Volmer equation is composed of two parts of current. It will be clear form the following
equations:
Anodic (forward) current equation
This portion of equation describes the current as the potential shifts towards the oxidative
condition. The equation is,

Cathodic (reverse) current equation

This portion of the equation describes the current as the potential towards reductive conditions.
The equation is,
Applications of Butler-Volmer equation

▪ It describes the relation between current passing through an electrode and potential difference
across it.
▪ This equation can be employed for modeling the behavior of electrode.
▪ This equation can be applied to understand the complex process occurring on the surface of
electrode including charge transfer reaction, kinetics and activation overpotential.
▪ It is applicable for the prediction of kinetics of reaction and to design and optimize electrode
system.
▪ This equation is useful in the study of corrosion processes. It is useful to understand the kinetics of
corrosion reactions and to develop strategies for corrosion control.
▪ It can be used to calculate the corrosion current for all activation-controlled corrosion process in all
regions (Tafel region, linear region and non-linear weak polarization region).
▪ This equation is applicable for modeling the behavior of batteries and to optimize their
performance.
Tafel equation
Tafel equation is a mathematical expression which shows the relation between rate of electrochemical
reaction and overpotential of the electrode. The Tafel equation is as follows:

The plus-minus sign depicts anodic (+) or cathodic (–) process.

In the equation,

η = overvoltage,
A = Tafel slope (tells about the kinetics of electrochemical process)
J = Current density in A/m2

J0 = Exchange current density in A/m2. It is the current density at which net rate of oxidation
is equal to the net rate of reduction at equilibrium.
This equation is particularly useful for understanding and analyzing the kinetics of electrochemical
reactions. A plot of log|i| in y-axis versus η in x-axis is plotted to obtain the Tafel plot. The linear region
gives the Tafel slope. From the Tafel slope transfer coefficient (α) is calculated. The intersection
between two Tafel regions occurs on the y-axis. The oxidative component is given by

The reductive component is given by,

α is transfer coefficient. Other terms have their usual meaning

Tafel plot shows the linear relation between log I versus overpotential. The slope of the curve is the Tafel
slope. The Tafel slope is related to the activation energy of the reaction. In this sense, it can be said that
the Tafel slope indicates the rate of reaction. The steeper the slope, higher the activation energy required
for reaction and slower the rate of reaction.

Schematic Tafel plot: (a) 𝐥𝐨𝐠 |𝐢| versus η (b) η versus log|i|
Applications:
▪ Both Butler-Volmer equation and Tafel equation are used to explain the kinetics of electochemical
reaction. Butler-Volmer equation is more general and is applicable to a wider range of electrochemical
reaction where as Tafel equation is applicable to situations where a small potential range is used.
▪ Tafel slope is applicable for the calculation of activation energy of reaction and hence rate of reaction.
▪ Tafel slope is a critical parameter to determine the corrosion behavior of material. Above the corrosion
potential, electrode materials will start to oxidize or corrode. Below the corrosion potential, the
material will be reduced and gets protected. This is also termed as cathodic protection.
▪ Tafel slope is useful to discern the type of reaction under study. Based on the Tafel slope, it can be
determined whether the reaction is activation–controlled or diffusion controlled or mixed-controlled
type.