Sengunthar Engineering College Department of chemistry

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ELECTROCHEMISTRY
Syllabus
Electrochemical cell - redox reaction, electrode potential- origin of electrode potential-
oxidation potential- reduction potential, measurement and applications - electrochemical series
and its significance - Nernst equation (derivation and problems).
Corrosion- causes- factors- typeschemical, electrochemical corrosion (galvanic,
differential aeration), corrosion control material selection and design aspects - electrochemical
protection sacrificial anode method and impressed current cathodic method.
Paints- constituents and function. Electroplating of Copper and electroless plating of
nickel.












Electrochemistry
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Electrochemistry is a branch of chemistry, which deals with the chemical reactions
produced by passing electric current through an electrolyte or the production of electric
current through chemical reactions.
Conductors
A substance or a material which allows passing electricity through it is called a
conductor. The ability of a material to conduct electric current is called conductance.
Example: All metals, graphite, fused salts, aqueous solutions of acids, bases, etc.,
Types of Conductors
There are mainly two types of conductors
1. Metallic conductors (or) Electronic conductors
Metallic conductors are solid substances, which conduct electric current due to the
movement of electrons from one end to another end.
Example: All metals, graphite.
2. Electrolytic Conductors
Electrolytic conductors conduct electric current due to the movement of ions in solution
or in fused state.
Example: Solutions of acids, bases, electrovalent substances.
Types of Electrolytic Conductors
The electrolytic conductors are further sub-classified into three types as follows.
(a) Strong Electrolytes
Substances which ionize completely almost at all dilutions are called strong electrolytes
Example: Solutions of HCl, NaOH, NaCl, KCl, etc.,
(b) Weak Electrolytes
Substances which ionize in very small amount even at very high dilution are called weak
electrolytes.
Example: solutions of CH
3
COOH, NH
4
OH, CaCO
3
, etc.,
(c) Non Electrolytes
Substances which do not ionize at any dilution are called non electrolytes.
Example: solutions of Glucose, sugar, alcohol and petrol, etc.,

Differences between metallic conduction and electrolytic conduction
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S.No Metallic Conduction electrolytic conduction
1 Flow of electrons in a metal is
called metallic Conduction
Movement of ions in a solution
response for electrolytic conductance
2 No chemical reactions or
chemical changes occur during
the passage of current
Chemical reactions or chemical
changes occur during the passage of
current
3 Conductance decreases with
increase of temperature
Conductance increases with increase
of temperature
4 No transfer of matter Transfer of matter takes place

Non-Conductors (or) Insulators
A substance or a material which does not allow passing electricity through it is called a non-
conductor or insulators.
Example: Plastics, wood, most of the non metals, etc.,
Important terms in electrochemistry
1) Current
Flow of electrons through a wire or any conductor is called current.
2) Electrode
Any material (or) a metallic rod/bar/strip used in electrochemical cell or electrolytic cell
for conducting electrons are called electrode.
3) Anode
Anode is an electrode where oxidation (loss of electrons) takes place.
4) Cathode
Cathode is the electrode where reduction (gain of electrons) takes place.
5) Cell
Cell is a device consisting two half cells. These two half cells are connected through a
wire. There are two types of cells.
1. Electrolytic cells. 2. Electrochemical cells (or) voltaic cells (or) galvanic cells.
6) Anode half cell or Anode compartment
Anode half cell is a half cell where oxidation occurs. It contains the anode.
7) Cathode half cell or cathode compartment
Cathode half cell is a half cell where reduction occurs. It contains the cathode.
Electrode potential
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It is the measure of tendency of a metallic electrode to lose or gain electrons. It is developed
when a metal is place in a solution of its own salt. It depends on the nature of metal, electrolyte
concentration and temperature.
Examples 1: Zn electrode dipped in ZnSO
4
solution
When Zn electrode is dipped in ZnSO
4
solution, Zn dissolved
into the solution as Zn
2+
ions. Now, the Zn electrode attains a
negative charge, due to the loss of its valence electrons
(oxidation). The negative charges developed on the electrode
attract the positive ions from solution. Due to this attraction the
positive ions remain close to the metal.
Example 2: Cu electrode dipped in CuSO
4
solution
When Cu electrode is dipped in CuSO
4
solution, Cu
2+
ions
from the solution deposit over the metal. Now, the Cu electrode
attains a positive charge, due to the accumulation of Cu
2+
ions on
the metal by gaining the electrons (reduction). The positive
charges developed on the electrode attract the negative ions
from solution. Due to this attraction, the negative ions remain
close to the metal.
Oxidation potential
It is the tendency of a metallic electrode to lose electrons. Ex: Zn in ZnSO
4
solution
Reduction potential
It is the tendency of a metallic electrode to gain electrons. Ex: Cu in CuSO
4
solution.
Single electrode potential (E)
It is the measure of tendency of a metal electrode to loose or gain electrons when it is contact
with a solution of its own salt is called as single electrode potential.
Standard electrode potential (E
O
)
It is the measure of tendency of a metal electrode to loose or gain electrons when it is contact
with a solution of its own salt of 1 molar concentration at 25
0
C is called as standard electrode
potential.

Measurement of Electrode potential Nernst equation
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Inorder to derive the Nernst equation, consider the following redox reaction
M
n+
+ ne

M
For such a redox reversible reaction, the free energy change (G) and its equilibrium constant
(K) are inter related as
G = RT ln K + RT ln [Product]
[Reactant]

= G + RT ln [Product] ........ (1)
[Reactant]
where,
G = Standard free energy change
The decrease in free energy (G) in the above reaction involves transfer of n number of
electrons, then n faraday of electricity will flow. If E is the emf of the cell, then the total
electrical energy (nEF) produced in the cell is
G = nEF
(or)
G = nEF ........ (2)
where,
G = decrease in free energy change.
(or)
G = decrease in standard free energy change.
Comparing equation 1 and 2, it becomes
- nEF = - nEF + RT ln [ M ]
[M
n+
] ......... (3)

Dividing the above equation (3) by - nF [Consider the activity of solid metal [M] = 1]
E = E RT ln 1
nF [ M
n+
]

In general, E = E RT ln [Product]
nF [Reactant]

(or)
E = E + RT ln [M
n+
]
nF
(or)
E = E + 2.303RT log [ M
n+
] ----------------- (4)
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nF

When, R = 8.314 J/K/mole; F = 96500 coulombs; T = 298 K (25C), the above equation
becomes

E = E
red
+ 0.0591 log [ M
n+
] --------------------- (5)
nF

In general, E = E
red
+ 0.0591 log C
nF
Similarly for oxidation potential
E = E
oxi
_ 0.0591 log [ M
n+
] ---------------------- (6)
nF
The above equation 5&6 are known as Nernst equation for single electrode potential.
Applications of Nernst equations
1. Nernst equation is used to calculate electrode potential of unknown metal.
2. Corrosion tendency of metals can be predicted.
Problem based on Nernst equation
Standard reduction potential of Cu is 0.34 V and the concentration of Cu
2+
ion is 0.015 M.
Find (i) reduction electrode potential of copper (ii) Free energy change of electrode reaction.
Ans:
Nernst equation for reduction potential of copper is
E = E
red
+ 0.0591 log [ M
n+
]
n
E = 0.34 + (0.0591/2) log (0.015) = 0.34 + 0.02955 (2) log (1.5)
So,
E = 0.3504 V,
Free energy change = G = - nEF = 2 0.3504 96500 = - 67627
Measurement of Single Electrode Potential
It is impossible to determine the absolute value of a single electrode potential. But, we
can measure the potential difference between two electrodes potentiometrically, by combining
them to form a complete cell. For this purpose, reference electrode is used.
Standard hydrogen electrode (SHE) is the commonly used reference electrode, whose
potential has been arbitrarily fixed as zero. The emf of the cell is measured and it is equal to the
potential of electrode. In some cases saturated calomel electrode is used as reference electrode.
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Reference Electrodes (Standard Electrodes)
Reference electrode is an electrode which has standard or known potential value. It is used to
measure the electrode potential of unknown electrode by combining with it. The important
primary reference electrode is a standard hydrogen electrode, the standard electrode potential of
which is taken as zero.
Example: std. hydrogen electrode; calomel electrode.
Need for secondary electrode
1. It is very difficult to set up a hydrogen electrode.
2. Maintaining the concentration of hydrogen ion at 1 molar and maintaining the pressure of
hydrogen gas at 1 atm are very difficult.
3. Hydrogen electrode gets poisoned when the contact solution containing impurities.
Hence, there is a need for other electrodes for the measurements of electrode potential; these
electrodes are called secondary reference electrodes.
Ex: Calomel electrodes.
Primary reference electrode
Standard hydrogen electrode (SHE)

Construction
Hydrogen electrode consists of platinum foil, that is
connected to a platinum wire and sealed in a glass tube.
Hydrogen gas is passed through the side arm of the glass
tube. This electrode, when dipped in a 1N HCl and hydrogen
gas at 1 atmospheric pressure is passed forms a standard
hydrogen electrode. The electrode potential of SHE is zero at
all temperatures.
It is represented as,

Pt , H
2
(1 atm)/H
+
(1 M); E = 0 V
Working
In a cell, when this electrode acts as anode, the electrode reaction can be written as
H
2
(g) 2H
+
+ 2e

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When this electrode acts as cathode, the electrode reaction can be written as
2H
+
+ 2e
-

H
2(g)
Limitations of using standard hydrogen electrode
1. It is very difficult to set up a hydrogen electrode.
2. Maintaining the concentration of hydrogen ion at 1 molar and maintaining the pressure of
hydrogen gas at 1 atm are very difficult.
3. Hydrogen electrode gets poisoned when the contact solution containing impurities.
Secondary reference electrode
Saturated Calomel Electrode.

Construction
Calomel electrode consists of a glass tube containing
mercury at the bottom over which mercurous chloride
is placed. The remaining portion of the tube is filled
with a saturated solution of KCl. The bottom of the tube
is sealed with a platinum wire. The side tube is used for
making electrical contact with a salt bridge. The
electrode potential of the calomel electrode is +
0.2422V.
It is represented as,

Hg , Hg
2
Cl
2
(s) , KCl (sat.solution); E = 0.2422 V

If the electrode acts as anode the reaction is
2Hg
(l)
> Hg
2
2+

+ 2e

Hg
2
2+
+ 2Cl

>Hg
2
Cl
2(s)
2Hg
(l)
+ 2Cl

Hg
2
Cl
2

(s)
+ 2e

If the electrode acts as cathode the reaction is
Hg
2
Cl
2
(s) Hg
2
2+
+ 2Cl

Hg
2
2+
+ 2e

2Hg
(l)

Hg
2
Cl
2(s)
+ 2e

2Hg
(l)
+ 2Cl

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The electrode potential is given by (for example cathode)
E
(Calomel)
= E
(Calomel)
_ RT ln a
Cl
-

2F
The electrode potential depends on the activity of the chloride ions and it decreases as
the activity of the chloride ions increases.


























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Anode half
cell
Oxidation
takes place
Cathode half
cell
Oxidation
takes place