Unit – II –ELECTROCHEMISTRY & CORROSION

Electrochemistry: Electrochemistry deals with the study of the chemical changes that leads to
generation of electric current by electrochemical process. In the electrochemical process,
chemical energy is converted into electrical energy.
Strong electrolyte: Substances which are easily dissolved and dissociate into ions in water are
called strong electrolytes. E.g., NaCl, KCl etc.
NaCl Na+ + Cl-
cation anion

Weak electrolytes: These substances dissolve in water but undergo partial dissociation. E.g.,
CH3COOH, NH4OH etc.
Non-electrolites: These substances dissolve in water but never dissociate into ions. E.g.,
glucose, alcohol etc.
Specific conductance: the conductance offered by one cubic cm of the electrolytes.
Equivalent conductance: the conductance offered by the dissociation of one gram equivalent of
an electrolyte.
Electrode potential (E): Potential difference produced between an electrode and the solution in
which it is immersed.
Oxidation potential: Oxidation potential is a measure of the tendency of a chemical species to
release electrons and thereby be oxidised.
Reduction potential: Reduction potential is a measure of the tendency of a chemical species to
acquire electrons and thereby be reduced.
Cell: A cell is a combination of two single electrodes connected by means of a salt bridge. Each
single electrode is called as half cell.
Electromotive force (emf): The emf of a cell is defined as the potential difference due to which
flow of current occurs from an electrode with a higher potential to an electrode with a lower
potential. It is represented by, Ecell = Ecathode - Eanode.
Standard electrode potential (E°): the electrode potential measured with an electrolyte of 1M
concentration and at 25°C is known as standard electrode potential.

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CONDUCTOMETRIC TITRATION
Conductometric titrations are based on the measurement of change in the conductance
due to the reaction between titrant and titrate. Conductance of electrolyte in the aqueous solution
increases with increase in number of ions, charge on the ions and mobility of the ions.
Conductometric titrations can be used to detect the end point of the chemical reactions such as
acid-base titration, redox reaction, precipitation reaction and complexometric titration.
(a) Acid-base titration (HCl Vs NaOH):
Burette is filled with 50 ml of NaOH solution with known strength (N1). A known
volume (V2) of HCl is taken in a glass beaker and a conductivity cell with known cell constant is
dipped in the HCl solution. Aliquots of NaOH solution is added and stirred well and the
conductance values are recorded. The conductance values are plotted against volume of NaOH as
shown in Figure. The high initial conductance is due to the presence of more number of H+ ions
with good mobility. As strong base is added, the H+ ions are replaced by the Na+ ions with less
ionic mobility. This results in the decrease in the H+ ions and hence the conductance decreses till
all the H+ ions are replaced by Na+ ions (Line AB in the figure).
Further addition of NaOH leads to increase in the conductance due to free OH- ions (Line
BC in fig). The value of x axis corresponding to the point B in the plot indicates the volume of
NaOH (V1) needed for the complete neutralization of acid. From the equation, V1N1 = V2N2, the
strength of acid is calculated as N2 = V1N1/ V2 g.eq/l.
The amount of acid = N2 x equivalent weight of HCl.

A C
Conductance

V1 ml

Volume of NaOH

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(b) Mixture of acid (acetic acid and HCl) Vs NaOH:
Different end points are observed when a mixture of acid is titrated against NaOH. Line AB
represents the titration of HCl Vs. NaOH leading to a decrease in conductance. This is due to the
neutralization of HCl by NaOH.
Line BC represents the gradual increase in the conductance due to the formation of the hghly
ionized sodium acetate by neutralization of weak acid by NaOH.
Line CD represents the increase in the conductance due to the presence of excess OH- ions.

D
A
Conductance

C
B

Volume of NaOH

Advantages of conductometric titrations:

1. More accurate results are obtained.
2. Measurement can be done for even diluted solutions.
3. Easy to detect the end point for the colored solutions.

ELECTROCHEMICAL SERIES:
Electrochemical series lists the metal in the order of increasing standard reduction
potential. The metals that undergo oxidation with respect to hydrogen are placed above
hydrogen. The metals that undergo reduction with respect to hydrogen are placed below
hydrogen.

Applications of electrochemical series:

1) Calculation of standard emf of a cell:
Using electrochemical series, emf of a cell can be calculated using the formula,
E° = E°cathode - E°anode

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2) Determination of the nature of a metal:
Using electrochemical series, the nature electrode can be predicted. For example, a metal with a
low reduction potential will undergo oxidation and hence acts as anode. A metal with a high
reduction potential will undergo reduction and hence acts as cathode. Thus, suitable materials
can be selected to form a cell.
3) Prediction of spontaneity of an electrochemical process:
The standard electrode potential (E°) is related to free energy change (∆G) by the expression,
∆G = -nFE°
Where, n is number of electrons transferred in the electrochemical reactions and F is Faraday’s
constant.
For a reaction to be spontaneous, ∆G should be negative. Hence if E° is positive then the cell
reaction occurs spontaneously.
4) Calculation of equilibrium constant (K) of an electrochemical reaction:
In the redox reaction, the standard electrode potential (E°) is related to K by the following
expression,
Log Keq = nE°/0.0591
The forward reaction is more favoured when E° is positive. When E° is negative, then K eq is
small and the reverse reaction is more favoured.
5) Prediction of activity of metal in acidic solutions:
The metals with negative reduction potential displace hydrogen from solution whereas metals
with positive reduction potential do not liberate hydrogen in acidic solution.
6) Prediction of metal- metal displacement:
The metals with a negative reduction potential will displace metals with a positive reduction
potential from solution of their electrolytes under suitable conditions.

NERNST EQUATION:
It represents the variation of electrode potential with variations in elctrolite concentration at
given temperature.
Consider the following redox reaction,
M1 + M2n+ M1n+ + M2
From thermodynamics, ∆G = ∆G° + RT ln K eq. (1)

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∆G = free energy change
∆G° = standard free energy change
R = gas constant (8.314 Jmol-1.K-1)
T = temperature
K = equilibrium constant.

Free energy change is related to its electrode potential as given below

∆G = -nFE
And
∆G° = -nFE°
F = Faraday’s constant (96500 coulombs)
Substituting the value of ∆G and ∆G° in the equation 1.

-nFE = -nFE° + RT ln K
Dividing throughout by –nF
E = E° – (RT/nF) . ln K
E = E° – (2.303RT/nF) . log K
E = E° – (0.0591/n). log [Products]/[Reactants]

Nernst equation for single electrode potential:

For oxidation (anodic) reaction:
E = E° – (0.0591/n). log [Mn+]
For reduction (cathodic) reaction:
E = E° + (0.0591/n). log [Mn+]

Types of electrodes:
a) Reference electrodes: Two types,
1) Primary reference electrodes: e.g., hydrogen electrode
2) Secondary reference electrodes: Ag/AgCl electrode, Hg/Hg2Cl2 electrodes.
b) Indicator electrodes: electrodes which change their potential with respect to the electrolyte
concentration and temperature. Example. Glass electrode, quinhydrone electrode.

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POLARISATION:
Polarisation is defined as variation in the electrode potential observed due to slow movement of
the metal ions from the bulk of the electrolyte solution to the electrode.
DECOMPOSITION POTENTIAL:
Decomposition potential is defined as the minimum external emf that must be applied to cause
steady electrolysis. It is also defined as the applied potential that equals the back emf.
OVER VOLTAGE:
Over voltage is defined as the excess potential over the theoretical decomposition potential that
must be applied to bring about continuous electrolysis.
Over voltage = Actual decomposition potential - theoretical decomposition potential.
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CORROSION
Corrosion is defined as the gradual degradation of the metal due to the chemical or
electrochemical reactions with its environment.
Examples: rusting of iron sheet, corrosion on buried pipes, and corrosion in boilers.
Disadvantages/effects of corrosion:
1. Quality of the metal is reduced
2. Corrosion products lead to contamination
3. Mainatanance cost is increased.
4. Efficiency of the machines comes down.
Types of corrosion:
1. Dry or chemical corrosion
2. Wet or electrochemical corrosion.
Mechanism of corrosion:
1. Dry or chemical corrosion: Dry corrosion occurs under dry condition. It is due to the reaction
of metals with the gases present in the atmosphere such as oxygen, halogen and hydrogen
sulphide.
a) Corrosion due to oxygen (oxidation corrosion): Initially, the oxygen molecules are
adsorbed on the metal surface due to weak van der waals force of attraction. At room
temperature, the metal loses electrons forming metal ions. The electrons are transferred to

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oxygen forming oxide ion. Hence, strong chemical bond is formed between metal and oxygen.
Considering a divalent metal ions, the following reaction occurs.
Oxidation: M → M2+ + 2e-
Reduction: 1/2O2 + 2e- → O2-
Net reaction: M2+ + O2- → MO (metal oxide)
This metal oxide covers on the surface acts as a barrier for further attack of the metal by oxygen.
Pilling-Bedworth rule:
According to this rule, the oxide layer formed on the surface of a metal will be protective and
non-porous if the volume of the oxide layer formed is more than the volume of the metal from
which it is formed.
If the volume of the oxide layer formed is smaller than the volume of the metal from which it is
formed, the oxide layer will be non-protective and porous.
Oxide layer is protective and non-porous, if volume of the oxide layer/ volume of the metal
consumed ˃ 1.
Example: Na, K, Mg, Ca form oxide layers that are porous and non-protective.
Al, Tungstan form oxide layers that are protective and non-porous.
Molybdenum form volatile oxide layer and hence they are unstable in air.
b) Corrosion due to other gases:
(i) Due to halogen: Metal reacts with halogen to form protective metal halides on its surface.
Example: Ag reacts with chlorine to form AgCl.
Metal like Tin forms tin halide, which is volatile.
(ii) Due to hydrogen sulphide: Metals react with H2S to form metal sulphides layer on their
surface. Example: Ag + H2S → AgS + H2 (non-porous, protective)
Fe + H2S → FeS + H2 (porous, non-protective).
In the FeS, due to the escape of excess hydrogen from the voids, blisters are formed. This is
called hydrogen embrittlement.
(c) Liquid – metal corrosion: when a hot liquid metal falls on the surface of solid metal, the
solid metals get corroded either due to the dissolution of the metal in the liquid or due to the
penetration of the liquid into voids of the metal.

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2. Wet or Electrochemical corrosion:
This corrosion occurs when two metals with different electrode potentials are in contact with a
electrolyte solution. The reactions are shown below;
At anode:
M1 → M1n+ + 2e-
Due to oxidation at cathode, the corrosion starts at anode. The electrons released at the anode
move towards the cathode.
At cathode:
(i) Reduction of metal ions: M2n+ + 2e- → M2
(ii) Evolution of hydrogen: In the absence of oxygen, hydrogen gas will be liberated as follows:
Acidic medium: 2H+ + 2e- → H2
Neutral/alkaline medium: 2H2O + 2e- → H2 + 2OH-
In the presence of oxygen, following reactions occur.
Acidic medium: 4H+ + O2+ 2e- → 2H2O
Neutral medium: 2H2O + O2 + 4e- → 4OH-

Mechanism of wet corrosion by (a) hydrogen evolution and (b) oxygen absorption
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DIFFERENCE BETWEEN DRY AND WET CORROSION:
Dry corrosion Wet corrosion

It occurs in the absence of moisture Occurs in the presence of moisture.

Occurs on homogeneous metal surface. Heterogeneous surface is essential.

Corrosion proceeds by dry gases on the Proceeds by the formation of tiny galvanic
metal surfaces. cells.

DIFFERENTIAL AERATION CORROSION/CONCENTRATION CELL CORROSION:

When a metal is exposed to varying concentration of air, differential aeration corrosion
occurs. Oxygen concentration cell is formed in this corrosion. The portion of metal that is freely
exposed to air forms the cathode and the portion of the metal that is denied access to the air acts
as the anode and suffers from corrosion.
Example: iron sheet partly covered with a glass plate.
At anode:
2Fe → 2Fe2+ + 4e-
At cathode:
(i) Under acidic condition:
4H+ + O2 + 4e- → 2H2O
2Fe2+ + 5H2O + 1/2 O2 → Fe2O3.3H2O + 4H+
Net reaction:
2Fe + 3 H2O + 3/2 O2 → Fe2O3.3H2O
(ii) Under neutral/alkaline condition:
2H2O + O2 + 4e-→4OH-
2Fe2+ + 4OH-→ 2 Fe(OH)2
2 Fe(OH)2 + H2O + 1/2 O2 → Fe2O3.3H2O
Net reaction:
2Fe + 3 H2O + 3/2 O2 → Fe2O3.3H2O

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GALVANIC SERIES:
The metals and alloys are arranged in the order of their decreasing oxidation tendency.
This series is known as galvanic series.
Mg
Mg alloys Anodic (active metals)
Zn
Al
Al alloys

Cu
Bronz
Cu-Ni alloys Cathodic (Noble metals)
Au
Pt

Application of galvanic series:

1. Provides information about corrosion behavior of the metal and alloys.
2. Proper selection of the metals and alloys can be made with the help of galvanic series. Lesser
the difference in the potential between the metals, lesser is the chance for corrosion.

FACTORS INFLUENCING CORROSION

1. Effect of metal on the rate of corrosion:
a) Purity of metal: Pure metal resists corrosion, while impurities in a metal form a local
galvanic cell (metal as anode and impurity as cathode) and result in the corrosion of metal. For
alloys the system is a homogeneous solid solution, hence no local action and no corrosion.
b) Position of metal in galvanic series: It decides the corrosion rate. A metal having higher
position in galvanic series undergoes corrosion when connected to another metal below it. Also,
more difference in the position of galvanic series will cause faster corrosion at anodic metal.
c) Relative areas of anode and cathode: Smaller the area of anode com pared to cathode will
lead to faster corrosion of anode. It is because the corrosion current at anode and at cathode will
be same. But for small anodic area the current density will be large at anode and larger cathodic

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area will demand more electron which will be fulfilled by fast reaction at anode, i.e. rapid
corrosion.
d) Nature of oxide film: An oxide film is formed by the reaction between metal and oxygen. If
this oxide film is porous and oxygen can be diffused through it, more corrosion is expected.
Also, if volume of metal oxide is more than the volume of metal least corrosion or no further
corrosion occurs.
e) Volatility and solubility of corrosion product: In both the cases, the corrosion will be faster.
MnO3, SnCl4 are volatile, so faster is corrosion of Sn in chlorine atmosphere. In case of soluble
corrosion product, it will be enhanced by water and metal surface will be exposed for further
corrosion.
2. Nature of the environment:
a) Moisture: In humidity, gases like CO2, SO2, NOx are dissolved which form electrolytes. It
will cause galvanic corrosion. Some oxides are water soluble, humidity washes away the
corrosion products and metal surface is further corroded.
b) Temperature: The rate of diffusion increases by rise in temperature, hence the rate of
corrosion is also increased. At higher temperature, passive metals also become active and
undergo corrosion.
c) pH value: In acidic medium (pH less than 7), corrosion is faster. Also, in basic medium pH >
7, some metals such as Pb, Zn, Al, etc. form complexes and hence they corrode. Pourbiax
relation between pH of medium and potential of metal deals with the corrosion process and it
gives idea how to reduce corrosion.
Example: Zn corrodes minimum at pH 11, but higher at pH more than 11.
At pH 5.5, Al corrodes minimum.
d) Oxygen concentration and oxygen concentration cell: Oxygen is one of the important
elements responsible for corrosion. It forms oxides and hydroxides in presence of water on the
surface of metal as corrosion product. Oxygen concentration cell is formed on the surface of
metal due to difference in oxygen concentration.
CORROSION CONTROL:
(1) Design and selection of metals:
(i) Proper designing of an object helps in prevention of corrosion.

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(ii) Contact of two dissimilar metals must be avoided. If it is unavoidable, anodic area should be
very large compared to cathodic area.
(iii) Two different metals used in the structure should be such that they are occupying near
positions in galvanic series.
(iv) Putting an insulator between two metals resists corrosion.
(v) As far as possible, metal used in a structure should be extremely pure. Small amount of
impurity causes corrosion.
(vi) While using an alloy, it should be completely homogeneous.
(vii) Design or fabricate equipment or metal parts in such a manner that they have minimised
sharp edges and corners and also avoid, as for as possible, the crevices in joints, etc.
(2) Cathodic protection methods: The principle behind the protection method involves the
anode metal to behave like a cathode metal.
(i) Sacrificial anodic protection: Underground steel pipes are protected from corrosion by this
method. A magnesium rod is fixed near the metal under protection and both are connected with a
conducting wire. Magnesium is more positive than iron and, hence, in electrochemical cell it acts
as anode and the iron acts as cathode. According to the principle of galvanic cell, it is anode that
undergoes oxidation, and, hence, corrosion occurs at anode saving cathode (iron) from corrosion.
Thus, magnesium scarifies itself for saving the iron.

Sacrificial anodic protection.

(ii) Impressed current method: The object to be protected is made cathode and it is connected
to the negative terminal of a DC (direct current) source. The positive terminal of the source is
connected to the other electrode made of graphite or platinum, lead or nickel. The impressed

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current opposes the galvanic current (corrosion current) and, hence, protection from corrosion
takes place.

Impressed current method.

Application of cathodic protection methods:
(i) Protection of buried pipelines, and
(ii) Protection of bottom structure of ships and boats. Here Zn or Mg is connected to the hull of
the ship.
(3) PROTECTIVE COATINGS: Protective coating is one of the methods used to control
corrosion. It involves the applications of suitable coating over the surface of the metal.
Examples: Metallic coatings, non-metallic coatings and organic coatings.
Metallic coatings:
(A) Electroplating: It involves the deposition of coat metal on the base metal surface by an
electrolytic process. Here, the base metal is the cathode and the coat metal used is anode. When a
DC current is supplied, the coat metal ions from the solution diffuse to the cathode where they
get reduced to the metal and adhere to the base metal surface.

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Factors affecting electroplating:
a) Current density: At lower current density, a smooth coating of the metal takes place. Higher
current densities lead to rough and non-adhering deposites.
b) Electrolyte concentration: An optimum concentration of the electrolyte concentration helps
in getting a smooth, adherent deposit. Very low concentration of the electrolyte leads to a
discontinuous deposit.
c) Temperature: In the temperature range 35-60ºC, the electroplating proceeds faster because of
the increase in the solubility of the electrolyte which increase the concentration of the coat metal
ions. Electroplating at high temperature generally promotes the corrosion due to hydrogen
evolution and decreases the stability of electrolytic bath solution.
d) pH of the electrolytic bath: Low pH results in hydrogen evolution and high pH results in
precipitation of metal as hydroxides. The optimum Ph range is 4 – 8.
Objective of electroplating:
(i) To improve corrosion resistance of the base metal
(ii) To increase wear and chemical resistance
(iii) To give pleasing appearance
(iv) To change the surface properties.

ELECTROPLATING OF COPPER:
Factors Sulphate bath Cyanide bath
Anode Copper Copper
Cathode Base metal Base metal
Electrolyte CuSO4 in water + H2SO4 CuCN + KCN + K2CO3 in water
Temperature 20-40ºC 40-50ºC
Current density 2-5 Amp/cm2 3-4 Amp/cm2
Applications Printed circuit boards Printed circuit boards

ELECTROPLATING OF NICKEL:
Anode Nickel
Cathode Base metal
Electrolyte NiSO4 + NiCl2 + Boric acid

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Temperature 40-50ºC
Current density 2.6 Amp/cm2
pH 4.5
Applications Under coat for chromium coating.

(B) Electroless plating:

In this technique, the coat metal is deposited over the surface of base metal by chemical
reduction of the corresponding salt using suitable reducing agent. This method does not require
electrical energy.
Process:
(i) Activation of base material surface:
Base material is treated with a solution of stannous chloride and then immersed in a solution of
palladium chloride.
SnCl2 + base material PdCl2 Pd coated base material + SnCl4

(ii) Coating metal on the activated base material:

Pd coated base material + Metal salt + Reducing agent Metal coated base material.
Merits of electroless plating:
1) No need to use electricity
2) Plating can be done on non-metallic surface
3) Any shape of the base material can be plated
4) It gives a uniform coating over the entire area of the surface.

ELECTROLESS PLATING OF COPPER AND NICKEL:

Factors Ni plating Cu plating
(1) Pretreatment:
a) Metallic surface Degreasing and acid cleaning Degreasing and acid cleaning
b) Non-metallic Treatment with SnCl2 Treatment with SnCl2
followed by PdCl2 followed by PdCl2
(2) Base metals Al, Cu, Fe and their alloys Fe, Co, Ni
(3) Plating bath:

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a) Electrolyte NiCl2 CuSO4
b) pH 4.5 - 5 10.5 - 11
c) Reducing agent Sodium hypophosphate Formaldehyde
d) Complexing agent Sodium succinate EDTA
e) Temperature 90 – 95ºC 25ºC
(4) Applications Printed circuit boards, vessels, Printed circuit boards.
pumps.

(C) Galvanizing: It is coating a layer of zinc on steel. It involves following steps;

i) Pretreatment: Acid picking with dil. H2SO4 at 60 - 90ºC for 20 minutes.
ii) The pretreated steel surface is dipped in a bath of molten zinc at 430ºC. To prevent the
oxidation of zinc, ammonium chloride is added as a flux to cover the surface of molten zinc bath.
iii) After sufficient time, the coat metal is taken out, passed between the rollers to remove the
excess coat metal.
iv) Finally, it is annealed at 650ºC and cooled slowly.

NON-METALLIC COATINGS:
ANODIZING: It is a surface conversion coating. This is used for the protection of non-ferrous
metals like Zn, Ni, Cr, Sn, Al, Mn etc. Anodizing method involves the electrolytic oxidation for
enhancing the thickness of the oxide film.
Process: the base metal to be treated is made as the anode and an inert metal as the cathode.
These metals are immersed in 10-15% sulfuric acid and a current of 0-5 amp is gradually applied
over the period of one hour. Oxygen liberated during the process combines with the base metal
ion forming the corresponding porous oxide. To reduce the porosity, this oxide coated metal is
immersed in boiling water. This leads to the formation of the hydrate. As the volume of the
hydrate expands, the pores get sealed and the oxide film becomes corrosion resistance.
Application:
(i) Used for oxide coating of air craft parts, refrigerators etc.
(ii) Used to get colored coats by adding suitable dyes to the electrolytic bath.

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ORGANIC COATINGS:
PAINTS AND ITS CONSTITUENTS: it is a suspension of one or more solid pigments in a
fluid medium consisting of a mixture of drying oil (vehicle), thinners, driers, fillers, antiskinning
agents and plastisisers. Evaporation of the thinners with subsequent oxidation of the drying
leaves a thin coating on the applied surface and protects the base metal against corrosion.
i) Pigments: These are organic or inorganic solid substance. Example, White lead, BaSO4,
Chrome red, Carbon black, CdS etc.
ii) Drying oil: These are the liquid phase of the paints in which pigments are dispersed.
Example, cotton seed oil, castor oil, lin seed oil.
iii) Thinners: They are volatile solvents which evaporate easily from the surface that is being
painted. Example, White sprit, ketones, esters and turpentine oil.
iv) Fillers: These are the solid substances added in a fixed quantity to the paint to improve the
qualities and reduce the cost. Example, Talc, China clay, Mica, asbestos.
v) Driers: These are substances which accelerate the drying of paints. Example, linoleates,
borates, rosinates of lead.
vi) Plasticizers: These are the materials added to the paint to improve the elasticity. Example,
Tributyl phthalate, tricresyl phosphate.
vii) Antiskinnng agent: They prevent the peeling of the paint film from the surface. Example,
Polyhydroxy phenol.

CONSTITUENTS OF VARNISHES:
1. Resin:
a) Natural resin, example, shellac, rosin.
b) Synthetic resin, example, phenol-formaldehyde, urea-formaldehyde resin.
2. Drying oils: Linseed oil, soyabeen oil, fish oil.
3. Thinners: Turpentine oil, petroleum sprit.
4. Driers: Linoleates, naphthanates of Pb, Co etc.
5. Antiskinning agent: Tert amyl phenol.

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