MODULE 1 – ELECTROCHEMISTRY & CORROSION SCIENCE

INTRODUCTION

Electrochemistry is a branch of chemistry, deals with the chemical applications of

electricity. It mainly deals with the chemical reactions produced by passing electric current
through an electrolyte or the production of electric current through chemical reactions.

Differences between Electrochemical cell and Electrolytic cell.

Electrochemical cell Electrolytic cell

convert chemical energy to electric energy convert electric energy to chemical energy
Cell EMF is +ve Cell EMF is – ve
Free energy change ∆G is -ve Free energy change ∆G is +ve
Anode is -ve terminal Anode is +ve terminal

ELECTROCHEMICAL CELLS OR GALVANIC CELLS

Galvanic cells are electrochemical cells in which the electrons, transferred due to redox
reaction, are converted into electrical energy. Eg: Daniel Cell

Daniel cell consists of a zinc electrode dipped in 1 M ZnSO4 solution and a copper
electrode dipped in 1 M CuSO4 solution. Each electrode is known as a half cell. The two
solutions are inter connected by a salt bridge and the two electrodes are connected by a wire
through a voltmeter.

Reactions occurring in the cell

At anode: Oxidation takes place in the zinc electrode by the liberation of electrons,
so this electrode is called negative electrode or anode.

At cathode: Reduction takes place in the copper electrode by the acceptance of

electrons, so this electrode is called the positive electrode or cathode.

Zn → Zn 2 + 2e − ( at anode )
2+
Cu + 2e → Cu −
( at cathode )
2+
Cu + Zn Zn 2+ + Cu ( net cell reaction )
The electrons liberated by the oxidation reaction flow through the external wire and are
consumed by the copper ions at the cathode.

The Daniel cell is represented as, Zn(s) / Zn2+ (aq) // Cu2+ (aq) / Cu(s).

Where anode is written on the left and cathode on right, the ‘//’ represents the salt bridge and
the ionic species are written on either side of the salt bridge.

SALT BRIDGE AND ITS SIGNIFICANCE

Salt bridge is usually an inverted U-tube filled with concentrated solution of inert electrolytes.
An inert electrolyte is one whose ions are neither involved in any electrochemical change nor
do they react chemically with the electrolytes in the two half-cells. Generally, salts like KCl,
KN03, NH4N03, etc., are used. For the preparation of salt bridge, gelatin or agar-agar is
dissolved in a hot concentrated aqueous solution of an inert electrolyte and the solution thus
formed is filled in the U-tube. On cooling the solution sets in the form of a gel in the U-tube.
The ends of the U-tube are plugged with cotton wool as to minimize diffusion effects. This is
used as a salt bridge.

Significance of salt bridge:

(i) It connects the solutions of two half-cells and completes the cell circuit.

(ii) It prevents transference or diffusion of the solutions from one half-cell to the other.

(iii) It keeps the solutions in two half-cells electrically neutral.

SINGLE ELECTRODE POTENTIAL

Origin of Electrode Potential

When a metal rod is in contact with a solution of its own ions, it may undergo either oxidation
(M Mn+ + ne) or reduction (Mn+ + ne M) depending on its nature.
If the metal has more cathode nature, Mn+ ions from solution enter the metal leaving negative
ions in solution. Thus +ive charge develops on metal. If the metal has more anode nature, Mn+
ions moving from metal to solution leaving behind electrons on metal. Thus, metal develops –
ive charge. Due to this, either negative or positive charge develops on the metal and the metal
rod begins to attract positive or negative charged free ions in solution. This results the
formation of a layer of negative ions or positive ions around the metal rod. Due to this layer
formation (HELMHOLTZ ELECTRICAL LAYER) a potential difference develops
between the metal and the solution and this prevents further exchange of ions between the metal
and its solution. This potential difference becomes constant at equilibrium and is called
standard electrode potential of the metal. It measures the tendency of the metallic electrode to
lose or gain electrons, when it is in contact with its own salt solution of 1M concentration at
250C.

The value of the electrode potential depends on

- Nature of the metal

- Concentration of the solution
- Temperature of the solution

Illustration

In order to understand the origin of electrode potential, the following two examples are
considered.

Example 1: - Zn electrode dipped in ZnSO4 solution

When Zn electrode is dipped in ZnSO4 solution, Zn goes into the solution as Zn ions due to
oxidation. Zn→ Zn2+ + 2e-

Now, the Zn electrode attains a negative charge, due to the accumulation of valence electrons
on the metal. 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 CuSO4 solution

When Cu electrode is dipped in CuSO4 solution, Cu2+ ions from the solution deposit over the
metal due to reduction. Cu2 + + 2e- → Cu

Now, the Cu electrode attains a positive charge, due to the accumulation of Cu ions on the
metal. 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.
Thus, a sort of layer (positive (or) negative ions) is formed all around the metal. This layer is
called Helmholtz electrical double layer. This layer prevents further passing of the positive
ions from or to the metal. A difference of potential is consequently set up between the metal
and the solution. At equilibrium, the potential difference becomes a constant value, which is
known as the electrode potential of a metal.

Single electrode potential (E) - It is the measure of tendency of a metallic electrode to lose or
gain electrons, when it is in contact with a solution of its own salt.

Standard electrode potential (E°)- It is the measure of tendency of a metallic electrode to

lose or gain electrons, when it is in contact with a solution of its own salt of 1 molar
concentration at 25°C.

Oxidation potential- If oxidation occurs at the electrode, at equilibrium, the potential of the
electrode is oxidation potential. Thus, the tendency of an electrode to lose electrons is called
the oxidation potential.

Reduction potential- If reduction occurs at the electrode, at equilibrium, the potential of the
electrode is reduction potential. Thus, the tendency of an electrode to gain electrons is called
the reduction potential.

ELECTROCHEMICAL SERIES OR EMF SERIES

When various electrodes (metals) are arranged in the order of their increasing values of
standard reduction potential on the hydrogen scale, then the arrangement is called
electrochemical series.

The standard electrode potential (reduction) of a number of electrodes is given in table. These
values are determined potentiometrically by combining the electrode with the standard
electrodes, whose electrode potential is zero.

Electrode Electrode Reaction E , volts Nature

Li+/Li Li+ + e Li -3.01 Anodic

 Mg2+/Mg Mg2+ + 2e Mg -2.37

Pb2+/Pb Pb2+ + 2e Pb -1.12

Zn2+/Zn Zn2+ + 2e Zn -0.76

Fe2+/Fe Fe2+ + 2e Fe -0.44

Sn2+/Sn Sn2+ + 2e Sn -0.136

H+/H2 2H+ 2e H2 0.00 Pt-reference

Cu2+/Cu Cu2+ + 2e Cu +0.34

Ag+/Ag Ag+ + e Ag +0.80

Au+/Au Au+ + e Au +1.50

Cathodic
½F2/F- ½F2 + e F- +2.87

Significance of emf series (or) Applications of electrochemical series

1. Calculation of standard emf of the cell

The standard emf of a cell (E°) can be calculated if the standard electrode potential
values are known using the following relation.

Ecell = ER.H .E = EL.H .E

2. Relative ease of oxidation (or) reduction

Higher the value of standard reduction potential (+ve value) greater is the tendency to
get reduced, (i.e. Metals on the top (-ve value) are more easily ionized) or (oxidized).

(a) The fluorine has higher positive value of standard reduction potential (+ 2.87 V),
and shows higher tendency towards reduction.

(b) The lithium has highest negative value (-3.01V) and shows higher tendency
towards oxidation.

3. Displacement reactions

(a) Displacement of one element by the other from its salt solution

Metals which lie higher in the emf series can displace those elements which lie below them in
the series. For example, we may know whether Cu will displace Zn from the solution or vice-
versa. We know that standard reduction potential of Cu & Zn.
 ECu 2+ /Cu = +0.34V and EZn2+ / Zn = −0.76V

So, Cu2+ has a greater tendency to acquire Cu form, than Zn2+ has for acquiring Zn form.

(b) Hydrogen displacement behaviour

Metals with negative reduction potential (i.e., the metals placed above H2 in the emf series)
will displace the hydrogen from an acid solution. Example Zinc reacts with dil. H2SO4 to give
H2 but Ag does not, why?

Zn + H 2 SO4 → ZnSO4 + H 2 
EZn = −0.76 volt

The metal with positive reduction potential (ie, the metals placed below H 2 in the emf series)
will not displace the hydrogen from an acid solution.

Ag + H2SO4 → No reaction, E° Ag = + 0.80 V

(c) A non-metal having higher reduction potential can displace a non-metal having lower
reduction potential

Eg. If we pass F2 gas through NaCl solution, displacement reaction takes place generating Cl2
gas and NaF.

2NaCl + F2 → NaF + Cl2

F2 + 2e → 2F-; E0 =+2.87 V

Cl2 + 2e → 2Cl-; E0= +1.36V

4. Predicting Spontaneity (or) feasibility of Redox Reactions

Spontaneity of redox reaction can be predicted from the emf (E°) value of the complete cell
reaction ( G = − nFE ) .

(i) If E° of the cell is positive, the reaction is spontaneous (or) feasible ( G = −ve ) .

(ii) If E° of the cell is negative, the reaction is not spontaneous (or) not feasible
( G = +ve) .
In general, an element having lower reduction potential can displace another metal having
higher reduction potential from its salt solution spontaneously.

5. Analysis of products of electrolysis

Eg; If we electrolyze a mixture of aqueous solution of KCl and KI using Pt electrodes. H2 is

liberated at cathode (-ive terminal) and I2 is liberated at anode (+ve terminal). The ions
approaching -ve terminal are H+ and Na+. The species having high reduction potential undergo
reduction (EH+/H2 = -0.41V at pH = 7 and E0 Na+/Na = -2.71V). Thus, H2 is liberated rather
than Na metal. Similarly, the ions approaching +ve terminal are Cl-, I-, OH-. The species
having low reduction potential get oxidized.

Nernst equation for electrode potential

Consider the following redox reaction,

M n+ + ne− M

For such a redox reversible reaction, the free energy change ( G ) and its reaction quotient (Q)

are inter related as, ( G ) = G + RT In Q where Q = [Product] / [Reactant]

( G ) =ΔG o +RT In
 Product  ............. (1) Where, G = Standard free energy change
 Reactant 
The above equation (1) is known as Van't Hoff isotherm.

The decrease in free energy ( −G ) in the above reaction will produce electrical energy. In the

cell, if the 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 ) ................. (2) Where, −G = decrease in free energy change.
−G = nE F

−G = decrease in standard free energy change.

Comparing equation 1 and 2, it becomes

−nEF = −nE F + RT In
M  . .............. (3)
 M n+ 

Dividing the above equation (3) by – nF

[ the activity of solid metal [M] = 1]

RT 1
E=E − In
nF  M n+ 

In general, E=E o -
RT
In
 Product 
nF  REactant 

RT 2.303RT
(or E=E + In  M n+  (or) E=E o + log  M n+  ...........(4)
nF nF
When, R = 8.314 J/K/mole; F = 96500 coulombs; T = 298 K (25°C), the above equation
becomes

0.0591
E = Ered + log  M n+  ............ (5)
n

0.0591
In general, E = Ered + log C
n

0.0591
Similarly, for oxidation potential, E = Eoxi − log  M n+  ............ (6)
n

The above equation 5 & 6 are known as "Nernst equation for single electrode potential".

Applications (or) Significance of Nernst equations (Electrode Potential)

1. Nernst equation is used to calculate equilibrium constant of a reaction.

2. Study the influence of concentration of electrolyte on electrode potential

3. It is used to calculate the EMF of a cell.

4. PH of a solution can be calculated by measuring the emf.

5. Determination of valencies of ions or the number of ions involved in the reaction.

Nernst Equation for cell potential

An electrochemical cell is obtained by coupling two half cells. EMF of the cell depends on the
concentration of electrolytes used in both electrodes. Effect of electrolyte concentration on emf
of the cell is given by Nernst equation.

For a general electrochemical reaction, a A+ b B ------- c C + d D

Nernst equation can be written as, E cell = E0 cell - 2.303RT / n F log [C]c [D]d / [A]a [B]b

Ecell = E0 cell - 0.0591 / n log log [C]c [D]d / [A]a [B]b at 250 C

Taking Daniel cell as eg. Zn(s) / Zn2+ (aq) (1M) // Cu2+ (aq) (1M) / Cu(s)

Ecell = E0 cell - 2.303RT / 2F log [Zn2+] /[Cu2+]

Ecell = E0 cell - 0.0591 / 2 log [Zn2+] / [Cu2+] at 250

Problems based on Nernst equation

Problem 1: - What is the potential of a lead electrode that is in contact with a solution of 0.015
M Pb2+ ions? Standard electrode potential (E°) for Pb →Pb2+ + 2e- is 0.13 volt.

Std. oxidation potential is given as, Pb →Pb2+ + 2e-; E° = 0.13 V

Given

Concentration of (Pb2+) = 0.015 M, E° = + 0.13 V (std. oxidation potential of Pb)

  The Nernst equation for oxidation potential of Pb is

2.303RT
E=E − log  Pb 2+ 
nF
0.0591
E=E − log  Pb 2+ 
n
0.0591
= 0.13 − log  0.015
2
= 0.13 − 0.02955 ( −1.824 )
= 0.13 + 0.0539

Oxidation potential of Pb = 0.184 volt.

Problem 2: - Calculate the electrode potential of zinc electrode dipped in 0.1 M ZnSO4
solution at 25°C.

Given, Concentration of ZnSO4 = 0.1 M; n = 2

E oZn 2+ /Zn =-0.763V (Known std. reduction potential value); E =?

 The Nernst equation for reduction potential of Zn2+ is

0.0591
E=E + log  Zn 2+  at 25o C
n

0.0591
E = −0.763 + log  0.1 = - 0.763 + (0.02955) (-1) = - 0.763 - 0.02955
2

Reduction potential of Zn = - 0.79255 V.

Problem 3:- Calculate the single electrode potential of zinc in 0.05 M ZnSO 4 solution at
25°C. EZn/ Zn = 0.763V .
2+

Given, Concentration of ZnSO4 = 0.05 M and EZn/ Zn = 0.763V (std. oxidation potential of Zn)
2+

,n=2

0.0591
 Nernst equation for oxidation potential of Zn is , E = E − log  Zn 2+ 
n

0.0591
= 0.763 − log  0.05 = 0.763 -0.02955(- 1.301) = 0.763 + 0.0384
2

Oxidation potential of Zn =0.8014 V.

Problem 4:- Calculate the reduction potential of Cu 2+ / Cu = 0.5M at 25oC. ECu 2+

/ Cu
= 0.337 V

Given, Concentration of [Cu2+] = 0.5 M and ECu 2+

/ Cu
= 0.337V ; n = 2

 The Nernst equation for reduction potential of Cu + is

 0.0591 0.0591
E=E + log Cu 2+  = 0.337 + log  0.5
n 2

= 0.337 + 0.02955(- 0.3010) = 0.337 - 0.0089

Reduction potential of Cu = 0.328 V.

Problem 5 : - Find the oxidation potential of Zn/Zn2+ = 0.2 M electrode at 25°C. Standard
oxidation potential of Zn/Zn2+ is 0.763 V.

Given, Concentration of [Zn2+] = 0.2 M and EZn/ Zn = 0.763V (std. oxidation potential of Zn)
2+

 The Nernst equation for oxidation potential of Zn is

0.0591 0.0591
E=E − log  Zn 2+  = 0.763 − log  0.2
n 2

= 0.763 - 0.02955(- 0.69897) = 0.763 + 0.02065

Oxidation Potential of Zn = 0.78365 V.

Problem 6: Calculate the amount of electrical energy available from a dry cell of EMF 1.5 V
which consumes 10g. Zn (at wt. of Zn = 65.5)

Ans:- The decrease of free energy per mole of Zn (65.5g) , ∆G = -nFE

= 2 x 96500 x 1.5 = 289500 J

Electrical energy available for 1g = 289500 J/ 65.5

Therefore, electrical energy available for 10g Zn = 289500 x10/ 65.5 = 44198J

Problem 7:-Calculate the equilibrium constant of Daniel cell reaction given that E0cell = 1.1 V

Nernst equation is given by E cell = E0 cell – 0.0591 / n log Q

When the cell reaction, Zn(s) + Cu2+ (aq) ------- Zn2+ (aq) + Cu(s) is at equilibrium, free energy ∆G
= 0, i.e. EMF of the cell, E cell = 0 and Q becomes K

0 = E0 cell – 0.0591 / n log K = E0 cell – 0.0591 / 2 log K

Log K = 1.1x2/ 0.0591 = 37.22

K = 1.67 x 1037

REFERENCE ELECTRODES (or) STANDARD ELECTRODES

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.
A reference electrode is one whose potential is known and hence can be used to compare the
potential of other electrodes. They can be divided into two types,
i) Primary reference electrode
ii) Secondary reference electrode
Standard hydrogen electrode is an eg. of primary reference electrode and its potential is taken
as zero at all temperatures. Calomel electrode, Ag- AgCl electrode, glass electrode,
quinhydrone electrode etc. are commonly used secondary reference electrodes. Secondary
reference electrodes are those electrodes whose potential being known can be combined with
other electrodes to determine their unknown potentials.

Standard hydrogen electrode (SHE) (Primary reference electrode)

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 IN 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 (1atm) / H + (1M ) ; E = 0V

In a cell, when this electrode acts as anode, the electrode reaction can be written as

H2 (g) →2H+ + 2e-

When this electrode acts as cathode, the electrode reaction can be written as

2H+ + 2e-→ H2 (g)

Limitations

(i) It requires hydrogen gas and is difficult to set up and transport. H2 gas is
inflammable.

(ii) It requires considerable volume of test solution.

(iii) The solution may poison the surface of the platinum electrode.
 (iv) The potential of the electrode is altered by changes in barometric pressure.

(v) Maintenance of 1M concentration is difficult.

Advantages

(i) It is a fundamental electrode to which all the pH measurements are ultimately

referred.

(ii) It shows no salt error, negligible internal resistance and negligible electrical
leakage error.

(iii) It can be used over the entire pH range

(iv) It is highly accurate.

Saturated calomel electrode (Secondary reference 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 KC1. 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 + 0.2422 V.

Calomel Electrode

It is represented as,

Hg, Hg2Cl2(s), KCl (sat. solution); E = 0.2422 V

2 Hg(1) → Hg 22+ + 2e −

If the electrode acts as anode the reaction is Hg 22+ + 2Cl − → Hg 2Cl2( s )

2 Hg (1) + 2Cl − Hg 2Cl2( s ) + 2e −

Hg 2Cl2( s ) → Hg 22+ + 2Cl −

If the electrode acts as cathode the reaction is Hg 22+ + 2e − → 2 Hg(1)

Hg 2Cl2( s ) + 2e − 2 Hg(1) + 2Cl −
 The electrode potential depends on the activity of the chloride ions and it decreases as
the activity of the chloride ions increases. The Nernst equation of this electrode at 250C is given
by

E cal = E0 cal – 0.0591/ 2 log [Cl-]2

E cal = 0.2810 – 0.0591/ 1 log [Cl-]

The single electrode potential of the three calomel electrodes on the hydrogen scale at
298 K are given as

0.1 N KC1 = 0.3338 V, 1.0 N KC1 = 0.2810 V, Saturated KC1 = 0.2422 V.

Advantages

1. It is simple to construct.

2. Cell potential measurements are reproducible and stable over a large period and
does not vary with temperature.

3. It is calibrated with respect to SHE

4. It is having least potential gradient with temperature.

5. Potential values are reliable and measurements can be made with great accuracy.

Disadvantages

1. It should not be used above 500C because the mercurous chloride brakes down,
yielding an unstable reading.

2. It may cause toxicity.

Glass membrane electrode (Internal Reference Electrode)

Construction

A glass membrane electrode is constructed in a similar way to that of pH electrode. It consists

of thin-walled glass bulb (the glass is a special type having low melting point and high electrical
conductivity) containing a Pt wire in 0.1M HC1. The glass electrode is represented as, Pt, 0.1
M HC1 / Glass. HC1 in the bulb furnishes a constant H+ ion concentration.
Glass electrode is used as the "internal reference electrode". The pH of the solutions, especially
coloured solutions containing oxidizing or reducing agents can be determined.

Principle

When two solutions of different pH values are separated by a thin glass membrane, there
develops a difference of potential between the two surfaces of the membrane. The potential
difference developed is proportional to the difference in pH value. The thin walled glass bulb
called glass membrane functions as an ion-exchange resin, and an equilibrium is set up between
the Na+ ions of glass and H+ ions in solution. The electrode reaction is H+ + Na+(glass) ----- Na+
+ H+(glass) and the electrode representation is: Ag/AgCl/0.1M H+/glass/H+(c=?). The potential
difference varies with the H+ ion concentration, and is given by the expression.

EG = E°G - 0.0592 log1/[H+]

EG = E°G - 0.0592 pH.

Where E°G is a constant for a particular variety of glass, E°G =0.6 0r 0.5 depending on
the variety of glass.

Advantages of Glass Electrode

(i) It can be easily constructed and readily used.

(ii) The results are accurate,

(iii) It is not easily poisoned.

(iv) Equilibrium is rapidly achieved.

Limitations

(i) Since the resistance is quite high, special electronic potentiometers are employed
for measurement.
 (ii) The glass electrode can be used in solutions only with pH range of 0 to 10.
However, above the pH 12 (high alkalinity), cations of the solution affect the
glass and make the electrode useless.

Determination of pH of a Solution using Glass Electrode

The glass electrode is placed in the solution under test and is coupled with saturated calomel
electrode as shown in the figure.

The emf of the cell is measured. From the emf, the pH of the solution is calculated as follows.

E Cell = E right - E left

E Cell = E°G - 0.0592 pH – 0.2422

E Cell = (E°G – 0.2422) - 0.0592 pH ---- (1)

pH = E°G – E Cell – 0.2422/ 0.0591

equation (1) has the form y = c + mx, the equation for a straight-line having intercept c and
slope m when we plot a graph between emf (y- axis) and pH (x- axis). The intercept c = E°G –
0.2422 and the slope m= -0.0591 at 250C.

CONDUCTIVITY OF ELECTROLYTES

Specific Conductance (K):- It is the conductance of 1 cm3 of a material or solution held between
two electrodes of 1cm2 area placed on the opposite pairs of faces of cube of edge length 1cm.

l
K =conductance×
a
l l 1
K=  Where, =c
R a R

Unit of Specific Conductance,

 cm
K=
ohm  cm 2
1
= = ohm −1cm −1or mho cm −1
ohm  cm

Cell constant (x):

It is the ratio of distance between two electrodes (l) and area of the electrodes (a).

l
x= Where, l = length in cm; a = area in cm2.
a

l l cm
K=  . Unit of cell constant x= 2
= cm −1
R a cm

Conductivity cell

A conductivity cell consists of two electrode plates coated with finely divided platinum black.
These two electrodes are welded with the ends of platinum wires that are sealed through two
glass tubes. The tubes are strongly fixed such that distance between electrodes maintains
unaltered.

Determination of cell constant

Cell constant is measured by filling the conductivity cell with a solution of known conductivity
like 0.1M KCl solution (K = 0.01288Scm-1 at 298K). By measuring the conductance of 0.1M
KCl solution in the given cell, the cell constant can be determined.

Cell constant = conductivity of 0.1M KCl solution (K) / conductance(C) of 0.1M KCl solution

Measurement of conductivity using digital conductivity meter

Conductivity cell is connected to the digital conductivity meter and appropriate temperature is
selected. Conductivity cell is then fully dipped into the sample solution taken in a beaker.
Measure the conductance of the solution by selecting the proper range switch (milli S or micro
S). Digital conductivity meter directly reads out the conductance.

Conductivity (K) = conductance x cell constant

Problem 1

A resistance of 0.1 N solution of a salt contained in a volume between two electrodes, 4 cm

apart and 10.7 cm2 in area was found to be 70 ohms. Calculate specific conductance of the
solution.

Given: R = 70 ohms, C =0.1 N, l =4 cm; a = 10.7 cm2

1 l 1 4
Sp. conductance (K) =  , K=  = 0.0053ohm-1cm-1
R a 70 10.7
CELL AND BATTERY

A battery is an arrangement of several electrochemical cells connected in series that can be

used as a source of direct electric current.

TYPES OF BATTERY

1. Primary Battery (or) Primary cells (or) Non-reversible Battery

In these cells, the electrode and the electrode reactions cannot be reversed by passing an
external electrical energy. The reactions occur only once and after use they become dead.
Therefore, they are not chargeable. Example: Dry cell, Daniel cell

2. Secondary Battery (or) Secondary cells (or) Reversible Battery

In these cells, the electrode reactions can be reversed by passing an external electrical energy.
Therefore, they can be recharged by passing electric current and used again and again. These
are also called Storage cells (or) Accumulators. Example: Lithium ion battery

3. Flow battery (or) Fuel cells

In these cells, the reactants, products and electrolytes are continuously passing through the cell.
Here chemical energy gets converted into electrical energy. Example: Hydrogen-oxygen fuel
cell.

Lithium –ion battery

In electrochemical series Li has the highest potential (3.05V) even enough to decompose water
and hence can be a good anode material for a high-density battery and therefore the electrolyte
needs to be some material other than water.
It is a type of rechargeable battery constructed on the principle of reversible migration of
lithium ions between anode and cathode during charging and discharging.
Construction
Lithium ion cells use a lithiated carbon intercalation material, written as Li x C (Li atoms are
inserted between the layers of carbon atoms) for the negative electrode (anode). Carbon
materials, like petroleum coke and graphite are the appropriate choices for the anode material.
A lithiated transition metal oxide intercalated compound is used for the positive electrode
(cathode). Lithium intercalation compounds like Li1-xCoO2, Li1-xNiO2, Li1-xMn2O4 are
generally used as cathode. The electrolyte is usually a lithium salt in an organic solvent.
Lithium per chlorate (LiClO4) in a mixture of propylene carbonate and ethylene carbonate is
used as electrolyte. A solid electrolyte separator separates the anode and cathode
compartments.
The basic cell representation is
Li x C6 | Li X in PC-EC | Li1-x MO2
Where Li X is lithium salt. PC-EC is a mixed propylene carbonate – ethylene carbonate solvent
and M is transition metal like (Co, Ni, Mn etc.). The emf of the cell varies from about 2.7 V –
4.23 V.

Discharging (Voltaic cell)

At anode, Li x C x Li+ + x e + C
At cathode, Li 1-x MO2 + x Li+ + x e Li MO2
Overall reaction
Li x C + Li1-x MO2 LiMO2 + C
Charging (Electrolytic cell)
At anode, Li MO2 Li1-x MO2 + x Li+ + x e
At cathode, x Li + + x e +C Li x C
Overall reaction
LiMO2 + C Li x C + Li1-x MO2
Here the electrochemical process involves the uptake of Lithium ions at the +ve electrode and
their release at –ve electrode during discharge. Thus Li+ ions move back and forth between the
positive and negative electrodes during charging and discharging. Since metallic lithium is not
present in the cell, lithium ion cells are less chemically active and hence safer and have a longer
cycle life than the cells containing metallic lithium.
When Li ion cells are allowed to charge completely (x=1) anodic material becomes Li1-1CoO2
or CoO2 which is an explosive material due to liberation of O2 gas on decomposition. There
for automatic built in circuit breakers are there inside battery which allows charging only up to
90 %(x=0.9)
Advantages
i. Available in large number of shapes and sizes.
ii. It is much lighter.
iii. It has low self-discharge capacity.
Disadvantages
i. Offers high internal resistance.
ii. On overheating, the cell ruptures ignite or explode.
 iii. Expensive to manufacture 40% > Ni-Cd
Applications
i. Ideal for portable devices like note-book computers.
ii. Used in mobile phones and other electronic devices.
iii. Used in small digital music devices like iPods MP3 players etc.
iv. Use in electric vehicles.

Fuel cell

Fuel cell is a voltaic cell, which converts the chemical energy of the fuels directly into
electricity without combustion. It converts the energy of the fuel directly into electricity. In
these cells, the reactants, products and electrolytes pass through the cell.

Fuel + Oxygen→ Oxidation products + Electricity.

Example: Hydrogen-oxygen fuel cell.

Hydrogen-Oxygen fuel cell

Hydrogen-oxygen fuel cell is the simplest and most successful fuel cell, in which the fuel-
hydrogen and the oxidizer-oxygen and the liquid electrolyte are continuously passed through
the cell.

Description

It consists of two porous electrodes anode and cathode. These porous electrodes are made of
compressed carbon containing a small amount of catalyst (Pt, Pd, and Ag). In between the two
electrodes an electrolytic solution such as 25% KOH or NaOH is filled. The two electrodes are
connected through the volt meter.

Working

Hydrogen (the fuel) is bubbled through the anode compartment, where it is oxidized. The
oxygen (oxidizer) is bubbled through the cathode compartment, where it is reduced.
Various chemical reactions

At Anode

Hydrogen gas, passed through the anode, is oxidized with the liberation of electrons which then
combine with hydroxide ions to form water.

H2 → 2 H+ + 2e-

2H+ + 2OH-→ 2H2O

H2 + 2OH-→ 2H2O + 2e-

Multiply by 2: 2H2 + 4OH- → 4H2O + 4e-

At cathode

The electrons, produced at the anode, pass through the external wire to the cathode where it is
absorbed by oxygen and water to produce hydroxide ions.

O2 + 4e- →2 O2-

2O2- + 2H2O →4OH-

O2 + 2H2O + 4e- → 4OH-

Overall cell reaction

At anode: 2H2 + 4OH- → 4H2O + 4e-

At cathode: O2 + 2H2O + 4e- → 4OH-

2H2 + O2 →2H2O

The emf of the cell = 0.8 to 1.0 V

Applications

1. H2-O2 fuel cells are used as auxiliary energy source in space vehicles, submarines
or other military-vehicles.

2. In case of H2-O2 fuel cells, the product of water is proved to be a valuable source
of fresh water by the astronauts.

Advantages of Fuel cells

1. Fuel cells are efficient (75%) and take less time for operation.

2. It is pollution free technique.

3. It produces electric current directly from the reaction of a fuel and an oxidizer.
 4. It produces drinking water.

Disadvantages of Fuel cells

1. Fuel cells cannot store electric energy as other cells do.

2. Electrodes are expensive and short lived.

3. Storage and handling of hydrogen gas is dangerous.

CORROSION AND ITS CONTROL

Metals are isolated from their ores, generally at high temperature and the process involves
increase in free energy. Most of the metals except noble metals like Au, Ag and Pt exist in
nature in combined forms as oxides, hydroxides, carbonates, chlorides sulphides, sulphites,
silicates etc. These are known as minerals or ores of the metals. These metal ores are reduced
to their metallic states during the extraction process. During the extraction of metals
considerable amount of energy in required. So isolated pure metals are in exited state (a higher
energy state) than their corresponding ores and they have a natural tendency to revert back to
combined state (or lower energy state). Hence when metals are put in to use in various forms
they are exposed to environment (such as dry Gases, moisture, liquids etc.) and the exposed
metal surfaces begin to decay. In other words, destruction or deterioration of the metal start at
the surface. This type of metallic destruction may be due to direct chemical attack or
electrochemical attacks.

Corrosion is a slow process of deterioration (or destruction) of metal from its surface due
to unwanted chemical or electrochemical interaction of metal with its environment. Thus
corrosion is a process ‘reverse of extraction of metals’,

Rusting of iron, tarnishing of silver, copper etc are egs.

Iron when exposed to moist air it undergoes rusting forming a layer of reddish scale and powder
of oxide (Fe3O4) and the iron becomes weak.

Copper when exposed to moist air contains CO2, gets covered with a green film of basic
Carbonate (CuCO3+Cu (OH) 2)

Classification of corrosion

Corrosion reactions are mainly of two types.

 I. Chemical corrosion (Dry Corrosion) II. Electrochemical corrosion (Wet corrosion)

I. Chemical Corrosion

This corrosion is mainly by the direct chemical action of atmosphere gases on the metal in the
absence of moisture. In this type of corrosion there occurs a chemical combination between the
metal and the oxidizing component of the atmosphere.

II. Electrochemical or wet corrosion

This type of corrosion is the result of setting up of a local electrochemical cell at the
surface of the metal. Electrochemical corrosion occurs under two conditions.

1. When a single metal is in contact with wet gas, moisture or an electrolytic solution
(impurities can act as cathode)
2. When two dissimilar metals or alloys are fully or partially immersed in a conducting
solution.

This corrosion occurs due to the existence of separate anodic and cathodic area between which
current flows through the conducting solution.
Oxidation takes place at the anodic area resulting in the destruction of metal or corrosion of
metal. At anode: M → Mn+ +ne

Reduction occurs at the cathode. At the cathode part, the dissolved constituents in the

conducting medium accept electrons to from non-metallic ions like OH-, O2- etc.

The metallic ions formed at the anode and non-metallic ions formed at the cathode diffuse
towards each other and hence from the corrosion product somewhere in between cathode and
anode.

Thus, we can sum up that electro chemical corrosion involves.

(i) The formation of anodic or cathodic areas or parts in contact with each other
(ii) Presence of a conducting medium
(iii) Corrosion of anodic areas only.
(iv) Formation of corrosion product somewhere between anodic and cathodic areas.

Mechanism of wet corrosion

Electrochemical corrosion involves flow of electron current between the anodic and cathodic
areas. The anodic reaction involves dissolution of metal as corresponding metallic ions with
the liberation of free electrons.
 M → Mn+ + ne-

The cathode reaction depends on the nature of the corrosive environment. The cathode
reactions can be either.

i. Evolution of hydrogen
ii. Absorption of oxygen

Electrochemical corrosion by evolution of hydrogen.

a. Hydrogen evolution corrosion in acid medium.

This type reaction occurs usually in acidic environments such as in industrial areas. Consider
the metal like Fe or Al in contact with HCl;

Hydrogen evolution corrosion in case of Fe in acid medium takes place due to the fact that
hydrogen electrode potential in acid medium (E0H+/H2 = 0) is higher than electrode potential of
Fe (E0 Fe2+/Fe = -0.44V)

The anodic reaction is dissolution of iron as ferrous ions with the liberation of electrons. The
H+ ions present in the acidic medium accept the electrons coming from the anode reaction and
H2 gas is evolved.

Fe → Fe2+ + 2ē (anodic reaction)

2H++2e → H2 (g) (cathode reaction)

The overall reaction is: Fe + 2H+ → Fe2+ + H2 (g)

These types of corrosion result in the displacement of hydrogen ions from acidic solution with
the consequent evolution of H2 gas by the metal. All metals above hydrogen in the
electrochemical series have the tendency to dissolve in acid solution.

b. Hydrogen evolution corrosion in alkaline medium

Hydrogen evolution corrosion does not take place in case of Fe immersed in alkaline medium
because Hydrogen electrode potential in alkaline medium (E0H2/OH- = -0.828V) is lower than
electrode potential of Fe (E0 Fe2+/Fe = -0.44V). Whereas metals like Al can give Hydrogen
evolution corrosion in alkaline medium also. This is due to the fact that electrode potential of
hydrogen electrode in alkaline medium (-0.828V) is higher than Al (E0 Al3+/Al = -1.66V)

Anode; Al → Al3+ + 3e; E0 = -1.66V

Cathode; 2H2O + 2e → H2 + 2OH-; E0 = -0.828V

Here corrosion cell potential is E0 Cell = E0 cathode- E0 anode = -.828- (-1.66) = 0.832V

Electrochemical corrosion by absorption of oxygen

a. Oxygen absorption corrosion in acid medium or neutral environment.

This type of corrosion occurs in neutral aqueous solution of electrolytes like NaCI solution
in presence of atmosphere oxygen. Eg: Rusting of iron. Eg. Iron forms a thin layer of iron
oxide on the surface and if this layer develops some cracks, small anodic areas will be formed
on the metal surface. Rest of the metal surface in contact with the environment will act as
cathode.

Now at the anodic areas iron dissolves as ferrous ions with the liberation of electrons.

Anode; Fe → Fe2+ + 2e- (Oxidation); E0 = -0.44V

Cathode; O2 + 4H+ +4e → 2H2O; E0 = +1.23V

Here corrosion cell potential in acid medium is E0 Cell = E0 cathode- E0 anode = 1.23 - (-0.44) =
1.67V.

Fe2+ produced here can further oxidized to Fe3+ in acidic or neutral environments since oxygen
electrode potential is greater than (E0 Fe3+/Fe2+ = +0.77V).

Fe2+ → Fe3+ = e; E0 = +0.77V

3+
The Fe ions produced here forms an insoluble precipitate of Fe (OH)3. is called yellow rust

If the moisture content is limited the corrosion product will be black anhydrous magnetite
(FeO. Fe2O3).
b. Oxygen absorption corrosion in alkaline medium.

This occurs when metal is in contact with water having dissolved oxygen in alkaline
environment.

Anode; Fe → Fe2+ + 2e- (Oxidation); E0 = -0.44V

The electrons so released move from the anodic to cathodic area through the metal where they
are taken up by oxygen molecules to become hydroxide ions.

1/ O2 + H O + 2e- → 2 OH - (reduction) E0 = +0.40V

2 2

Here corrosion cell potential in alkaline medium is E0 Cell = E0 cathode- E0 anode = 0.40 - (-0.44) =
0.84V.

The Fe2+ ions formed her cannot further oxidized to Fe3+ in alkaline environments, since
oxygen electrode potential is less than (E0 Fe3+/Fe2+ = +0.77V) in alkaline medium. Here no
insoluble precipitate of Fe (OH)3 is produced. Thus, no intense localized corrosion.

Comparison of chemical corrosion with electrochemical corrosion

Chemical corrosion Electrochemical corrosion

It occurs in dry condition. It occurs is wet condition (Electrolyte or

moisture)

It involves the direct chemical attack of the It involves the setting up of a large number
metal by envt. of galvanic cells.

It is explained by absorption mechanism It is explained by mechanism of electro

chemical reactions.

It occurs on both homogeneous & It occurs only on heterogeneous surfaces

heterogeneous surfaces

Corrosion is uniform. Corrosion is not uniform if the anode area is

small

It is a slow process. It is a fast process.

Corrosion products accumulate at the same Corrosion occurs at the anode, but product
place where corrosion occurs. accumulate near the cathode.

Galvanic Series

There are some exceptions when we consider the activity (tendency to undergo corrosion) of
metals in the electrochemical series. For eg: Ag placed below Ti in the ECS undergoes more
corrosion than Ti and similarly Zn placed below Al undergoes more corrosion than Al. This is
because metals like Al and Ti develop a strong oxide layer on the surface, thereby making their
potentials more positive. ECS do not account for these exceptions and cannot account for the
corrosion of alloys. Hence a more practical series is developed and is referred to as galvanic
series. This series is developed based on the corrosion behavior of metals and alloys in a
particular environment like sea water. This series can be used to study the corrosion behavior
of metal as well as alloys. Thus, galvanic series is the arrangement of elements and alloys
in the decreasing under of activity towards corrosion.

Electrochemical series Vs Galvanic Series

Electrochemical series Galvanic series

Electrode potentials are measured by dipping This series was developed by studying
pure metals in their solutions of IM corrosion of metals and alloys in unpolluted
concentration, without any oxide film on sea water without their oxide film if any
them. removed.

The position of a given metal in The position of a given metal may shift
electrochemical is fixed.

It gives no information regarding position of Since alloys are included in galvanic series,
alloys, so their corrn can’t be studied from so their corrn can be studied from this series.
this series.
This series comprises of metals and non- This series comprises of metals and alloys.
metals.
It predicts the relative displacement It predicts the relative corrosion tendencies.
tendencies.

CORROSION CONTROL

The Proverb ‘Prevention is better than cure’ is very correct in the field of corrosion.

1. Cathodic protection: In this method, the metal which is to be protected is forces to act
as cathode so that corrosion will not occur. There are two type of cathodic protection.

a) Sacrificial anodic protection:

In this protection method the metallic structure (to be protected) is connected by a wire to a
more anodic metal so that all the corrosion is concentrated at this more active metal. The more
active metal itself gets corroded slowly. While the parent structure (Cathodic) is protected. The
more active metal is called ‘Sacrificial anode’. The corroded sacrificial anode block, is replaced
by fresh one when consumed completely. Metals commonly med as sacrificial anodes are Mg,
Zn AI and their alloys. The important application of this method includes protection of buried
pipes, underground cables, marine structure etc.
b) Impressed current cathodic protection
As a result of corrosion an electronic flow occurs from the anodic part to cathodic part and it
is known as corrosion current. In this method an impressed current from a DC source is applied
in opposite direction to neutralize corrosion current and convert the corroding metal from anode
to cathode. Usually impressed current is derived from a battery with an insoluble anode like
Graphite or silica, iron, stainless steel, Pt etc. The anode is to be kept in a region of good
conductivity.

This method is very effective in arresting corrosion for buried structures such as storage tanks,
pipelines, ships etc. This method is useful for long term operation for large structures.

Problems and limitations with cathodic protection

1) Cathodic protection system which is efficiency protecting a pipeline may increase the
corrosion of an adjacent pipeline or an adjacent useful structure because of stray
currents. This may lead to unexpected legal and technical problems.
2) Capital investment and maintenance costs.
3) The chemical reactions occurring at the surface of the protected structure may cause
problems. If the cathodic reaction produces hydrogen, it may have a deleterious effect
(eg: blistering) on the metal itself. If the metal is coated, the coating may get peeled off.
4) Possibility of soil and micro biological corrosion effects should also be considered in
case of underground structures.

Electroplating or electrodeposition
It is the process by which the coating metal is deposited on the base metal by passing a direct
current through and electrolytic solution containing the soluble salt of the Coating metal.
The base metal to be plated is usually made as the cathode whereas the anode is either the
coating metal itself or an inert material of good electrical conductivity like graphite.

Electroplating of metals is done to protect them from corrosion and for decoration purpose. For
example, the vessels of iron are electroplated with copper or silver or gold to make it attractive
and to protect from rusting.

Electroplating of Copper

Copper electroplating is the process of electroplating a layer of copper onto the surface of a
metal object. Eg. Electroplating iron object with copper metal

To deposit a layer of copper metal on an iron object, take a glass jar and fill it with copper
sulphate solution (electrolyte). Connect the plate of copper metal to the positive terminal
(anode) of battery and iron object to the negative terminal (cathode) of the battery. Now, dip
these two electrodes in the solution of copper sulphate. When an electric current is passed
through the CuSO4 solution, you will find that a thin layer of copper metal is deposited on the
cathode (iron object) and an equivalent amount of copper is lost by the anode (copper plate)
and is dissolved into the solution.

ELECTROLESS PLATING

“Without using electrical energy, the deposition of a noble metal from its salt solution on a
catalytically active less noble metal surface by a suitable reducing agent is known as electro
less plating.” It is also known as auto-catalytic plating. It is a chemical reduction process which
once initiated, become autocatalytic hence the name. The process is similar to electroplating
except that no outside current is needed.
Theory of Autocatalytic Plating:
In Electro less plating, metallic ions are reduced to the metal with the help of reducing agents
and deposited on a catalytic surface.
Metal ion + Reducing agent Catalytic Metal plated over a catalyst surface + oxidized product.
Surface
Advantages
(a) In electro less plating the use of electrical contacts or electrical power is eliminated.
(b) Throwing power of electro less bath is better so intricate parts with irregular shapes can
be uniformly coated.
(c) Plastics and other insulators and semiconductors can also be plated by electro less
plating.
(d) Resulting deposits have unique chemical, mechanical and magnetic properties.
Process of Electroless plating
Steps
1. Preparation of the surface to be plated(activation)
Etching- acid treatment
Electroplating –coating of metals
Chemical treatment- plastic objects and printed circuit boards are treated with SnCl2
and PdCl2
2. Preparation of plating bath; - Plating bath is composed of
i. Soluble salt of metal to be plated.
ii. Reducing agent like formaldehyde, hypophosphate etc.
iii. Complexing agent like tartrate, citrate, succinate etc. This improves the quality of the
deposit
iv. Exaltant like succinate, fluoride, glycinate etc. This entrances the plating rate.
v. Stabilizer like thiourea, cations of lead, calcium etc. is added to prevent the decomposition
of the plating bath solution.
vi. Buffer like sodium acetate etc. is added to control the pH of the bath.
3. Procedure
The article to be plated is immersed in plating bath

Eg: Electro less plating of Copper.

- to deposit a layer of Copper on a substrate without the use of electrical energy
- commonly used for making printed circuit boards
Steps
i. Pretreatment and Activation of the surface: By treatment with organic solvents followed by
acid treatment, the surface is degreased first.
ii. Preparation of Plating Bath Solution: A solution of Cupric salt, Formaldehyde as a reducing
agent, sodium acetate buffer, sodium succinate as complexing agent and an exaltant.
iii. Procedure: Object is immersed in plating bath.
Reactions
At Cathode, Cu2+ + 2 ē Cu
At anode, 2HCHO + 4OH- 2HCOO- + 2H2O+ H2 + 2 ē
Overall reaction, Ni2+ + H2 PO-2 + H2 O Ni + H2 PO-3 + 2H+
PH of plating bath solution = above 12
Uses
i. – used in double or multilayer printed circuit boards
ii. – used as a base coating for subsequent electroplating
………………