MODULE I

ELECTROCHEMISTRY AND CORROSION

The branch of chemistry which deals with two forms of energy such as electrical energy
and chemical energy and the inter-conversion of one form to another is called electrochemistry.
Thus there are two types of electro chemical changes. On the basis of electrochemical changes,
cells are of two types.
1. Electrolytic cell
2. Galvanic cell (Voltaic cell) (Electro chemical cell)

Differences between electrolytic cell & galvanic cell

Electrolytic cell Electro chemical cell
 It is used for the conversion of electrical  It is used for the conversion of chemical
energy to chemical energy. energy to electrical energy.
 It requires EMF.  It produces EMF.
 Anode is +ve and cathode is –ve.  Anode is –ve and cathode is +ve.
 Discharges of ions occur at both the  Discharges of ions occur only at cathode.
electrodes.
 Non-spontaneous reaction occurs.  Spontaneous reaction occurs.
 These are irreversible.  These may be reversible.

Comparison of electrolytic cell & galvanic cell

Electrolytic cell Electro chemical cell
 Oxidation takes place at the anode and  Oxidation takes place at the anode and
reduction at the cathode. reduction at the cathode.
 Flow of electrons from anode to cathode.  Flow of electrons from anode to cathode.
 Electrons leave the cell at anode and enter  Electrons leave the cell at anode and enter
the cell at cathode. the cell at cathode.

Electrode potential and its origin

When a metal rod is immersed in a solution of its own ion, it will either undergo
oxidation or reduction. As a result metal rod attains positive or negative charge. If the metal rod
attains the positive charge, then it can attract the negatively charged free ions from the solution
& if the metal rod attains negative charge, then it can attract the positively charged free ions from
the solution. As a result a layer of both positive and negative charge is produced on the metal
rod. This will lead to the development of a potential and is called electrode potential.
Electrode potential (E) is defined as the tendency of an electrode to lose or gain
electrons when it is immersed in a solution of its own ions. Electrode potential is of two types.
They are
1. Oxidation potential
2. Reduction potential
Oxidation potential
It is defined as the tendency of an electrode to lose electrons when it is immersed in a
solution of its own ions.
Reduction potential
It is defined as the tendency of an electrode to gain electrons when it is immersed in a
solution of its own ions.

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 Electrode potential becomes constant at equilibrium then it is called standard
electrode potential (E0). It is defined as the tendency of an electrode to lose or gain electrons
when it is immersed in a solution of its own ions of 1M concentration, 1atm pressure and 298K
or 25ºC.
It is not possible to find out the absolute value of electrode potential, since neither oxidation nor
reduction takes place independently both occur simultaneously. Hence we can find out the
relative value of electrode potential by coupling it with universally accepted reference electrode
such as SHE or NHE. Its potential is arbitrarily fixed as zero. It can function as an anode or
cathode depending on the nature of the other electrode to which it is connected.
In order to measure the standard electrode potential of Zn rod, (Zn rod dipped in 1M ZnSO 4
solution) Zn electrode is coupled with SHE internally using salt bridge and externally using volt
meter. Zn has greater tendency for oxidation than SHE. So Zn can function as anode and SHE
can function as the cathode. The resultant cell potential can be read directly from the volt meter.

The resultant cell can be represented in the following manner,

Zn/Zn2+//H+(1M)/H2(1atm)/Pt
E0 Cell = E0cathode – E0anode
= E0 SHE-E0Zn/Zn2+
0.76 V = 0 - E0 Zn/Zn2+
(E0Zn/Zn2+= -0.76V)

Helmholtz electrical double layer

When an electrode is immersed in a solution of its own ions an electrical double layer is
produced. It is the double layer of both positive and negative charges. Electrical double layer
corresponds to an electrical capacitor. Electrical properties can be explained qualitatively by
using the concept of electrical double layer at the solid liquid interphase. This concept was
proposed by the scientist, Helmholtz. He considered that electrical double layer is produced at
the surface of separation between the two phases, i.e. the solid electrode and liquid electrolyte.
Electrical double layer consists of two parts.
1). Fixed part 2) Diffused part
Fixed part: It is fixed to the solid electrode. It contains either positive or negative ions.
Diffused part: It extends some distance into the solution. It contains both positive and negative
ions. The existence of charges of opposite signs on the diffused to the fixed part of the electrical
double layer develops a potential between the two layers. This potential is called electro kinetic
potential or zeta potential.

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According to electrostatic theory, the potential difference between the two layers (ф) is given by
Ф=
Where ‘σ’ is the charge density, i.e. ⁄

‘a’ is the distance between the layers of positive and negative charges.
‘ ’ is the dielectric constant of the medium and 0 that of free space.

Electrochemical series
An electrochemical series is a series in which the electrodes are arranged in the increasing
order of reduction potential or decreasing order of oxidation potential. On moving down the
series, reduction potential increases and oxidation potential decreases. Thus this series gives the
increased tendency of electrodes to get reduced or decreases tendency of electrodes to get
oxidised. The electrodes present at the top of the series can function as anode and those present
at the bottom of the series can function as cathode. This series is also called activity series, since
the electrodes at the top of the series is more reactive than those present at the bottom.
Anodic (Active)
Potassium (K)
Calcium (Ca)
Sodium (Na)
Magnesium (Mg)
Aluminium (Al)
Zinc (Zn)
Iron (Fe)
Nickel (Ni)
Tin (Sn)
Leads (Pb)
Hydrogen (H)
Copper (Cu)
Mercury (Hg)
Silver (Ag)
Platinum (Pt)
Gold (Au)
Fluorine (F)
Cathodic (Noble)
Hydrogen has zero reduction potential. Above hydrogen, all the electrodes have negative
reduction potential and below hydrogen, all the electrodes have positive reduction potential.

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Applications of electrochemical series
1. To know the relative ease of oxidation and reduction:
Greater the reduction potential, more easily the substance undergoes reduction and is a
better oxidising agent. (Eg. Fluorine). Similarly greater the oxidation potential, more easily the
substance undergoes oxidation and is a better reducing agent. (Eg.Pottasium).
2. To predict whether the metal will react with acid to give hydrogen gas:
Metals present above hydrogen in the electrochemical series can react with acids to give
hydrogen gas. This is because these metals have greater tendency to undergo oxidation with
respect to hydrogen, since they have negative reduction potential.
3. To calculate the standard emf of the cell:
Eº Cell = Eº Cathode – E ºAnode
If we know the position of electrodes in the electrochemical series, we can easily predict which
electrode can function as anode and which one can function as cathode.
4. Displacement reactions
A metal with lower reduction potential can displace a metal with higher reduction potential
from its salt solution. Zn can displace Cu from CuSO4 solution.
5. To predict the spontaneity of any redox reaction
For any spontaneous reaction, free energy change (ΔG) should be negative. ΔG = -nFEcell
Hence, Ecell should be positive for spontaneous reaction. Ecell of the cell can be calculated from
the redox potentials by using the relation Ecell= E cathode-E anode
Relationship between electrical energy and free energy
The electrical energy produced by the working of the cell is the product of quantity of
electricity passed through the cell and emf of the cell. If in a particular cell reaction, ‘n’ is the
number of electrons get transferred, then the quantity of electricity passed through the cell is ‘nF’
and E is the emf of the cell.
Then electrical energy = nFE
But Gibbs and Helmholtz suggested that electrical energy produced due to the working of the
cell is always accompanied with decrease in free energy.
Then electrical energy = nFE = - ΔG
ΔG = -nFE
Criteria for spontaneity in terms of cell emf
Case 1: If ∆G < 0 or ∆G is –ve, then Ecell > 0 or Ecell is +ve and the reaction will be
spontaneous.
Case 2: If ∆G = 0, then Ecell = 0 and the reaction will be in equilibrium.
Case 3: If ∆G > 0 or ∆G is +ve, then Ecell < 0 or Ecell is -ve and the reaction will be non-
spontaneous.
Nernst equation
Nernst equation is the fundamental equation that gives the relationship between electrode
potential and concentration of electrolyte. To derive Nernst equation, consider a general
reversible reaction.
Mn+ + ne-→ M
For a reversible reaction, free energy change (∆G) is related to the equilibrium
constant (K) by an expression.
∆G = ∆G0 + RT ln K (1)
Where ∆G is the free energy change, ∆G0 is the standard free energy change, R is the universal
gas constant, K is the equilibrium constant and T is the temperature in Kelvin.
K=
According to Gibbs-Helmholtz suggestion,

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 ∆G = -nFE & ∆G0 = -nFE0 (2)
Substituting equation (2) in equation (1)
-nFE = -nFE0 + RT ln
Dividing above equation by –nF, on both sides and convert natural log into base 10, we get
E = E0 - 2.303 log
Since [M] = 1, then the equation becomes;
E = E0 – 2.303 log
E = E0 + 2.303 log [Mn+]
On substituting R = 8.314J/K, T = 298K & F = 96500C, we get simplified form of Nernst
equation;
E = E0 + log [Mn+]
Where E is the electrode potential, E 0 is the standard electrode potential.
For a reaction of the type aA + bB ⇌ cC + dD, Nernst equation becomes,
E=E0+ log
From the above equation, it can be concluded that
(1) When increases E increases
(2) The electrode potential E decreases as the increase in temperature.
(3) The electrode potential normally refers to the reduction reaction at an electrode.
Applications of Nernst equation
1. Nernst equation can be used to study the effect of electrolyte concentration on electrode
potential.
2. It can be used for the calculation of the potential of a cell under nonstandard conditions
3. Determination of unknown concentration of one of the ionic species in a cell is possible with
the help of Nernst equation, if E0(cell) and concentration of the other ionic species are known
4. The PH of a solution can be calculated from the measurement of electrode potential
Nernst equation can be used for finding the valency of an ion or the number of electrons
involved in the electrochemical reaction.
 Calculate the equilibrium constant for Daniel cell at 25 0C. E0cell= 1.1V.
Log K = = = 37.22
37
K = 1.68 X 10
 Calculate the standard emf of H2 – O2 fuel cell. (E0values for hydrogen and oxygen half
cells are -0.40V & 0.83V respectively.
Eocell = E0Cathode – E0Anode = E0O2 – E0H2= 0.83 – (-0.40) = 1.23V
0
 At 25 C the standard emf of a cell having reaction involving two electron charge is found to
be 0.295V. Calculate the equilibrium constant of the reaction.
Log K = = =10
10
K = 10
 What is the concentration of Ni2+ in the cell at 250C, if the emf is 0.601V? Given that E 0
Ni(s)/Ni2+ is -0.25V & E0 Cu(s)/Cu2+ is 0.34V. Ni(s)/Ni2+ (a=?)//Cu2+ (0.75M)/Cu(s).

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 Ecell = Eocell + log
Where = 0.34 –( -0.25) = 0.59, Ecell= 0.601V
Eocell
0.601 = 0.59 + 0.0295 log
= log
= 2.356.
Therefore [Ni2+] = 0.3183M

 Calculate the emf of the cell Zn/Zn2+ (0.01M)//Cu2+ (0.1M)/Cu. Write its half-cell reactions
isE0Zn is -0.76V and E0Cu is +0.34V.
The cell reaction is
Zn(s) + Cu2+ (aq) → Zn2+(aq) + Cu(s)
Nernst equation for this cell reaction is
E cell = E0 cell + log
But E0cell = E0R –E0L= 0.34 + 0.76 =1.1V
Therefore E cell = 1.1+ log =1.1295V
 Calculate the equilibrium constant of the reaction, Cu + 2Ag+ → Cu2+ + 2Ag
(E0 Ag(s)/Ag+ is 0.80V & E0 Cu2+ /Cu(s) is 0.34V.)
= E0 Ag(s)/Ag+ - E0 Cu2+ /Cu(s) = 0.80 – 0.34 = 0.46
Log K = = = 15.57
15
K = 3.775 x 10
 Calculate the emf of the following cell at 250C,
Zn|Zn2+(a = 0.0004) || Cd2+(a = 0.2) |Cd; ( E0Cd2+ /Cd =-0.403V & E0Zn2+/Zn =-0.76V)
E0cell = E0cathode – E0anode = E0Cd2+/Cd – E0Zn2+/Zn = -0.403 +0.76
= 0.357V
0
E cell = E cell + log =0.357 + log
= 0.4367V
 Find the single electrode potential for copper metal in contact with0.1M Cu 2+ solution at
298K. E0Cu2+/Cu = 0.34V
ECu = E0Cu + log [Cu2+] = 0.34 + log [0.1]
= 0.31045V
 Determine the standard emf of the cell and standard free energy change of the cell reaction.
Zn, Zn2+ || Ni2+, Ni. The standard reduction potentials of Zn2+, Zn and Ni2+, Ni half cells are
- 0.76 V and - 0.25 V respectively.
Eocell = E cathode - E anode = - 0.25 - (- 0.76) = + 0.51 V
Eocell is + ve and ∆Go should be - ve.
∆Go = - n FEocell
∆Go = - (2X 96500 X 0.51) = - 98430 Joules
 Calculate the amount of electrical energy available from dry cell of EMF 1.5 V which
consumes 10g Zn.( At wt. of Zn = 65.5g)
∆G = -nFE = -2X96500X1.5 = 289500J
Therefore electric energy available for 10g Zn = = 44198 J

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Types of electrodes
1) Metal-metal ion electrode
2) Gas electrode
3) Metal-metal insoluble salt electrode
4) Redox electrode
5) Ion selective electrode
1. Metal-metal ion electrode
A metal is immersed in its own ionic solution, resultant electrode is called
metal-metal ion electrode.
Zn/Zn2+, Cu/Cu2+
E cell = E0 cell + 0.0591 log [Zn2+]
Here the electrode potential depends on the [Mn+]
2. Gas electrode
In gas electrode, gas is passed through an inert electrode like platinum which is
immersed in a solution containing its own ion.
Hydrogen electrode (Pt/H2/H+)
Here the electrode potential depends on the [ion] and the pressure at which gas is
bubbled.
3. Metal-metal insoluble salt electrode
In metal-metal insoluble salt electrode, metal is covered with a paste of its
insoluble metal salt which is in contact with a solution containing a common ion with the
insoluble salt.
Hg/Hg2Cl2/KCl
Ecal = E0cal - log [Cl-]2= E0cal - log[Cl-]
Here the electrode potential depends on the [common ion]
4. Redox electrode
An electrode is in contact with a redox system is called redox electrode.
Pt|Fe2+|Fe3+, Pt|Ce4+|Ce3+.
E cell = E0 cell + 0.0591 log
In these electrodes the electrode potential depends on the ratio of concentration of all
ionic species involved in the redox reaction.
5. Ion selective electrode
In this electrode, the sensing part of the electrode is made up of an ion selective
membrane.
Eg. Glass electrode consists of an ion selective membrane sensitive to H+ ions.
Reference electrode
It is not possible to find out the absolute value of electrode potential, since neither
oxidation nor reduction takes place independently both occur simultaneously. Hence we can find
out the relative value of electrode potential by coupling it with universally accepted reference
electrode.
An ideal reference electrode is one whose potential is accurately known, constant and
is completely sensitive to the concentration of analyte solution.
Types of reference electrodes
Reference electrodes are of two types. They are
1. Primary reference electrode (SHE)

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2. Secondary reference electrode (Calomel electrode and glass electrode)
Standard Hydrogen Electrode (SHE)
It consists of platinum foil coated with Pt black which is immersed in a solution of 1M
HCl. Hydrogen gas at 1atm pressure is bubbled over the electrode

Characteristics of SHE
1. Its potential is arbitrarily fixed as zero.
2. It is reversible electrode, i.e. it can function as an anode or cathode depending on the nature of
the other electrode to which it is connected.
If it functions as an anode, it can be represented as
Pt, H2 (g) 1atm / H+ (1M)
Cell reaction:
½ H2 → H+ + 1e-
If it functions as a cathode, it can be represented as
H+ (1M)/ H2 (g) 1atm, Pt
Cell reaction:
H+ + 1e-→ ½ H2

Uses:
It is used for determining unknown potential of an electrode.
Working of SHE (Determination of Eº using SHE)
Consider a Zinc rod dipped in ZnSO4 solution of 1M concentration which is coupled
with SHE externally using voltmeter and internally through salt bridge. Now, the resultant cell
can be represented as,
Zn(S)/ Zn2+ (1M)//H+(1M)/Pt, H2 (g) 1atm

E0 Cell = E0cathode – E0anode

= E0 SHE-E0Zn/Zn2+
0.76 V = 0 - E0 Zn/Zn2+
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 E0Zn/Zn2+= -0.76V
Eº Cell can be directly read out from the voltmeter and Eº Cathode is zero. Hence we can find
out EºAnode(EºZn).
Draw backs of SHE
1. It is very difficult to set up.
2. It cannot be used as a reference electrode if the solution contains reducible substances such as
copper, silver etc.
3. It causes poisoning of the Pt foil.
Secondary Reference Electrode
Secondary Reference Electrode is a reference electrode with known constant potential
and can be coupled with other electrodes to determine the unknown potential.
Calomel Electrode

Calomel electrode consists of a glass having side tube on both sides. Mercury covered with a
paste of Hg2Cl2 is taken at the bottom the glass tube. Inside the glass tube 0.1N or 1N or
saturated KCl solution is taken. A Pt wire is dipped into the glass tube containing Hg, which
helps for electrical contact. Potential of calomel electrode depends on the concentration of KCl
solution taken in the glass tube.
Calomel electrode can be represented as, Pt,Hg(l)| Hg2Cl2(s)|KCl(sat)
Ecal = E0cal - log [Cl-]2= E0cal - log[Cl-]= E0cal - log[Cl-]
Saturated Calomel Electrode is generally used, since it is easy to set up and its emf will
not change with chemical reaction.
Oxidation
2Hg (l) → 2Hg+ + 2e-
2Hg+ + 2Cl- → Hg2Cl2
Overall oxidation reaction
2Hg (l)+ 2Cl-→ Hg2Cl2+ 2e-
Reduction
Hg2Cl2 → 2Hg+ + 2Cl-
2Hg+ + 2e- → 2Hg
Overall reduction reaction
Hg2Cl2+ 2e-→ 2Hg (l)+ 2Cl-
Overall reaction when oxidation takes place is just reverse of the overall reaction when reduction
takes place. Hence calomel electrode is reversible with respect to chloride ions.

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Working of Calomel electrode (Determination of electrode potential using calomel
electrode)
In order to measure the electrode potential of an electrode, (Zn electrode) it is
coupled with SCE using a digital volt meter. The volt meter reading will give the cell
emf. The reduction potential of SCE is 0.2422V is higher than the reduction potential of
Zn2+/Zn (-0.76V). Therefore reduction reaction takes place at SCE.

Hg2Cl2 + 2e- →2Hg + 2Cl-

Zn → Zn2+ + 2e-
The resultant cell can be represented as
Zn/Zn2+//KCl(sat)/Hg2Cl2(s)/Hg(l)/Pt
E cell = ER – EL = Ecal – E Zn/Zn2+ = 0.2422 - E Zn/Zn2+
E Zn/Zn2+ = 0.2422 - E cell
E cell can be read directly from volt meter.
Advantages of Calomel electrode
1. It is very easy to set up.
2. Its emf will not change with chemical reaction.
Glass electrode
Glass electrode is a secondary reference electrode. Corning 015glass has been
used for making glass electrode. It is a special type of glass with low melting point
and high electrical conductivity. It consists of 72% SiO2, 6% CaO & 22% Na2O.
Construction;
It consists of a thin glass bulb in which Ag wire coated AgCl is used as an internal reference
electrode. It is then filled with 0.1N HCl solution.

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 Ag,AgCl(s)/HCl(0.1N)/Glass//
Glass electrode works on the principle that potential difference between thesurface of the glass
membrane and a solution is a linear function of P H. Here the glass membrane acts as an ion
selective membrane sensitive to [H+]. So an ion exchange reaction occurs between singly
charged cations of glass (Na+) & H+ ions of solution.Finally an equilibrium is established
between (Na+) ions of glass & H+ ions of solution.
H+(solution) + Na+Gl-→Na+(solution) +H+Gl-
EG = E0G + 0.0591 log [H+] = E0G - 0.0591 PH
The potential of glass electrode varies with concentration of H + ions. E0 G is constant and it
depends on the nature of the glass and also the PH of the solution taken inside the glass bulb.
E0G= 0.6990 V
The concentration of H+ ion inside the glass is constant,i.e. PH is constant. But when it is dipped
into a solution of unknown PH, concentration of H + ion inside the glass bulb changes. As a result,
PH changes. This results in the development of a potential difference.
Determination of PH using glass electrode
Glass electrode is used as an internal reference electrode. In order to determine the unknown PH
of a solution, glass electrode is coupled with SCE and the resultant cell can be represented like
this, Ag,AgCl(S)/0.1N HCl/Glass/Solution of Unknown PH// KCl (sat)/Hg2Cl2(s)/Hg(l)/Pt

Ecell = ER - EL = ESCE - EG
= 0.2422 – (E0G - 0.0591 PH)
= 0.2422 – E0G + 0.0591 PH
H
E0G of glass electrode can be determined by using a solution of known P .
0.0591 PH = Ecell + E0G – 0.2422
PH =

Advantages of glass electrode

1. It is very simple to operate.

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2. It can be use to find the PH of oxidising, reducing and even coloured solutions.
3. Glass electrode works effectively in the PH range of 1-9 and is unaffected by oxidising,
reducing and poisoning agents.
4. Electrodes made of special glasses can be used upto a PHof 12.
Draw backs of glass electrode
1. It cannot be used as a reference electrode for solutions having PH greater than 12.
2. Glass membrane has very high resistance. So ordinary potentiometers cannot be used for
determining potential of electrode instead special electronic potentiometers has to be used.

 Find out the pH of a solution measured using Hydrogen electrode which is coupled with
saturated calomel electrode. EMF of the combined cell is 0.523V at 250C. Given that
ESCE= 0.2422V.
E cell = E cal – EH2 = 0.2422 + 0.0591 PH = 0.523V
PH = = 4.75
 Potential of H2 electrode set up in acid solution of unknown strength is 0.295 volts
at 250C when coupled with SHE. Find the PH of the solution.
EH2 = E0H2 + 0.0591 log [H+] = -0.0591PH
E Cell = E Cathode – E Anode = E SHE - EH2 = 0 + 0.0591 PH = 0.0591PH
PH = = = 4.99
 Find out the PH of a solution in which a glass electrode is dipped and is coupled with
SCE. The EMF of the combined cell is 0.205V at 25°C. Given that E SCE = 0.2422V and
E° Glass = 0.57V.
PH = = = 9.02
Primary and secondary cells
Cells which becomes dead over a period of time, because the chemical reaction occurs only
once. After that the cell becomes exhausted or discharged.They cannot be recharged or reused
again.
Eg. Dry cell, daniel cell, mercury cell etc.
Daniel cell
It is also called electrochemical cell or voltaic cell
It consists of Zn rod dipped in ZnSO4 solution and Cu rod dipped inZCuSO4 solution. These
two electrodes are connected externally using a volt meter and internally using salt bridge. The
resultant cell can be represented like this.

Zn(s)/Zn2+(aqs)//Cu2+(aqs)/Cu(s)

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Types of electrodes
1) Metal-metal ion electrode
2) Gas electrode
3) Metal-metal insoluble salt electrode
4) Redox electrode
5) Ion selective electrode
1. Metal-metal ion electrode
A metal is immersed in its own ionic solution, resultant electrode is called
metal-metal ion electrode.
Zn/Zn2+, Cu/Cu2+
E cell = E0 cell + 0.0591 log [Zn2+]
Here the electrode potential depends on the [Mn+]
2. Gas electrode
In gas electrode, gas is passed through an inert electrode like platinum which is
immersed in a solution containing its own ion.
Hydrogen electrode (Pt/H2/H+)
Here the electrode potential depends on the [ion] and the pressure at which gas is
bubbled.
3. Metal-metal insoluble salt electrode
In metal-metal insoluble salt electrode, metal is covered with a paste of its
insoluble metal salt which is in contact with a solution containing a common ion with the
insoluble salt.
Hg/Hg2Cl2/KCl
Ecal = E0cal - log [Cl-]2= E0cal - log[Cl-]
Here the electrode potential depends on the [common ion]
4. Redox electrode
An electrode is in contact with a redox system is called redox electrode.
Pt|Fe2+|Fe3+, Pt|Ce4+|Ce3+.
E cell = E0 cell + 0.0591 log
In these electrodes the electrode potential depends on the ratio of concentration of all
ionic species involved in the redox reaction.
5. Ion selective electrode
In this electrode, the sensing part of the electrode is made up of an ion selective
membrane.
Eg. Glass electrode consists of an ion selective membrane sensitive to H+ ions.
Reference electrode
It is not possible to find out the absolute value of electrode potential, since neither
oxidation nor reduction takes place independently both occur simultaneously. Hence we can find
out the relative value of electrode potential by coupling it with universally accepted reference
electrode.
An ideal reference electrode is one whose potential is accurately known, constant and
is completely sensitive to the concentration of analyte solution.
Types of reference electrodes
Reference electrodes are of two types. They are
1. Primary reference electrode (SHE)

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2. Secondary reference electrode (Calomel electrode and glass electrode)
Standard Hydrogen Electrode (SHE)
It consists of platinum foil coated with Pt black which is immersed in a solution of 1M
HCl. Hydrogen gas at 1atm pressure is bubbled over the electrode

Characteristics of SHE
1. Its potential is arbitrarily fixed as zero.
2. It is reversible electrode, i.e. it can function as an anode or cathode depending on the nature of
the other electrode to which it is connected.
If it functions as an anode, it can be represented as
Pt, H2 (g) 1atm / H+ (1M)
Cell reaction:
½ H2 → H+ + 1e-
If it functions as a cathode, it can be represented as
H+ (1M)/ H2 (g) 1atm, Pt
Cell reaction:
H+ + 1e-→ ½ H2

Uses:
It is used for determining unknown potential of an electrode.
Working of SHE (Determination of Eº using SHE)
Consider a Zinc rod dipped in ZnSO4 solution of 1M concentration which is coupled
with SHE externally using voltmeter and internally through salt bridge. Now, the resultant cell
can be represented as,
Zn(S)/ Zn2+ (1M)//H+(1M)/Pt, H2 (g) 1atm

E0 Cell = E0cathode – E0anode

= E0 SHE-E0Zn/Zn2+
0.76 V = 0 - E0 Zn/Zn2+
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 E0Zn/Zn2+= -0.76V
Eº Cell can be directly read out from the voltmeter and Eº Cathode is zero. Hence we can find
out EºAnode(EºZn).
Draw backs of SHE
1. It is very difficult to set up.
2. It cannot be used as a reference electrode if the solution contains reducible substances such as
copper, silver etc.
3. It causes poisoning of the Pt foil.
Secondary Reference Electrode
Secondary Reference Electrode is a reference electrode with known constant potential
and can be coupled with other electrodes to determine the unknown potential.
Calomel Electrode

Calomel electrode consists of a glass having side tube on both sides. Mercury covered with a
paste of Hg2Cl2 is taken at the bottom the glass tube. Inside the glass tube 0.1N or 1N or
saturated KCl solution is taken. A Pt wire is dipped into the glass tube containing Hg, which
helps for electrical contact. Potential of calomel electrode depends on the concentration of KCl
solution taken in the glass tube.
Calomel electrode can be represented as, Pt,Hg(l)| Hg2Cl2(s)|KCl(sat)
Ecal = E0cal - log [Cl-]2= E0cal - log[Cl-]= E0cal - log[Cl-]
Saturated Calomel Electrode is generally used, since it is easy to set up and its emf will
not change with chemical reaction.
Oxidation
2Hg (l) → 2Hg+ + 2e-
2Hg+ + 2Cl- → Hg2Cl2
Overall oxidation reaction
2Hg (l)+ 2Cl-→ Hg2Cl2+ 2e-
Reduction
Hg2Cl2 → 2Hg+ + 2Cl-
2Hg+ + 2e- → 2Hg
Overall reduction reaction
Hg2Cl2+ 2e-→ 2Hg (l)+ 2Cl-
Overall reaction when oxidation takes place is just reverse of the overall reaction when reduction
takes place. Hence calomel electrode is reversible with respect to chloride ions.

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 R=ρx
Conductance:
It is the reciprocal of resistance.
C=
Specific Resistance (Resistivity):
It is the resistance of a conductor of unit length and unit area of cross section. Or it is the
resistance of unit volume of a conductor. Its unit is Ωcm
ρ=Rx
Specific Conductance (Conductivity):
It is the reciprocal of resistivity. It is also defined as the conductance of unit length and
unit area of cross section of a conductor. Its unit is Scm-1
K= X =CX
Molar conductance:
Molar conductance is the conductance of a solution containing 1mol of an electrolyte
which is placed between two electrodes which are separated by unit distance. It is denoted by the
letter λm. Its unit is Scm-1 mol-1.
λm =
Equivalent conductance:
Equivalent conductance is the conductance of a solution containing 1gram equivalent of
an electrolyte which is placed between two electrodes which are separated by unit distance. It is
denoted by the letter λ. Its unit is Scm-1equi-1.
λ=
The experimental arrangement and procedure for measuring conductance of an
electrolytic solution
Conductivity of the solution = C X = X
Thus for the measurement of conductivity of solution resistance of the solution is to be
determined. Wheat stone bridge method is used for this purpose. In this method, a conductivity
cell containing the solution is made one arm of the wheat stone bridge apparatus. The electrodes
of the cell are made up of platinum coated with platinum black. Then the conductivity cell is
placed in a thermostat to keep the temperature constant. In order to prevent electrolysis, an
Alternating Current is used. When current passes through the circuit, the resistors R2, R3 and R4
are so adjusted that a null point is obtained in the detector.

At the null point,

𝐑𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 𝐑𝟑 𝐑𝟐𝐑𝟑
= 𝐑𝟒 R solution =
𝐑𝟐 𝐑𝟒

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The reciprocal of this resistance will give the conductance of the solution. From the conductance
we get the specific conductance of the solution. Since conductivity of the solution = C X , where
‛l’ is the distance between the electrodes and ‛A’ is the area of cross section of electrodes. For a
particular conductivity cell, is constant and is called cell constant.

K = C X Cell constant

𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒊𝒗𝒊𝒕𝒚 𝑲
Cell constant =𝑪𝒐𝒏𝒅𝒖𝒄𝒕𝒂𝒏𝒄𝒆 = 𝑪

PROBLEMS
1. The specific conductivity of ⁄ KCl solution at 250C is 0.0002765ohm-1cm-1. If the
resistance of the cell containing this solution is 500Ω, what is its cell constant?
K=CX = X
Cell constant = K X R = 0.0002765 X 500 =0.13825cm-1
2. The specific conductance of a decinormal solution of KCl at 18º C is 0.0112Ω -1cm-1. The
resistance of the cell containing the solution at 18º C was found to be 55Ω. What is cell
constant.
K = C X = X = X cell constant = 0.0112Ω-1cm-1
Cell constant = K X R = 0.0112 X 55 = 0.616 cm-1
3. Find the specific conductance of a given solution at 298K. The resistance of the solution and
0.1M KCl solution are found to be 75k Ω and 300k Ω respectively at 298K in the same
conductivity cell. Specific conductance of KCl is 0.012Scm-1.
K=CX = X = X cell constant = 0.012Scm-1
Cell constant = K X R = 0.012 X 300 = 3.6 cm-1
K = C X = X Cell constant = X 3.6 = 0.048Scm-1
4. The decinormal solution of an electrolyte in a conductivity cell whose electrodes are 2.1 cm
apart and 4.2 cm2 in area offered a resistance of 32 Ω. Find the equivalent conductance of the
solution.
λEq = = = = 156.25 S cm-1 Eq -1
5. Calculate the conductivity of given NaCl solution at 298K, which shows a conductance of 560
𝝁Ω-1 in the given cell at 298K. A standard solution of 0.1M KCl shows a conductance of
1200𝝁Ω-1 in that cell. Given that conductivity of 0.1M KCl at 298K is 0.01288 Ω -1 cm-1.
K KCl = CKCl X Cell constant
Cell constant = = = 10.73 cm-1
K NaCl = CNaCl X Cell constant = 560 X X 10.73 = 6.01 X Ω-1 cm-1
Corrosion
Corrosion is the slow process of deterioration or destruction of the metal through the
chemical or electrochemical changes taking place at its surface. Corrosion reactions are of two
types. On the basis of this, theories of corrosion are of two types.
I. Dry corrosion (Chemical corrosion)
II. Wet corrosion (Electrochemical corrosion)
I. Dry corrosion:

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 Corrosion of this type gases occurs by the direct chemical attack of atmospheric gases on the
metal in the absence of moisture. They are of three types.
1. Oxidation corrosion
2. Corrosion by other gases
3. Liquid metal corrosion
1. Oxidation corrosion:
It occurs due to the direct action of oxygen on metals in the absence of moisture to form
metal oxide. Alkali metals and alkaline earth metals undergo this type of corrosion even at low
temperature, whereas noble metals like gold, silver and platinum undergo oxidative corrosion
only at high temperature.
Mechanism:
Oxidation occurs at the surface of the metal to form the metal oxide. On oxidation, the metal
atoms change to metal ions (Mn+) and oxygen changes to oxide ions (O2-). These oppositely
charged ions then combine together to form the metallic oxide.
2M → 2Mn+ + 2ne- (Oxidation)
nO2 + 2ne- → 2nO2- (Reduction)
2M + nO2 → 2Mn+ + 2nO2-(Overall reaction)
Thus a thin layer of metal oxide is formed on the surface of the metal. The nature of the oxide
film determines the further destruction of the metal. Films can be of different types.
a) Stable film:
Stable films can adhere tightly to the metal surface. This film can act as a protective coating
to prevent further deterioration of the metal. Oxide films of Al, Sn, Cu, Pb etc. are included in
this film.
b) Unstable films:
Unstable films readily decompose back to metal and oxygen. In this case metal will not
undergo further deterioration. This type of film is obtained in the case of metals like gold, silver
and platinum.
c) Volatile film:
This type of film volatalises off as soon as it is formed. Hence the underlying metal surface
again becomes exposed for further attack of oxygen and this process continues. Here corrosion
becomes a continuous process and the observed destruction will be maximum. Molybdenum can
produce volatile oxide film.
d) Porous oxide film:
If the oxide film formed is porous, then the atmospheric oxygen can penetrate through the
film to attack the underlying metal. Here also corrosion becomes a continuous process leading to
the total destruction of the metal. Iron can produce this type of film.
2. Corrosion by other gases:
Similar to oxygen, some other gases also bring dry corrosion. They are SO 2, CO2, Cl2, H2S,
F2, H2 etc. Extend of corrosion is determined by its chemical affinity towards the metal. It also
depends upon the nature of the film, whether the film is porous or protective.
3. Liquid metal corrosion:
This type of corrosion is seen in nuclear power stations. It occurs due to the chemical action
of flowing liquid metal on solid metal or alloys at high temperature. In such cases, solid metal
may dissolve in the liquid metal or liquid metal may penetrate into the internals of solid metals.
II. Wet corrosion (Electrochemical corrosion)
This type of corrosion can occur when a conducting liquid is in contact with a metal or
when two dissimilar metals or alloys are partially immersed in a conducting solution.
Oxidation takes place at the anodic area, resulting in the corrosion of the metal.
M → Mn+ + 2ne- (Oxidation)
n+
The M ions so formed dissolves in the solution.

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 Reduction occurs at the cathodic area. At the cathodic area, the dissolved constituents in the
conducting medium accept electrons to form ions like OH -, O2- etc. The non-metallic ions so
formed combine with the Mn+ to form corrosion product. The electrons released at the anode
flow through the metal and get consumed in the cathodic reaction, either for the evolution of
hydrogen or for the absorption of oxygen.
2H+ + 2e- → H2 (g)
½ O2 + H2O + 2e- → 2OH-
Corrosion with evolution of H2 occurs, when the anodic area is very large and cathodic area is
small and it usually occurs in acidic environments. Absorption of O2 occurs in neutral or slightly
alkaline medium.
Rusting of iron
In this initially a thin film of iron oxide is formed on the surface of iron metal. Some cracks
are developed on the iron oxide film. The surface of the metal acts as the anodic area, whereas
the interior of the metal behaves as cathode.
At the anodic area, Fe dissolves as Fe2+ ions with the liberation of electrons.
Fe → Fe2+ + 2e- (Oxidation)
The electrons thus released from the anode move to the cathodic area through the metal. These
electrons are then taken up oxygen molecule to form OH- ions.
½ O2 + H2O + 2e- → 2OH-
The Fe2+ ions formed at the anodic area and the OH- ions formed at the cathodic area combine to
form Fe(OH)2 precipitate.
In the presence of excess of oxygen, Fe(OH) 2 precipitate easily oxidises to get yellow rust having
the formula, Fe2O3.2H2O
2Fe(OH)2 + ⁄ O2 → Fe2O3.2H2O
If the amount of oxygen is limited, then the corrosion product is black rust (Hydrated magnetite)
3Fe(OH)2 + ⁄ O2 → Fe3O4.3H2O
Galvanic series
Relative corrosion affinities of metals and alloys can be explained by using a series called
galvanic series. This series can be prepared by studying the corrosion affinities of metals and
alloys in unpolluted sea water without their oxide films. A metal high in this series is more
anodic and undergoes corrosion faster than the metal below it. The position of a metal in the
form of an alloy is different from that of the pure metal in this series.

Comparison of electrochemical series and galvanic series

Electrochemical Series Galvanic series
 E is measured only for metals and non-  E is measured only for metals and alloys.
o o

metals.
 Eo is measured by dipping pure metals in  Eo is measured by dipping metals and alloys in
their 1M salt solution. unpolluted sea water.
 SHE is used as the reference electrode.  Calomel electrode is used as the reference
electrode.
 Position of the metals is fixed.  Position of the metal and alloys may change.
 It predicts the relative displacement  It predicts the corrosion tendencies.
tendencies.

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 R=ρx
Conductance:
It is the reciprocal of resistance.
C=
Specific Resistance (Resistivity):
It is the resistance of a conductor of unit length and unit area of cross section. Or it is the
resistance of unit volume of a conductor. Its unit is Ωcm
ρ=Rx
Specific Conductance (Conductivity):
It is the reciprocal of resistivity. It is also defined as the conductance of unit length and
unit area of cross section of a conductor. Its unit is Scm-1
K= X =CX
Molar conductance:
Molar conductance is the conductance of a solution containing 1mol of an electrolyte
which is placed between two electrodes which are separated by unit distance. It is denoted by the
letter λm. Its unit is Scm-1 mol-1.
λm =
Equivalent conductance:
Equivalent conductance is the conductance of a solution containing 1gram equivalent of
an electrolyte which is placed between two electrodes which are separated by unit distance. It is
denoted by the letter λ. Its unit is Scm-1equi-1.
λ=
The experimental arrangement and procedure for measuring conductance of an
electrolytic solution
Conductivity of the solution = C X = X
Thus for the measurement of conductivity of solution resistance of the solution is to be
determined. Wheat stone bridge method is used for this purpose. In this method, a conductivity
cell containing the solution is made one arm of the wheat stone bridge apparatus. The electrodes
of the cell are made up of platinum coated with platinum black. Then the conductivity cell is
placed in a thermostat to keep the temperature constant. In order to prevent electrolysis, an
Alternating Current is used. When current passes through the circuit, the resistors R2, R3 and R4
are so adjusted that a null point is obtained in the detector.

At the null point,

𝐑𝐬𝐨𝐥𝐮𝐭𝐢𝐨𝐧 𝐑𝟑 𝐑𝟐𝐑𝟑
= 𝐑𝟒 R solution =
𝐑𝟐 𝐑𝟒

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required can be obtained from a battery with an insoluble anode made of graphite or high silica
iron. This method is used for the protection of open water box coolers, water tanks etc.

Comparison of sacrificial anode protection and impressed current cathodic protection

Sacrificial anode protection Impressed current cathodic protection

 No external power supply is required.  External power supply is required.
 Economical for short term protection.  More suitable for long term protection.
 Investment is less.  High investment is required.
 Requires periodical replacement of anodic  Anodes are relatively stable and do not
material. corrode.
 Suitable when current requirements and  Suitable when current requirements and
resistivity of the electrolyte are relatively resistivity of the electrolyte are relatively
low. high.
Electroless plating (Autocatalytic plating)
It is the method of depositing a metal from its salt solution on the catalytically active
surface of the metal to be plated using a suitable reducing agent without using electrical energy.
In this process, metal piece to be plated is immersed in a mixture of reducing agent and a
complex compound. The reducing agent reduces metal ion into metal which gets plated over the
catalytically active surface of the metal to produce a thin uniform coating. This process is a
controlled chemical reduction and is catalyzed by the metal or alloy being deposited. This
method allows the easy preparation of films of low thickness using simple equipments. Most
common electroless plating is electroless nickel plating.
Electroless Nickel plating
Pretreatment and activation of the surface
The surface to be plated is first degreased by using organic solvents or alkali. It is then
followed by acid treatment. Surface of stainless steel is then activated by dipping in a hot
solution of 50% dil.H2SO4. Mg alloy surface can be activated by thin coating of Zn and Copper
over it. Metals like Cu, Al and alloys like brass can be directly Ni plated without activation. Non-
metallic articles like plastics, glasses are activated by dipping them in the solution of SnCl2 and
HCl followed by dipping in PdCl2 solution. A thin layer of Pd will be formed on the surface
upon drying.
Procedure
The pretreated object is immersed in the plating bath containing Nickel sulphate salt
(Coating), hypophosphate reducing agent (Metal deposition), complexing agent like Sodium
succinate (Quality improvement) and a buffer like Sodium Acetate (P H maintenance). Air is then
applied and heated. Electroless plating of Ni takes place as follows.

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 NiSO4 + NaH2PO2 + H2O → Ni (Plated) + NaH2PO3 + H2SO4
Applications of electroless Ni plating
 It is extensively used in electronic applications.
 Electroless Ni plated polymers like ABS are used for decoration purpose.
 It is also used automotive fields.
Advantages
 No electricity is required.
 This can be carried out on insulators on insulators and semiconductor materials.
 This can be used to obtain uniform coating on irregular shaped objects.
 These deposits are more compact and highly adherent.
Electroless Copper plating
In this method, article to be plated is immersed in a plating bath containing CuSO 4 (As a
source of Cu), formaldehyde (Reducing Agent), buffer solution of NaOH and Rochelle salt and a
complexing reagent. Air is bubbled slowly through the medium to control the formation of
cuprous oxide. Electroless plating of Cu takes place as follows.
Oxidation
2HCHO + 4OH- → H2 (Gas) + 2HCOO- + 2H2O +2e-
Reduction
Cu2+ + 2e- → Cu
Net reaction
2HCHO + 4OH- + Cu2+ → H2 (Gas) + 2HCOO- + 2H2O + Cu
Applications of electroless Cu plating
 Widely used for metalizing printed circuit boards.
 Used for plating on non-conductors.
 It is also used for making decorative plating on plastics.
Advantages
 This method produces even coatings.
 It does not use electrical power.
 This coating is having improved hardness, strength, ductility and resistance to corrosion.
Disadvantages
 The reducing agent, formaldehyde is a human health hazard.
 The instability of the electroless copper bath creates difficulties in process control.

Prepared by Raji Sankar, Assistant Professor

Dept. of mathematics & Basic sciences,
Sree Buddha College of Engineering, Pattoor

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