Course: Applied Chemistry (1004)

UNIT IV - ELECTROCHEMISTRY & CORROSION

INSULATORS
Substances which do not allow the passage of electricity through them are called insulators.
Eg:- Plastic, glass, rubber etc.

CONDUCTORS
Substances which allow the passage of electricity through them are called conductors.
Eg:- Metals, Graphite, Electrolytes etc.

METALLIC CONDUCTORS (Electronic conductors)

These conductors allow the passage of electricity through them without undergoing any
chemical change.
Eg:- Aluminium, Copper, Silver etc.
In metallic conductors, conduction is due to the direct flow of electrons.

ELECTROLYTES & NON-ELECTROLYTES

Substances which conduct electricity either in molten state or in aqueous solutions are called
electrolytes.
Eg:- Molten NaCl, KCl solution etc
Substances which do not conduct electricity either in molten state or in aqueous solutions are
called non-electrolytes.
Eg: Sugar, Urea etc.

STRONG ELECTROLYTES
The electrolytes which are almost completely dissociated into ions in solution are called strong
electrolytes.
Eg:- HCl , KCl , NaOH , KOH etc.

WEAK ELECTYROLYTES
The electrolytes which do not ionize completely in solution are called weak electrolytes.
Eg:- CH3COOH, NH4OH , H2CO3 etc.

DIFFERENCES BETWEEN METALLIC CONDUCTORS AND ELECTROLYTIC CONDUCTORS

Metallic conductors Electrolytic conductors

1.In metallic conductors, the conduction is due 1. In electrolytic conductors, the conduction
to the direct flow of electrons. is due to the movement of ions
2. No chemical change take place due to conduction 2. It involves the decomposition of
electrolyte due to chemical reaction.
3. It does not involve the transfer of matter 3. It involves the transfer of matter as ions
4. Metallic conduction decreases with increase of 4. Electrolytic conduction increases with
temperature increase of temperature.

ELECTROLYSIS & ELECTROLYTIC CELL

It is the process of decomposition of an electrolyte by the passage of electricity through it. In
this process, electrical energy is converted to chemical energy.
 The device used to carry out the electrolysis is called electrolytic cell.

ELECTROLYSIS OF MOLTEN NaCl

Molten NaCl is taken in a container and two electrodes are dipped in it (cathode and anode).
These electrodes are then connected to a battery and electric current is passed thorough the molten
NaCl in the container. Molten NaCl contains Na + ions and Cl – ions.
On passing electric current, Na + ions move towards cathode and Cl – ions move towards anode.
At cathode, Na+ ions undergo reduction and gets deposited as sodium metal
Na + + e - --------------------→ Na ( Reduction)
–
At anode, Cl ions undergo oxidation and gets liberated as Cl2 gas.

Cl - ----------------------→ Cl + e – (Oxidation)
Cl + Cl ------------------→ Cl2(g)
ie, after electrolysis, sodium metal is deposited at the cathode and Cl2 gas is liberated from the anode.

FARADAY’S FIRST LAW OF ELECTROLYSIS

According to this law, the mass of substance deposited or liberated at an electrode as a result of
electrolysis is directly proportional to the quantity of electricity passed through the electrolyte.

m=zQ

where, m = mass of substance produced at the electrode

z = electrochemical equivalent (ece) of the substance deposited at the electrode
Electrochemical equivalent is the mass of substance produced at the electrode by passing a current
of One Ampere for one second through the electrolyte.

m = z It

where, I = strength of current in Amperes,

t = time in seconds
Q = Quantity of electric current
Problem 1
Calculate amount of Cu deposited when 8 A current is used for 30 minutes to electrolyse
CuSO4 solution. (ece of copper is 0.000329 g/Coulomb)
Ans:-
 m = mass of Cu deposited = ?
z = electrochemical equivalent of Cu = 0.000329 g/C
I = strength of current = 8 A
t = time = 30 minutes = 30 X 60 s = 1800 s
m = z I t = 0.000329 X 8 X 1800 = 4.737 g
Problem 2
Find the mass of the copper metal produced during passage of 4 A current through copper
sulphate solution for 20 minutes. (ece of copper is 0.000329 g/Coulomb)
Ans:-
m = mass of Cu deposited = ?
z = electrochemical equivalent of Cu = 0.000329 g/C
I = strength of current = 4 A
t = time = 20 minutes = 20 X 60 s = 1200 s

m = z I t = 0.000329 X 4 X 1200 = 1.5792 g

FARADAY’S SECOND LAW OF ELECTROLYSIS

When same quantity of electricity is passed through solutions of different electrolytes, the
masses of substances deposited at the respective electrodes are directly proportional to their
equivalent masses (equivalent weights)
m1/m2 = E1/E2

where m1 and m2 are the masses of substances deposited at the electrodes, E1 and E2 are equivalent
weights of the substances respectively.
Problem 1
Two electrolytic cells containing electrolytes CuSO4 and AgNO3 respectively were connected in
series and same quantity of electric current is passed through them until 1.5 g of Cu were deposited at
cathode of the cell. Calculate the mass of Ag deposited at the cathode of the electrolytic cell containing
AgNO3 solution. (Atomic weights of Cu and Ag are 63.5 and 108 respectively)
Ans:-
m Cu = mass of Cu deposited = 1.5 g
m Ag = mass of Ag deposited = ?
E Cu = Equivalent mass of Cu = Atomic mass = 63.5 = 31.75
Valency 2
E Ag = Equivalent mass of Ag = Atomic mass = 108 = 108
Valency 1
mCu = ECu
mAg EAg

ie, 1.5 = 31.75

mAg 108
.: mAg = 1.5 X 108 = 5.102 g
31.75
Problem 2
Two electrolytic cells containing electrolytes CuSO4 and AgNO3 respectively were connected in
series and same quantity of electric current is passed through them until 8.3 g of Cu were deposited at
cathode of the cell. Calculate the mass of Ag deposited at the cathode of the electrolytic cell containing
AgNO3 solution. (Atomic weights of Cu and Ag are 63.5 and 108 respectively)
Ans:-
m Cu = mass of Cu deposited = 8.3 g
m Ag = mass of Ag deposited = ?
E Cu = Equivalent mass of Cu = Atomic mass = 63.5 = 31.75
Valency 2
E Ag = Equivalent mass of Ag = Atomic mass = 108 = 108
Valency 1

mCu = ECu
mAg EAg

ie, 8.3 = 31.75

mAg 108

.: mAg = 8.3 X 108 = 28.23 g

31.75
FARADAY(F)
One Faraday is the electricity carried by one mole of electrons (ie charge carried by 6.022 X 10 23
electrons) 1 F = 96500 C

APPLICATIONS OF ELECTROLYSIS
Following are the important applications of electrolysis.
1.Electroplating
It is the process of producing thin coating of a metal on the surface of another metal by
electrolysis.
The object to be electroplated is taken as the cathode and the metal to be deposited on the object is
made the anode. The electrolyte is a solution of soluble salt of the superior metal. When electric
current is passed through the electrolyte solution, metal at the anode goes into the solution and gets
deposited in the form of a thin layer on the object (cathode).
Generally superior metals like gold, silver, nickel etc are deposited over inferior metals like iron,
copper etc.
Electroplating is mainly used to protect a metal from corrosion, to improve its physical appearance,
to modify its hardness etc.

Eg:-Electroplating of nickel on an object (mild steel spoon)

In this process, a Nickel plate is taken as anode and steel spoon is taken as cathode. The electrolyte
is a solution of Nickel sulphate. On passing electric current through the electrolyte solution, Nickel
from the anode undergoes oxidation to form Nickel ions
Ni -----→ Ni 2+ + 2 e – (oxidation)
The Ni 2+ ions then undergo reduction at the cathode and get deposited as a thin coating of Nickel
metal on the cathode (steel spoon)
N i 2+ + 2 e - -------→ Ni (reduction)

2.Electrolytic refining (or electrorefining)

It is the process of converting impure metal to pure metal with the help of electrolysis.
Eg:- Copper is refined using an electrolytic method. Anodes are of impure copper and pure copper
strips are taken as cathode. The electrolyte is acidified solution of copper sulphate and the net result of
electrolysis is the transfer of copper in pure form from the anode to the cathode.
 At anode : Cu -----------------→ Cu2+ + 2e- (oxidation)
(impure copper)

At cathode : Cu2+ + 2 e - ---------------→ Cu (reduction)

(pure copper)
3.Anodising
It is the process of producing a protective metal oxide coating on the surface of a metal like Al or
Mg by electrolysis
In this process, the metallic object is made the anode, cathode is graphite rod or lead sheet. The
electrolyte is an oxidizing electrolyte like dilute sulphuric acid or phosphoric acid.
On passing electric current through the electrolyte solution, an oxide layer is formed on the
surface of the metallic object (anode).
Anodizing is used to protect the objects from corrosion. It is also used for decorative purposes.
Oxidation, Reduction and Redox reactions

Oxidation is a process which involves loss of electrons.

eg:- Zn --------→ Zn 2+ + 2e-
Reduction is a process which involves gain of electrons.
eg:- Cu 2+ + 2e - --------→ Cu
Reaction which involves both oxidation and reduction is called redox reaction.
eg:- Zn + Cu2+ -----→ Zn 2+ + Cu

ELECTROCHEMICAL CELL (GALVANIC CELL OR VOLTAIC CELL)

It is the device used to convert chemical energy produced during redox reaction into electrical
energy.
eg:- DANIEL CELL
Daniel cell consists of two half cells ie, Zinc half cell (anode half cell) and Copper half cell
(cathode half cell).
In the zinc half cell, a zinc rod is dipped into ZnSO4 solution taken in a container. In the copper
half cell, a copper rod is dipped into CuSO4 solution taken in another container . These two
electrodes (zinc electrode and copper electrode) are then connected to a voltmeter through a wire.
The two half cells are connected by a salt bridge.

(Daniel cell)
 A salt bridge is an inverted U - tube containing salt solutions like KCl, KNO3 etc. When the
circuit is completed, it is observed that electric current flows through the external circuit. It is due to
the following reactions. (ie, reaction at Zn anode and Cu cathode).

At anode
Zn(s) -------→ Zn 2+ + 2 e – (oxidation)
At cathode
Cu 2+ + 2 e - -----→ Cu(s) (reduction)
The overall reaction (net reaction) is
Zn + Cu 2+ -----→ Zn2+ + Cu

Functions of salt bridge

A salt bridge helps to maintain electrical neutrality of the solutions in the two half cells and it helps
to complete the cell circuit.

Different types of Electrochemical cells

1.Primary cells
These are the cells which cannot be recharged. ie, the electrode reactions cannot be reversed by
passing electric current from an external source.
In primary cell, the redox reaction occur only once and the cell become inactive after completion
of the reaction. Eg:- Daniel cell, Dry cell, Mercury cell.
2.Secondary cells
These are the cells which can be recharged. ie, the electrode reactions can be reversed by
passing electric current from an external source.
eg:- Lead storage battery, Nickel-Cadmium cell (Nicad cell) etc.
FUEL CELLS
Fuel cells are Galvanic cells in which energy produced by the oxidation of fuels is directly
converted into electrical energy.
eg:- Hydrogen – Oxygen fuel cell.
Fuel cells are mainly used in space vehicles, in military vehicles, submarines. etc.
Advantages of fuel cells
Following are the advantages of fuel cells
1.In fuel cells, energy of the fuel is directly converted into electrical energy
2. They are light and compact
3.They do not cause pollution
4.They are more efficient
5.The energy supply is continuous
ELECTRODE POTENTIAL(E)
The tendency of an electrode to lose or gain electrons when it is in contact with a solution of its
own ions is called electrode potential. The tendency to lose electrons is called oxidation potential
where as the tendency to gain electrons is called reduction potential.
Standard Electrode Potential(Eo)
If the electrode is suspended in a solution of 1 M concentration and temperature is kept 298 K, the
electrode potential is called standard electrode potential.
Cell potential (Cell voltage or EMF of the cell)
The difference in potentials of two half cells of a cell is known as Electro Motive Force (EMF) of
the cell or cell potential.
ie, the difference between electrode potentials of the two half cells.
 Ecell = Ecathode – Eanode

Similarly, standard cell potential is given by the equation.

E o cell = Eo cathode - Eo anode

Problem
Calculate the standard emf (std cell potential) of the Daniel cell. The standard electrode potentials
of Cu and Zn are 0.34 V and -0.76 V respectively.
Ans: E o cell = Eo cathode - Eo anode
= EoCu - Eo Zn
= 0.34 - (-0.76) = 0.34 + 0.76 = 1.1 V
ELECTROCHEMICAL SERIES(Activity series)
The arrangement of elements in the order of increasing values of standard reduction potentials
is called electrochemical series.

APPLICATIONS OF ELECTROCHEMICAL SERIES

Following are the important applications of electrochemical series.
1. Electrochemical series helps to calculate the standard EMF of a Galvanic cell from the
standard electrode potential values.
2. Electrochemical series helps to compare the reactivity of metals.
3. Metals near the top of the series are strongly electropositive and lose electrons
readily.
4. It helps to predict the spontaneity of any redox reaction. If EMF of the cell is
positive, it is spontaneous, otherwise not.
5. The metals higher in the electrochemical series displaces other metals lower in the
series from their salt solutions.
6. It helps to compare the reducing and oxidizing powers of various elements used as
the electrodes.
CORROSION
It is the slow destruction of a metal due to it’s reaction with the gases in air and moisture
present in the atmosphere.
Due to corrosion the metal is converted to metal oxide, metal sulphide , metal carbonate etc.
Corrosion of iron is called rusting. (ie, the conversion of iron into hydrated ferric oxide ie, rust).

FACTORS AFFECTING CORROSION

Following are the factors affecting rate of corrosion.
1. Presence of impurities in the atmosphere
The presence of gases like CO2, H2S, SO2 etc in the atmosphere increases the speed of corrosion.
2. Temperature
Rate of corrosion increases with increase of temperature.
3. Air and moisture
Presence of moisture (humidity) in the air increases the rate of corrosion.
4.Presence of impurities in the metal
The rate of corrosion increases with the amount of impurities in the metal. Impure metals undergo
corrosion easily than pure metals.
5. Influence of pH
In acidic medium, the pH will be less than 7 and the corrosion will be more compared to neutral
medium and basic medium
6.Nature of corrosion product
If the corrosion product is insoluble compound then the rate of corrosion will be less.
7. Presence of Electrolyte
Corrosion will be faster in the presence of electrolytes. For example, iron undergoes rusting more
rapidly in saline water in comparison to pure water.
8. Reactivity of the metal
The more reactive metals are more easily corroded.
METHODS TO PREVENT CORROSION
Corrosion can be prevented by the following methods.
1.BARRIER PROTECTION (Protective coatings)
In this method, a protective coating is applied on the surface of the metal so that a barrier is made
between the metal surface and the atmosphere. Protective coatings may be:
Metallic coating ( eg:- coating of zinc over iron)
Non metallic coating eg:- chromate coating or anodizing (oxide coating)
Organic coating ( eg:- paint, plastic, rubber coating etc.)
2.Cathodic Protection
In this method, a reactive metal plate such as Zinc or Magnesium is connected to the metal to be
protected from corrosion.
eg:- Iron pipes are protected from corrosion by connecting them with metals like Zinc, Magnesium
etc.
In this case, Zinc or Magnesium undergoes oxidation and corroded instead of iron pipe. The iron
pipe becomes cathode and protected from corrosion.
4.ALLOYING WITH OTHER ELEMENTS
By converting the metal into alloys, corrosion can be prevented.
eg:- Stainless steel is an alloy of Iron
5. GALVANIZATION
The process of coating iron objects with zinc is called galvanization. As a result of galvanization,
the metal iron is protected from corrosion.
6. MAINTAINING PURITY OF METAL
Pure metals are corrosion resistant. By increasing the purity of the metal, corrosion can be
prevented.
7. BY USING ANTI RUST SOLUTIONS
It is the method in which alkaline phosphate or alkaline chromate solutions are used. So that
metal chromate or metal phosphate coatings are formed on the surface of the metallic objects. Such
coatings act as a protective coating, which helps to prevent corrosion.

QUESTIONS

1. What are metallic conductors? Give examples

2. What are electrolytes? Give examples.
3. Distinguish between metallic conductors and electrolytic conductors
4. Define electrolysis .
5. Explain electrolysis of molten NaCl
6. State Faraday’s first law and second law of electrolysis
7. Find the mass of the copper metal produced during passage of 4 A current through copper
sulphate solution for 25 minutes. (ece of copper is 0.000329 g/Coulomb)
8. Two electrolytic cells containing electrolytes CuSO 4 and AgNO3 respectively were connected in
series and same quantity of electric current is passed through them until 6.9 g of Cu were deposited
at cathode of the cell. Calculate the mass of Ag deposited at the cathode of the electrolytic cell
containing AgNO3 solution. (Atomic weights of Cu and Ag are 63.5 and 108 respectively)
9. What is electroplating? Explain electroplating of nickel on an object (mild steel spoon) .
10. Explain the following applications of electrolysis (a) electrolytic refining (b) anodising
11. Define: oxidation, reduction and redox reactions. Give one example each.
12. What is electrochemical cell ? Describe Daniel cell.
13. Distinguish between primary cell and secondary cell.
14. What are fuel cells? Give one example.
15. What are the advantages of fuel cells?
16. What is electrochemical series? Give the applications of electrochemical series.
17. Define corrosion. Explain the factors affecting rate of corrosion.
18. Explain the various methods for the prevention of corrosion.
19. What is cathodic protection?
20. Reduction potentials of Zn and Ag electrodes are -0.76 V and 0.8 V respectively. Compute the
emf if a cell is constructed using these electrodes
21. What is galvanization?
22. Explain barrier protection method for the prevention of corrosion.

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