Unit no.

08

ELECTROCHEMISTRY

Q Define the following terms.

1. Electrochemistry
The branch of chemistry in which chemical energy is converted in to electrical energy or
electrical energy is converted in to chemical energy is called Electrochemistry.

Electrochemistry gives the relationship between electricity and chemical reactions.

2. Electrical energy

It is the energy that is associated with electric charges and their movements.

3. Chemical energy

It is the energy that is associated with atoms / molecules and can be released during a chemical reaction.

4. Conductors

The substances which allow passing electric current through it but is not chemically changed during the
conduction.

Example: Copper, Iron, Aluminum, Gold, mostly all metals.

5. Non-Conductors

The substance which does not allow the passage of electric current is called non-conductor.

Example: Non-Metal like sulphur, diamond, phosphorus.

Sometimes these non-conductors are used to protect something from electricity then they are called
insulators such as plastic.

6. Current

Flow of electric charges is called current. Current is the rate at which the charges flow. It is measured in
units called Ampere.

7. Electricity

Flow of current is called electricity.

8. Unit

A reference value of the quantity used to express other of same quantity is called unit.

9. Ampere:{A}
In international system (S.I.) the fundamental unit of electric current is Ampere. It is defined as the
current passed through a circuit for one second, 0.001118g or 1.118×10-6 kg of Ag is deposited from its
electrolyte AgNO3 solution the electric current is called one Ampere.

10. Coulomb

In international system (SI) the fundamental unit of electric charge is coulomb (C).

When one Ampere of current is passed for one second this quantity of electric charge is called coulomb.

Coulomb = Ampere (A)×time (s).

Coulomb is the product of ampere and time in seconds.

11. Electrode

The plates or rods which carry the electricity in to the solution are called electrodes.

12. Cathode

The electrode connected to the negative terminal of a battery is called cathode.

13. Anode

The electrode connected to the positive terminal of a battery is called anode.

14. Electrolytes

Compounds which conduct electricity in their molten or aqueous solution are called electrolytes.
All electrolytes are ionic or polar compounds. In solid states substances do not conduct electricity because
their ions are tightly packed hence are not free to move, but when dissolved in water or made molten there
by decomposed in to ion hence conduct current. All the conductors are not electrolytes. Current can be
passed through it for a long time but it cannot decompose. Metals are good conductors but not
electrolytes.

Examples: molten sodium chloride, molten magnasium chloride. Etc.

15. Non-Electrolytes

Compounds which do not conduct electricity even in molten or aqueous solution are called non-
electrolytes; such compounds do not ionize so they can not conduct current.

Example: Many molecular compounds and covalent compounds are non-electrolytes as sugar, petrol
starch etc.

16. Electrolysis

The process of chemical decomposition of an electrolyte in solution or in molten state by passage of

electrical current is called electrolysis or electrolytic conduction.
The apparatus which is used for electrolysis is called electrolytic cell.

Qno2. Explain the process of electrolysis in molten sodium chloride (NaCl).

Solid Sodium Chloride (NaCl) does not conduct current because of tightly packed arrangement of ions in
sodium chloride (NaCl). To make it conduct electricity sodium chloride is melted, so that ions are freed
and can move freely to conduct electricity.

Construction of cell

The electrolysis of molten sodium chloride is carried out in electrolytic cell some molten sodium chloride
is taken in electrolytic cell. Two platiuium rods act as electrodes are dipped in fused NaCl. One electrode
is connected to negative terminal of battery called cathode by wires and other is connected to positive
terminal of battery called anode by wires.

Working of cell

As the current is passed electrolysis starts. The positive ion (Na+) cations move towards cathode while
negative ion (Cl-) anions move towards anode.

Electrolysis of Molten NaCl

Reaction at cathode (Reduction)

Na+ ions move towards cathode and gain one electron and become neutralized sodium (Na) atom and
deposited at cathode as sodium metal.

Na++ e- → Na

Reaction at Anode (Oxidation)

Cl- ions move towards anode and lose one electron and become neutral chlorine atom and liberated from
anode.

Cl- → Cl + e-

But we know that chlorine atom does not exist independently, they can exist in molecular chlorine (Cl2).

2 Cl- → Cl2 + 2e
Over all reaction

2 NaCl → 2Na++ Cl2-

2 Na++ 2e → 2Na Cathode reactions

2 Cl- → Cl2+ 2e Anode reaction

By combining two equations

2 Na++ 2e → 2Na

2 Cl- → Cl2+ 2e

2 Na++ 2Cl- → 2Na+Cl2

Conclusion

The electrolytes of molten NaCl gives sodium (Na) metal at cathode and chlorine gas (Cl2) at anode.

Qno3. Describe the process of electrolysis of water?

Water is weak electrolyte. It ionizes in the following ways.

H2O → H+ + OH-

In pure water out of 6×108 molecules only one molecule is ionized. In this way pure water does not
conduct current. To make it conduct electricity few drops of dilute H2SO4 is added. The electrolytic cell
used for the electrolysis of water.

2H2O → H3O++OH-

Construction of cell
Acidified water was taken in electrolytic cell. Two platinum rods act as electrodes was dipped in acidified
water in electrolytic cell. One electrode is connected to negative terminal of battery called cathode and
other to the positive terminal of battery called anode by wires.

Working of cell

As the current is passed electrolysis starts. Positive ion (H+) move towards cathode and negative ions (O-)
move towards anode.

2 H2O → H3O++ OH-

Reaction at cathode (Reduction)

Hydronium ion H3O gains electron from cathode and gives H2 molecules.

2H3O + 2e → H2 + 2H2O

Reaction at Anode (Oxidation)

Anode is deficient of electron. OH- ions loses its electron at anode and

O2 gas is liberated at anode.

40H- → O2 + 2H2O+4e

Over all reaction

Electrons are not balanced in above equations. Cathode is deficient of two electrons so the equation of
cathode is multiplied by 2.
2(2H3O+ + 2e → H2+2H2O) Cathode Reaction

4H3O+ + 4e → 2H2+4H2O

40H- → O2 + 2H2O+4e Anode reaction

4H3O+ + 40H- → 2H2+ O2 + 6H2O

4H3O+ and 40H- together will be equal to 8H2O so,

8H2O→ 6H2O + 2H2+O2

Or 8H2O - 6H2O → 2H2+O2

Or 2H2O → 2H2+O2

Overall reaction

2H2O electric current→ 2H2 (cathode product) + O2 (Anode product)

Conclusion

On electrolysis of water we get two volume of hydrogen gas at cathode and one volume of oxygen at
anode. Humphrey Davy used the result to confirm the formula of water as H2O (2:1) ratio of hydrogen
and oxygen.

Qno4. Explain Faraday’s laws of electrolysis. Explain his 1st law of electrolysis.

Faraday’s laws of electrolysis

Michael Faraday studied the quantitative aspect of electrolysis. He discovered that there exists a definite
relationship between the amounts of product and current used in this process. In 1834 he formulated two
quantitative laws which are known as Faraday’s law of electrolysis.

Faraday’s first law of electrolysis

The amount of given substance is liberated or deposited at an electrode during electrolysis is directly
proportional to the quantity of electricity which passes through the electrolytic solution.

Explanation

If (w) is amount of substance liberated or deposited at electrode during electrolysis. When (A) Ampere of
current was passed for (time) second then,

W ∞ A×t

W=Z×A×t

Z= w /A×t
Here (Z) is called electro chemical equivalent for any given substance. If one Ampere of current was
passed for one second the (w) will be.

W=Z×1×1

W=Z

That is amount of substance which is exactly equal to electro chemical equivalent.

Electro chemical equivalent (Z)

The amount of substance deposited or liberated when one coulomb of electric charge passed. It is denoted
by Z.

Unit of Electro chemical equivalent

Z=W /A×t

Z=g /A×sec

.: A×sec = coulomb (c)

g/c or kg/c

so, Electrochemical equivalent in g/c or kg/c.

Example

A current of 0.5 ampere was passed through a solution of CuSO4 for one hour. Calculate the mass of
copper metal deposited on the cathode.

Cu=0.000329g/c=3.29×10-4g/c.

Or 3.294×10-7kg/c.

Solution

Data

Current in ampere (A) = 0.5

Time in second (1hour) =1×60×60=3600s
Z for Cu metal = 3.294×10-4g/c = 3.294×10-7kg/c.

Formula

W= Z×A×t

= 3.294×10-7×0.5×3600

= 5.929×10-4kg
Mass of copper metal deposited

= 5.292×10-4kg

Or 0.5929g.

Example2.

A current of 10 amperes was passed for 15 minutes in a solution of silver nitrate (AgNo3). The mass of
silver deposited was found to be 1.0062×10-2kg. Calculate the electro chemical equivalent (z) of Ag
metal.

Solution

Data

Current in ampere = 10
Time in seconds (15m) = 15×60=900s.
Mass of Ag metal deposited = 1.0062×10-2kg.

Formula

W=ZAt

Or Z=W / At =

W= 1.0062×10-2kg / 10 A × 900 S

= 1.0062 × 10-2 x 10-3 / 9

=0.1118×10-5kg/c

=1.118×10-6kg/c

=0.00118g/c.

Qno5. State and explain Faraday’s 2nd law of electrolysis.

Statement

When the same quantity of electricity is passed through different electrolytes connected in series then the
amount of substance deposited or liberated at electrodes is directly proportional to their equivalent
masses.

Equivalent mass = Atomic mass

Valency

Verification of 2nd law of Faraday

If three different electrolytes of AgNO3, CuSO4 and Al(NO3)3 are connected in a series and same amount
of current 1F (96500c) was passed then the mass of Ag, Cu and Al is deposited to their respective
electrode is directly proportional to their equivalent masses that is =

Silver (Ag) = 108/1 = 108g rate of deposition of Ag.

Copper (Cu) = 63.5/2 = 31.75g rate of deposition of Cu.

Aluminum (Al)= 27/3 = 9g rate of deposition of Al

Rate of deposition of Ag, Cu, Al respectively Ag> Cu> Al.

Faraday=

The quantity of electric charge that deposits or liberates exactly one gram equivalent of substance is
called one Faraday.

1F = 96500c

Qno6. What is relationship between Equivalent mass and Electrochemical Equivalent?

One Faraday (96500c) electric charge is required to deposit one gram equivalent mass of any substance
means gram equivalent mass of a substance is 96500c time greater than its electrochemical equivalent.

Gram equivalent mass = 96500 × Z

or e = 96500 × Z

Or F×Z = 96500c = 1F

Example1.

When an aqueous solution of copper sulphate is electrolysed copper metal is deposited at the cathode.

Cu2+ (aq) +2e- → Cu (s) at cathode.

If a constant current was passed for 5 hours and 404 mg of cu was deposited. Calculate the current passed
through CuSo4.

Solution

Amount of Cu deposited = 404 mg = 0.404g

Gain of 2e- means 2F electric charge

Atomic mass of Cu = 63.5.

63g of Cu is deposited by 2F electric charge.

1g of Cu is deposited by electric charge.= 2/63.5

: 0.404g of Cu is deposited by 2 × 0.404

63.5

=0.0127 F

We know

1F = 96500 coulomb

:. 0.0127F = 0.0127×96500=1225.6c

: Coulomb = Ampere × t (sec)(t = 5 hours)

: Ampere = C/ t = 1225.6

5×60×60

= 0.0680A

= 6.80 × 10-2 ampere.

Exmple2.

How many grams of oxygen gas is liberated by the electrolysis of water after passing 0.0565 ampere for
185 second.

Solution
Equation

2H2O → O2 (g) + 4H++4e-

According to equation 4 Faraday is required to liberate 32g of O2.

Data

Current in ampere = 0.0565A

Time in second = 185

Coulomb = ampere × time (s)

= 0.0565×185=10.45c

F=C / 96500 = 10.45/ 96500 = 0.000108F

Now

4F electric charge liberates 32g O2

1F electric charge liberates O2 = 32 / 4

.: 0.000108 electric charge liberates = 32 × 0.000108

= 0.000864g

=8.64×10-4g O2.

Qno7. Define the following terms.

1. Batteries

The devices which produce electricity by the chemical reaction are called betteries.it is the combination of
more than one cells.

2. Primary Cell/ Irreversible cell

The cell which has short life and cannot be recharged.

e.g: dry cell mercury cell.

3. Secondary Cell / Reversible cell

The cell which can be recharged by passing direct current so it can be used again and again.

e.g: Car battery.

4. Electrochemical Cell

The cell which converts chemical energy in to electrical energy or electrical enegry in to chemical energy
is called Electrochemical cell. Oxidation, Reduction reactions occur in electrochemical cell.

e.g: Galvanic cell or Voltage cell.

Qno8. What is Daniel cell? Write its constriction and working.

A Daniel cell is simple advance or voltaic cell. It is an electro chemical cell, in which chemical energy is
converted in to electrical energy. The energy is produced by spontaneous oxidation reduction reaction.

Construction

Daniel cell consists of two half cell, in one cell Zinc metal rod acts as anode and is immersed in 1 molar
zinc sulphate solution (ZnSO4) and in other half cell copper metal rod acts as cathode and is immersed in
copper sulphate solution (CuSO4). Two half cels are connected together to form a complete cell. Two half
cells are separated by a porous partition called (salt bridge). This salt bridge allows the passage of ions
from one half cell to other but prevent the solution from mixing. A volt meter is connected to the both
electrodes by wires.
Working of cell

As the current passes, zinc loses its electron in znSO4 solution as zn2+ after lossing two electrons and thus
oxidation occurs and zinc acts as anode or negative electrode. Copper accepts two electrons of cuso4 and
thus reduction occurs, thus cu acts as cathode or positive electrode and Cu2+ ion deposited on it as copper
metal.

In this process zn electrode dissolves in ZnSO4 solution and reduces in size, while copper electrode grows
in size due to deposition of Cu metal.

Reaction at Anode

Zn → Zn +2+2e (Oxidation)

Reaction at Cathode

Cu2++2e- → Cu (Reduction)

Over all reaction

Zn + Cu 2+ → Zn 2++Cu

Qno9. Calculate the amount of silver deposited when 10 ampere of current is passed for 50 minutes
through a solution of AgNO3.

(Z of Ag = 0.00118g/c)

Solution

Data
Current in Ampere (A) = 10

Time in seconds = 50×60=3000s

Z of Ag = 0.00118g/c

Formula

W = Z × A×t

= 0.00118×10×3000

= 35.4g

Amount of silver deposited = 35.4g.

Qno10. When molten NaCl is electrolyzed sodium metal is liberated at cathode by the reaction Na++e- →
Na(s). How many grams of sodium are liberated when 5×103c of electric charge is passed through the
cell.

Data

Electric charge = 5×103c

We know

1F = 96500c

1C = 1 F

96500

So 5×103c = 1 × 5× 103

96500

= 0.0518F

1F deposits sodium = 23g

0.0518 F deposit sodium = 23×0.0518

= 1.19g.

Qno11. Describe the construction and working of dry cell.

Introduction

A voltaic cell in which the electrolyte is in the form of paste is called a dry cell. It is a primary cell in
which chemical energyis converted in to electrical energy. The most commonly used dry cell is usually
referred to as flash light, torches, games, shavers, calculators, clocks, and many portable electronic
devices. In the dry cell there in no free flow of liquid hence called dry cell this is irreversible cell.

Construction

In dry cell a cup shaped outer zn vessel act as anode which is filled with a thick moist paste of manganese
dioxide (MnO2) carbon powder and paste zinc chloride (ZnCl2) Ammonium chloride (NH4Cl) and water
act as electrolyte this electrolytic solution is made viscous by mixing starch. The graphite rod is immersed
in the paste which acts as cathode. The upper part of graphite rod is covered with a copper strip. The
upper part of the cell is sealed with wax. The whole cell is covered with safety cover.

Working of cell

When zinc and graphite electrodes are connected with metallic wire reaction take place. Oxidation occurs
at zinc container and zinc is oxidized at the zinc anode form zn2+ ions moves towards paste and goes to
graphite cathode.

Reaction at Anode

Zn → Zn 2+ + 2e- (Oxidation)

Reaction at Cathode

2MnO2(s) + 2NH 4 (aq) + 2e → Mn2O3(s) + 2NH3(aq) + H2O(l)

+ -

In this cell graphite rod only act as conductor and does not undergo reduction. Only MnO2 is reduced. Dry
cells are not rechargeable.

Qno12. Discuss lead storage battery.

Introduction

It is a secondary battery and is a reversible cell. It can be recharged to its original condition so it can be
reused.

Construction
In lead storage battery six voltaic cells are connected together and a series of anode and cathode of these
cells are connected. Each cell produces 2 volt so total voltage of battery is 12 volt. Anodes are made of
lead alloy and red lead dioxide pbO2 act as cathode. The electrodes are immersed in 30% dilute H2SO4
acts as electrolyte which are separated by perforated plate.

Reaction at Anode (Oxidation)

Lead dissolves therefore oxidation occurs.

Pb → pb2++ 2e

Reaction at cathode (Reduction)

pbO2 + 4H+ + 2e → 2pb2+ + 2H2O

Over all reaction

Pb(s) + pbO2 (s) + 2H2SO4 → 2pbSO4 + 2H2O

Discharging

In both oxidation and reduction pb2+ ions produce. These ions react with SO4-2 ions of H2SO4 to produce
which insoluble precipitate of lead sulphate pbSO4 and water and (oil) over both electrodes. Due to
coating in large amount of pbSO4 battery works slow and said to be discharged.

Pb2+ + SO4-2 → pbSO4

Recharging

If the battery is connected to an external source the reaction become reverse and electrons flow to
opposite direction and the battery is recharged.

2PbSO4 + 2H2O → Pb + PbO2 + 2H2SO4

Lead storage battery can be recharged but be charging again and again its life span is limited. This is
because small amount of lead sulphate continuously fall from electrode and collect on the bottom of the
cell. Eventually electrode loses so much lead sulphate that the recharging process is ineffective.

Qno13. What is salt bridge?

Salt bridge is reverse u-shaped tube containing conducting solution which allows the passage of ions from
one half cell to other but prevent the two solutions from mixing.

Qno14. Predict what would be formed (1) At the anode (2) At the cathode when each of the molten
salts is electrolyzed using insert electrodes.

1. NaCl

At the Anode

Cl- → Cl +e-

Cl + Cl → Cl2 + 2e-

2. At the Cathode

Na + 2e → Na

2Na++2e → 2Na

3. MgBr2

Br - → Br + e

Br +
Br → Br2 + 2e-

At the Cathode

Mg 2++ 2e → Mg

4. CaCl2

At the Anode

Cl- → Cl+e-

Cl + Cl → Cl2 + 2e-

At the cathode

Ca2+ + 2e → Ca.

Qno15. What is electroplating. Describe Nickel plating.

Electroplating
The process of electrolysis in which one metal is deposited on another metal with the help of
electricity is called electroplating.

Nickel plating

Construction of cell

For electroplating of nickel an electrolytic cell is used. Nickel sulphate (NiSO4) is used as electrolyte
in which pure metal nickel electrode acts as anode and nickel plated spoon acts as cathode. Both
electrodes are connected with a battery.

Working of cell

As current is passed through solution Nickel from anode dissolves in Nickel sulphate solution as Ni2+
ion are formed by releasing two electrons and oxidation occurs. Then these Ni2+ ions move towards
cathode. It gains two electrons from cathode and deposited on spoon and reaction occurs.

Reaction at anode (Oxidation)

Ni (s) → Ni2+ + 2e-

Reaction at cathode (Resection)

Ni2+ + 2e- → Ni

Over all reaction

The movement of Nickel from anode as Ni2+ through Nickel sulphate solution towards cathode and
deposited on it.

Redox reaction is given as:

Ni (s) (anode) → Ni (s) (cathode)

Qno16. Describe chromium plating?

Construction of cell

The process of Electroplating of Chromium is carried out in electrolytic cell. Chromium sulphate [Cr2
(SO4)3] is taken as electrolyte piece of chromium metal is taken as the anode and thing to be
electroplated (spoon) is taken as cathode. Two electrodes are immersed in chromium sulphate
solution the other end of both electrodes is connected to a battery through wires as source of
electricity.

Working of cell

As the current is passed through electrode chromium metal dissolves in solution and form Cr3+ ion by
losing three electron their Cr3+ ions move towards cathode where they gain three electrons and
reduced to deposited chromium metal on the spoon (cathode).

Reaction at anode (Oxidation)

Cr → Cr3+ (aq) + 3e

Reaction at cathode (Reduction)

Cr3+ + 3e- → Cr (s) reduction

Electroplating is simple transfer of Cr as Cr3+ ion through the solution of Cr2 (SO4)3 towards cathode
and coated over metal.

Over all redox reaction is given as.

Cr (S) anode → Cr (S) Cathode

Cr (S) (anode) → Cr (S) (Cathode)

Fill in the blanks

1. The substance used for electrolysis is called electrolytic cell.

2. When molten sodium chloride is electrolyzed sodium is formed at cathode.
3. One Faraday is equivalent to 96500 coulombs.
 4. The electrolyte in lead storage battery is dilute sulphuric acid.
5. Dry cell is an irreversible cell.

Write true or false.

1. Sugar is an electrolyte. (false)

2. Electrolytic conduction is also known as electrolysis. (true)
3. Z is called as electrochemical equivalent.(true)
4. The unit of electrochemical equivalent is ampere x second (false)
5. Deniel cell is a voltaic cell(true)
6. Lead storage battery is a primary cell(false)