ELECTROCHEMISTRY

{PART-1}
 ELECTROCHEMISTRY

• Electrochemistry is the branch of

chemistry which deals with the study of
the inter relationship between
electrical energy and chemical energy.
 CELLS
• The chemical changes involving production or
consumption of electricity are called electrochemical
changes.
• Cells are the devices which are used for carrying out
electro chemical changes .
• There are 2 types of cells.
(1) Electrolytic cells
(2) Electrochemical cells
 ELETROLYTIC CELLS
• These are the devices which convert electrical
energy in to chemical energy.

Electrolytes
• The substances which conduct electricity in their
molten state or in their solution state are called
electrolytes.
• There are two types of electrolytes.
1. Strong electrolytes
2. Weak electrolytes
 Strong electrolytes
• The substances which are completely ionized in
solution are strong electrolytes.
• All strong acids and strong bases are strong
electrolytes.

Weak electrolytes
• The substances which are partially ionized in solution
are called weak electrolytes.
• All weak acids and weak bases are weak electrolytes.
Electrolysis
• It is the process of decomposition of an electrolyte
by the passage of electricity through its aqueous
solution or in molten state.
• The apparatus used for carrying out electrolysis is
called electrolytic cell.
+ –

Anode Cathode

Electrolyte
• The electrode at which oxidation takes place is
called ‘anode’ and the electrode at which reduction
takes place is called ‘cathode’.
• Electrolysis involves the following 3 steps.
1. Ionization /dissociation of electrolyte.
2. Migration of ions to the respective electrode.
3. Discharge of ions at the respective electrode.
 Electrolysis of some simple salts
1. Electrolysis of molten NaCl using
inert electrodes.
Electrolysis
NaCl Na+ + Cl–
At cathode:
Na+ + 1e– Na (Reduction)

At anode:
Cl- ½ Cl2 + 1 e– (Oxidation)
Preferential discharge theory
• It states that ‘ if more than one type of ions are
attracted towards a particular electrode, then the
one discharged is the ion which requires least
energy’.
• The potential required for an ion to discharge at a
particular electrode is called discharge potential.
• The ion with least discharge potential will be
deposited first.
• The decreasing order of discharge potentials of
some cations and anions are given below.
• For cations:
K+ > Na+ > Al3+ > Zn2+ > H+ > Cu2+ > Ag+
• For anions:
SO42- > NO3- > OH- > Cl- > Br- > I-
2. Electrolysis of aqueous NaCl using
inert electrodes.
Electrolysis
NaCl Na+ + Cl–
Electrolysis
H2O H+ + OH–

At cathode:
H+ + 1e– ½ H2 (Reduction)

At anode:
Cl- ½ Cl2 + 1 e– (Oxidation)
3. Electrolysis of aqueous CuSO4 using
inert electrodes.

CuSO4 Electrolysis Cu2+ + SO42–

Electrolysis
H2O H+ + OH–

At cathode:

Cu2+ + 2e–  Cu (Reduction)

At anode:
2OH- ½ O2 + H2O+ 2 e– (Oxidation)
4. Electrolysis of aqueous CuSO4 using
copper electrodes.
• It is used for the electrolytic refining of Cu.
• Here impure Cu is taken as the anode and pure
cathode is taken as the cathode.
• CuSO4 is taken as the electrolyte
At anode:
Cu Cu2+ + 2 e– (Oxidation)
At cathode
Cu2+ + 2e–  Cu (Reduction)
 FARADAY’S LAWS OF ELECTROLYSIS

Faraday’s first law of electrolysis:

It states that ‘’the amount of substance
deposited at an electrode is directly proportional
to the quantity of electricity passed through it’’.
That is ; m ∝ Q
or m = ZQ
or m=ZIt (Q = I t)
• Where
m - mass of substance deposited in gram
Q - Quantity of electricity passed through it in C
I - Current in ampere
t - Time in seconds
Z - Electrochemical equivalent
• When I = 1 A, t = 1 s, then m = Z
• That is Electrochemical equivalent of a substance is
the weight of substance liberated or deposited at an
electrode by passing 1A of current for 1 second.
NOTE
• The charge of one electron = 1.602 × 10–19 C
• The charge of one mol of electrons
= 1.602 × 10–19 C × 6.023 × 1023
= 96488.46 C
≈ 96500 C
• This quantity is called 1 faraday (F).
• That is 1F = 96500 C
• Na+ + 1e–  Na
• Here one electron produces one sodium atom.
• Passing one mole of electrons will produce one
mole of sodium.
• Na+ + 1e–  Na
1 mol 1 mol 1 mol
1F 23 g (Atomic wt. / Eq. wt
Ca2+ + 2e–  Ca
2F 40 g (Atomic wt.)
1F 20 g (Eq. wt.)
• Thus, the mass of substance deposited when 96500 C
of charge passed is called Equivalent weight (E).
• The amount of substance deposited at an electrode
when one coulomb of charge passed through the
electrolyte is called electrochemical equivalent (Z) .
• 96500 C --------E
1 C---------------Z
• That is , Z = E/96500
• Hence Faradays first law m= ZIt can be written as
m=( E/96500 ) × I × t
 Faraday’s second law of electrolysis:
• It states that “when a same quantity of electricity is
passed through different electrolytes connected on
series, then the amount of substance deposited at
an electrode is will be in the ratio of their equivalent
weights”.
• That is weight of substance deposited is directly
proportional to their equivalent weights.
W∝E
or W1 /W2 = E1/E2
 mass of H2 Eq.wt. of H2

mass of Cu Eq.wt. of Cu

mass of Cu Eq.wt. of Cu
OR

mass of Ag Eq.wt. of Ag

mass of Ag Eq.wt. of Ag
OR 
mass of H2 Eq.wt. of H2
QUESTIONS
1. The substance evolved at the cathode
during the electrolysis of aqueous
silver nitrate solution using platinum
electrode is
(a) H2
(b) O2
(c) Ag
(d) NO2
2. In the electrolysis of aqueous solution of
copper sulphate using copper strips as
anode and cathode, the anode reaction is
(a) Cu2+ + 2e–  Cu
(b) Cu  Cu2+ + 2e-
(c) 2OH– H2O + ½ O2 + 2e-
(d) SO42-  SO4 + 2e-
3. How many grams of cobalt metal will be
deposited when a solution of cobalt (II)
chloride is electrolyzed with a current of
10 amperes for 109 minutes (Atomic mass
of Co = 59 u)?
(a) 0.66
(b) 4.0
(c) 20.0
(d) 40.0
4. One Faraday of electricity is passed through
molten Al2O3, aqueous solution of CuSO4
and molten NaCl taken in three different
electrolytic cells connected in series. The
mole ratio of Al, Cu and Na deposited at
the respective cathode is
(a) 2 : 3 : 6 (b) 6 : 2 : 3
(c) 6 : 3 : 2 (d) 1 : 2 : 3
5. How many moles of Pt may be deposited
on the cathode when 0.80 F of electricity is
passed through a 1.0 M solution of Pt4+?
(a) 1.0 mol
(b) 0.20 mol
(c) 0.40 mol
(d) 0.80 mol
6. The quantity of electricity required to
completely oxidise 0.1 mol MnO42– to
MnO4– is
(1) 2  96500 C
(2) 9650 C
(3) 96.50 C
(4) 96500 C
7. When molten magnesium oxide was
electrolysed for a certain period, 150 mg
of Mg was deposited on the cathode. The
volume of oxygen gas in cm3 at STP
conditions liberated at the anode during
the same period is
(a) 140 (b) 280
(c) 70 (d) 120
8. The weight of silver (at. wt. = 108)
displaced by a quantity of electricity
which displaces 5600 mL of O2 at STP
will be
(1) 10.8 g
(2) 54.0 g
(3) 108.0 g
(4) 5.4 g
9. A factory produces 40 kg of calcium in two
hours by electrolysis. How much
aluminium can be produced by the same
current in two hours?
(A) 22 kg
(B) 18 kg
(C) 9 kg
(D) 27 kg
10. The cost of electricity producing 1 kg of
Mg from molten MgCl2 by electrolysis is
Rs 9. The cost of electricity to produce 10
kg of Al by electrolysis of Al2O3 dissolved
in molten cryolite would be
(a) Rs. 120 (b) Rs. 90
(c) Rs. 12 (d) Rs. 9
THANK YOU