Unit – Iii Electrochemistry
Electrochemistry is the branch of chemistry that deals
with the interconversion of chemical energy into electrical
energy and vice versa. It deals with the study of electrical
properties of electrolytes and also the chemical changes
brought about by electrical energy.
Important Terms and their Definitions Used in Electrochemistry
Conductor: It is a substance which allows the electric current
to pass through it. Ex: - All metals, graphite, fused (molten)
salts, aqueous solution of acids, bases, salts.
Insulator: It is a substance which does not allow the electric
current to pass through it. Ex:-wood, paper, plastic, alcohol
etc.
Arrhenius Theory
Postulates of Arrhenius Theory :
When dissolved in water, neutral electrolyte molecules are split up into
two types of charged particles. These particles were called ions and the
process was termed ionization. The positively charged particles were
called cations and those having negative charge were called anions.
The ions present in solution constantly reunite to form neutral molecules.
Thus there is a state of equilibrium between the undissociated molecules
and the ions.
AB↔A+ + B−
Cations are generally metallic radicals obtained by loss of electrons from
metallic atoms. Anions are generally non-metallic radicals obtained by
gain of electrons from non-metallic atoms or group of non metals.
The number of positive or negative charges on the cation or anion
corresponds to the valency of the element or radical from which the ion is
derived.
ELECTROCHEMISTRY
ELECTROCHEMICAL CELL ELECTROLYTIC CELL
Converts chemical energy Converts electrical energy
To electrical energy To chemical energy
Electrolytic cell: The device which converts electrical
energy into chemical energy, i.e. non-spontaneous
chemical reaction is carried out using electrical energy is
called as electrolytic cell.
For example: Electroplating, electro-typing, electro-
refining, electrolysis.
Electrochemical cell: The device which converts
chemical energy into electrical energy by means of
spontaneous chemical reaction is called as
electrochemical cell.
For example: Dry cell or Leclanche cell, Daniel cell, Lead
acid storage battery cell, Nickel cadmium.
Sr. No. Electrochemical cell Electrolytic cell
1) It is a device which converts It is a device which converts
chemical energy into electrical electrical energy into chemical
energy. energy.
2) Spontaneous chemical reaction is Non-spontaneous chemical reaction
used to generate electricity. is carried out by using electric
current.
3) In this, cathode is the positive In this, cathode is the negative
terminal and anode is the negative terminal and anode is the positive
terminal of the battery. terminal of the battery.
4) For example: Galvanic cell, Daniel For example: Electroplating,
cell Electrolysis of CuSO4.
Type of conductors
Metallic conductor: These are the metallic substances
which conduct electricity through them without undergoing
any chemical changes. Metals and their alloys carry electric
current due to the flow of electrons in the metal atoms. Ex:
- Metals like copper, aluminium silver etc.
Electrolytic conductor or Electrolyte: These are the
substance which in fused state or in aqueous solution
liberate ions and allow electric current to pass through it
resulting in chemical decomposition. In this type of
conductors, charge is carried by ions. i.e Conduction will
not occur unless the ions are free to move.
Differences between metallic & electrolytic conductor
Sr. Metallic conductor Electrolytic conductor
No
.
1. These are the substances which These are the substance which in
conduct electricity due to the flow of fused state or in aqueous solution
electrons. Ex: - all metals. liberates ions & allows electric
current to pass through it resulting
in chemical decomposition Ex: -
acids, bases & salts.
2. It does not involve any transfer of It involves transfer of matter.
matter.
3. It shows the decreases in conductance It shows the increases in
(increase in resistance) as the conductance as the temperature
temperature increases. increases.
Electrolyte: The substances which conduct electricity in molten state or in
aqueous solution and undergo chemical changes are called as electrolyte.
Electrolytes are of following types:
Strong electrolytes: Electrolytes which are highly ionised in solution or in
fused state, hence having high degree of ionisation are called as strong
electrolytes.
For example: - Strong acids like HCl, H2SO4, HNO3 , strong bases like NaOH,
KOH & almost all soluble salts. CuSO4, NaCl etc.
Weak electrolyte: The substance which ionizes to a small extent in fused state
or in aqueous solution hence having low degree of ionisation are called as
weak electrolytes.
For example: Weak acids like carbonic acid(H2CO3),acetic acid(CH3COOH),
Oxalic acid(C2O4H2), Boric acid(H3BO3) and weak bases like NH4OH,Ca(OH)2
& salts like BaSO4, Al(OH) 3 etc.
Non electrolyte: The substances which cannot conduct electricity either in
molten state or in aqueous solution are called as non-electrolytes.
For example: Oils, CCl4, alcohol, sugar, petrol etc.
Distinguish between Cathode and Anode
Sr. Cathode Anode
No.
1) It is negative electrode, It is connected to the positive
connected to the negative terminal of the battery when
terminal of the battery when electric current is passed
electric current is passed through an electrolyte.
through an electrolyte.
2) Spontaneously it takes part in Spontaneously oxidation
reduction reaction. reaction occurs at anode.
3) During electrolysis, flow of During electrolysis, flow of
electrons is from negative electrons is from anode to
terminal to the cathode. the positive terminal of the
battery.
Construction and Working of Daniel Cell
a)Daniel cell with porous partition b) Daniel cell with salt bridge
The most common example of electrochemical or galvanic
cell is Daniel cell. It consists of a zinc electrode immersed
in zinc sulphate solution and copper electrode immersed in
copper sulphate solution. Both the electrolytes ZnSO 4 and
CuSO4 are separated by porous partition or salt bridge.
Because of high oxidation potential zinc acts as anode and
copper acts as cathode. The e.m.f. developed is due to the
reactions occurring at cathode and anode.
Anodic oxidation : Zn Zn2+ + 2e⊝
Cathodic reduction: Cu2+ + 2e⊝ Cu
A copper ion in the copper sulphate solution accepts the
liberated electrons, undergoes reduction and gets deposited
on cathode.
Thus surface atoms of the zinc rod pass into the solution
and undergo corrosion.
The e.m.f. of the cell is 1.1 volts.
⊝ Zn ZnSO4 (1M) CuSO4 (1M) Cu
Mechanism of Electrolysis
E.g. Electrolysis of copper sulphate using copper electrodes.
Process:
1) Two copper electrodes are immersed in CuSO4 solution.
One copper electrode is connected to positive terminal of the battery which acts as a
anode. The other copper electrode is connected to the negative terminal of the
battery and acts as a cathode.
i) Aqueous solution of copper sulphate acts as an electrolyte. It undergoes dissociation.
2+ 2
CuSO4 Cu + SO 4
+
H2O H + OH
2+ 2 +
The solution contains Cu ,SO 4 , H and OH ions.
2+
1) After passage of electric current, Cu ions get discharged at the cathode in preference to
+
H ions and undergo reduction.
Cu + 2e⊝ Cu
2+
…Cathodic reduction
2) At anode surface metal atoms undergo oxidation with liberation of electrons.
Cu + 2e⊝ …Anodic oxidation
2+
Cu
Net result:
1) Copper metal is deposited at cathode and size of cathode increases.
2) Size of anode decreases.
APPLICATIONS OF ELECTROLYSIS
ELECTROPLATING
ELECTRO-REFINING
Electroplating: “Coating of superior metal on inferior metal by means of electric current is
called as electroplating”.
For example: Silver plating
Process:
1) Article to be electroplated is cleaned by using alkali, acid and finally with water to remove
impurities present on the surface of article.
2) Cleaned article or spoon is connected to negative terminal of the battery (cathode). Pure
silver rod is connected to the positive terminal of the battery (anode).
3) Both cathode and anode are immersed in potassium argentocyanide solution which acts as
an electrolyte.
4) Dissociation reaction of K [Ag (CN) 2] is as follows:
After passage of electric current, Ag+ ions from electrolyte gets deposit on iron
spoon and undergo reduction.
Cathodic reduction: Ag + e⊝ Ag
+
At the same time surface silver atoms at anode undergo oxidation and pass into the solution.
Anodic oxidation: Ag Ag + e⊝
+
+ +
Uniform coating of silver metal is obtained on iron spoon, while more active K and H ions
remain in the solution as they require very high voltage for their discharge.
Purposes of electroplating
1) Protection of base metal from corrosion.
2) A coating of superior metal on inferior metal is done to make it attractive.
3) The broken machine parts can be repaired by electroplating.
b) Electro refining of Copper
Electro refining: “It is the process of obtaining extra pure metal from impure metal by using
electric current”.
For example: Electro-refining of blister copper.
Blister copper contain 3-5 % impurities of active metals like zinc, iron, nickel and passive
metals like platinum, gold, antimony, silver.
Process:
1) The process is carried out in large tank. The thick block of blister copper is connected to
anode and thin wire of pure copper is connected to the cathode. Mixture of 15 % CuSO4
and 5-10 % H2SO4 is used as an electrolyte.
2) A direct current of low voltage is passed through an electrolyte, at this voltage, impurities
of more active metals like Zn, Ni, Fe pass into the solution in the form of ions. The less
active metals like Ag, Au, Pt gets settle down at the bottom forming ‘anode mud’ from
which they are extracted.
2+
3) At proper voltage only Cu ions are discharged at the cathode, undergo reduction and
gets deposit on cathode.
Cu + 2e⊝ Cu
2+
…Cathodic reduction
Cu Cu + 2e⊝
2+
…Anodic oxidation
99.99 % pure copper is obtained by this process.
I) Faraday's First Law
Statement: “The weight of the substance deposited or liberated at respective electrode during
electrolysis is directly proportional to the quantity of electricity passed through an
electrolyte”.
Fig. 5.8.1
If ‘W’ is the weight of the substance liberated or deposited at an electrode and ‘Q’ is the
quantity of electricity passed through an electrolyte, then
W Q
But Q=Ct
Where C = Current in amperes, t = Time in seconds
Substituting the value in equation (2.8.1)
W=ZCt
Where ‘Z’ is constant. It is called as electrochemical equivalent (E.C.E.) of a substance.
In equation (5.8.2) if C = 1 amp and t = 1 sec.
Then, W=Z×1×1
W=Z
The electrochemical equivalent (Z) is defined as “The weight of a substance liberated or
deposited when a current of one ampere is passed for one second through an electrolyte”.
Faraday’s Second Law
Statement: “When the same quantity of electricity is
passed through different electrolytes arranged in series,
then the amount of substance liberated or deposited at the
respective electrode is directly proportional to its chemical
equivalent”.
If the same quantity of current is passed through two electrolytes CuSO4 and AgNO3
arranged in series, then (W1) weight of the (Cu) copper and (W2) weight of the silver (Ag)
deposited, will be equal to their chemical equivalents of Cu and Ag respectively.
Weight of copper deposited C.E. of copper
Weight of silver deposited = C.E. of silver
[C.E. - Chemical Equivalent (Equivalent weight)]
WCu ECu
WAg EAg=
W1 E1
In general, =
W2 E2
Relation between C.E. and E.C.E.
Faraday: “One Faraday is the quantity of electricity required to liberate or deposit one
gram equivalent weight of the substance”.
1 Faraday = 96,500 Coulombs
Coulomb: “The quantity of electricity that passes through a circuit when a current of one
ampere strength is passed through the circuit for one second”, is called as Coulomb.
Therefore, equivalent weight of the substance is 96,500 times the electrochemical equivalent.
C.E. (equivalent weight) = 96,500 x E.C.E.
(Electrochemical equivalent)
Important Formulae
1) W=ZCt or W = ZQ
2) CE = 96500 × ECE (Z)
Atomic weight
3) Equivalent weight = Valency
WA EA
4) WB EB=
Molecular weight of base
5)Equivalent weight of base = Acidity of base
Molecular weight of acid
6) Equivalent weight of acid = Basicity of acid
Problems:
Example 2.8.1 : A current of 3 amperes passing through silver nitrate solution for 20 min.
deposit 4.09 gms of silver, what is the ECE and CE of silver ?
Solution: By Faraday’s first law
W=ZCt
Given: Current (C) = 3 amp.
t = 20 min. = 20 60 = 1200 sec.
W = 4.09 gms.
ECE = ?
CE = ?
W=ZCt
4.09 = Z 3 20 60
4.09
Z= = 0.001136 gm/Coulombs
3 20 60
CE = 96500 ECE = 96500 0.001136
= 109.21 gms.
Result: Electrochemical equivalent (Z) = 0.001136 gm / Coulombs chemical equivalent (CE) =
109.21 gms
Example 2.8.4: A given quantity of electricity is passed through two cells containing CuSO4
and AgNO3 solutions respectively. If 0.99 gram Ag and 0.29 gm of Cu are deposited, find
equivalent weight of Ag.
[Equivalent weight of Cu = 31.6]
Solution: Given:
Weight of Ag deposit = 0.99 gms
Weight of Cu deposit = 0.29 gms
Equivalent weight of Cu = 31.6 gms.
Equivalent weight of Ag =?
Using Faraday’s second law:
WAg EAg
WCu = ECu
0.99
Equivalent weight of Ag deposited = 0.29 31.6 = 107.87 gms.
Equivalent wt of Ag is 107.87 gms. …Ans.
1) A solution of metal salt was electrolyzed for 10 minutes with a
current of 1.5 ampere. The weight of the metal deposited is 0.685
gms. What is the equivalent weight of the metal?
2) Calculate the time in second in which 0.3 gm of Copper is
liberated from copper sulphate, when a current of 0.5 ampere is
passed. (Equivalent weight of Cu = 31.6 gm)
Same quantity of current was passed through CuSO4 and AgNO3 solutions. If 3.207 gms
Cu is deposited, Calculate weight of silver deposited. Equivalent weight of copper = 31.77
gms. Equivalent weight of
Ag = 108 gms.
[Ans.: Weight of silver deposited = 10.902 gms.]
When the same amount of current is passed through the solutions of CuSO4 and ZnSO4 then
0.7 and 0.716 gms of Cu and Zn get deposited on respective electrodes. Calculate equivalent
weight of zinc. (Atomic weight of copper = 63.5 gms)
Equivalent weight of Zn =32.4757 gms.
A given quantity of electricity is passed through two cells containing CuSO4 and AgNO3
solutions respectively. If 0.99 gram Ag and 0.29 gm of Cu are deposited, find equivalent
weight of Ag.
[Equivalent weight of Cu = 31.6]
Solution: Given:
Weight of Ag deposit = 0.99 gms
Weight of Cu deposit = 0.29 gms
Equivalent weight of Cu = 31.6 gms.
Equivalent weight of Ag =?
Using Faraday’s second law:
WAg EAg
=
WCu ECu
0.99
Equivalent weight of Ag deposited = 0.29 31.6 = 107.87 gms.
Equivalent wt of Ag is 107.87 gms.
What current strength in amperes is required to deposit
12.7 gms of iodine from KI solution in half an hour? (Atomic weight of iodine = 127 gms)
Solution: Given: Weight of iodine required to deposit = 12.7 gms
t = 30 min. = 30 60 = 1800 secs.
Atomic weight of I2 = CE = 127 gms.
CE = 96500 ECE
CE 127
ECE = 96500 = 96500
Z = 0.0013 gms/Coulomb
By Faraday’s first law,
W=ZCt
W 12.7
C= =
Z t 0.0013 1800
12.7
= = 5.42 amperes
2.34
When the same amount of current is passed through the solutions of CuSO4 and ZnSO4 then
0.7 and 0.716 gms of Cu and Zn get deposited on respective electrodes. Calculate equivalent
weight of zinc. (Atomic weight of copper = 63.5 gms)
Solution: Given:
Weight of Cu deposited = 0.7 gms
Weight of Zn deposited = 0.716 gms
Atomic weight
Equivalent weight of Cu = Valency
63.5
= 2 = 31.75 gms
EZn = ?
Using Faraday’s second law
WCu ECu
WZn = EZn
0.7 31.75
0.716 = EZn
0.716 31.75
EZn =
0.7
Equivalent weight of Zn = 32.4757 gms.
Problems for Practice
Example 2.8.6: A solution of metal salt was electrolyzed for 10 minutes with a current of
1.5 ampere. The weight of metal deposited was 0.685 gm. What is the equivalent weight of
the metal?
[Ans.: Equivalent weight of metal = 73.44 gms. ]
Example 2.8.7: A current of 5.0 ampere flowing for 0.5 hour deposits 3.0489 of a metal at
cathode. Calculate the equivalent weight of the metal.
[1 Faraday = 96500 Coulomb]
[Ans.: Equivalent weight of metal = 32.81 gms.]
Example 2.8.8: A solution of a bivalent metal salt was electrolyzed for 10 minutes with
a current of 1.5 ampere. The weight of the metal deposited was 0.685 gm. What is the
atomic weight of the metal?
[Ans.: Atomic weight of the metal is 146.89 gms.]
Example 2.8.9: Same quantity of current was passed through CuSO4 and AgNO3
solutions. If 3.207 gms Cu is deposited, Calculate weight of silver deposited. Equivalent
weight of copper = 31.77 gms. Equivalent weight of
Ag = 108 gms.
[Ans.: Weight of silver deposited = 10.902 gms.]
Example 2.8.10: What current strength in amperes will be required to liberate 12.7 gms of
iodine from KI solution in 40 minutes? (Given ECE of iodine = 0.0013)
[Ans. : Current (C) = 4.07 amperes]
Example 2.8.11: A solution of metal salt was electrolyzed for 10 minutes with a current of
1.5 ampere. The weight of the metal deposited is 0.685 gms. What is the equivalent weight
of the metal?
[Ans.: Equivalent weight of the metal is 73.44 gms.]
