Cambridge Court World School

Chapter – 2
Electro Chemistry
Electrochemistry is the branch of chemistry which deals with electrical & chemical energy changes.Electric
energy can be converted into chemical energy and vice versa.
 1  C E  E E  E l ectro ch em i cal cel l s  C h em i cal E n erg y  E l ectri cal E n erg y

2 E E C E  E l ectrol y ti c cel l s  E l ectri cal E n erg y  C h em i cal E n erg y

General Terms
1. Resistance [R]– Obstruction offered by any substance in the flow of current.Its unit is ohm[Ω].

R  where   length of conductor, a = cross – sectional area of conductor
a


 R  . If l = 1cm, a = 1cm2 then R =p wherep is resistivity
a

Ra
2. Resistivity p[ ]-   ; R  oh m ,   oh m .cm or oh m .m [Ω – m]
l

ifl = 1 cm, a = 1 cm2 then p=R Hence, Resistance of a substance having unit length & unit area is
resistivity. Its unit is  cm or Ω – m.
3. Conductance[C or G] – Ease in the flow of current by a substance.

1
It is equal to the reciprocal of resistance i.e. C /G  ;  1 or s (sem i n s)
R

4. Specific conductance/conductivity[k-kappa]- It is the reciprocal of specific resistance or it is the

conductance produced by one centimetre cube of an electrolytic conductor.It is inverse of resistivity.

1 1 
k=  
 R a

or k=C ×l /a or k  C  c e ll c o n s ta n t

ifl = 1 cm, a = 1 cm2 then K  G Hence, Conductance of substance having unit length & unit area
is conductivity.
1 1
Unit at specific conductance: ohm cm or  1 cm
1
or S cm
1
( C .G .S )

Representation of specific conductance:

1 cm

1 cm

1 cm

5. Cell constant –It is ratio of distance between electrodes to area of electrodes. Its unit is cm-.
l
cel l con s tan t  ; l  d i s tan ce b etw een el ectrod es
a
a  area of el ectrod es
K
or C C 
G
 Or Cell constant = K x R
6. Molar conductivity (  m ) : - Conductivity of one molar substance which is taken between two
electrodes at 1cm distance and 1 cm2 area.

i.e. Molar conductance ( m )  S p e c ific c o n d u c ta n c e  V ( m l)

 m  K  V ( m l)

K 1 0 0 0 1 1
m  Unit of molar conductance is ohm cm
2
m ol .
M

Limiting Molar conductivity: (  m  ) Molar conductivity at infinite dilution or at zero concentration is

known as ‘Limiting molar conductivity’.
K 1 0 0 0
 m  ; S  C m / m ol.
2

M
7. Equivalent conductance (↑ eq
): -Conductance of all ions which are produced by the ionisation of one equivalent
of an electrolyte in a given solution.

i.e. Equivalent conductance (  )  s p e c ific c o n d u c ta n c e  V (m l)

or,   K  V ( m l)

K 1 0 0 0 1 1
or,   , Unit of equivalent conductance is ohm cm
2
e q u iv .
N

Intext Q. Resistance of a conductivity cell filled with 0.1 M KCl is 100 ohm. If resistance of same cell filled
with 0.02 M KCl is 520 ohm. Calculate conductivity and molar conductivity of 0.02 M KCl solution. If
conductivity of 0.1 M KCl is 1.29 S cm-1.
Ans.
*
 G  cel l con s tan t  con d u cti v i ty  R e si s tan ce

 1 .2 9  1 0 0  1 2 9 m 1  1 .2 9 cm 1
Conductivity of 0.02 M KCl solution,
*
1 l G 129 1
K     0 .2 4 8 Sm
k a R 520
Concentration[M] = 0.02 mol/litre

K 1 0 0 0 0 .2 4 8  l 0 0 0 248
M ol ar C on d u cti v i ty    2
M 0 .0 2 2 1 0
 1 2 4 1 0 2
 1 .2 4  1 0 3 S  m 2 / m ol.

Intext Q. 0.5 N solution of a salt placed between two platinum electrode 2.0 cm apart and of area of cross-section
4.0 sq. cm has a resistance of 25 ohms. Calculate the equivalent conductance of solution.

Solution: Specific conductance () = Conductance  Cell constant

1  1 2 
=   =    = 0.02 ohm–1 cm–1
R a  25 4 

s p e c ific c o n d u c ta n c e 1 0 0 0 6 .0 2 1 0 0 0 –1 2 –1
c = 1
= = 40 ohm cm eq
C ( e q u iv L ) 0 .5

2
Variation of Conductivity and Molar conductivity (^m) with concentration (c)
Conductivity-With increase in conc. conductivity increases or with increase in dilution conductivity
decreases because number of ions decreases in 1cm3 of solution.
1
Molar conductivity (^m)-With increase in conc. molar conductivity decreases.  m 
c
or with dilution molar conductivity increases as With dilution, mobility of free ions increases and
hence molar conductivity increases.
Graph between ^m vs. c for strong and weak electrolyte

W h en c  O , th en  m  

 m
 l i m i ti n g m ol ar con d u cti v i ty 

In case of strong electrolyte- Molar conductivity (^m) generally high at all concentrations due to
complete dissociation.On increasing dilution molar conductivity increases as mobility of free ions
increases and approaches to infinity when conc. of undissociated electrolyte become zero due to its
complete dissociation.

Debye Huckel Onsager equation-

1 2
 m   ºm  A  C  A= Constant which depends upon the viscosity and
dielectric constant of solvent.
In case of weak electrolyte-Molar conductivity (^m) generally low due to incomplete dissociation molar
conductivity slowly increases with increase of dilution and it cannot be approached to infinity because of
its partial dissociation.It steeply increases near the infinite dilution but conc. of undissociated electrolyte
can’t be zero.
KOHLRAUSCH’S LAW OF INDEPENDENT MIGRATION OF IONS
At infinite dilution, conductance of any electrolyte is the sum of contribution of its constituents ions i.e.
anions and cations.Kohl – Rausch law is used to calculate molar conductivity of weak elecetrolytes.
+ -
According to it molar conductivity of an electrolyte is sum of ionic conductivities of ions i.e.  &/  .

 m           ;    con d u cti v i ty of cati on

   con d u cti v i ty of an i on

for eg.  N aC l.    n o. of cati on

m   N a 1  C l 1    n o. of an i on

Applications of Kohl-Rausch Law

Calculate of molar conductivity of electrolyte -  m          
(1) C al cu l ati on of m ol ar con d u cti v i ty

 cm  D i ss  D eg ree of d i ssoci ati on of an el ectrol y te.

( 2)  D i ss 
 m  m c  M ol ar con d u cti v i ty at g i v en con c.
C2
(3) D i ssoci ati on con stan t k 
1
, where C = conc. of electrolyte.
(4) Solubility(S)-It is maximum molarity of saturated solution.It can be calculated with help of
molar conductivity.

3
 K 1 0 0 0
 m  ; S Cm2 / m ol.
M
Intext Q.Molar conductivity of 1.5 M CaCl2 is 130.6 S-Cm2/mol.Calculate  D i ss if  C a   9 2 .5,   4 5 .3 S- 2
Cl
2
Cm /mol respectively.

C aC l 2   m  9 2 .5  1  4 5 .3  2
Ans.
 9 2 .5  9 0 .6  1 8 3 .1
  1 3 0 .6 s  cm 2 / m ol
c
m

1 3 0 .6 1306
 D i ss    0 .7
1 8 3 .1 1831
2
C
2
1 .5   0 .7 
D i ssoci ati on con st an t K    2 .4 5
1 1  0 .7

Electrochemical cells[Galvanic Cells]-These are made of two half cells which are connected with the
help of a voltmeter and a salt bridge.Salt bridge is an inversed tube containing KCl with agar-agar
which is dipped into electrolytes of both half cells.A half cell contains a metal electrode which is
dipped into electrolyte solution of same metal ions.

There are two half cells as follows.

i)Left Half Cell/Oxidation Half Cell/Anodic Half Cell –[OHC]-It contains a more reactive metal
electrode[anode] and electrolyte of same metal ions.In this half cell, oxidation reaction takes
place.

ii)Right Half Cell/Reduction Half Cell/Cathodic Half Cell –[RHC]-It contains a less reactive metal
electrode[cathode] and electrolyte of same metal ions.In this half cell, reduction reaction takes
place.

NOTE-In electrochemical cells anode is negative terminal as it acts as source of electrons and
cathode is positive terminal.

OHC- Oxidation Half Reaction Zn(S)  Zn2+(aq) + 2e-

RHC- Reduction Half Reaction Cu2+ (aq) + 2e-  Cu (S)

Net cell reaction Zn(S) + Cu2+ (aq)  Zn2+ (aq) + Cu(s)

Representation of cells
2+
i. OHC Reactant/Product Zn(S)/Zn (aq)
4
 2+
ii. RHC Reactant/ Product Cu (aq)/ Cu(S)

iii. Net Cell [OHC//RHC] Zn(s)/ Zn2+(aq)// Cu2+(aq)/Cu/(s)

Ex- 2Ag (s) + Cu2+ (aq.)  2Ag+ (aq.) + Cu(s)

OHC 2Ag(s)/2Ag+(aq.)

RHC Cu2+ (aq.)/ Cu(s)

Net cell 2Ag(s)/2Ag+(aq.)// Cu2+ (aq.)/ Cu(s)

Ex- Zn/ Zn2+ (aq.) // Ag+ (aq.)/ Ag(s)

OH reaction Zn  Zn2+ + 2e-

RH reaction Ag+ + 1e-  Ag

+ 2+
Net Reaction Zn(s) + 2Ag (aq.)  Zn (aq) + 2Ag (s)

Formation of cell reaction from cell representation

 2
A g (S ) / A g ( aq.) // C u (aq .) /C u (S )

(R ) (P ) (R ) (P )
 
Ag  A g  1e
2
Cu  2e  C u
2 A g (S )  C u 2  (aq .)  2 A g  (aq .)  C u (S )
n  n o . of ex ch an g ab l e el ectron es i n reacti on
Role of salt bridge
1. It maintains electrical neutrality & keeps continuous working of cell. During working of cell excess of
positive charge becomes at oxidation half cell due to migration of metal ions from anode to electrolyte
which can restrict flow of electrons in cell. At the same time excess of negative charge becomes at
reduction half cell due to reduction of metal ions of electrolyte. It causes electrical imbalance in cell
which can stop working of cell. To avoid this situation ions of salt bridge move towards excess of
opposite charge to neutralize it.
2.It allows the flow of current by completing the circuit.

EMF of cell (Electro Motive Force)-It is the potential difference between two half cells if no current is
drawn from cell.
0 0
EMFcell = E R - E L, S.I unit = Volt
0
Where E R = Electrode potential of right half cell or reduction potential
0
E L =Electrode potential of left half cell or Oxidation potential
0 0
E R > E L , means emf of cell must be positive.

Intext Q. Calculate emf of following cell using following data.

Zn(s)/ Zn2+(aq)// Cu2+(aq)/Cu/(s) , EºZn2+/Zn = -0.76V, EºCu2+/Cu = +0.34 V

Ans. EMF = EºR - EºL

= +0.34 –(-0.76)= +1.10 V

5
Intext Q. Write cell reaction & calculate EMF of following cell.

Sn(s)/Sn2+(aq.) // Cr2+/Cr(s) , Eº Sn2+/Sn = -0.36V , EºCr2+/Cr = -0.27 V

Ans. Sn(S) + Cr2+ (aq) Sn2+ (aq) + Cr(s)

EMF = EºR - EºL

= -0.27 - (-0.36) = 0.09 V

Reference electrode (Standard or Normal Hydrogen Electrode): SHE/NHE

By this device, we measure, the standard electrode potential of half cell. It consists of a small platinum strip
coated with platinum black so as to absorb H2 gas. A platinum wire is welded to the platinum strip and sealed in a
glass tube. The entire arrangement dipped into 1 M HCl solution at 298 K and specified pressure of H2 gas.

SHE is used to calculate the standard electrode potential of an element. Its characteristic are as follows

i) Its potential (Eº) = 0

ii) It acts as anode as well as cathode depends on reactivity of other element. If other element is more
reactive than Hydrogen, then Hydrogen is reduced & act as cathode or If other element is less reactive
than hydrogen,then Hydrogen is oxidized and acts as anode.

Chemical reactions

SHE (Anode) – Pt,H2 (g)/ 2H+(aq)

H2(g)  2H+ + 2e-

+
SHE (cathode) – 2H (aq)/H2(g), Pt

2H+ + 2e-  H2(g)

Note:-Elements having Eº=-ve are more reactive than H and Elements having E0 = +ve are less reactive
than H.

Some other reference electrode:


(i) Calomel electrode – Hg, Hg2Cl2 / Cl (aq)


(ii) Silver – silver chloride electrode – Ag, AgCl / Cl (aq)

Reactivity or Electrochemical series-It is arrangement of elements in increasing value of their

reduction potentials (Eº).It gives an idea about reactivity or oxidizing/reducing nature of
elements.

6
 Most (-) Eº ← Most Oxidized Species

(Reductants) Oxidation

SHE = 0 Reduction Potential (Eº)

(Oxidants) Reduction Increases and Reactivity

decreases

Most  Eº ← Most Reduced Species

Various types of half cells:

Type Representation


(1.) Metal – metal ion half cell M /M (aq)


(2.) Gas – ion half cell P t(H 2 ) / H (aq)


(3.) Metal insoluble salt anion half cell A g, A g C l / C l (aq)

2 3
(4.) Oxidation – Reduction half cell P t, F e / Fe


(5.) Metal – metal – oxide – hydroxide half cell H g, H g O / O H (aq)


(6.) Quinhydrone half cell P t / Q u in h y d ro n e / H (aq)

Nernst Equation: It gives dependence of EMF on concentration of ions present in solution.

2 .3 0 3 R T  con c. of P 
E cel l  E ºcel l  l og  
nF  con c. of R 
Where

T  K el v i n  2 9 8, n  n o. of ex . e , R  8 .3 1 4 J/K
F  F arad ay con s tan t, F  9 6 5 0 0 c / m ol.
A t t  25ºc : 

0 .0 5 9 con c. of P
E cel l  E ºcel l  l og at 2 5 º C
n con c. of R

Applications of Nernst equation

2 .3 0 3 R T  con c. of P 
1. Calculation of ECell from Nernst equation. E cel l  E ºcel l  l og  
nF  con c. of R 

2. Calculation of G[Free energy change]

G = - nFEcell
Standard free energy change(Maximum work of cell)G0] = - nFE0cell

7
3. Calculation of KC (equilibrium constant)
con c. of p rod u cts
At equilibrium, K C
con c. of reac tan ts
G  0  E C el l
0
0 .0 5 9
E  E º l og K C
, A t equ i l i b ri u m E cel l
0
n
0 .0 5 9 E º n
E º l og K C
, K C
 A n ti l og
n 0 .0 5 9

Intext Q. Calculate cell potential of following cell.

2 2
Z n (S ) /Z n (1 .5 M ) //C u ( 0 .5 M ) /C u (S )

1. (R ) (P ) (R ) (P ) Ans.
  0 .7 6 v ,
E ºZ n E ºC u   0 .3 4 v
E ºcel l  E º R  E º L  0 .3 4  (  0 .7 6 )  1 .1 V

0 .0 5 9 1 .5 
E cel l  1 .1  l og
2  0 .5 

Zn  Z n 2  2e
2
Cu  2e  Z n 2  C u
Zn  C u 2  Z n 2  C u
0 .0 5 9
E cel l  1 .1   0 .4 8
2
 1 .1  0 .0 5 9  0 .2 4
 1 .1  0 .0 1 4 1 6  0 .0 8 5 8 4 V

Intext Q. C al cu l ate E M F an d G . of following cell.

3 2
C r (S ) / C r ( 0 .5 M ) / /S n ( 0 .5 M ) / S n (S ) 3
, 2C r  3S n 2  
 2 C r 3   3S n
E ºC r  0 .5 4 V E ºS n  0 .4 1 V

G   n F E C el l
( M ax . w ork of cel l ) F  96500 C
2
0 .0 5 9  0 .5 
E C el l
 0 .9 5  l og 3
6  0 .5 
Ans. E C el l
 0 .9 4 7 V
G  n F E C el l
  6  9 6 5 0 0 C  0 .9 4 7 V
  54834 J

Intext Q. Calculate KC of following cell if reaction is in equilibrium.

3 2
C r (S ) / C r (1 .5 M ) // S n (1 .5 M ) / S n (S )
Eº
Cr
3
/C r
  0 .5 4 V , Eº
Sn
2
/S n
  0 .6 3 V .
n 2
Ans. 2C r  3S
(1 .5 M )
(12 C.5r M3 )  3S n

8
 E ºC el l  0 .6 3  0 .5 4  1 .1 7 V
2
0 .0 5 9  1 .5  0 .0 5 9
E ºC el l  1 .1 7 V  l og 2
 1 .1 7    l og 2  1 0 g 3 
6  1 .5  6

0 .0 5 9
 1 .1 7   0 .3 0  0 .4 7 7 
6
0 .0 5 9
 1 .1 7   (  0 .1 7 7 )
6
0 .0 5 9
 1 .1 7   0 .1 7 7  1 .1 7 1 7
6
E º n
K C
 A n ti l og
0 .0 5 9
1 .1 7  6
K C
 A n ti l og
0 .0 5 9
= Anti log 118.98 = Antilog 0.98 x 10118
= 9.5 x 10118

Commercial batteries/cells
1. Primary Cell:-Which can’t be charged. Ex. Dry cell, Button cells.
2. Secondary cell:- Which can be charged. Ex. Lead cell ,NiCad Cell
Primary cells

(i) Dry Cell –It is compact form of Lechlanche cell.It is used in clocks and transtisters. In this cell, Zn
metal acts as anode & graphite rod acts as cathode. A paste of NH4Cl + and MnCl2 taken as
electrolyte.

Intext Q. Cell potential of dry cell doesn’t remain constant throughout life. Why?
Ans. Because conc. of electrolyte doesn’t remain constant. As conc. decreases with the working of
cell,Cell potential also decreases.

 Cell potential of dry cell decreases even not in use because of corrosion/decay of zinc plate in
presence of air.
 Ammonia consumed inside the cell with zinc as the following reaction:
2
Zn
2
 4 N H 3   Z n  N H 3  4  com p l ex i on

Tetrammine Zine (II) ion

(ii) Mercury/button cell-It is used in low current devices like hearing aids and watches.In this cell, lead
plat act as anode & HgO and graphite acts as cathode. Electrodes are dipped into KOH which
acts as electrolyte. Both electrodes are in the form at tightly compacted powders separated by a moist
paper of HgO containing some NaOH / KOH. Moistened paper serves as salt bridge.

Anode  Pb + 2OH-  PbO + H2O + 2e-

Cathode  HgO + H2O + 2e-  Hg + 2OH
Pb + HgO  PbO + Hg Net Reaction

9
  Mercury cell gives constant cell potential because conc. of electrolyte remains constant. Its
working can be stopped only when electrodes are decayed.

Secondary cells
(i) Lead Cell lead Storage battery:[Car batteries] –It is used in automobiles and inverters. In this cell,
alternate lead plates act as anode & PbO2 plate act as cathode. Cone H2SO acts as electrolyte.


A n od e  PbS O 4  2e
 P b  S O 24 

C ath od e  P b O 2  4 H   S O 24  2 e  
 PbS O 4  2H 2O
Pb  P b O 2  4 H  2S O 24   P b S O 4  2 H 2 O
 White colour solid lead sulphate deposits on Pb and PbO2 electrodes. That’s why it is called lead
storage battery.
 Due to consumption of H2SO4 and formation of water the density of H2SO4 solution decreases.
 Recharging of cell- Electricity is passed from an electric source then electrochemical cell is
convert into electrolytic cell. A n od e as C ath od e, C ath od e as A n od e
Reactions on recharging
 2
A n od e  PbS O 4  2H 2O  PbO 2  4H  S O 4  2e
C ath od e  PbS O 4  2e  Pb  S O 42
2PbS O 4  2 H 2 O  P b O 2  P b  4 H   2S O 4 2 

(ii) Nicad cell[Nickel- cadmium battery]-Used in mobile chargers.

It consists of cadmium anode and the cathode is made of nickel oxide. These are immersed in
KOH solution.
 
A n od e : C d  s   2 O H  aq   C d  O H   s   2 e
2


C ath od e : N i O 2  s   2 H 2 O  l   2 e  N i  O H 2  2O H 
N et reacti on :

C d (s)  N i O 2 (s)  2 H 2 O (l )  C d (O H ) 2 (s)  N i (O H ) 2

Electrolytic Cells-The cells which convert electrical energy into chemical energy, are called as
electrolytic cells.In electrolytic cells both electrodes are immersed into same electrolyte.Anode is +ive
terminal and cathode is –ive terminal.Both electrodes are made of metals or graphite rods as per
application of cell.

10
Applications of Electrolytic Cells
1. Electrolytic Refining:It is applicable for refining of less reactive metals like Copper, Gold, Silver
etc.In electrolytic refining impure metal is taken as anode and pure metal is taken as cathode.
Both electrodes are immersed into electrolyte of same metal ions.Pure metal is deposited at
cathode and impurities settled down as anode mud.Ex-Refining of Copper.

A n od e  C u  C u 2  2e

C ath od e  C u 2  2 e   C u  P u re 


2. Manufacturing of elements from

electrolysis of their salts:In this process
salt is taken as electrolyte solution and
electrodes are made of platinum or
graphite rods.Ex-Calcium from CaCl2 .
C aC l 2  C a 2  2C l 
A n od e  2C l   C l 2  2e
C ath od e  C a 2  2e  C a
Faraday’s Law of electrolysis
(i) I law of Faraday-Mass deposited at electrodes is directly proportional to supplied current.
Mass deposited  current supplied
m Q

Q  nF (F  96500 C ) ; n  n o . of e i n g i v en reacti on

I tM
Q It m  ; M  atom i c m ass.
nF

Intext Q. Copper Sulphate is electrolysed with a current of 20 amperes for 25 minutes, how much copper
will be deposited at cathode?
Ans. Cu → Cu2++2e-

11
 IT M
m 
nf
2 0  2 5  6 0  6 3 .5 6 3 .5  6 3010
m     9 .1 g m
2  96500 3 8 .6 386

Intext Q. Calculate charge required to convert 1 mol Fe2O3 into FeO.

1
1 F e2O 3  2F e O  O 2
2

Ans. 2e  2 F e3  2 F e 2 
Q  n F  2  96500  193000 C
2
Fe  2e  F e
Intext Q. K2Cr2O7 gives CrCl3. How much charge is required in coloumbs ?
Ans.
6 3  6
K 2 C r2 O 7  C r C l 3 ;  6 e 2 C r  2 C r 3
n  6, Q  nF  6  96500 C  579000 C

(ii) II law of Faraday-If two or more elements are deposited on supplying of same charge, then ratio of
their masses depends on their equivalent masses.
mA EM MM
 A
; EM 
mB EM B n

M a s s o f h y d ro g e n EH M a ss of C oppe r E
 or  Cu

M a ss of cop p e r E Cu
M a s s o f S ilv e r E Ag

Applications of electrolysis:

(1) Determination of equivalent masses of element (2) Electrometallurgy

(3) Manufacturing of non – metals (By electrolysis process) (4)Electro – refining of metals

(5) Manufacturing of compounds (6) Electroplating

Calculation of thickness of coated layer during electrolysis:

If volume of coated layer   a  b  c  c m 3

Mass of the deposited substance  v o lu m e  d e n s ity   a  b  c   d e n s ity

I  t E
or, a  b  c   d e n s ity 
96500

EFFICIENCY OF CURRENT DURING ELECTROLYSIS

12
 E ffe c tiv e c u rre n t
% current efficiency  1 0 0
A m m e te r c u rre n t

Fuel Cells: The devices which convert fuel energy into electric energy are called Fuel Cells.Ex-Bacon cell
[H2 – O2 Cell],CH4-O2 cell, C2H6-O2,C3H8-O2 cell etc.
Requirements:- of Fuel cell
(1) Fuel → H2, CH4, C2H6 (2) Oxidant → O2, KMnO4, K2CrO7
(3) Electrolyte → KOH, NaOH

Bacon Cell (H2 – O2 Cell) – In this cell, H2 gas is passed into left tube which acts as anode & O2 gas is
passed into right tube which acts as cathode. KOH is electrolyte.

A n od e ( O x i.)  H 2  2O H   2H 2O  2e  2
C ath od e ( R ed )  O 2  2H 2O  4e  4O H
N et R e acti on  2H 2  O 2  2H 2O
Advantages
1. Eco-friendly, pollution free cell.
2. No change in conc. of electrolyte so it gives constant cell potential.
3. Highly efficient (70 – 80% efficient)
Electrochemical theory of Rusting
Corrosion:- Conversion of metals into their oxides in presence of air/water is called corrosion.
Rusting:- Conversion of ‘Iron’ into its oxide in presence of air/water is called rusting.Rusting is also
based on Redox reaction in which iron surface is oxidised to Fe2O3.
Rusting is a redox reaction by which metal gets oxidised by air in presence of moisture. Small cathodic and anodic
cells are set up on metal. The area of metal in contact with water acts as anode. Metal loses electrons to form
cations. Anode reaction Fe  F e 2   2 e 

The electrons flow along the metal into the cathode area. Where O2 is reduced to hydroxyl ions in presence of H2O.
H 2O d r o p 
O 2 + 2 H 2O + 4 e 


e


 Fe
2+
Fe + 2e

Ir o n p ie c e

Cathode reaction O 2
 2 H 2 O  4 e   4 O H 

The over all reaction is 2F e  O 2  2 H 2 O  2 F e  O H  2

Fe(OH)2 may dehydrate to form its oxide FeO, which than further gets oxidised to Fe2O3. Which is further hydrated
to form rust. F e 2O 3
 n H 2 O  F e 2 O 3 .n H 2 O  ru s t 

Prevention of Rusting 1.Oiling and Painting.

13
2.Zinc Plating on iron (Galvanisation).Zinc is more reactive than Fe as it reacts with O2 to protect Fe
from Rusting (Sacrificial protection).
3.Cathodic protection-Iron plate is connected with reactive metal like magnesium.When more reactive
metal is connected with Iron, it acts as anode and its oxidization takes place and iron acts as cathode
and is reduced which prevents its rusting.

4. Anti-rust solution (Ex. Chromate compound, red oxide etc.) can be used to prevent rusting.

Imprtant Exercise Questions[NCERT]

Q.1 Given the standard electrode potentials, K+/K = -2.93 V, Ag+/Ag = 0.80 V; Hg = 0.79V; Mg2+/Mg = -
2.37 V, Cr3+/Cr = -0.74V

Arrange these metals in their increasing order of reducing power.

Ans. Higher is the value of oxidation potential (or lower the Eϴred) greater is the tendency of element to
oxidise and higher will be its reducing power. Thus, the correct arrangement in decreasing order
of their Eϴred values is

Ag < Hg <Cr < Mg < K

Q.2 Write the Nernst equation and the e.m.f of the following cells at 298 K:

i) Mg(s)| Mg2+ (0.001M)|| Cu2+ (0.0001M)| Cu(s) (Al CBSE 2007)

ii) Fe(s)|Fe2+ (0.001M)|| H+ |(1M) H2(g) (1bar) |Pt(s)

iii) Sn(s)|Sn2+(0.050M) || H+ (0.020M)|H2(g) (1bar) |Pt(s)

iv) Pt(s)|Br2 (l)| Br-(0.010M) ||H+ (0.30M) |H2(g) (1 bar) | Pt (s)

Given Eϴ Mg2+/Mg = -2.37V, Eϴ Cu2+/Cu = +0.34V,

Eϴ Fe2+Fe = -0.44 V, EϴSn2+/Sn = -0.14 V, Eϴ Br 2 Br- = +1.08 V

Ans. i) Cell reaction is

Mg + Cu2+  Mg2+ + Cu (n = 2)

Applying Nernst equation,

2
0 . 0591 [ Cu ]
E cell  E  cell  log 2
2 [ Mg ]

4
0 . 0591 10
E cell  0 . 34  ( 2 . 37 )  log 3
= 2.70 – 0.02955 = 2.68 V.
2 10

ii) Cell reaction if Fe + 2H+  Fe2+ + H2 (n = 2)

14
  2
 0 . 0591 [H ]
E cell E cell  log 2
2 [ Fe ]

2
0 . 0591 (1) 0 . 0591
E cell
 0  ( 0 . 44 )  log 3
= 0.44 + ( 3 )  0 . 44  0 . 0887 = 0.523V
2 10 2

iii) Cell reaction is Sn + 2H+  Sn2+ + H2 (n = 2)

According to Nernst equn.

 2
0 . 0591 [H ]
E cell  E  cell  log 2
2 [ Sn ]

2
0 . 0591 ( 0 . 02 ) 0 . 0591
0  ( 0 . 14 )  log = 0.14 - (2.0969) = 0.078V
2 0 . 05 2

iv) According to the given cell, the net cell reaction, is 2 Br- + 2H+  Br2 + H2 it involves the
transference of 2e-

Applying Nernst equation we have

0 . 0591
E cell  E  cell  log [ Br
 2
] [H

]
2

0 . 0591 0 . 0591 -8
E cell  ( 0  1 . 08 )  2
log ( 0 . 01 ) ( 0 . 03 )
2
= 1.08 + log (9 x 10 )
2 2

0 . 0591
= 1.08 + (-7.045) = -1.08 – 0.208 = -1.288 V
2

Since Ecell is –ve, it means that the representation of the cell is wrong. For cell to show +ve emf
it should be Pt, H2 (1 bar)/H+ (0.03M) || Br2(l )/Br- (0.01M)

Q.3 Conductivity of 0.00241 M acetic acid is 7.896 x 10-5 S cm-1. Calculate its molar conductivity and
if Aºm for acetic acid is 390.5 S cm2 mol-1, what is its dissociation constant?

K  1000 7 . 896  10 5 ( S cm 1 )  1000 3

( cm L )
1
2 -1
Ans. A
c
m   1
= 32.76 S cm mol
Molarity 0 . 0024 ( mol L )

c
A 32 . 76
   8 . 4  10  2
m

A ºm 390 . 5

c  ( 8 . 4  10 2 ) 2
2
0 . 00241
K    1 . 86  10  5
1  1  0 . 084

Q.4 How much charge is required for the following reduction of

i) 1 mol of Al3+ to Al.

ii) 1 mol of Cu2+ of Cu

iii) 1 mol of MnO-4 to Mn2+

Ans. i) The electrode reaction is Al3+ + 3 e  Al

Quantity of charge required for reduction of 1 mol of Al3+ = 3F = 3  9600 C = 289500 C

15
ii) The electrode reaction is Cu2+ + 2 e  Cu

Charge required for reducing 1 mol of Cu2+ = 2F = 2  96500 C = 193000 C

iii) The reaction involved is MnO4- + 5 e  Mn2+

(O. N. Mn changes from +5 to +2)

Charge required for reduction of 1 mol of MnO-4 = 5F

= 5  96500 C = 482500 C.

Q.5 How much electricity in terms of Faraday is required to produce?

i) 20.0 g of Ca from molten CaCl2

ii) 40.0 g of Al from molten Al2O3

Ans. i) The electrode reaction is Cu2+ + 2 e  Cu

40 g

Electricity required for production of 40 g of Ca = 2F

Electricity required for production of 20 g of Ca = 1F or 96500 C

3+
ii) The electrode reaction is Al + 3 e  Al
27 g

Electricity required for producing 27 g of Al = 3F

3F  40 3  96500  40
Electricity required for producing 40 g of Al = 
27 27

= 4.4 F or 428888.9 C.

Q.6 How much electricity is required in coulomb for the oxidation of

i) 1 mol of H2O to O2

ii) 1 mol of FeO to FeO3.

Ans. i) The reaction involved is 2H2O  O2 + 4H+ + 4 e

Electricity required for oxidation of 1 mol of H2O = 2F or 2  96500 = 193000 C

ii) The electrode reaction is

(+2) (+3)
2FeO  Fe2O3 + 2 e

Electricity required for oxidation of 1 mol of FeO = 1F or 96500 C.

Q.7 A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5 amperes
for 20 minutes. What mass of Ni is deposited at the cathode? (At. mass of Ni = 58.7 u)

Ans. Quantity of electricity passed = 5(A)  20  60 (s) = 6000 C

The electrode reaction is Ni2+ + 2 e  Ni

58.7 g

2  96500 C of electricity produces Ni = 58.7 g

16
 58 . 7  6000
6000 C of electricity produce Ni =  1 . 825 g
2  96500

Q.8 Three electrolytic cells A, B, C containing solution of ZnSO4, AgNO3 and CuSO4, respectively are
connected in series. A steady current of 1.5 amperes was passed through them untill 1.45 g of
silver deposited at the cathode of cell B. How long did the current flow? What mass of
copper and of zinc were deposited? At. masses of Ag, Cu, Zn are 108 u, 63.5 u and 65 u
respectively.

Ans. Electrode reaction involving deposition of Ag

Ag+ + e  Ag
108 g

96500  1 . 45
Electricity required for deposition of 1.45 g of Ag =  1295 .6 C
108

Now, 1295.6 C = 1.5(A)  t(s)

1295 . 6 863 . 73
t   863 . 73 s  min
1 .5 60

Reaction for deposition of Cu and Zn are respectively

2+ 2+
Cu + 2e-  Cu Zn + 2 e  Zn
63.5 g 65 g

63 . 5  1295 . 6
Copper deposited by 1295.6 C =  0 . 426 g
2  96500

65 1295 . 6
Zn deposited by 1295.6 C =  0 . 436 g
2  96500

Q.9 Predict the products of electrolysis in each of the following:

i) An aqueous solution of AgNo3 with silver electrodes

ii) An aqueous solution of AgNo3 with platinum electrodes

iii) A dilute solution of H2SO4 with platinum electrodes iv) An aqueous solution of CuCl2 with
platinum electrodes.

Given that

EƟred H2O = - 0.41 V; EƟoxl of H2O = -1.23V; EƟ Ag+/Ag = + 0.80 V; EƟcu2+/Cu = 0.34V
-
i) AgNO3  Ag+ + NO3
At cathode: Ag+ ion will reduce in preference to H2O ,Ag+ + e  Ag

At anode: Ag will get oxidise in preference to H2O, Ag+  Ag+ + e

-
ii) AgNO3  Ag+ + NO3
At cathode: Ag+ + e  Ag
At anode: H2O will oxidise in preference to NO3- ions

17
 1
H2O  2H+ + O2 + 2 e
2

iii) H2SO4  2H+ + SO42-

At cathode: 2H+ + 2 e  H2

+ 1
At anode: H2O  2H + O2 + 2 e
2

iv) CuCl2  Cu2+ + 2Cl-

At cathode: Cu2+ will get reduced in preference to H2O
Cu2+  2 e  Cu
At anode: Cl- ion will oxidise in preference to H2O
2Cl-  Cl2 + 2 e

Competition Plus
ELECTROLYSIS

Process in which electrolyte is decomposed into its constituents by passing electricity through its aqueous
solution or fused (molten) state.

Cathode Anode

Deposition
Deposition of cations
of anions

Electrolytic solution

E le c tro ly te C A


NaC l Na  C l


Reaction occurring at cathode  Reduction reaction (Gain of e )


Na  e  ( fro m c a th o d e ) N a


Reaction occurring at anode  Oxidation reaction (Loss of e )


Cl  C l  e  (Go to anode) (Primary reaction)

C l  C l  C l2 ( g ) ( S e c o n d a ry re a c tio n )

m o le c u le

PREFERENTIAL DISCHARGING THEORY

18
If more than one type of ions are available during electrolysis, then that ion is discharged first at respective
electrodes which requires least energy i.e. discharging potential.

(i) Electrolysis of sodium chloride solution: Ions produced during electrolysis:


NaC l Na  C l


H 2O H O H

At cathode, H  ions are discharged in preference to N a  ions as the discharge potential of H


ions is lower
than N a  ions. Similarly at anode, C l  ions are discharged in preference to O H  ions.


At cathode: 2H

 2 e   H 2 , At anode: 2C l  C l 2  2 e 

 
Thus Na and O H remain in solution.

(i) Electrolysis of copper sulphate solution using platinum electrodes:


C uS O 4
Cu  S O 
4


H 2O H O H


At cathode: Cu  2 e   C u

 1
At anode: 2O H  H 2 O  O 2
 2e 
2

(iii) Electrolysis of sodium sulphate solution using inert electrodes:


N a 2S O 4
2N a  S O 
4


H 2O H O H


At cathode: 2H  2 e   H 2

 1
At anode: 2O H  H 2 O  O 2
 2e 
2

(iv) Electrolysis of copper sulphate solution using copper electrodes :


C uS O 4
Cu  S O 
4


At cathode, copper is deposited. Cu  2 e   C u


At anode, Cu – electrode oxidised to Cu ions which dissolve equivalent amount of copper at the anode.

Cu  C u   2 e 

Cu  S O 
4
 C u S O 4  2 e 

During electrolysis, copper is transferred from anode to cathode.

Q.The pH of a solution of NaCl is 7. This solution is electrolysed. What would be the pH of the solution after
electrolysis?

19
Solution: Greater than 7, due to the formation of OH ions.

Exercise 1.

Predict the products of electrolysis in each of the following case

(i) AgNO3 using Pt electrodes (ii) CuSO4 using Cu electrodes

(iii) Molten NaBr (iv) Aqueous NaCl

Exercise 2.

(i) A current of 1.70 ampere is passed through 300 ml of 0.160 M solution of zinc sulphate for 30 seconds with
a current efficiency of 90%. Find out the molarity of Zn ++ ions after the deposition of zinc. Assume the
volume of the remaining solution is constant during electrolysis.

(ii) Calculate the volume of Cl2 at NTP produced during electrolysis of MgCl2 which produces 6.50 g Mg.

Ionisation constant and degree of dissociation of weak acid or weak base:

 
If cell reaction is P t(H 2 ) / H , H A ( C 1 ) // A g (C 2
) / Ag


0 .0 5 9 1 [H ]
E c e ll
 E oc e ll  lo g

1 [A g ]

1/2
0 .0 5 9 1 (K C)
E c e ll
 E oc e ll  lo g
a

1 C 2

By this expression, we can calculate the value of Ka for acid.

K
If value of Ka and C are known, then we can calculate the value of   a

Determination of pH of a solution:
 
If cell reaction is: P t(H 2 ), (1 a tm ) / H (p H  x ) // C l (1 M ) / H g 2 C l 2 , H g


0 .0 5 9 1 [H ]
2
 [ C l ] 2
E  E oc e ll  lo g
 H g 2 C l2 ( s )
c e ll
2 H 2(g)

0 .0 5 9 1 2
 E c e ll  E oc e ll  lo g H  
2  

or, E c e ll
 E oc e ll  0 . 0 5 9 1 p H

E  E co e ll
or, pH  c e ll

0 .0 5 9 1

DETERMINATION OF THERMODYNAMICAL DATA

 d ( G ) 
G  H  T   (Gibbs – Helmholtz equation)
 d t p

dE 
  n F E  H  n F T  c e ll 
 d T 

20
 dE 
or, H  n F E c e ll  n F T  c e ll 
 d T 

 dE  
or, H  n F E c e ll  T  c e ll 
  d T  

 d E c e ll  H E c e ll
   (Temperature coefficient of the emf of the cell)
 d T  n F T T

Intext Q. A solution containing one mole per litre of each Cu(NO3)2; AgNO3; Hg2(NO3)2 ; Mg(NO3)2 is being
electrolysed using inert electrodes. The values of standard electrode potentials (reduction
potentials in volts are Ag/Ag + =0.80 V, 2Hg/Hg2 ++ = 0.79V, Cu/Cu ++ = + 0.24 V, Mg/Mg ++ = –2.37 V.
With increasing voltage, the sequence of deposition of metals on the cathode will be
(A) Ag, Hg, Cu (B) Cu, Hg, Ag
(C) Ag, Hg, Cu, Mg (D) Mg, Cu, Hg, Ag
Solution: Greater the value of standard reduction potential, greater will be it’s tendency to undergo reduction.
So the sequence of deposition of metals on cathode will be Ag, Hg, Cu. Here, magnesium will not
be deposited because it’s standard reduction potential is negative.

So it has strong tendency to undergo oxidation. Therefore, on electrolysis of Mg(NO3)2 solution, H2 gas will be
evolved at cathode. Hence, (A) is correct.

Intext Q. One coulomb of charge passes through solution of AgNO3 and CuSO4 connected in series and the
conc. of two solutions being in the ratio 1:2. The ratio of weight of Ag and Cu deposited on Pt
electrode is
(A) 107.9 : 63.54 (B) 54 : 31.77
(C) 107.9 : 31.77 (D) 54 : 63.54
W
Solution: Faraday’s IInd Law = constant
E

W W M
(Ag+ + e–  Ag, EAg =
Ag
So,  Cu
)
E Ag
E Cu
1

W E 1 0 7 .9 M
(Cu+2 + 2e–  Cu, ECu =
Ag Ag
   )
W Cu
E Cu
6 3 .5 4 / 2 2

1 0 7 .9
= Hence, (C) is correct.
3 1 .7 7

Intext Q.0.3605 g of a metal is deposited on the electrode by passing 1.2 ampere current for 15 minutes through
its salt. Atomic weight of the metal is 96. What will be its valency?

E
Solution: w  I  t
F

A to m ic w e ig h t
E  E q u iv a le n t w e ig h t 
V a le n c y

A to m ic w e ig h t  I  t
w e ig h t 
V a le n c y F

A to m ic w e ig h t  I  t 96 1 .2 1 5  6 0
or, V a le n c y   3
w e ig h t  F 0 .3 6 0 5 96500

Intext Q.A current of 4 amp was passed for 1.5 hours through a solution of copper sulphate when 3.2 g of copper
was deposited. Calculate the current efficiency.
21
 E
Solution:  w   I  t (According to first law of electrolysis)
F

w F
 U s e d a m p e re (I) 
E t

3 .2 96500 2
  1 .8
6 3 .5 1 .5  3 6 0 0

1 .8
% e ffic ie n c y  1 0 0  4 5 %
4

Intext Q.How many gm of silver could be plated out on a serving tray by electrolysis of a solution containing silver
in +1 oxidation state for a period of 8.0 hours at a current of 8.46 amperes? What is the area of the
tray if the thickness of the silver plating is 0.00254 cm? Density of silver is 10.5 g / cm 3.

Solution: Total electricity passed   8 . 4 6  8  3 6 0 0  C

E 108  8 .4 6  8  3 6 0 0
Deposited mass w  I  t  = 271.65 g
F 96500

2 7 1 .6 5
Volume of Ag   2 5 .9 cm
3

1 0 .5

V o lu m e o f A g 2 5 .9
 
Area of tray T h ic k n e s s 0 .0 0 2 5 4

 1 .0 2 1 0 4 cm
2

Intext Q. A current of 40 microamperes is passed through a solution of AgNO3 for 32 minutes using Pt
electrodes. An uniform thick layer of Ag is deposited covering 43% cathode surface. What is the
total surface area of cathode, if each Ag atom covers 5.4 10 -16 cm 2?
Solution: Total charge passed = (4 10–6  32  60) C = 0.0768 C
Ag+ + e–  Ag
108  0 .0 7 6 8
So, weight of Ag deposited at cathode surface = gm
96500
= 8.6  10-5 gm
8 .6  1 0 5
Now, total no. of Ag atoms deposited =  6 .0 2 3 1 0 23
108
= 4.8  1017
So, surface area of cathode which is covered by Ag atoms
= (4.8  1017  5.4  10–16)= 259.2 cm2
2 5 9 .2 1 0 0 2 2
Total surface area = cm = 602.8 cm
43

Type of Electrochemical cell: (i)Electrode cell (ii)Concentration cell

Electrode cell:
Different electrolytes are used in both half cell.

0 .0 5 9 1
Resultant cell emf determined by E c e ll
 E oc e ll  lo g Q
n

Concentration cell:

Same type of electrolytes used in both half cell but concentration of these electrolytes are different.

22
 0 .0 5 9 1
Resultant cell emf determined by E c e ll
 E oc e ll  lo g Q
n

Here, E
o
c e ll
0

0 .0 5 9 1 1
 E c e ll  lo g
n Q

Exercise 3.

(i) The standard oxidation potential of Ni/Ni 2+ electrode is 0.236 V. If this is combined with a hydrogen
electrode in acid solution, at what pH of the solution will be measured emf be zero at 25 C? Assume [Ni 22+]
= 1 M and P H 2  1 a tm .

(ii) The voltage of the cell given below is 0.46 V

Also Zn
2+
+ 2e  Z n  s  , E
0
= - 0 .7 6 3 V .

H +
 S O 32 - 
Calculate the value of K2, where K2 =   
H S O 3 
-
 

23
 ASSIGNMENT Chapter – 3, Electro Chemistry
MISCELLANEOUS EXERCISES

Level - 1
1. Define electrochemical equivalent. How is it related to the equivalent weight of the element?

2. What is the effect of dilution on specific conductivity and equivalent conductivity? Explain briefly giving
reasons.

3. What are primary cells? How does a dry cell function?

4. What is understood by a normal hydrogen electrode? Give its significance?

5. Explain the function of salt bridge in an electrochemical cell.

6. What is an electrochemical series? How does it help us in predicting whether a redox reaction is feasible in a
given direction or not?

o 2 2
7. What does positive value of E c e ll
in case of galvanic cell like Zn / Zn II C u / Cu indicate?

o
8. Write Nernst equation for the general electrochemical change of the following type at 25 C.


aA  b B 
ne
cC  d D

9. What is rusting? Indicate the chemical changes in rust formation.

10. How does electrochemical series help in?

(i) Comparing the relative oxidising or reducing powers of different elements.

(ii) Predicting whether a metal will react with the acid to give hydrogen gas or not.

11. Why fluorine cannot be obtained by electrolysis of aqueous HF solution, though it is a good conductor of
electricity?

12. What would happen if no salt bridge were used in an electrochemical cell
(like Zn – Cu) cell?

13. Explain the terms, equivalent conductivity and molar conductivity. How are they
inter – related?

14. Give the construction of a lead battery. Explain giving reactions how it can be recharged.

15. Give a short account of corrosion and its mechanism.

Level-II

1. A solution of Ni(NO3)2 is electrolysed between platinum electrodes using a current of 5.0 amp for 30 minutes.
How much of nickel will be produced at the cathode.

6
2. A cell contains two hydrogen electrodes. The negative electrode is in contact with a solution of 10 M

24
 o
hydrogen ions. The emf of the cell is 0.118 V at 25 C. Calculate the concentration of hydrogen ions at the
positive electrodes.

3. The resistance of a decinormal solution of an electrolyte in a conductivity cell was found to be 245 ohms.
Calculate the equivalent conductivity of the solution if the electrodes in the cell were 2 cm apart and each has
an area of 3.5 square cm.

4. A 100 watt, 110 volt incandescent lamp is connected in series with an electrolytic cell containing cadmium
sulphate solution. What mass of cadmium will be deposited by the current flowing for 10 hrs.

5. Calculate the emf of the following cell

2 2
Fe / Fe II S n / Sn a = 0.6 , a = 0.2 , E Fo e  0 . 4 4 V o lt, E
o
Sn
 0 . 1 4 V o lt

6. A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298 K. Calculate
the electrode potential E o   0 . 7 6 eV .
 Zn /Zn 

2 
7. Calculate the potential (emf) of the cell Cd / Cd (0 .1 0 M ) II H ( 0 . 2 0 M ) / P t, H 2 ( 0 . 5 a tm )

8. The standard electrode potentials are given as E

o
2
 0 .3 4 V and E
o
  0 .8 0 V. Calculate the cell
Cu /C u Ag /Ag

 2 o
potential (E) for the cell containing 0.100 M Ag a n d 4 .0 0 M C u at 25 C.

1
9. For the reaction; N 2(g)  3H 2(g) 2N H 3(g ) , enthalpy and entropy changes are -92.4 kJ and 1 9 8 . 2 Jk

1 1
respectively. Calculate the equilibrium constant of the reaction (R = 8.314 J k m ol ).

o
10. Calculate the cell e.m.f. at 25 C for the following cell:

2 2
M g(s) / M g (0 .0 1 M ) II S n (0 .1 M ) / S n (s ) ,Given E
o
2
 2 . 3 4 V , E
o
2
 0 . 1 3 6 V
Mg /M g Sn /S n

Calculate the maximum work that can be accomplished by the operation of this cell.

Level-III

1. Conductivity of two electrolyte solutions A and B each having a concentration of 0.1 M are
8 .5  1 0 2 a n d 4 .1 1 0
4
S cm
1
respectively. Which of the two offers less resistance to the flow of current.

2. The electrolysis of a metal salt solution was carried out by passing a current of 4 amp for 45 minutes. It
1
resulted in the deposition of 2.977 g of the metal. If atomic mass of the metal is 106.4 g m ol , calculate the
charge on the metal cation.

 
3. Iodine (I2) and bromine (Br2) are added to a solution containing iodide (I ) a n d b ro m id e (B r ) ions. What
reaction would occur if the concentration of each species is 1 M? The electrode potential for the reactions are:

E
o
  0 .5 4 V, E
o
  1 .0 8 V
I2 / I B r2 / B r

4. The atomic mass of a metal M is 52.01. When the metal chloride of the metal ‘M’ is electrolysed, metal is
deposited at the cathode. Chlorine gas is evolved at anode. For every gram of metal deposited, 725 ml of dry
o
Cl2 gas is evolved at 25 C and 740 mm Hg. Find the formula of the chloride of the metal.

5. The standard reduction potential at o

25 C of the reaction H 2O  2 e   H 2  2 O H  is -0.8277 V. Calculate
the equilibrium constant for the reaction

25
 2H 2 O  H 3 O   O H  at 25 C.
o

C u / C uS O 4
II C u S O 4
/ Cu o
6. The emf of the cell is -0.03V at 25 C. Calculate the value
a  0 .1 x

of x.

7. The mass of copper deposited from a solution of copper sulphate by a uniform current of
1 amp flowing for 33 minutes is 0.65 g. Find the electro – chemical equivalent of hydrogen from the result.

8. An electrode is prepared by dipping a silver rod in a saturated solution of AgCl and another electrode is
prepared by dipping a silver rod in a saturated solution of Ag2CrO4. These two electrodes are used to construct
o
a galvanic cell. Calculate the emf of such a galvanic cell at 25 C. It is given that
1 0 1 2
K sp
, AgC l  1 .8 1 0 and K sp
, A g 2 C rO 4
 2 .4 1 0

2
9. The standard reduction potential for Cu /C u is +0.34 Volt. Calculate the reduction potential at pH = 14 for
1 9
the above couple. K sp
o f C a ( O H ) 2 is 1 . 0 1 0 .

10. Calculate the equilibrium constant for the reaction

2
Fe  C e 4   F e 3   C e 3 

Given E
o
4 3
 1 .4 4 V and E
o
3 2
 0 .6 8 V.
Ce /C e Fe /F e

Ch.3,Electrochemistry: ASSIGNMENTS

Objective:

Level – I

1. A redox reaction is spontaneous in a given direction, if:

(A) EMF is zero (B) EMF is negative

(C) EMF is positive (D) None of these

2. Which of the following is a secondary cell?

(A) Dry cell (B) Mercury cell (C)Ni – Cd cell (D) H2 – O2 cell

3. The amount of electricity required to deposit 1 mol of Aluminium from a solution of AlCl3 will be

(A) 0.33 F (B) 1 F (C)3 F (D)1 amp

4. The standard EMF for the cell reaction

Zn  C u 2   Z n 2   C u is 1.1 Volt at 2 5 o C . The emf of the cell reaction when 0.1 M Cu2+ and 0.1 M Zn2+
o
solutions are used, at 2 5 C is

(A) 1.10 V (B) 0.10 V (C)-1.10 V (D)-11.0 V

26
 N o
5. The specific conductance of a solution of KCl at 25 C is 0.002765 mho. If the resistance of a cell
50
containing this solution is 400 ohms. What is cell constant?

(A) 2 (B)1.106 (C)3 (D)3.2

6. A current of 2.0 A passed for 5 hours through a molten metal salt deposits 22.2 g of metal (Atomic weight =
177). The oxidation state of the metal in the metal salt is:

(A) +1 (B)+2 (C)+3 (D)+4

7. The conductivity of a saturated solution of BaSO4 is 3 .0 6  1 0 6 ohm

1
cm
1
and its equivalent conductance is
1 2 1
1.53 ohm cm e q u iv . The Ksp for BaSO4 will be

(A) 4  1 0 1 2 (B) 2 . 5  1 0 9 (C) 2 . 5  1 0 1 3 (D) 4  1 0 6

o 2 2 o
8. E for the cell Zn / Zn (aq)
II C u (aq)
/ Cu is 1.10 V at 25 C. The equilibrium constant for the reaction

Zn  C u 2 ( a q ) Cu  Z n 2 ( a q ) is of the order of

3 7
(A) 10 (B) 10
37
(C) 1 0 1 7 (D) 1 0 1 7

9. For the cell reaction, C u 2 ( c 1 aq)

 Z n ( s )  Z n 2 ( c 2 aq)
 C u ( s ) of an electrochemical cell, the change in free
energy, G , at a given temperature is a function of

c 
(A)  n c 1 (B) n  2 
 c1 

(C)  n c 2 (D)  n ( c 1  c 2 )

10. Which of the following graphs will correctly correlate Ecell as a function of concentrations for the cell (for
different M and M)?

Zn(s) + Cu+2(M)  Zn+2(M) + Cu(s), E

0
c e ll
= 1.10 V

2
[Z n ]
X-axis: lo g 2
, Y-axis: Ecell
[C u ]

(A) (B)
1 .1 0 V
1 .1 0 V

- 1 .0 0 + 1 .0 - 1 .0 0 + 1 .0

(C) (D)

1 .1 0 V
1 .1 0 V

- 1 .0 0 + 1 .0 - 1 .0 0 + 1 .0

27
 
11. Cu (aq)
is unstable in solution and undergoes simultaneous oxidation and reduction according to the reaction.


2C u (aq)
 C u 2 ( a q )  C u ( s )

o
Choose correct E for the above reaction if

E
o
2
 0 .3 4 V and E
o
2   0 .1 5 V
Cu /C u Cu /C u

(A) + 0.49 V (B) + 0.38 V (C) 0 . 1 9 V (D) 0 . 3 8 V

12. For the cell

2 2
Z n(s) / Z n (aq)
II F e (aq)
/ F e (s)

E
o
2
 0 .7 6 V and E
o
2
 0 .4 4 V , th e E
o
c e ll
is
Zn /Zn Fe / Fe

(A) -1.20 V (B) -0.32 V (C) 1.20 V (D) 0.32 V

13. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 because

(A) Zn acts as oxidising agent when reacts with HNO3

(B) HNO3 is weaker acid than H2SO4¬ and HCl

(C) In electrochemical series, Zn is above hydrogen


(D) NO 3
is reduced in preference to hydronium ion

14. At cathode, the electrolysis of aqueous Na2SO4 gives

(A) Na (B)H2 (C)SO3 (D)SO2

15. What will be the emf of the given cell


P t / H 2 (P 1 ) / H (aq)
/ H 2 (P 2 ) / P t

RT P1 RT P1
(A) n (B) n
F P2 2F P2

RT P2
(C) n (D) None of these
F P1

16. A current is passed through 2 voltameters connected in series. The first voltameter contains XSO4(g)(aq.) the
relative atomic masses of X and Y are in the ratio of 2:1. The ratio of the mass of X liberated to the mass of Y
liberated is

(A) 1:1 (B)1:2 (C) 2:1 (D)None of these

17. The correct statement among the following is:

(A) The EMF of a cell is an extensive property and so is the G of the cell reaction

(B) The EMF of a cell is an intensive property and so is the G of the cell reaction

28
 (C) The EMF of a cell is an intensive property whereas G of the cell reaction is an extensive property.

(D) The EMF of a cell is an extensive property but G of the cell reaction is intensive.

18. Moderate electrical conductivity is shown by

(A) Silica (B)Graphite (C)Diamond (D) carborundum

19. The standard reduction potentials of the elements A, B and C are + 2.73V, - 1.85 V and -1.36 respectively. The
order of their reducing power is

(A) B > C > A (B) A > B > C

(C) C > B > A (D) B > A > C

20. In electrolysis of alkaline water, a total of 1 mole of gases is evolved. The amount of water decomposed would
be

(A) 1 mol (B) 2 mol

(C) 1/3 mol (D) 2/3 mol

Level – II

1. Z n(s)  C l 2 (1 a tm )  Z n 2   2 C l 

o
The E of the cell is 2.12 V. To increase E

(A) Zn2+ concentration should be increased

(B) Zn2+ concentration should be decreased


(C) Cl concentration should be increased

(D) Partial pressure of Cl2 should be decreased

2
2. C r2 O 7
 I   I 2  C r 3 

E
o
c e ll
 0 .7 9 V, E
o
2
 1 .3 3 V, EI
o
2
?
C r2 O
7

(A) 0.54 V (B) -0.054 V

(C) +0.18 V (D) -0.18 V

3. Time required to deposit one millimole of aluminium metal by the passage of 9.65 amp. through aqueous
solution of aluminium ion is

(A) 30 sec. (B) 10 sec.

(C) 30,000 sec. (D) 10,000 sec.

4. An electric current is passed through silver voltameter connected to a water voltameter. The cathode of the
silver voltameter weighed 0.108 g more at the end of the electrolysis. The volume of oxygen evolved at STP is

(A) 56 ml (B) 550 ml (C)5.6 ml (D)11.2 ml

5. The standard reduction potentials for two reactions are given below :

A g C l( s )  e   A g ( s )  C l ( a q ) , E
o
 0 .2 2 V

29
 
Ag (aq)
 e   A g ( s ) , E
o
 0 .8 0 V

The solubility product of AgCl under standard conditions of temperature (298 K) is given by :

(A) 1 .6  1 0 5 (B) 1 .5  1 0 1 0

(C) 3 .2  1 0 1 0 (D) 3 .2  1 0 8

6. On the basis of information available from the reaction

4 2 1
AlO 2
 A l2 O 3 , G  8 2 7 kJ m ol of O 2, the minimum emf required to carry out electrolysis of
3 3
Al2O3 is :

(A) 2.14 V (B) 4.28 V

(C) 6.42 V (D) 8.56 V

7. A Chemist found that the standard electrode potential E 0 2 , of the zinc electrode is –0.763 Volt. Which cell
Zn / zn

will give this value of EMF?

(A) Pt, H2 (1 atm) | H+ (10M) || Zn+2 (10M) | Zn

(B) Pt, H2 (1 atm) | H+ (1M) || Zn+2 (1M) | Zn

(C) Zn | Zn+2 (1M) || H+ (1M) | H2 (1 atm), Pt

(D) Zn | Zn+2 (10M) || H+ (10M) | H2 (1 atm), Pt

8. The standard reduction potentials at 298 K for the half reactions are given against each

2
Zn (aq)
 2e  2 Z n(s);  0 .7 6 2 V

3
Cr (aq)
 3e  C r( s ) ;  0 .7 4 0 V


2H (aq)
 2e  H 2(g ); 0 .0 0 V

3
Fe (aq)
 3e  Fe
2
(aq)
; 0 .7 7 0 V

Which is strongest reducing agent?

2+
(A) Zn(s) (B) Cr(s) (C) H2(g) (D)Fe (aq)

9. When a lead storage battery is discharged

(A) SO2 is evolved (B) Lead sulphate is consumed

(C) Lead is formed (D) Sulphuric acid is consumed

10. A dilute aqueous solution of Na2SO4 is electrolysed using Platinum electrodes. The products at the anode and
cathode are

(A) O2, H2 (B) S 2 O 82  , Na (C)O2, Na (D) S 2O

2
8
, H2

2+ 2+ +
11. The standard reduction potential of Cu / Cu and Cu / Cu are 0.337 and 0.153 V respectively. The standard
2+
electrode potential of Cu / Cu half cell is

30
 (A) 0.184 V (B)0.827 V (C) 0.521 V (D) 0.490 V

  o
12. A gas X at 1 atm is bubbled through a solution containing a mixture of 1 M y and 1M z at 25 C. If the
reduction potential of z > y > x, then

(A) y will be oxidise x and not z (B) y will be oxidise z and not x

(C) y will be oxidise both x and z (B) y will reduce both x and z

13. The correct order of equivalent conductance of infinite dilution of LiCl, NaCl and KCl is

(A) LiCl > NaCl > KCl (B) KCl > NaCl > LiCl

(C) NaCl > KCl > LiCl (D) LiCl > KCl > NaCl

14. Saturated solution of KNO3 is used to make salt bridge because

 
(A) Velocity of K+ is greater than that of NO 3
(B) Velocity of NO 3
is greater than that of K+


(C) Velocity of both K+ and NO 3
are nearly the same (D) KNO3 is highly soluble in water

15. In an electrolytic cell, flow of electron is from

(A) Cathode to anode in the solution (B) Cathode to anode through external supply

(C) Cathode to anode through internal supply (D) Anode to cathode through internal supply

Level - I
1.C 2.C 3.C 4.A 5.B 6.C 7.D 8.B 9.B 10.B 11.B 12.D

13.D 14.B 15.B 16.A 17.C 18.B 19.A 20.D

Level – II 1.B 2.A 3.A 4.C 5.B 6.A 7. C 8.A 9.D 10.B 11.C 12.A 13.B 14C 15B

31
32