CHEMISTRY LECTURE NOTES

TOPIC : ELECTROCHEMISTRY
(LECTURE NO. 1 TO 10)
(2012-13)
 Year concered Topic Nature of questions
2007 Reduction potential Linked Comprehension Type
(Total No. of  Standard reduction potential of some of the half cells were given.
Que. = 7) Feasibility of some oxidiation and reduction were asked in the statement. (No. of
Questions = 2)
 Sodium fusion extract (from aniline) + FeSO4 + H2SO4 (in the presence of air) 
Prussion blue precipitate
Precipitate complex = ?

Electrolysis Linked Comprehension Type

A 4.0 M aqueous solution of NaCl prepared in 500 mL is electrolysed (Given)
 Total no. of moles of chlorine gas evolved = ?
 On using Hg-electrode, the maximum weight of amalgan formed = ?
 Total charge required for complete electrolysis = ?

Simple Redox Matrix-Match Type

Out of various given ionic reactions which involve redox or disproportionation = ?

2006 Galvanic cell Linked Comprehension Type

(Total No. of The action of Tollen's reagent is explained with all concerned Eºcell is given
Que. = 4) information.
 In K = ? (For the oxidation reaction of glucose)
 The effect of addition of NH3 to solution as pH raises in terms of Eoxid. and Ered.
 Statement question based on spontaneity of some of the reactions.

Conductivity Calculation - Based

–7
Conductivity of AgBr and 10 mole AgNO3 solution = ?
+ – –
Ksp (AgBr) and equivalent conductivity at infinite dilution for Ag , Br and NO3 are
given.
2005 Gibbs free energy 2+
 Gº for rusting of ion = ? Standard reduction potential of H2O (H+) and Fe are
(Total No. of given.
Que. = 2)  log10 Ksp of AgCl = ?
– +
Gº (AgCl), Gº (Cl ) and Gº (Ag ) are given
Galvanic cell log10 Q = ? Zn—Ag Cell ;
(Nernst equation) +
Eº for Ag and Zn
2+
are given

2004 Keq—Eºcell 2+ 2+
 Keq = ? (For Zn / Zn (0.1 M) || Fe (0.01 M) / Fe) ; emf is given.
(Total No. of 2+ 2+ + 3+
Keq = ? (For Cu + ln Cu + ln ) ;
Que. = 2)
Eº for half cells are given.
2003 Electrolytic cell  Direction of flow of electrons = ?
(Total No. of Galvanic cell Two Zn—Cu cell differ in their emf by 0.03 V, cell of higher emf has 0.5 M CuSO4;
Que. = 2) [CuSO4) in other cell = ?

Conclusion :
Analysis in the light of new pattern estabishes high importance of this unit, especially in term of passage
based questions. In year 2007, two passage (6 Qs) and 1 Matrix-Match (one of the most scoring type) have
been asked, it’s really surprising! The recent trends suggest that you take more, conceptual and less
mathematical approach to this unit. The three major segments of erlectrochemistry can be arranged as
follows in decreasing significance (on the basis of analysis)
 Galvanic cell
 Electrolytic cell
 Conductivity
RT
The interrelationship in between thermodynamic parameters (Gº – nFEºcell, Eºcell = ln K) and equilib-
nF
rium constant also requires your extra attention.

Page # 1
 LECTURE - 1
Electrochemistry

Electrochemical cells Electrolysis Electrical

Galvanic cells (Galvano) Electrolytic cells Conductance
Voltaic cells (Volta)
Redox cells
I. Electrochemical cell : A device which converts chemical energy into electrical energy.
(Through Redox reactions)

Zn(rod)

2+ –
Zn Zn + 2e Zn2+
CuSO4(aq)

2+ –
(heat will be generated)
Cu + 2e Cu(s)

Cu(s)

Zn + CuSO4 ZnSO4 + Cu

 Whenever a metal rod is placed in contact with its salt solution (with its ions)
following two tendancies (or case) are observed.

1. Solution pressure  de electronation

2. Osmotic pressure  electronation

CASE-I (SOLUTION PRESSURE)

For some metals the atoms from neutral rod will move into solution in the form of ions leaving behind the e–
on the rod.

Metal (M)

n+
M

M(s) Mn+(aq) + ne–

(i) This tendancy is called solution pressure
(ii) In solution [Mn+] 

(iii) On rod –ve change 

Page # 2
Note-1 This process will not take place till indefinite time because after some time sufficient –ve charge will be
develop on the rod which will attract extra Mn+ ions from the solution and the rate of deposition of the ions on
the metal rod becomes equal to rate of dissociation of the metal atoms into the solution.
Example : Zn rod placed in contact with ZnSO4 / ZnCl2 / Zn(NO3)2

– –
– – Zn (rod)
– –
– –
– –
– –
– –
– –
– –
– –
+ – – +
+ – – +
– –
+ – – +
+ – – + Solution is extra +ve
– –
+ – –
– – +
+ – – +
+ – – +
– –
+ – – +
+ + + + +

Because of this charge seperation there will be a potential difference between the metal rod and its solution
which is called electrode potential and the metal rod in contact with its salt solution is called an electrode.
 The above type of electrode is called anode
(a) For anode S.P. > O.P.
(b) Anode will be of -ve polarity
(c) Oxidation will take place on anode

Zn  Zn2+ + 2e–

(d) Anode will be the source of the electron it will send e– into the outer circuit.

CASE-II (OSMOTIC PRESSURE)

Osmotic pressure : Tendancy of metal ions to get deposited on metal rod.

+ +
+ + M (Metal)
+ +
+ +
+ +
+ +
– + + –
– + + –
– + + –
– + + – Solution is extra –ve
– + + –
– –
– + + –
– + + –
– + + –
– – – –

In some metals the opposite tendancy (deposition of ions on the metal rod) or osmotic pressure dominates
our solution pressure. This type of electrode is called cathode.
(a) O.P > S.P
(b) Cathode will be of +ve (positive) polarity
(c) Reduction will take place at cathode
Cu2+ + 2e–  Cu(s)
(d) Cathode will consume / gain electron from the outer circuit
Note : Electrode for which OP = SP
Null electrodes / inert electrodes
Example : (Platinum)

Page # 3
Galvanic Cell
Construction of electrochemical cells

- -
e e

+
Zinc (anode) Salt bridge Copper (cathode)
KCl

Zn(s) Zn+2(aq) +2e - Cu +2(aq) + 2e - Cu(s)

Anodic compartment cathodic compartment

Note : (i) Direction of current from cathode to anode

(ii) Direction of flow of e– from anode to cathode

SALT BRIDGE :
Filter
paper

KCl

1. A glass tube / polythene tube (U-shaped) is filled with a paste of any electrolyte (generally KCl) with
agar-agar powder and dride.
It will form net like structure or porus structure through which ions can move.

2. Electrolyte to be used in salt bridge should be such that the speed of its cations is equal to speed of its
anions.
speed of cation = speed of anion
mobility of cation = mobility of anion
transport no of cation = transport no of anion

3. If in any compartment there are silver ions Ag+ or mercurous (Hg22+) or Mercuric ions (Hg2+) or T  + (thalium)
then KCl should not be used otherwise there will be precipitation of AgCl, HgCl2, TlCl at the mouth of salt
bridge. And salt bridge will stop functioning.
In this case KNO3 or NH4NO3 are generally used (speeds are different but we have to use bacause no other
option)

4. Salt bridge completes the internal circuit of the cell as will as maintains electrical neutrality.

5. Salt bridge also minimises liquid-liquid juction polential.

Page # 4
 Electrical double layer
liquid-liquid juction polential : 
Whenever two liequides of cathodic and anodic compartments are
brought in contact, there will be generation of electrical double – +
– +
layer due to which a potential different is generated called liquid- – + –
+
liquid junction potential which opposes the e.m.f. of the cell or – + –
+
– + – +
potential difference of the cell. – + – +
– + – +
– +
– – +
+ –
ZnSO4 + – CuSO4

IUPAC NOTATION FOR REPRESENTATION OF AN ELECTROCHEMICAL CELL

Anode | | Cathode

Salt bridge

Zn(s) | Zn2+ (aq) | | Cu2+ (aq) | Cu(s)

 
Phase diff. Phase diff.

CELL REACTION :
Anode : Zn(s)  Zn2+(aq) + 2e–
Cathode : Cu2+(aq) + 2e–  Cu(s)
–––––––––––––––––––––––––––––––––––
Zn + Cu2+(aq)  Zn2+(aq) + Cu

ELECTRODE POTENTIAL
EZn | Zn2+ = oxidation potential of zinc electrode
(aq)

E Zn 2  = Reduction potential of zinc electrode

( aq ) | Zn

For any electrode  oxidiation potential = – Reduction potential

Ecell = R.P of cathode – R.P of anode

(always true)
Ecell = R.P. of cathode + O.P of anode
Ecell is always a +ve quantity & Anode will be electrode of low R.P
Zn(s) | Zn2+ (0.1M, aq) | | Cu2+ (1M, aq) | Cu(s)
Ecell = E Cu2  / Cu – E 2 
aq Zn ( aq ) / Zn

Zn Rod.
Standard electrode potentials :
E º Zn / Zn 2  = SOP of Zinc
( aq )

E º Zn 2  / Zn = SRP of Zinc
( aq )

EºCell = SRP of cathode – SRP of anode

(At any temperature but temperature should be constant) [ZnSO4] = 1 M
EºCell = Eº Cu2aq / Cu – Eº Zn 2aq / Zn

Ex. Cu(s) | Cu2+

(aq)
+
|| Ag(aq) | Ag(s)
Anode : Cu  Cu2+ + 2e–
Cathode : Ag+ + e–  Ag] × 2
–––––––––––––––––––––––––––––––
Cu + 2Ag+(aq) 2Ag + Cu2+
(aq)

EºCell = Eº Ag / Ag – Eº Cu2  / Cu

Page # 5
 STANDARD HYDROGEN ELECTRODE (SHE)

H2(g) (a)
(at 1 atm)

Pt black
electrode
H3O+(aq)
(1M) Solution of H+(aq) ion
[Acid solution]
[H+] = 1M
Hydrogen Electrode

Note = The SRP or SOP of SHE is taken to be zero, at all temperatures but actually it is not zero.

Anode : H2(g)  2H+(aq) + 2e– (oxidation)

Cathode : 2H+(aq) + 2e–  H2(g) (Redction)

Representation of SHE

For Anode : Pt(s) | H2(g) (1 atm) | H+(aq) (1 M) | |


Metals will be at the ends

For Cathode : | | H+(aq) (1 M) | H2(g) (1 atm) | Pt(s)


Metals will be at the ends

 SRP or SOP of all other electodes are calculated by making a cell using standard hydrogen electrode (SHE)
and the other electrode and then potential difference of this cell is measured using potentio-meter

V
e
–

Zn (rod) H2 (g)

Zn2+ 1M
(1 M)

EºCell = SRP of cathode – SRP of anode

always +ve  For spontaneous cell reaction

Page # 6
 LECTURE - 2
ELECTRO CHEMICAL SERIES :
The SRP values of different electrodes are claculated with reference to (SHE) and are arranged in a series
(in increasing order) and the series is called electrochemical series.

Half cell reaction EºRP in volts

Li+ + e–  Li –3.05 V [Strongest reducing agent]

K+ + e–  K –2.936 V

Ca2+ + 2e–  Ca – 2.87 V

Na+ + e–  Na – 2.71V

Mg2+ + 2e–  Mg – 2.36 V

Al3+ + 3e–  Al – 1.66 V

2H2O + 2e–  H2(g) + 2OH– – 0.828 V

Zn2+ + 2e–  Zn(s) – 0.76 V

Fe2+ + 2e–  Fe – 0.44 V

Pb2 (s) + 2e–  Pb(s) + 2– –0.305 V

Sn2+ + 2e  Sn(s) – 0.14 V

Pb2+ + 2e  Pb(s) – 0.13 V

Fe3+ + 3e–  Fe –0.04 V

* 2D+ + 2e–  D2 (g) – 0.01 V

2H+ + 2e–  H2 (g) 0.00 V

AgCl + e+  Ag (s) + Cl– 0.22 V

Cu2+ + 2e–  Cu(s) 0.34 V.

Cu+ + e–  Cu(s) 0.52 V.

Fe3+ + e–  Fe2+ 0.77 V

Ag+ + e–  Ag 0.80 V

F2 + 2e–  2F– 2.87 V [Strongest Oxidasing Agent]

Note : Reactivity of metal decrease on moving down the group.

FEATURES OF ELECTROCHEMICAL SERIES :

1. Greater the value of S.R.P. greater will be tendeancy to get reduced, so, the element or compound will be
stronger oxidising agnent.
2. Smaller the value of SRP (higher the value of SOP) so greater will be the tendancy to get oxidised hence
compound or elements will be a better reducing agent.
+7 +2
Ex.1 MnO4–  Mn2+ Eº = 1.51 V
Both are reduced
+6 +3
Cr2O72–  Cr3+ Eº = 1.40 V

which is better oxidising agnet

Ans. Mn O4–  Mn2+

Page # 7
Ex.2 E º MnO  | Mn 2  = 1.51 V
4

Eº Cr 3  | Cr2O 7 = –1.40 V

Sol. Eº Cr O  | Cr 3  = 1.40
2 7

 Ans is MnO4–  Mn2+

3. Anode – Electrode higher up in the series

Cathode – any electrode lower in series in comparison to anode

4. Metals which are higher up in the series can displace metals in lower in the series from their salt solution
CuSO4 + Zn  ZnSO4 + Cu

ZnSO4 + Cu  X (no reaction)

Ex.3 Zn  Zn2+ + 2e– SRP = –0.76 V

Cu2+ + 2e–  Cu SRP = + 0.34 V

Eºcell = 1.10 V
If reaction is reversed then
Eºcell = –0.76 – 0.34 = – 1.10 (not possible) because Eºcell (–ve) is not possible.

Standered E.M.F. = Eºcell

5. On moving down the series the electro (+ve) nature of the metals or elements decreases and also the
reactivity of metals decreases.
(Alkali or alkaline earth metlas) + cold water  H2(g)
Fe, Ni, Co, Pb, Sn + Steam  H2(g)
Cu, Ag, Au + Cold watrer or Steam  No reaction.

6. Metals placed above than hydrogen can release H2 gas on reaction with dilute acid solution.
Mg + HCl  MgCl2 + H2
Cu + HCl  X

7. Thermal stability of metal oxide : Depends upon electropositive nature of metal. As electropositive
nature decreases from top to bottom. The thermal stability of the oxide also decrease from top to bottom.

BaO, Na2O, Al2O3  Nodecomposition.
 
(a) Ag2O  2Ag + 1/2 O2 ; (b) 2HgO  2Hg + O2

NUMERICALS :
Q.1 Calculate E°cell of the cell made of electrodes
Eº Ag | Ag = –0.80 V (oxidation)

E º MnO  | Mn 2  = 1.51 V (reduction)

4

Sol. Eºcell = SRP cathode – SRP of anode

Eº Ag | Ag
= 0.80 V (Anode)

Eºcell = 1.51 – 0.80 = 0.71 V

Page # 8
Q.2 Check the following cell is feasible or not
Ag(s) | Ag+(aq) | | Cu2+(aq) | Cu(s)

Given : Eº Ag | Ag = – 0.80 V

 Eº Cu | Cu2  = – 0.34 V

Sol. E0 = 0.80 V
Ag | Ag

E0 = 0.34 V
Cu2  | Cu

 Eºcell = – 0.34 – 0.80 = –0.46 (not possible) (–ve)

CALCULATION OF SRP OF AN ELECTRODE FROM THE GIVEN SRP VALUE OF OTHER ELECTRODES.

The gibbs energy change of a reaction of a cell (electrode) is given by

Gº = – nFEºcell
= –nFEºelectrode
where
n  no. e– involved in cell (electrode) reaction
F  Faraday’s constant = 96500 C  (96485 C)
= change on 1 mole of e–
= (1.6 × 10–19 C) × 6.022 × 1023
= 96500 C
Note : 1. E.M.F. is an intensive properties (not dependent on mass or size) so we can not add or subtract.
Eº value of two reaction to calcualte Eº of any other reaction.
2. G is an extensive properties we can add or subtract. G value of two reaction.

Q.3 Claculate Eº Cu  | Cu
=?
given that
Eº Cu2  | Cu = 0.337 V

Eº Cu2  | Cu = 0.153 V

(i) Cu2+ + 2e–  Cu Eº = 0.337 V

Gº1 = –n1FEº1 (n1 = 2)
(ii) Cu2+ + e–  Cu+ Eº = 0.153 V
G20 = –n2FEº2 (n2 = 1)

Target Cu+ + e–  Cu Eº3 = ?

Gº3 = –n3FEº3 (n3 = 1)
Gº3 = Gº1 – Gº2
+Gº3 = –2F × 0.337 + F × 0.153
–FEº3 = – 2F × 0.337 + F × 0.153
 Eº3 = 0.521

Q.4 Calculate
Eº MnO  | MnO = ?
4 2

given that
E º MnO  | Mn 2  = 1.51
4

E º MnO | Mn 2  = 1.23 V
2

Page # 9
Sol. MnO4–  Mn2+ + 5e– Eº = 1.51

MnO2  Mn2+ + 2e– Eº = 1.23

____________________________________________________
MnO4–  MnO2 + 3e–

(1) 5e– + 8H+ + MnO4–  Mn2+ + 4H2O

(2) 2e– + 4H+ + MnO2  Mn2+ + 2H2O

Target MnO4– + 4H+ + 3e–  MnO2 + 2H2O

Target = (1) – (2)

Gº3 = Gº1 – Gº2
– 3 FEº3 = (–5 FEº1) – (–2 FEº2)
–3F × Eº3 = – 5 × 1.51 F + 2 × 1.23 F
2.46  7.55 5.09
Eº3 = = = 1.69
3 3

n1E º1 n 2E º 2
or Eº3 =
n1  n 2

1.51 5  2  (1.23) 7.55  2.46

Eº = = = 1.69
( 5  2) 3

Note : 1. If Gº = –ve (negative) then process is spoutaneous.

2. Eº is intensive properties so it does not change by multiplying or dividing the reaction with
any coefficient but Gº is extensive properties so it change.
Ex.1 Zn2+ + 2e–  Zn(s) Eº = – 0.79 V
 Gº = –2 × 96500 × (–0.79)
2Zn2+ + 4e–  2Zn(s) Eº = – 0.79 V
 Gº = –4 × 96500 × (–0.79)

Ex.2 Zn  Zn2+(aq) + 2e– E º Zn | Zn 2  = 0.79 V

 Gº = –nFEº
Gº = –2 × 96500 × (0.79)

3. Gº = The max. amount of useful work which can be obtained from a given cell
Gº = –nFEºcell
For electrode Gº = –nFEºelectrode

Ex. Electrode
5e– + 8H+ + MnO4–  Mn2+ + 4H2O E º MnO  | Mn 2  = 1.51
4

Gº = –5 × 96500 × Eºelectrode

4. For a cell reaction n = no. of e– which are cancelled out during formation of cell reaction.
Ex. Anode : Zn  Zn2+ + 2e–

cathode : Ag+ + e–  Ag] × 2

_______________________________
Zn + 2Ag+ 2Ag + Zn2+  Gº = –nF Eºcell
n=2
Here two electron have been cancelled during formation of cell reaction that why n = 2.

Page # 10
Q.1 Predict whether the following equation will lake place or not
Cu(s) + 2H+(aq)  Cu2+(aq) + H2(g)
Given that Eº Cu2  | Cu = 0.34 V ; E º H | H2 =0

Sol. Anode Cu(s)  Cu2+(aq) + 2e–

Cathode 2H+(aq) + 2e–  H2(g)

_______________________________
Cu(s) + 2H+(aq)  Cu2+(aq) + H2(g)

Gº = –2 × F × (– 0.34) = +ve

 Gº is positive that why this reaction will not take place.

Note : If reaction is not in standard state then use Ecell and if reaction is in standard state use Eºcell.

Q.2 Predect the feasibility of reaction

Given Eº Fe 3  | Fe 2 
= + 0.77 V

EºI | I–
= 0.54 V
2

Reaction 2Fe3+ + 2–  2Fe2+ + 2

Sol. Cathode : 2Fe3+ + 2e  2Fe2+ Reduction

Anode : 2–  2 Oxidation

Eºcell = 0.77 – 0.54 = 0.23 (Eºcell = SRP of cathode – SRP of anode)
 Eºcell = +ve
 This reaction is feasible

Page # 11
 LECTURE - 3
NERNST EQUATION
(Effect of concentration and temp of an emf of cell)

 G = Gº + RT nQ (where Q is raection quotient)

At chemical equilibrium, G = 0
Gº = may or may not be equal to zero
= it is constant for a given reaction
O = Gº + RT n Q c d 
 Where Q  [C] [D] 

Gº = – RT n Q

 [ A ]a [B]b 
At equilibrium Q = Keq
Gº = – RT n Keq

for a cell
Gº = –nF Eºcell
G = –nF Ecell
But
G = Gº + RT nQ
– nFEcell = –nF Eºcell + RT n Q
RT
Ecell = Eºcell – n Q
nF

2.303 RT
Ecell = Eºcell – log Q
nF
R = 8.312 J/mol-K.

At 298 K
2.303  8.319  298
Ecell = Eºcell – log Q
n  96500

0.0591
Ecell = Eºcell – log Q [At 298 K]
n

At chemical equilibrium
G = 0
But G = –nFEcell
So Ecell = 0

Note-1 At chemical equilibrium cell is completely discharged, it will stop its functioning, it will not generate any
energy.
0.591
 0 = Eºcell – log Keq
n

0.591
Eºcell = log Keq
n

nE ocell
log Keq =
0.0591
Note-2 Nernst equation for an electrode reaction
Mn+ (aq) + ne– M(s)

0.0591  [M ( s ) ]  0.0591  1 
ERP = EºSRP – log  n   ;
 ERP = EºSRP – log  n 

n  [M ( aq) ]  n  M ( aq) 

Page # 12
Q. Will reduction potential (RP) of Zn electrode decrease or increase if conc. of (Zn2+) = 0.1 M in compression
of Zn.
Sol. Zn2+ + 2e–  Zn

0.0591  1 
ERP = EºSRP – log  
2  0 .1 

0.0591
= EºSRP –
2

CONCENTRATION CELLS :
Cells in which both the electrodes are of same nature but the concentration of ions are different.

Zn( s ) Zn 2 ( aq) Zn 2 ( aq ) Zn( s )

C1 C2
for concentration cell Eºcell = 0
But if concentrations are different then Ecell  0
Ex. Anode : Zn(s)  Zn2+(aq) + 2e–

Cathode : Zn2+(aq) + 2e–  Zn(s)

________________________________________________
[Zn(s)]anode + [Zn2+(aq)]cathod [Zn2+(aq)]anode + [Zn(s)]cathod
2
Zncathod Zn2anode


C2 C1

0.0591 [ Zn 2 ]anode
Ecell = Eºcell – log
2 [ Zn2  ]cathod

0.0591  C1 
=– log  

2 C
 2
For spontaneous cell reaction Ecell > 0 that’s why C1 < C2

Note-1 In case of CONCENTRATION CELLS for spontaneous cell reaction

concentration of anodic compartment < cathodic compartment
2 Greater the SRP value greater will be oxidising power
Ex. In which solution the oxidising power of KMnO4 will be greater.
(a) 0.01 M H2SO4 solution
(b) 0.001 M H2SO4 Solution
In both case concentration of species (MnO4– & Mn2+) are equal
Sol. H2SO4 2H+ + SO42–.
(0.02)
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

0.0591  [Mn2  ] 
ERP = EºSRP – log 
5  [MnO  ] [H ]8 
 4 

0.0591  1 
ERP1 = EºSRP – log  8


5  (0.02) 

0.0591  1 
ERP2 = EºSRP – log  8


5  (0.002 ) 
 ERP1 > ERP2

Page # 13
Q. Calculate E Cu2  / Cu at pH = 14 given that KSP of Cu(OH)2 = 10–19 and Eº Cu2  / Cu = 0.34 V at 298 K
 PH = 14  [OH] = 1
Cu(OH)2(s) Cu2+ (aq) + 2OH– (aq)
KSP = [Cu2+ (aq)] [OH–(aq) ]2
 10–19 = [Cu2+] [OH–]2 = [Cu2+] [1]2
[Cu2+] = 10–19 M
Cu2+(aq) + 2e–  Cu(s)

0.059 1
ERP = EºSRP log
2 [Cu 2 ]

 0.059 
  0.34   19  V
 2 

Q. If for the concentration cell.

n 1 1
x(s) x ( aq ) ( M) x n( aq

) ( M) x
20 2 (s)

Ecell = 0.029 V at 298 K calculate n.

Sol. X(s)  Xn+(aq) + ne– anodic reaction

Xn+(aq) + ne– X(s) cathodic reaction

Xn+(aq)cathod Xn+(aq)anode

0.059 [ X n ]anode
0.029 = 0 – log
n [ X n ]cathod

1
( )
0.059
 0.029 = 0 – log 20
n 1
( )
2
0.059 1
0.029 = – log
n 10
0.059
0.029 = – log 10–1
n
0.059
0.029 =
n
 n=2

Q. If H– electrode is acting as anode

H2(g)  2H+(aq) + 2e–
P(pressure) C(concentration)

0.059 [H  ( aq ) ] 2
EOP = EºSOP – log
2 [H2 ( g) ]

Note : Concentration of gases are written in terms of their partial pressure (atm)

0.059  C2 
EOP = EºSOP – log  
2  P 
 

 Conc 
Activity of an ion =  1 M 
 
 Pgas 
Activity of any gas =  1 atm 
 
Page # 14
Q. A hydrogen electrode is immersed in a solution pH = 0 (HCl). By how much will the reuction potential change
if an equivalent amount of NaOH is added to this solution, so that solution becomes neutral ( PH2 = 1 atm)
T = 298 K

Sol. 2H+(aq) + 2e–  H2(g)

0.0591  (PH2 ) 
ERP = EºSRP – log   

n  [H ( aq) ] 

0.059  1
ERP = 0 – log  2 
1 1 

0.059  1 
ERP1 = 0 – log  2 = 0
1 1 

ERP1 = 0

0.059 1 0.059
ERPfinal = 0 – log 7 2 = × 14V = 0.4137 V
2 (10 ) 2
Change in reduction potential [0.4137 – 0] = 0.4137.

Q. Calculate Ecell of :

H2 HCOOH( aq.) CH3 COOH H2

Pt 1atm C1 Ka1 C 2 Ka 2 1atm Pt(s).

0.059 C1 Ka1
Prove that Ecell = – log C Ka .
2 2 2
Sol. HCOOH H COO + H+
–

C1 (1 – 1) c11 c11

Anode H2 (g)  2Ha+ + 2e–

Cathode 2H+C (aq) + 2e–  H2(g)

(H2(g))a + 2H+c(aq) 2Ha+(aq) + (H2(g))c

0.059 [H  ]a2 [PH2 ]c

 Ecell = 0 – log (PH2 )c  (PH2 )a = 1 atm
2 [H  ]C2 [PH2 ]a

 [H+]a = c 1Ka1 [H+]c = c 2 ka 2

0.059 c1 ka1
 Ecell =  log c ka
2 2 2

Q. Calculate Ecell for :

H2 (g) 1N KOH N H2 (g)

( aq.)
Pt 1atm   75% 10 HCl( aq.) 1atm Pt(s).
  90%
Sol. Anodic reaction
 KOH K+ + OH–
1N
1 – 0.75 0.75N 0.75 N

10 14
 [H+]a =
0.75

Page # 15
 Cathodic reaction
HCl H+ + Cl–
10–1 0 0
10–1 × 0.9 10–1 × 0.9

0 .9
 [H+] =
10

0.059 [H  ] a
 Ecell = 0 – log
2 [H  ]c

0.059 10 14 10 

Ecell = – log  0.75  0.9 
2  

0.059 10 10
=– log
2 675

0.059
=– [– 10 – log 675]
2

0.059
= [– 10 – (log 52 + log 32)] Ans. 0.378
2
Q. At 298 K, the equilibrium constant of reaction.
Zn+2 + 4NH3 [Zn(NH3)4]+2 is 109.

If E º [ Zn(NH3 )4 ]  2 / Zn  4NH3 = – 1.03 V..

then value of Eº Zn / Zn 2 is .

Sol. (i) Zn2+ + 4NH3 [Zn(NH3)4]2+ Keq. = 109

(ii) [Zn (NH3)4]2+ + 2e–  Zn + 4NH3 Eº = – 1.03V

(iii) Zn  Zn2+ + 2e – E°1 = ? Target equation

Equation (i) = – Equation (ii) – Eqaution (iii)
G°1 = – G°2 – G°3
– RT nQ = + 2 × F × (– 1.03) – (– 2FE°1)
– 2.303 × RT log 109 = – 2.06 F + 2FEº1
 2.303RT 
  × 9 = – 2.06 + 2E°
 F  1

– 0.059 × 9 = – 2.06 + 2E°1

E°1 = (1.03 – 4.5 × 0.059)V
= 0.77 V

Page # 16
 LECTURE - 4
TYPES OF ELECTRODE

1. Metal-metal soluble salt electrode

Zn/ZnSO4(aq)
Cu/CuSO4(aq)
Ag/AgNO3(aq)
2. Gas electrode
Pt |H2(g) | H+(aq)
Pt |Cl2(g) | Cl– (aq)
3. Metal – metal insoluble salt electrode
In this half cell, a metal coated with its insoluble salt is in contact with a soltuion containing the anion of
the insolubule salt.
(i) Constraction :

KCl Ag Rod Ag Rod

AgCl(s)

aq. solution of
AgNO3

AgCl(s) KCl Solution

(ii) Half cell reaction :

(a) If it act as Anode : At anode oxidation take place.
If it is normal silver electrode than.
Ag(s)  Ag+(aq) + e– ..... (i)
But solution have Cl–(aq) ion so Ag+(aq) & Cl–(aq) Form PPT of AgCl(s)
Ag+(aq) + Cl–(aq)  AgCl(s) ..... (ii)
Overall half cell reaction at anode [from eq. (i) & (ii)].
Ag(s) + Cl–(aq)  AgCl(s) + e– ..... (iii)

(b) If it act as cathode : At cathode reduction take place.

If it is normal silver electrode than.
Ag+(aq) + e–  Ag(s) ..... (i)
AgCl(s)  Ag+(aq) + Cl–(aq) ..... (ii)
Overall half cell reaction at cathode [from eq. (i) & (ii)].
AgCl(s) + e–  Ag(s) + Cl–(aq) ..... (iii)
(iii) Cell representation :

(a) (aq) | | (aq)

(b) Metal will be at the end.
(c) Metal insoluble salt will be in middle.

Anode : Ag(s) | AgCl(s) | Cl–(aq) || ––––––––––––––

Eº Ag( s )|AgCl( s )|Cl ( aq)
Cathode : –––––––––––––––––– || Cl–(aq) | AgCl(s) | Ag(s)
Eº Cl ( aq ) |AgCl( s ) |Ag( s )

Page # 17
(iv) Relation between Eº Cl ( aq) |AgCl( s) |Ag( s)
& Ksp of AgCl.
If a cell is constructed using metal-metal soluble salt and metal-metal unsoluble salt electrode.
0
Given E0 = 0.80 V, ECl– |AgCl| Ag = 0.22 V
Ag | Ag

Anode Cathode
Ag | AgCl | Cl– (aq) || Ag+(aq) | Ag
Anode : Ag(s) + Cl–(aq)  AgCl(s) + e– (Metal-metal insoluble salt)
Cathode : Ag+ + e–  Ag (Metal-metal soluble salt)

Overall cell reaction :

Ag+ (aq)c + Cl–(aq)a  AgCl(s)

At equilibrium the concentration of [Ag+]a = [Ag+]C

So that at equilibirum Ecell = 0

0.059 [ AgCl( s)]

But Ecell = E0cell – log
1 [ Ag  ]c [Cl  ]a
At equilibrium

0.059 1
0 = E0cell – log [ Ag  ] [Cl  ]
1 c a

Now for AgCl

AgCl(s)  Ag+(aq)a + Cl–(aq)a
Ksp = [Ag+]a [Cl–]a
K sp ( AgCl)
So [Cl–]a =
[ Ag  ] a

0.059 [ Ag  ]a
0
0=E – log [At equilibrium the concentration of [Ag+]a = [Ag+]C ]
cell
1 [ Ag  ]a  K sp

0.059 1
E0cell = log K
1 sp

0.059
E0cell = – log Ksp
1

E0cell = E0Cathode – E0Anode

0 0
= E Ag / Ag – E Cl / AgCl / Ag

0.059 1
So Eº Ag |Ag – EºCl – | AgCl|Ag = log K
1 sp

0.059
E 0Cl / AgCl / Ag = E 0Ag / Ag + log Ksp
1
Some other example :
Pb | PbSO4 | SO42– || Pb2+ | Pb
White ppt.
0.059
E 0SO2  | PbSO 0
= EPb 2  | Pb + log Ksp
4 4 |Pb 2

Page # 18
Note : (1) If both electrode are Metal-Metal soluble salt electron than.

e
–
e–
Ag Salt Bridge Ag

AgNO3(aq) AgNO3(aq)

Then Eºcell = 0
and reaction wise concentration cell (Salts of all nitrates are soluble)

(2) If one electrode is Metal-Metal soluble salt electrode and another is Metal-Metal insoluble salt electrode

e
–
e–
Ag Salt Bridge Ag
KCl

AgCl(s)
AgNO3(aq)
+ +
[Ag ]a 1M [Ag ]c = 1M

Here [Eºcell  0]
0
E0cell = E 0 – E Cl |AgCl |Ag
Ag |Ag

0.059
=– log Ksp
1
Anode : Ag(s) + Cl–(aq)  AgCl(s) + e– (Metal-metal insoluble salt)
Cathode : Ag+ + e–  Ag (Metal-metal soluble salt)

Overall cell reaction :

Ag+ (aq)c + Cl–(aq)a  AgCl(s)

E0cell = E0Cathode – E0Anode

0 0
= E Ag / Ag – E Cl / AgCl / Ag

0.059
E0cell = – log Ksp
1
0.059
E 0Cl / AgCl / Ag = E 0Ag / Ag + log Ksp
1

Page # 19
Ex. Calculate Ksp of AgI with the help of following cell.
Ag | AgI(s) | 0.05 M KI (aq) || 0.05 M AgNO3 | Ag(s)
Ecell = 0.7884 at 298 K
Sol. First methode : - If E0cell = 0
+
Anode : Ag  Ag a + e–
Cathode : Ag+C + e–  Ag
Agc+ Aga+
According to nernst equation.

0.059 [ Ag  ]a
0
Ecell = E – log
cell
1 [ Ag  ]c

0.059 [ Ag  ]a
0.7884 = 0 – log
1 0.05
0.7884
– = log [Ag+]a – log (5 x 10–2)
0.059
0.7884
log [Ag+]a = – 1.3 –
0.059
[Ag+]a = 2.17 × 10–15
Ksp = [Ag+]a [I–]a
Ksp = 2.17 × 10–15 × 0.05 = 1 × 10–16.

Second Methode : If E0cell 

0.059 1 0.059
Ecell = E0cell – log But E0cell = – log Ksp
1 [ Ag ]c [  ]a

1

0.059  
E0cell = – log [ Ag ]c [ ]a
1

0.059 0.059 1
Ecell = – log Ksp – log
1 1 [ Ag ]c [  ]a


0.059 [ Ag  ]a [  ]a
So Ecell =– log
1 [ Ag  ]c [  ]a

0.059 [ Ag  ]a
Ecell =– log
1 [ Ag  ]c

Page # 20
 LECTURE - 5
Ex. Consider the cell at 25°C
Ag(s) | AgBr(s) | Br–(aq) || Cl–(aq) | AgCl(s) | Ag
If Ksp of AgBr and AgCl are 5 x 10–13 and 10–10 respectively for what ratio of conc. of Br–(aq) and Cl–(aq)
would be emf be equal to zero.
Sol. First methode : - If cell is taken to be conc. cell then E0cell = 0
Anode : Ag  Ag+a + e–

Cathode : Ag+c + e–  Ag

_______________________
Ag+c Ag+a
Now usesing nernst equation

0.059 [ Ag  ]a
Ecell = E0cell – log
1 [ Ag  ]c

0.059 [ Ag  ]a
0=0– log
1 [ Ag  ]c
 [Ag+]a = [Ag+]C
K sp of ( AgBr ) K sp of ( AgCl) 5 x 10 13 [Br  ] 5 1
=  = = =
[Br  ] [Cl  ] 10 10 [Cl ] 1000 200

Second Methode : If E0cell 

If cell is taken to normal all :
E0cell = Eº Cl / AgCl / Ag – E 0Br  / AgBr / Ag

 0.059 
= E Ag / Ag 
 1

log K sp ( AgCl) – E Ag / Ag  0.059 log K sp ( AgBr )


0.059 K sp ( AgCl)
 ECell = + 0.059 log Ksp (AgCl) – log Ksp (AgBr) = 0.059 log K ( AgBr )
1 sp

Anode : Ag + Br–  AgBr + e–

Cathode : AgCl + e–  Ag + Cl–

Br– + AgCl(s) Cl– + AgBr(s)

0.059  Cl  
Ecell = E°cell – log   
1  Br 
0.059 K sp ( AgCl) 0.059  Cl  
log K ( AgBr ) = log   
1 sp 1  Br 
K sp ( AgCl)  Cl   [Br – ] K sp [ AgBr ] 1
K sp ( AgBr ) =   So, = K [ AgCl] = .
 Br  200
–
[Cl ] sp

(4) Calomel Electrode :

A calomel cell consists of a platinum electrode dipping into mercury in contact with calomel
(dimercury (I) chloride, Hg2Cl2) and potassium chloride solution.
 Usually the solution is saturated with potassium chloride.
The cell has an e.m.f. of 0.246 V at 25ºC

Page # 21
 Standrad (normal) calomel electrode when [Cl– ] = 1M = 1N

At Anode At Cathode
2Hg()  Hg22 (aq) + 2e– Hg22 + 2e–  Hg()

Hg22 (aq) + 2Cl–  Hg2Cl2(s) Hg2Cl2  Hg22 (aq) + 2Cl–(aq)

2Hg() + 2Cl–(aq)  Hg2Cl2(s) + 2e– Hg2Cl2(s) + 2e–  Hg() + 2Cl-

Cell representation Cell representation

Pt(s) |Hg() | Hg2Cl2(s) | Cl–(aq)|| cathode (Anode) || Cl–(aq) | Hg2Cl2|Hg() | Pt(s)
0
EPt Hg |Hg Cl  = SOP E 0Cl |Hg Cl = SRP
2 2 Cl 2 2 |Hg(  )

E Cl / Hg 0 RT
2 Cl2 / Hg = E Cl / Hg Cl – n[Cl–]
2 2 / Hg F

CALCULATION OF DIFFERENT THERMODYNAMICS FUNCTION OF CELL REACTION

(1) G° = – n F E0cell

G = – n F Ecell

(2) G = H – TS (But : H = E + PV)

 G = (E + PV) – TS
dG = dE + PdV + VdP – TdS– SdT
(a) From 1st law of thermodynamics
dE = dq + dW
= dq – pdV
dq = dE + pdV

(b) From 2nd law of thermodynmics

dq
dS =
T
dq = TdS

Using 1st law and 2nd law of thermodynmics

dG = (dE + PdV) + Vdp –TdS – SdT  dG = Vdp – SdT

If a cell reaction is taking place at constant pressure (which is generally the case).
dG = Vdp – SdT
at constant pressure
So, Vdp = 0
And dG = – SdT
 dG 
 S = –  dT  (At costant pressure)
 p

 d( G) 
S = –   (At costant pressure)
 dT  P
G = –n F Ecell
d 
S = –  dt (E cell )  (–nF)
 p
d 
S = nF  dt (E cell ) 
 p
dE
= temp. cofficient of the cell
dT
E = a + bT + CT2 + ...............
Page # 22
 3. G = H – TS

H = G + TS
dE cell
H = –n F Ecell + n F T
dT

4. Cp of cell reaction

dH
Cp =
dT

d
Cp = (H)
dT

d  dE cell 
=  n F E cell  n F T 
dT  dT 

dE cell dE cell d2E cell d2E cell

= –n F +nF +nFT So Cp = n F T
dT dT dT 2 dT 2

Q. The standard potential of the following cell is 0.23 V at 15ºC & 0.21 at 35ºC.
Pt | H2 (g) | HCl (aq) | AgCl (s) | Ag (s)
(i) Write the cell reaction.
(ii) Calculate Hº, Sº for the cell reaction by assuming that these quantities remain unchanged in the range
15ºC to 35ºC.
(iii) Calculate the solubility of AgCl in water at 25ºC. Given standard reduction potential of the Ag+ / Ag couple
is 0.80 V at 25ºC. [JEE 2001]
fuEu lsy d k
Pt | H2 (g) | HCl (aq) | AgCl (s) | Ag (s)
ekud foHko 15ºC rFkk 35ºC ij Ø e'k%0.23 V rFkk 0.21 gSA
(i) lsy vfHkfØ ;kfy f[k;sA
(ii) lsy vfHkfØ ;k d sfy , Hº, Sº d h x.kuk d jksA ,sl k ekursgq, fd 15ºC ls35ºC d h ijkl esa;g ek=kk vifjofrZr
jgrhgSA
(iii) 25ºC ij t y es aAgCl d h foy s;rk d h x.kuk d jksA 25ºC ij Ag+ / Ag ;qXe d k ekud vip;u foHko 0.80 V fn;k
x;k gSA [JEE 2001]
Ans. Hº = – 49987 J mol–1, Sº = – 96.5 J mol–1 K–1, s = 1.24 × 10–5 M
 dE 
Sol.   = 0.21 – 0.23 = 1 × 10–3 volt deg-1.
 dT P 20
Sº = – 96500 × 10–3 J/K/mol. = – 96.5 J/K/mol.
(i) Cell reaction :
H2 + 2AgCl (s)  2H+ + 2Ag(s) + 2Cl–.
(ii) Sº = – 96.5 J/K/mol.
– 22195 = Hº – 288 × Sº
– 20265 = Hº – 288 × Sº
Sº = – 96.5 J/K/mol.
Hº = – 49987 J/mol.
(iii) Cl–/AgCl/Ag,
K SP
Ag+ (C) + e–  Ag, C =
1

0.0591 1
0.22 = 0.80 – log
1 C
C = KSP = 1.53 × 10–10 .
Solubility = KSP = 1.24 × 10–5 M. Ans.

Page # 23
 LECTURE - 6
SECTION : (B)
ELECTROLYSIS AND ELECTROLYTIC CELLS :
Whenever an electrochemical cell is charged it behaves like electrolytic cell.

E
E > Ecell
–
e –
e
e
–
e
–

i zn i
zn cu
cu
2+

2n2+(aq) Cu (aq)
2+ Cu2+(aq)
2n (aq)
2+
2n cu2+
2n 2+ cu2+
Charging
Discharging “ ACT as Electrolytic Cell”
“ACT as Electrochemical” Ecell is forced by E to due reverse reaction

Zn + Cu2+(aq) Zn2+(aq) + Cu Cu  Cu2+ + 2e– (Anode)

Zn2+ + 2e–  Zn (Cathode)

Electrolysis : –

The process of decomposition of an electrolyte on passing electricity or electrical current through its aqoues
solution or through its molten state. The cell used for this proecess is called an electrolytic cell.

–
i e

Cathode Anode

+ –
B A
+ –
Electrolyte(B A )

Anode = Electrode connected with positive terminal of the battery

Cathode = Electrode connected with negative terminal of the battery.
During electrolysis cations will be attracted towards cathode and will get neutralised after accepting elctrons
from the cathode.
Anions will be attracted towards Anode and will get neutrilised after reliasing extra (– ve) charge.
Cathode : B+ + e– B

B   e   A  e 
Anode :
B  A   B  A

SOME EXAMPLES OF ELECTROLYSIS

Note : In case two or more types of positive and negative ion are present in solution during electrolysis certain ion
are discharged or liberated at the electrode in preference to other. In general in such competition the cation
which is stronger oxidising agent (High value of SRP) is discharged first at the cathode.

Page # 24
 (a) K+, Ca+2, Na+, Mg+2, Al+3, Zn+2, Fe+2, H+, Cu+2, Ag+, Au+3.

Increasing order of deposition.

(b) Similarly the anion which is strogner reducing agent(low value of SRP or high value of SOP) is liberated
first at the anode.
4SO 2 – , NO – , OH– , Cl– , Br – , I 
3
      
Increa sin g order of diposition

(A) Electrolysis of Molten PbBr2 :

i e–
1
Anode : Br– Br2 (g) + e–
2
Cathode : Pb 2   2e   Pb(s )
Cathode Anode

Over all reaction Pb 2  2Br   Pb  Br2 (g)

Pb2+ Br
–

(B) Electrolysic of molten NaCl :

Molten PbBr2
Anode : 2Cl –
Cl2 + 2e –

Cathode : 
Na  e  Na 

2Na   2Cl   2Na  Cl2 (g)

Note : During electrolysis of aqueous solution of electrolyte, some times water is However involved in the electrode
reaction rather than the ion derived from the solute. The reaction involving water at electrode reaction are :
At. Anode : 2H2O  O2 + 4H+ + 4e– . 0 = 1.23 V..
ERP

0
At. Cathode : 2H2O + 2e  H2(g) + 2OH– (aq.) ERP = – 0.83 V..
(C) Electrolysis of Water :
Water is a bad conuctor of electricity so to make it conducting some H2SO4 is added into it.

H2SO4 2H+ + SO42 –

H2 O H+ + OH–

Species present in soltuion H+ , OH–, SO42– , H2O

Here volume of H2 produced = 2 [volume of O2 produced]

Anode : 2OH–  O2 + 2H+ + 4e–

(i) 2OH– + 2OH–  O2 + 2H+ + 2OH– + 4e–
4OH–  O2 + 2H2O + 4e– EºSRP = 0.40 V
(ii) SO42–  will not get oxidised
(iii) 2H2O  O2 + 4H+ + 4e– EºSRP = + 1.23 (it will get oxidised)

Page # 25
## Whenever there are many anions/spcies which are compiting to get oxidise at anode, than species with
maximum SOP, will get oxidised perfectly.

Since in this solution OH– ions are negligible, so water will get oxidised.
Anode : 2H2O  O2 + 4H+ + 4e– EºSRP = – 1.23
Cathode : (i) 2H+ + 2e–  H2 EºSRP = O.OV
(ii) 2H2O + 2e–  H2(g) + 2OH– E°SRP = – 0. 83 V

## At cathode, the species with maximum SRP will get reduced.

Cathode : 2H+ + 2e–  H2 (g)

Anode : 2H2O  O 2  4H  4e 

Over all reaction 2H2 O  O 2  2H2

(D) Electrolysis of aq. solution of NaBr :

Species present in solution Na+ , Br– , H+, OH– , H2O

Cathode : Possible reaction

(i) Na+ + e–  Na E°SRP = –2.71 (This not take reaction place)
(ii) 2H2O + 2e–  H2(g) + 2OH– E°SRP = – 0.83 V(This reaction take place)

Anode : Possible reaction

(i) 2Br–  Br2 (g) + 2e– E°SOP = – 1.08 V
+
(ii) 2H2O ()  O2 (g) + 4H + 4e –
E°SOP = – 1.23 V

2H2O + 2Br–  Br2 (g) + H2(g) + 2OH–

Note : The SRP value of Na is much less then H2O that’s why we can’t obtain Na from it’s NaCl(aq) solution.

(E) Electrolysis of aq. solution of CuSO4 :

Species present in solution Cu2+, SO42– , H+, OH– , H2O

Cathode Possibilities :
(i) Cu2+ + 2e–  Cu E° = + 0.34
(ii) 2H2O + 2e–  H2+ 2OH– (aq) E° = – 0.83 V

Anode Possibilities :
(i) 2H2O  O 2  4H  4e  E°OX = – 1.23 V

Over all reaction 2H2 O  2Cu 2   2Cu  O 2  4H

Note : A minimum e.m.f is required for the electrolysis of a solution.The minimum e.m.f required for the electrolysis
can be computed by the standard appropriate electrode potentials for redox change. However, the actual
volatage required for a reaction is some times much greater than the theoretical voltage based on electrode
potential. The additional voltage required to cause electrolysis is called the over voltage. The over voltage is
believed to be caused by slow reactions rates at the electrode.
(F) Electrolysis of NaCl(aq.).
Species present in solution Na+, Cl– , H+, OH–, H2O
Cathode Possibilities :

2H2O + 2e–  H2 (g) + 2OH– , EºRP = – 0.83.

Page # 26
 Anode Possibilities :

(i) 2Cl–  Cl2 (g) + 2e–. EºOX = – 1.36 V.

(ii) 2H2O  O2 + 4H+ + 4e–. EºOX = – 1.23 V. (It should take place)

## At anode according to thermodynamics oxidation of water H2O should take place instead of Cl– ions. But the
rate of reaction of oxidation of water is very slow and to make it fast some extra potential difference is applied
during electrolysis of aq. NaCl. At this extra or greater potential (over voltage), the rate of oxidation of chloride
ions dominants over the oxidation of H2O.
ECell = SRP of cathode – SRP of anode
= – 0.83 – 1.23 = – 2.06 (we will get O2, but the rate is very slow)
For obtaining O2 we have to increase potential difference (PD)
O2 Oxide should take place but due to the chemical kinetics Cl2 productiontakes place.
At Ecell = – 0.83 – 1.36 = – 2.19 Rate of production of O2 is still very slow but at this voltate due to chemical
kinetics production of Cl2 takes place.

ATTACKABLE ELECTROLYSIS :
* Electrolysis of aq. CuSO4 using Cu electrode Cu Cu

If we use pt or graphite electrodes then ; aq.CuSO4

Anode : 2H2O  O2 + 4H+ + 4e–

Cathode : Cu2+ + 2e–  Cu
+2
Concentration of Cu remains same
If we use Cu electrodes then ;
Anode Possibilities :
(i) SO4 – not posible
2H2O  O2 + 4H+ + 4e– E0 = – 1.23 V
2+
Cu  Cu  2e –
EOx0 = –0.34 V (This reaction take place)

Cathode Possibilities :
(i) Cu2+ + 2e–  Cu EºRP = + 0.34 V (This reaction take place)
(ii) 2H2O + 2e–  H2(g) + 2OH–(aq.) EºRP = – 0.83 V

Note : Concentration of Cu2+ in CuSO4 is remain same

Other Example :
(i) Anode if Zinc then : Zn  Zn2+ + 2e Eºox = + 0.76 V (This reaction take place)
(more than water)
(ii) If Anode is Ag then : Ag  Ag+ + e– Eºox = –0.80 V (This reaction take place)
(still more than water)
If Cathode is Ag then : Ag+ + e+  Ag ERP = +0.80 V (This reaction take place)

Page # 27
 LECTURE - 7
FARADAY’S LAW OF ELECTROLYSIS
(i) Faraday’s Ist law :
The weight or amount of any substance produced during electrolysis is proportional to amount of charge or
electricity passed into the solution.
W Q Q = it
Q
W  it i=
t

dQ
i
dt

W = z it Q=  i . dt
Where : z = electrochemical equivalent of substance deposited
Electrochemical equivalent :
Amount or weight of substance produced when 1A (ampere) of current is passed for 1 sec.
1
Cu2+ + 2e–  Cu One mole of e– will produce mole of Cu
2
Ag+ + e–  Ag One mole of e– will produce 1 mole of Ag
1
A3+ + 3e–  A One mole of e– will produce mole of A
3
1 mole of electron (1Farady of electricity) will always produce 1 equivalent of substance
1 Farady = charge on one mole of e–
= (1.6 × 10– 19C) × (6.022 × 1023)  96500 C
On passing 1 Farady of electricity charge, one equivalent of a substance produced.
 96500 C charge prouduce = E gm of substance (where E = eq. wt. of substance)
E
 1C charge prouduce = gm of substance
96500
E  E  E
 it =
 z=
96500
so w= 
 96500  96500  i . dt
Result Faraday’s Ist law :
E E
W= it = Q
96500 96500

Ex. How many columbs of of charge are required for following reduction.
(i) 1 mole of Cu2+ to Cu
(ii) 1 mole of MnO4– to Mn2+
Sol. (i) Q = 96500 × 2 C (2 mole of e– ) = 2F of charge
(ii) MnO4– + 8H+ + 5e–  Mn2+ + 4H2O (Q = 5 × 96500 C = 5F)

Ex. How many gms of Cu will get disposited by passing 2 Ampere for 30 minites in aq. CuSO4 and what will the
wt. of O2 produced at anode.
Sol. Posible reaction
Cathode : Cu2+ + 2e–  Cu

Anode : 2H2O  O2 + 4H+ + 4e–

(i) Calculation of weight of Cu

Two mole of e– required for deps. of 1 moleof Cu.
 2 × 96500 C charge is diposited weight of Cu = 64 gm
64
 2 × 30 × 60 C charge is diposited weight of Cu = × 30 × 60 × 2 gm = 1.2 gram.
2  96500
Page # 28
 (ii) Calculation of weight of O2
4 mole e– required for deps. of 1 mole of O2 or 22 .4 L of O2 at STP
 4 × 96500 C charge is diposited mole of O2 = 1 mole
1
 3600 C charge is diposited mole of O2 = × 3600 moles
4  96500
3600  32
= gm of O2
4  96500
3600  22.4
Volume of O2 produced = L
4  96500

ELECTROPLATING OF Ag OR Au ON Fe SPOON

Anode

Cathode
Ag or Fe
Au rod

Anode possiblities : Ag  Ag+ + e– EOX = – 0.80 V (This reaction take place)
2H2O  O2 + 4H+ + 4e – EOX = – 1.23

Cathode Possibilities :
Ag+ + e–  Ag ERP = + 0.80 (This reaction take place)

2H2O + 2e–  H2 (g) + 2OH– E°RP = – 0.83 V

Q. Silver is electrodisposited on a vessel of total surface area 800 cm2 by passing a current of 0.2 amperes for
3 hours. Calculate the thickness of silver disposited given that density of silver is 9.67 gm/cm3.
Sol. W = Zit

 E 
W=  
 96500 

 108   2 
W=     (3 × 3600)
 96500   10 

108  6  36
=
965  10

108  6  36  100
 Volume = cm3
965  10  964

108  6  36  100 2916

 Thickness = = cm
965  10  967  800 9331500

=  3.125  10 4 cm.

Page # 29
Ex. In an aqueous solution of silver nitrate (AgNO3) a variable current is passed for 4 sec., calculate amount of
silver deposited.
When i = 2t While (0  t  2)
i = 8 – 2t While (2  t  4)
i= (t > 4 sec.)

Sol. W=Z×Q (Where Q =  i.dt )

108
(i) W=
96500
×  i.dt
4
3
2
108 2
= 96500 2t  1
0
t
1 2 3 4 5
2
108  2  t 2  108  2
= 96500   2  = 2
  0
96500

2 4

(ii) Q=  i.dt =  2t.dt   (8  2t ) dt

0 2

Q=8C
 96500 C charge diposite at weight of Ag = 108 gm
108
 8 C charge diposited at weight of Ag = × 8 gm
96500

(2) Faraday’s IInd law :

If equal amount of electricity or change is passed through two different solutions then weights of the
substance deposited or produced in these two solutinos are in the ratio of their equivalent weights.
wt. of Cu deposited (one subs) E W1 E2
 Cu st
wt. of Ag deposited (other subs) E Ag  W2 = E1 (I law)

To pass equal charge generally solutions are connected in series.

DC source

e– t

Anode Cathode Anode Cathode

CuSO4(aq.) AgNO3(aq.)

W Cu E Cu
W Ag = E Ag

actual mass deposited/produced

CURRENT EFFICIENCY =  100
Theoritical mass deposited/produced
CONDITION FOR SIMULTANEOUS DEPOSITION OF Cu & Fe AT CATHODE
1 1
Eº Cu2  / Cu  0.0591 log 0.0591
2 = Eº Fe2  / Fe – log
2 Cu 2 Fe 2
Condition for the simultaneous deposition of Cu & Fe on cathode.
Page # 30
 LECTURE - 8
Some Primary Cells
 Primary cells : These cells can not be recharge dry cell (lechlanche cells)
mercury cells (miniature cell used in ethes electronic devices), Ecell = constant
as all substances used are either pure solids or pure liquids.
 Secondary cells : Lead storage batteries used is automobiles (Cars/bikes)
Anode : Pb(s) ; Cathode : PbO2(s)
H2SO4(conc.) about 38% sol. of H2SO4 is taken.
Anode : Pb(s)  Pb2+ (aq) + 2e–
Pb2+(aq) + SO 24 (aq)  PbSO4(s)

Pb(s) + SO 24 (aq)  PbSO4 + 2e–

most of the PbSO4(s) ppt sticks to the lead rod.
Cathode : 2e– + 4H+ + PbO2(s)  Pb2+(aq) + 2H2O()
Pb2+(aq) + SO 24 (aq) +4H+ + 2e–  PbSO4(s) + 2H2O()
PbSO4(s) sticks to cathode rod.
Pb(s) + PbO2 + 4H+ + 2 SO 24 (aq)  2PbSO4(s) + 2H2O()
Ecell = 2.05 V

Note : During the working of the cell discharge H2SO4 will be consumed so it's concentration in the solution
hence density of the solution will decrease during charging of the cell PbSO4 will get converted into
Pb(s) and, PbO2(s) and H2SO4 will be produced.

Q. During the discharge of a lead storage battery, the density of sulphuric acid fell from 1.294 to
1.139 g.ml–1. H2SO4 of density 1.294 gmL–1 is 39% and that of density 1.139 gmL–1 is 20% by weight. The
battery holds 3.5L of acid and the volume practically remains constant during discharge. Calculate the
number of ampere hours for which the battery must have been used. The discharging and charging reactions
are :
lhlklap k;d lsy d sfujkos'ku d snkSjku]lY¶;qfjd vEy d k?kuRo 1.294 ls1.139g.ml–1 gks rkgS A 1.294gmL–1 ?kuRo
d sH2SO4 d kHkkj çfr'kr 39% gS]rFkk1.139 gmL–1 ?kuRo d sH2SO4 d kHkkj çfr'kr 20% gSA cSVjhesa3.5L vEy gS
o fujkos'ku d snkSjku iz;ksxkRed vk;ru fLFkj gSA cSVjh d s}kjk mi;ksx esafy ;sx;s,fEi;j ?kaVksad h la[;k Kkr d jksA
fujkos
'ku rFkkvkos'ku d hvfHkfØ ;kfuEu gSa&
Pb + SO42–  PbSO4 + 2e— (Anodic reaction) ,uks M vfHkfØ ;k
PbO2 + 4H + SO4 + 2e¯  PbSO4 + 2H2O (Cathode reaction) d S
+ 2– FkksM vfHkfØ ;k
Ans. 265 Amp. hr.
Sol. Pb + SO42–  PbSO4 + 2e– Anode

PbO2 + 4H2 + SO42– + 2e–  PbSO4 + 2H2O (cathode)

Pb + PbO2 + 2SO42– + 4H+  2PbSO4 + 2H2O

1.294  3500  0.39  1.139  3500  0.20
nH cousumed =
2SO4 98
= 9.8878, Amp hr. = 265 amp.

Page # 31
 FUEL CELLS
In these cells fuel can be supplied continuously during the operation of the cell, so are considered to be
better then galvanic cells.
Hydrogen oxygen fuel cells :
porous electrodes of graphites
& some catalyst pt in particle
from is distributed on these
electrodes

Anode Cathode
H2gas
– +
H2(g) KOH O2
(aq) Porous electrode
Electrolyte

Porous electrodes of graphites and some

catalyst pt in partical form is distributed on these electrode
aq. KOH solution
between electrodes
Cell Reaction :

Anode : H2(g) + 2OH– (aq)  2H2O (l) + 2e– ] × 2.

Cathode : O2 + 2H2O (l) + 4e–  4OH– (aq.)

H2 (g) + O2 (g)  2H2O (l). Eº = 1.22 V.

Q. In a H2 – O2 fuel cell, 6.72 L of hydrogen at NTP reacts in 15 minutes, the average current produced in
amperes is
NTP ij H2 – O2 bZ
/ku lsy esa]gkbMªkst u d s6.72 L ls15 feuV esafØ ;k d jrk gSA ,fEi;j esamRiUu vkSl r /kkjk gSµ
(A*) 64.3 amp (B) 643.3 amp (C) 6.43 amp (D) 0.643 amp

i  15  60 6.72
Sol. = ×2  i = 64.3 amp.
96500 22.4

Q. A fuel cell uses CH4(g) and forms CO32– at the anode. It is used to power a car with 80 Amp. for 0.96 hr. How
many litres of CH4(g) (stp.) would be required ? (Vm = 22.4 L/mol) (F = 96500). Assume 100% efficiency.
,d bZ/ku lsy CH4(g) d kmi;ksx d jrkgSrFkk,uksM ij CO32– cukrkgSA bld kmi;ks
x d kj d ks0.96 ?ka
Vsrd 80 Amp.
d slkFkpy kuses
afd ;kt krkgS
A bl gsrqvko';d CH4(g) (STP ij) d keku y hVj es
aifjd fy r d jks
A (Vm = 22.4 L/mol)
a
(F = 96500). ;g ekud j fd n{krk 100% gS A
Ans. 8

Sol. CH4 + 10OH¯  CO32– + 7H2O + 8e–

80 x 3600 x 0.96
No. of Faradays required =
96500

1 80 x 3600 x 0.96
Hence mol. of CH4 required = x
8 96500

1 80 x 3600 x 0.96
VCH4 = x x 22.4 L
8 96500
= 8.356 x 0.96 = 8.02 L.

Page # 32
 LECTURE - 9
SECTON : (C)
ELECTROLYTIC CONDUCTION
Conductors Insulators Semiconductors
Metals Genrally non–metals Si, Ge
Conductors :
(1) Electronic conductors
(2) Electrolytic conductors
Electronic Conductors : No decomposition of any substance current flow because of e– (charge carriers are e–)
 On increasing temprature (T), resistance (R) increases.
Electrolytic Conductors : Solutions of electrolytes (WA, SA, WB, SB, salt solution)
– When current is passed there will be decomposition of electrolyte (electrolysis)
– Charge carriers are ions.
– On increasing temprature (T), resistance (R) decrease. (because more charge carriers are produced)
– Factors effecting electrolytic conductance :
(1) Nature of the electrolyte,
(2) Nature of the solvent : polar more conductance
non–polar less conductance
(3) Concentration : Generally on increasing concentration conductivity decreases.
(4) Temperature : On increasing temprature (T), conductivity increases
DEFINITION OF R, CONDUCTANCE (C OR G), RESISTIVITY (), CONDUCTIVITY (k,, KAPPA)
Resistance (R) : is the measure of opposition shown by any substance to electrical flow
OR
Resistance is the hindrance provided by a conductor in the passage of current. (R is expressed in ohm or
in ). The resistance ‘R’ of a conductor (metallic or electrolytic) is directly proportional to its lenght and
inversely proportional to its cross-sectional area A. Therefore.
R
1

a

 R=×
a
where  is a constant of proportionality is called resistivity defined as the resistance offered by a conduc-
tor of unit length and unit cross-sectional area.
Ohm’s law : The current strength (i) carried by a conductor is directly proportional to electrical potential
difference between the two ends of conductor.
iV
V
or i R – ohm ()
R
 V = R

V aR
R = (m) SI unit
i 
volt
In SI unit, ohm or  = =  cm (in case of solution generally used)
ampere
  specific resistance or resistivity. ;   specific conductance or conductivity.
CONDUCTANCE (C OR G)  Inverse of R :
The conductance offered by an electrolytic conductor is expressed in terms of reciprocal of resistance as
its is the ease provided by solution in the passage of current.
1
C= = –1 (mho)
R
The SI unit of conductance is siemens represented by “s”.
[C expressed in ohm–1 or in –1 or mho or Siemens (S)]
 Moh scale  on this scale hardness of substance is measured (diamond = 10).
Page # 33
CONDUCTIVITY ( or ) or specific conductance (specific conductivity) kappa
1  
= = = C.
 aR a


  = C.
a
= –1 m–1 (SI unit)
= –1 cm–1 [In this chapter we use this unit]
or ( expressed in S Cm–1)
Note : 1. IUPAC has recommended the use of the term conductivity in place of the term specific conductance
previously used for conducting power of 1 cm cube of a solution.
Conductivity / specific conductance of a solution :
The conductance of the solution of unit length (1cm) between the electrodes and in which electrodes are of
unit area of cross–section (1cm2) is equal to conductivity of that solution.

1cm
2
1cm 1cm2

OR

The conductance of 1cm3 of a solution is called its conductivity.

(+) (–)

1cm

2
a = 1cm

R
1
R
A a a

 1
=C =  
a R a
where,  = length of electrolyte solution between electrodes
a = area of cross-section of electrode
Note : 1. Conductivity of a conductor is reciprocal to its resistivity.

2.   is known as cell constant expressed in cm–1 and in SI unit as m–1.
a
3. Conductance is an additive property. For example, an aqueous solution containing several
electrolytes, the total conductance is given by CT =  Ci + Cwater, where  Ci is total conductances
of all the ions and Cwater is conductance of water utilized for making the solution.
4. Cwater is often negligible in comparion to  Ci as repeatedly distilled water (known as conductivity
water) of very low conductivity 3.5 × 10–5 S m–1 is used for making solution.
5. If electrodes are of different area of cross–section then common area of electrodes is taken as
effective area of cross–section.
Page # 34
 a1
a2

Ex. Three different solution of same electrolyte and of same concentration are prepared find out which solution
will have greater conductance and which have greater conductivity.
(i) Ist solution is present between two electrodes of area of cross section 5cm2 and distance between the
electrodes = 2cm.
(ii) 2nd solution between two electrodes of a = 4cm2 and distance = 3 cm.
(iii) 3rd solution between electrodes with a = 2cm2 & d = 1cm.
a a 5
Sol.  C= (i)  = 1.5 ,
  2

a 4
(ii)  = 1.33  is same
 3

a 2
(iii)  =2
 1

Result : Conductivity is same for all the electrolytes as concentration of the electrolyte is same that why the
cell which have low value of cell constant have greater conductance.

ELECTROLYTIC CONDUCTION :
(1) Conductivity (K) : Conductance of a unit cube (1cm3) of solution is called its conductivity.

K = C
a

2. Molar conductivity : – (m)

The conductance of solution kept between the electrodes at unit distance apart and having area of
cross-section large enough to accomodate sufficient volume of the solution that contains 1 mole of
electrolyte.
Relationship between conductivity () and molar conductivity (m or m) :
Let V cm3 of the solution containing 1 mole of electrolyte be palced betwen two large electrode 1 cm apart.

Let measured condctance of the solution = x.

The solution contains 1 gram/mole of electrolyte so the measured conductance also represent the molar
conductivity of solution.
M = X.
But we know that conductivity (K) is the conductance of 1 centimeter cube of solution.
X 1 1000
= Molarity (M) = Vml
V
M 1000
or  = , M =
V V

1000
M =  × V. V=
M

K  1000
M = Unit of M = –1 cm2 mole–1
M

Page # 35
(3) Equivalent conductivity : Equivalent conductivity of a solution is defined as conductance of all the ions
produced by 1gm equivalent of the electrolyte dissolved in V cm3 of the solution when the distance between
the electrodes is 1cm and area of the electrodes is so large that whole of the solution is contained between
them.
Let V cm3 of the solution containing 1 gm equivalent of electrolyte be palced between two large electrode
1 cm apart.
Let measured condctance of the solution = x.
The solution contains 1 gram/eq. of electrolyte so the measured conductance also represent the eq. conduc-
tivity of solution.
N = X.
But we know that conductivity (K) is the conductance of 1 centimeter cube of solution.

X 1 1000
= Normalty (N) = Vml
V

N 1000
or  = , N =
V V
1000
N =  × V. V=
N
K  1000
N =
N

1 cm

1 cm
eq =  × volution solution containing one 1gm eq. of electrolyte

1000  cm3 
 
=× (–1 cm–1)  eq 
N  
= –1 cm2 equivalent–1

1
Q. K = conductivity of N KCl at 298K is = 0.001765 –1cm–1 and resistance of cell containing this
50
solution is 100. Calculate the cell constant. Also find out equivalent conductivity of above solution.
Sol. (i) Calculation of cell constant
 1 
 =C = .
a R a
 
 Cell constant =
a C


  = K.R.
a
= 0.001765 × 100
= 0.1765

Page # 36
 (ii) Calcuation of equivalent conductivity of solution
  1000 1000
eq. = ; eq = (0.001765 –1 cm–1)  50 cm3/eq
N 1
= 17.65 × 5 –1 cm2 eq.–1 = 88.25 –1 cm2 eq–1.

PRACTICAL MEASUREMENT OF , C, eq. & M OF A SOLUTION

(laboratory or experimental measurement)
1
C = conductance = x–y
R R1 R3
y
Wheatstone bridge principle is used for calculation of resistance of x > i
i

>
conducting cell. > > R5 >
If In the weatstone bridge (i-x)
R2 > (R)
R1 R3

>
(i-x+y)
R2 = R4 then y = 0

(known)
R5 can be removed, no current will pass through it. R1 x (unknown)
R1 x i > i

>
= > > G >
R2 R (i-x)
R2 > (R)
variable
R1

>
(known) resistance
 x=R
R2

R0 R R0
= R . .
R1 2
cu
R2 2 strips G
 R = R0 R = R0  R1 R2
1 1
1 shding 2
1 contact
R1 R2 a a
 C= 1 2
R
 
 k=C
a

Calculation of conductance / resistance by principle of wheat stone bridge


k=C = (conductance × cell constant)
a
1000
eq. =  × normality

Q. The resistance of a solution 'A' is 50 ohms and that of solution 'B' is 100 ohms, both solutions being taken in
the same conductivity cell. If equal volumes of solution A. and B are mixed, what will be the resistance of the
mixture using the same cell. (Assume that there is no increase in the degree of dissociation of A and B on
mixing.
foy ;u 'A' d kizfrjks
/k50 vks
e o foy ;u 'B' d kizfrjks
/k100 vks
e gS
A nksuksafoy ;u d ksleku pkyd rklsy esay s
rsgSA ;fn
foy ;u A o B d sleku vk;ru d ksfefJr d j fn;k t k, rksleku lsy d k mi;ksx d jrsgq, feJ.k d k izfrjks/k fd ruk
gksxkA (ekuk fd A o B d ksfefJr d jusij fo;kst u d h nj esac<+ksrjh ughagksrh gS½A
Ans. R = 66.67 ohms
1  1 
Sol. RA = 500 ; RB = 100 ; KA =  ; KB = 
50 A 100 A
when equal volmes one taken the
1 2 1  1 
Kresultant =  =  + 
R1 A 50 A 100 A

2 150 2  50  100 200

= R1 = = = 66.7
R1 50  100 150 3
Page # 37
 LECTURE - 10
VARIATION OF CONDUCTIVITIES WITH DILUTION :
(i) Varition of 
On dilution (or on decreasing concentration)  (specific conductance of solution decreases)

(ii) Varition of eq / M

eq or M increases on dilution
Because effect of volume increment is greater than effect of decreament in .

Variation of eq / M of a solution with concentration :

(i) Strong electrolyte
These solution are found to follow debye huckle onsagar eqation at low concentrations.
Mc = M – b c (For uni-univalent strong electrolyte)

= M – b c [b is a constant]

 M or M0 = molar conductivity at infinite dilution
= molar conductivity at zero concentration
b = constant (b dependence on stoichiometry of electrolyte).

0
M = M
Practical value

c
M
weak electrolytes

c (mole litre–1)1/2

(ii) Weak electrolytes :

For the same concentration of weak electrolytes as of strong electrolytes the eq or M values are very low
in comparison to those of strong electrolytes.
at  dilution WE (Weak electrolytes) is also 100% dissociated so have high values of eq or M .
In case of SE (Strong electrolytes) we can calculated M or M0 by extrapolation of their straight line variation
of M with c
But in case of weak electrolytes we can not be calculated M or M0 by extraplotation or parctical method.

KOHLRAUSCH LAW :
At infinite dilution when the dissociation of electrolyte is complate each ion makes a definate contribution
towards the molar conductivity of electrolyte, Ir-respect of the nature of the other ion with it is associated.
or
Statement :-
At infinite dilution each ion makes a definite contribution towards equivalente conductance of electrolyte
irrespective of the nature of ion with which it is associated and the value of equivalent conductance at infinite
dilution for any electrolyte is the sum of contributions from its constituents ions.
m0 diff. common ions diff.
KCl 235 NaCl
NaCl 200 35 NaBr 55

KBr 195 KCl

NaBr 160 35 KBr 55

K 155 RbCl
Na 120 35 RbBr 55
 
M (KCl) = K  +  Cl 
Page # 38
(i) Equivalent Conductivity :
eq(electrolyte) = C+ + a –


Limting ionic conductivity of cation
 
eq(NaCl ) =  Na  +  Cl 

 
eq(BaCl ) =  Ba  2 +  Cl 

eq( AlCl3 ) = Al  3 + Cl –

 
eq (Al2(SO4)3) =  Al  3 +  SO 4 2 

(ii) Molar conductivity :

0M = m0c + n0a
where m & n are no of cations and anions present in one formula unit of the electrolyte
0M (NaCl) = 0Na+ + 0Cl–
0M (BaCl ) = 0Ba2+ + 20Cl–
2
0M (AlCl ) = 0Al3+ + 30Cl–
3
0M (Al = 20Al3+ + 30SO 2–
2(SO4)3) 4

APPLICATION OF KOHLRAUSCH LAW :

(1) Calculation of 0M of weak electrolytes :
0M (CH COOH) = 0CH COO– + 0 H+
3 3
0M (CH = 0CH – + 0 Na+
3COONa) 3COO
0M (HCl) = 0H+ + 0Cl–
0M (NaCl) = 0Na+ + 0Cl–
0M (CH = 0M(CH + 0M(HCl) – 0M(NaCl)
3COOHl) 3COONa)
Q. Calculate molar conductivity at  dilute of CH3COOH if molar conductivity at  dilute of CH3COONa, HCl, and
NaCl are 91.6, 425.0 and 128.1–1cm2mole–1.
Ans. 388.5–1 cm2 mole–1.

Q. If molar conductivity it  dilute of Ba(OH)2, BaCl2 and NH4Cl are 523.28, 280.0, 129.8–1 cm2 mole–1. Calculate
molar conductivity at  dilute of NH4OH.
Ans. 251.44.

( 2M NH 4 Cl  M Ba( OH ) 2 – M BaCl2 )

M NH =
4 OH
2
2  129 .8  523 .28  280 .0
=
2
299 .6  523 .28  280
=
2
492.88
=
2
= 246.44
Ans. is 246.44 –1cm2 mole–1

(2) Calculation of degree of dissociation and Keq of weak electrolytes (dissociation constants) :
Let at concentration C if molar conductivity = mC
and at  dilution the molar conductivity = m
cm
then =
0m
c 2
Keq =
(1   )
Q. The molar conductivity of CH3COOH at 298 and concentration of 0.1 M and 0.01 M are 5.20 and 49.2–1 cm2
mole–1. Then calculate  at these concentration given that :

M [H ] = 349.80 ; M CH3COO – = 40.9.

Sol.  0M (CH = 0CH – +  0 H+
3COOH) 3COO

0M (CH = 349.8 + 40.9 = 390.7

3COOH)

5.20 5.20
 1(at concentration = 0.1 M) = =  100  1.3%
390.7 390.7
49.2
2 (at concentration = 0.01 M) = × 100%  12.5%
390.7
(3) To evaluate absolute ionic mobilities :
Ionic Mobility :
It is the distance travelled by the ion per second under the potential gradient of 1 volts per cm. It’s unit is
cm2 volt–1 sec–1.

Potential gradient :
The ratio of potential difference across the electrode to the distance between. Them,
V
1V

a a

+ –
1 cm
Potential gradient =

Absolute ionic mobility :

Ionic mobility at inifinite dilution is called absolute ionic mobility and represented by 0c or 0a
or
Speed of the ion at infinite dilution under unit potential gradrent (in cm2 sec–1 vol–1).
0c  c  a0  a
0
0c = F  0c ; 0a = F ×  a 

  speed
Ionic Mobility  
( V /  )  potential gradient

 cm / sec 
=   = cm2 volt–1 sec–1
 volt / cm 

Transport Number :
It is the fraction of total current carried by each ion of the electrolyte. Now greater the mobility of the ion larger
will be magnetuted of current carried by the ion and consquently larger will be its transpart number.

 c   a 
tc =      , ta =      .
 c a  a c

Where tc = Transport Number of cation & ta = Transport Number of anion

 c   a 
tc =   , ta =   
  c   a    c   a 
Q. The limiting molar conductivity ºK+ = 64.35 –1cm2 mole–1 in KCl solution. What is limiting ionic mobility of
K+ ion

0c = F  0c
64.35
c = = 6.67 × 10–4 cm2 sec–1 volt–1
96500
(4) To calculate solubility of sparingly soluble salt & their Ksp values :
The saturated solutions of sparingly soluble salts can be taken to be infinitely dilute
0 0
ºM(AgCl) =  M( Ag  ) +  M ( Cl – )
1000 1000
=  × molarity =  × so lubility

SOME IMPORTANT RELATIONS :

(1) Calculation of c /  of weak electrolyte

cM
= for weak electrolyte
0M
(2) Mc = M for any strong electrolyte

= ºM (Cation) + ºM (Anion)

Result : 0.1M CH3COOH  CM   0M Weak electrolyte

0.1M NaCl, cM = 0M Strong electrolyte
C 2
for weak electrolyte Ka or Kb =
1 
0
(3) 0c = F  0c ; 0a = F ×  a 

(4) Solubility of sparingly soluble salt & their Ksp

1000
Mc = M =  × so lubility
Ksp =

Q. The sp. cond. of a saturated solution of AgCl at 25°C after subtracting the sp. conductance of conductivity of
 2
water is 2.28 × 10–6 mho cm–1. Find the solubility product of AgCl at 25°C. (  AgCl  138.3 mho cm )

25ºC ij AgCl d slrà

Ir foy;u d hfof'k"V pkyd rk]ikuhd hfof'k"V pkyd rkls?kVkusd sckn 2.28 × 10–6 mho cm–1 gSa]
25ºC ij AgCl d k foy s
;rk xq.kuQ y Kkr d jksA (AgCl  138.3 mho cm 2 )
Ans. 2.70 × 10–10 (mole/litre)2.
1000  2.28  10 6
Sol. KAgCI = 2.28 × 10–6 Scm–1, 138.3 =
S
S = 1.65 × 10–5 Ksp = (S)2 = 2.72 × 10–10 M2.

Q. We have taken a saturated solution of AgBr.KSP of AgBr is 12 × 10–14. If 10–7 mole of AgNO3 are added to 1
litre of this solution find conductivity (specific conductance) of this solution in terms of 10–7 Sm–1 mol–1.
Given : º(Ag+) = 6 × 10–3 S m2 mol–1, º(Br–) = 8 × 10–3 S m2 mol–1, º(NO– ) = 7 × 10–3 S m2 mol–1.
3
[JEE–2006]
ge AgBr d k ,d larÌr foy ;u y srsgSA AgBr d k KSP 12 × 10–14 gSA ;fn AgNO3 d s10–7 eksy d ksbl foy ;u d s1
y hVj esat ksM +k x;kA bl foy ;u d h 10–7 Sm–1 mol–1 d sinksaesapky d rk ¼fof'k"V pky d rk½ Kkr d jksA
fn;k x;k gS% º(Ag+) = 6 × 10–3 S m2 mol–1, º(Br–) = 8 × 10–3 S m2 mol–1, º(NO–3) = 7 × 10–3 S m2 mol–1.
[JEE–2006]
Ans. 55 S m–1
Sol. AgBr (s) Ag+ + Br–
(S + 10–7) × S = KSP = 12 × 10–14 .
Page # 41
 S = 3 × 10-7 M.
[Ag+] = 4 × 10–7 M ; [Br–] = 3 × 10–7 M ; [NO3–] = 10–7 M.
ºKCl = ºK+ + ºCl– .
KKCl = 4 × 10–4 × 6 × 10–3 + 3 × 10–4 × 8 × 10–3 + 1 × 10–4 × 7 × 10–3.
KKCl = 24 + 24 + 7.
KKCl = 55 Scm–1.

(5) Calculation of Kw of water :

0 0
Q. If observed conductivity of pure water at 25ºC is = 5.54 × 10–8 –1cm–1 and  H = 349.8 ;  OH – = 198.5.
Then calculate Kw of water

Sol. 0H2O = 0H+ + °OH–

= 548.3
1000
Mc(H =  × molarity
2O)

1000
Mc(H = 5.54 × 10–8 ×
2O) molarity  (Concentration of those H2O molecules which are dissociated)

5.54 10 8 1000

548.3 =
[H2 O] dissociate

[H2O]dissociate = 1.01 × 10–7 M

 [H+] = 1.01 × 10–7 M

Kw = [H+] [OH–] = 1.01 × 1.01 × 10–14
= 1.02 × 10–14 at 25°C.
Note : (i) Conductance of mixture of two electrolytes
Ctotal =  Celectrolytes + Cwater ; Ktotal =  Kelectrolytes + Kwater
(ii) All the electrolytes will be parallel b/w two electrodes.
(iii) C or K is propertional to concentration of the solution [for any strong electrolyte (100% dissolvated)]

Page # 42