Electrochemistry (Booklet)

Electrochemistry Page No.
[1]
Electrochemistry
JEE MAINS SYLLABUS
 Electrolytic and metallic conduction, conductance in electrolytic solutions, specific and
molar conductivities and their variation with concentration.
 Kohlrausch‟s law and its applications.
 Electrochemical cells: Electrolytic and Galvanic cells, different types of electrodes,
electrode potentials including standard electrode potential, half – cell and cell reactions,
emf of a Galvanic cell and its measurement.
 Nernst equation and its applications; Relationship between cell potential and Gibbs‟
energy change.
 Dry cell and lead accumulator, Fuel cells.
 Electrolytic cell and faraday‟s law of electrolysis
 Corrosion and its prevention.
JEE ADVANCED SYLLABUS

 Electrochemical cells and cell reactions; Standard electrode potentials; Nernst equation
and its relation to Delta G.
 Electrochemical series, emf of galvanic cells, Faraday‟s laws of electrolysis.
 Electrolytic conductance, specific, equivalent and molar conductivity, Kohlrausch‟s law,
and Concentration cells.
Raman Niwas (Near Aakashwani), Mahmoorganj, Varanasi. Ph. (0542) – 2363455, website: www.catjee.in
Electrochemistry Page No.[2]
1. Electrochemical Cell
1.1 Electrode: An element (generally a metal rod) in contact with its ions in aqueous solution,
is called electrode.
Example: A zinc rod, dipped in a solution of ZnSO4 (aq)
A copper rod, dipped in a solution of CuSO4 (aq)
1.2 Electrochemical or Voltaic or galvanic cell: It is a system consisting of electrodes, in

which a chemical reaction occurs to generate electric current.
Example: The simplest electrochemical cell to study is Daniel cell, which is shown in the
figure below.
This is prepared by dipping Zn rod in a solution of ZnSO 4 in one beaker and by dipping
Cu rod in a solution of CuSO4 in another beaker. Now, the two electrodes (called half cells)
are connected wire through an ammeter.
As soon as the connection is made, Zn rod starts dissolving i.e. Zn atom changes to Zn 2+
by losing 2 electrons. The Zn2+ ion passes into the solution, thereby increasing its
concentration and 2 electrons remain on the Zn rod. Thus, ZnSO4 solution now has +2
unit extra charge and Zn rod has 2 unit extra charge. Thus, there is a charge separation
of 4 units between the Zn rod and ZnSO4 solution. This charge separation develops a
potential referred as oxidation potential since oxidation takes place on this electrode. The
potential is called standard oxidation potential (represented by E0Zn (s)|Zn 2 (aq) ), if the
concentration of Zn2+ in the solution in 1 M and temperature is 27C. This half cell is
represented by Zn (s)|Zn 2 (aq) .
Similar potential is developed at Cu 2  aq  |Cu  s  halfcell also, when Cu2+ discharges and
deposits on Cu rod. This potential is referred as reduction potential as reduction takes
place on this electrode. The potential is called standard reduction potential (represented
by E0Cu2 (aq)|Cu(s) ), if the concentration of Cu2+ in the solution in 1 M and temperature is 27C.
This half cell is represented by Cu 2 (aq) | Cu(s) .
Current flow
Flow of e
Ammeter
Anode () Cathode (+)

Zn strip Salt bridge Cu strip
(KCl or KNO3)
ZnSO4 CuSO4
solution Solution
Figure : Setup of a Daniel cell
The zinc rod which has the electron left by the zinc (that got oxidized) becomes negatively
charged while the Cu rod which lost electrons to Cu 2+ becomes positively charged. Thus,
electric current flows through the connected wire, which is indicated by a deflection in
ammeter showing that a chemical reaction is occurring in the cell. During the course of
reaction, zinc rod gets dissolved and copper gets deposited on the copper rod. Thus, the
concentration of the anode solution increases while that of cathode solution decreases.
The flow of electrons occur from the zinc rod to copper rod in the external circuit (wire)
and indirectly from cathode to anode in the internal circuit (solution). The current flow is
in the direction opposite to electron flow. The reactions occurring at the two electrodes are
At anode: Zn(s)  Zn2+(aq) + 2e
At cathode: Cu2+(aq) + 2e  Cu(s)
This current flow stops after some time. Think, why it happens? Answer is, let one mole of
Zn atom dissolves to form Zn2+, which passes into the solution and 2 mole of electrons
remain on the rod. Thus, rod becomes negatively charged and the solution becomes
positively charged. With the passage of time, the solution becomes so much positively
charged that any Zn atom getting oxidised and trying to get into solution, would be
repelled by the solution and thus the oxidation of Zn stops. Same phenomenon occurs at
cathode and the reduction of Cu2+ at cathode ceases. As the flow of electrons stop, so does
the flow of current. This problem can be removed with the use of salt bridge. The salt
bridge contains a highly soluble electrolyte (like KCl, NH4NO3, NH4Cl, KNO3 etc) in which
ionic mobilities (freedom of movement) of cation and anion are of comparable order.
Now, let us examine the function of salt bridge. Since zinc ions are produced as electrons
leave the zinc electrode, this tends to produce a net positive charge in the left
compartment. The salt bridge then throws cations having equivalent charge into the
solution to maintain electrical neutrality. Thus, the salt bridge keeps the solution neutral
by passing appropriate amounts of cations or anions to the two halfcells (compartments).
With the use of salt bridge, the flow of electrons becomes continuous and cell continues to
operate. But after some more time, cell again ceases to operate. Can you guess why it
stops operating now?
1.3 Cell Notation:

(i) Anode is written on the left side and cathode is written on the right side.
(ii) Phase boundaries are indicated by vertical line: Zn(s) | Zn 2 (aq)
phase boundary
(iii) Concentration of the electrolytes in the anode and cathode is written in

parenthesis.
(iv) In case of a gas, the partial pressure is to be mentioned in atm, mm Hg or bar.
(v) A comma is used to separate two chemical species present in the same solution.
(vi) A double vertical line i.e. | | denotes a salt bridge.
Zn(s) | Zn 2 (aq) || Cu 2 (aq) | Cu(s)
Phase separator Salt bridge Phase separator
 Anode   Cathode 
Note: When the half-reaction involves a gas, an inert material such as platinum serves as
a terminal and as an electrode surface on which the half-reaction occurs. The platinum
catalyzes the half-reaction. Hydrogen is bubbled over a platinum plate that is immersed in

an acidic solution. The cathode half-reaction is 2H (aq)  H 2 (g) .
The notation for the hydrogen electrode, written as a cathode, is H (aq) | H2 (g) | Pt
Illustration: Represent a cell in which zinc electrode serves as anode and hydrogen electrode
serves as cathode at standard condition.
Solution: Cell notation: Zn (s) | Zn2+ (1.0 M) || H+ (1.0 M) | H2 (1.0 bar) | Pt
Illustration: Represent the following cell based on reactions given.

(i) Cl2(aq)  2e  
 2Cl(aq)

(ii) Fe3(aq) 
 e  2
 Fe(aq)
2
(iii) Cd(aq) 
 2e  Cd(s) (iv) 2Tl (s) + Sn2+ (aq)  2Tl+ (aq) + Sn(s)

Solution: (i) || Cl2 (g) | Cl (aq) | Pt (ii) || Fe3(aq) 2+
, Fe(aq) | Pt

(iii) || Cd 2(aq) | Cd(s) (iv) Tl(s) | Tl+(aq) || Sn2+(aq) | Sn(s)
Illustration: Writing the cell Reaction from the Cell Notation

a) Write the cell reaction for the voltaic cell: Tl(s) | Tl+(aq) || Sn2+(aq) | Sn(s)
b) Write the cell reaction for the voltaic cell: Zn(z) | Zn2+(aq) || Fe3+(aq), Fe2+(aq) | Pt
Solution: The cell notation gives the species involved in each half-reaction. Complete & balance
each half-reaction, then multiply by factors so that when you add the half-reactions,
the electrons get cancelled.
a) Anode half reaction: Tl(s)  Tl+(aq) + e–,
Cathode half reaction: Sn2+(aa) + 2e–  Sn(s)

Multiplying the anode reaction by 2 and then adding the two half-cell
reactions:
Net Cell Reaction: 2Tl(s) + Sn2+(aq)  2Tl+(aq) + Sn(s)
b) Anode half reaction: Zn(s)  Zn2+(aq) + 2e–.

Cathode half reaction: Fe3+(aq) + e–  Fe2+(aq)
Net Cell Reaction: Zn(s) + 2Fe3+(aq)  Zn2+(aq) + 2Fe2+(aq)
In chapter exercise – 01 (Introduction to electrochemical cell)

Subjective:
1. Define electrode? Give example.
2. Define electrochemical cell.
3. Represent the galvanic cell in which the reaction:
Zn(s)  2Ag  (aq)  Zn2 (aq)  2Ag(s) takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell
(iii) Individual reaction at each electrode.
4. Represent the galvanic cell in which the cell reaction is Cu + 2Ag +  2Ag + Cu2+
Objective:
1. Which one of the following reactions cannot be used to set up an electrochemical cell?
(a) Fe + 2H+  Fe+2 + H2 (b) Mn + Sn+2  Mn+2 + Sn
(c) Cl2 + 2KBr  2KCl + Br2 (d) AgNO3 + NaCl  AgCl + NaNO3
2. If the salt bridge is removed suddenly from a working cell, the voltage
(a) increases
(b) decreases to a constant nonzero value
(c) drops to zero
(d) may increase or decrease depending upon cell reaction.
3. An electrochemical cell stops working after some time because
(a) electrode potential of both the electrodes becomes zero
(b) Electrode potential of both the electrodes becomes equal
(c) one of the electrode is eaten up
(d) the reaction starts proceeding in opposite direction
4. In an electrochemical process, a salt bridge is used:
(a) to maintain electrical neutrality in each solution
(b) to complete the external circuit so that current can flow for long time
(c) to mix the solution of anodic and cathodic compartment
(d) to supply voltage
5. In a Galvanic cell electron flows
(a) from cathode to anode in outer circuit.
(b) from anode to cathode in outer circuit.
(c) from cathode to anode inside (internal circuit) the cell.
(d) none of the above
6. During the passage of electricity through the solution of an electrolyte, current is carried
by
(a) cations only (b) anions only
(c) both cations and anions, usually in equal fraction
(d) both cation and anions, usually in different fraction
7. Cell reaction for the cell : Zn | Zn+2 (1.0 M) || Cd+2 (1.0 M) | Cd is given by
(a) Cd  Cd+2 + 2e– (b) Zn+2  Zn – 2e–
(c) Cd + Zn+2  Zn + Cd+2 (d) Zn + Cd+2  Zn+2 + Cd
8. The cell reaction: Zn + 2Ag+  Zn+2 + Ag, is best represented by
(a) Ag | Ag+ | | Zn | Zn2 (b) Zn | Zn+2 | | Ag+ | Ag
(c) 2Ag | Ag+ | | Zn | Zn+2 (d) Zn | Zn+2 | | 2Ag | Ag+
9. Select the correct cell reaction of the Pt(s)|Cl2(g)|Cl (aq)||Ag  (aq)|Ag(s)
(a) Cl2(g)  Ag  (aq)  Ag(s)  2Cl (aq) (b) Cl2(g)  Ag(s)  2Cl (aq)  Ag  (aq)
(c) 2Cl (aq)  2Ag  (aq)  Ag(s)  Cl2(g) (d) AgCl(s)  Ag  (aq)  Cl (aq)
ANSWER KEYS
Que. 1 2 3 4 5 6 7 8 9
Ans. d c b a b d d b c
2. Electrode Potential:
2.1 Standard Electrode Potential:
An electrode potential is the potential difference developed at the interface between the
electrode and the solution. It represents the tendency of reaction occurring at particular
electrode.
At anode: Oxidation: M(s)   Mn  (aq)  ne EOxidation Potential ( EOP )  EM(s)|Mn (aq)
Higher the value of oxidation potential of anode, higher will be the tendency of oxidation
reaction occurring at anode. If the tendency of a substance to get oxidized is more, it‟s
power to reduce other substance will be higher and hence it will be called a stronger
reducing agent.
At cathode: Reduction: Mn  (aq)  ne 

 M(s) EReduction Potential (E RP )  E Mn (aq)|M(s)
Higher the value of reduction potential of cathode, higher will be the tendency of reduction
reaction occurring at cathode. If the tendency of a substance to get reduced is more, it‟s
power to oxidize other substance will be higher and hence it will be called a stronger
oxidizing agent.
For a given electrode : Oxidation potential for a half-reaction = reduction potential for
the reverse half-reaction  EOP  ERP
E Zn|Zn 2  oxidation potential of zinc electrode = 0.76 V
( aq )
E Zn 2  Reduction potential of zinc electrode = ―0.76 V

( aq ) |Zn
The electrode potential is an intensive property. This means that its value is independent
of the amount of species in the reaction. Thus, the electrode potential for the half-
reaction.
2Cu2+(aq) + 4e–  2Cu(s) is the same as for Cu2+(aq)  Cu(s)
Illustration: Electrode potential of the metals in their respective solution are provided. Arrange
the metals in their increasing order of reducing power.
K+/K = – 2.93V, Ag+/Ag = + 0.80V, Hg+/Hg = +0.79V, Mg2+/Mg = – 2.37V, Cr3+/Cr =
–0.74V
Solution: We know that the reducing power of a metal depends upon its tendency to lose
electrons. Thus lower the reduction potential, more the tendency to get oxidized
and thus more will be the reducing power. Hence increasing order of reducing
power is:
Ag < Hg < Cr < Mg < K
2.2 Electrochemical series:

The standard reduction potential (SRP) values of different electrodes arranged in the
decreasing order is called electrochemical series.
2.3 Features of Electrochemical series:
(i). Greater the value of S.R.P. greater will be tendency to get reduced, so, the element
or compound will be stronger oxidizing agent.
(ii). Smaller the value of SRP (higher the value of SOP) so greater will be the tendency to
get oxidized hence compound or elements will be a better reducing agent.
Illustration: MnO4 
 Mn 2  EoMnO |Mn2  1.51 V and Cr2O72 
 Cr 3  EoCr O2 |Cr3  1.40 V . Which is
4 2 7
better oxidizing agent among KMnO4 and K 2Cr2O7 ?
Solution: MnO4  Mn2 : because it has higher reduction potential.
(iii). Metals which are lower in the series (having lower reduction and higher oxidation
potential) are more reactive and hence can displace metals in higher in the series
from their salt solution.
Illustration: CuSo4  Zn  ZnSO4  Cu  but ZnSO4  Cu  X (no reaction) , why?
Solution: Zn  Zn2  2e SOP = 0.76 V
Cu  Cu2  2e SRP = + 0.34 V

(iv). Metals placed below hydrogen can release H2 (g) on reaction with dilute acid
solution.
Mg  HCl(aq)  MgCl2  H2
Cu  HCl(aq)  no reaction
In chapter exercise – 02 (Electrode Potential)
Subjective:
1. What is electrode potential?
2. If EoMn |M  1 V then find the value of E oM|Mn . Also write the reaction concerned with potential
E oMn |M & E oM|Mn .
3. What do you mean by electrochemical series?

4. EoLi |Li  3.05 V, EoK |K  2.93 V, EoBa 2 |Ba  2.91 V, EoZn 2 |Zn  0.76 V, EAg
o

|Ag
 0.8 V : Arrange the
following metal in order of their reducing strength.
Objective:
1. Given: Eο +  +0.34 V , Eο +  1.66 V , Eο +  0.76 V , Eο +  0.28 V
A /A B /B C /C D /D
The most reactive metal which displaces other metals from their salt solution is:
(a) C (b) D (c) B (d) A
2. The position of some metals in the electrochemical series in decreasing electropositive
character is given as: Mg > Al > Zn > Cu > Ag. What will happen if a copper spoon is used to
stir a solution of aluminium nitrate?
(a) The spoon will get coated with aluminium.
(b) An alloy of copper and aluminium is formed.
(c) The solution becomes blue.
(d) There is not any reaction.
3. Four elements A, B, C, D have reduction potentials
–2.71, + 0.77, + 1.42 and – 0.76 V respectively. Which of the following statements is
correct about them?
(a) A is the strongest reducing agent and it can displace B in a chemical reaction
(b) C is the strongest reducing agent and it can replace B in a chemical reaction
(c) A is the strongest reducing agent and it can be replaced by C in a chemical reaction
(d) C is the strongest reducing agent and it can be replaced by D in a chemical reaction
4. When a piece of a copper wire is immersed in a solution of AgNO3, the colour of the solution
becomes blue. The is due to the :
(a) Formation of a soluble complex (b) Oxidation of copper
(c) Oxidation of silver (d) Reduction of copper
5. If the half cell reaction A (s)+ e¯  A¯ (aq) has a large negative reduction potential, it
follows that:
(a) A is readily reduced (b) A is readily oxidised
(c) A¯ is readily reduced (d) A¯ is readily oxidised
6. The metal that cannot be produced on reduction of its oxide by aluminium is:
(a) K (b) Mn (c) Cr (d) Fe
7. A student made the following observations in the laboratory,
(i) Clean copper metal did not react with 1 molar Pb(NO3)2 solution
(ii) Clean lead metal dissolved in a 1 molar AgNO 3 solution and crystals of Ag metal
appeared
(iii) Clean silver metal did not react with 1 molar Cu(NO3)2 solution.
The order of decreasing reducing character of the three metals is:
(a) Cu, Pb, Ag (b) Cu, Ag, Pb (c) Pb, Cu, Ag (d) Pb, Ag, Cu
ANSWER KEYS
QUE. 1 2 3 4 5 6 7
ANS. c d a b d a c
3. Gibb’s free energy and Cell potential:
3.1 Relation between Gibb’s free energy and cell potential:

The Gibb‟s energy change of a reaction of a cell (electrode) is given by  GCell  nFEcell
where , n = number of e– involved in cell (electrode) reaction
F = Faraday‟s constant = change on 1 mole of e–  1.6  1019 C   6.022  1023
= 96352 C  96500 C
As potential is intensive property so it can‟t be added or substracted directly. But G is
extensive property and follows Hess law.
Example: Zn2  2e  Zn(s) E  0.79 V , G  2  96500   0.79 
2Zn2  4e  2Zn(s) E  0.79 V , G  4  96500   0.79 
So G of various reactions can be added or substracted to get G of resultant reaction,

then Potential of resultant reaction can be calculated from G.
Illustration: Calculate EoCu|Cu  ? Given that EoCu2 Cu  0.337 V , EoCu2|Cu  0.153 V
Solution: (i) Cu2  2e  Cu , Eo  0.337 V , G10  n1FE10 (n1  2)
(ii) Cu2  e  Cu E  0.153 V , Go2  n2FE20 (n2  1)
Target Cu  e  Cu , E03  ? Go3  n3FE3o (n3  1)
From Hess‟ law: Go3  G1o  Go2  Go3  2F  0.337  F  0.153
 FEo3  2F  0.337  F  0.153  Eo3  0.521
Illustration: Calculate EoMnO|MnO  ? Given that EoMnO Mn2  1.51 , EoMnO |Mn2  1.23 V
4 2 4 2
Solution: MnO4  Mn2  5e E1o  1.51 (i)
MnO2  Mn2  2e Eo2  1.23 (ii)
Target : MnO4  MnO2  3e E3o  ? (iii)

(iii) = (i) ― (ii)  Go3  G1o  Go2  3FEo3  5 FE1o  2FEo2   
2.46  7.55 5.09
3F  Eo3  5  1.51F  2  1.23 F  Eo3    1.69
3 3
Illustration: Calculate the cell potential of the cell Represented by the following reaction:
 2
Cu(s)  2H(aq )  Cu(aq )  H2(g) . Given that ECu2|Cu  0.34 V , EH| H  0 ?
o o
2
2 
Solution: Anode : Cu(s)  Cu(aq )  2e n1=2 (i)
EoCu2|Cu  0.34 V , G1o = ―n1F(0.34 V) = ―2 F(0.34 V)
 
Cathode: 2H(aq )  2e  H2(g ) n2=2 (ii)
EoH| H  0 , G o2 = ―n2F(0 V) = ―2 F(0 V)

2
 2
Cu(s)  2H(aq )  Cu(aq )  H2(g) n3=2 (iii)
Eo3  ? , G 3o = ―n3F Eo3  G 3o = G1o + G o2
n3FE3o  (n1FE1o )  (n 2 FEo2 )  E3o  E1o  Eo2 = 0.34 (As n1  n 2  n 3  2 )
Note:
(i) While calculating potential of a complete cell reaction, individual electrode potential can
be added directly as electrons involved in each individual and resultant reactions are
same and cancelled out.
(ii) Potential of the cell = Ecell = oxidation potential of anode + reduction potential of
cathode
ECell  ERP, Cathode  EOP, Anode  ERP, Cathode  ERP, Anode
(iii) For a cell to function of feasible cell reaction: GCell  0 & ECell  0
Illustration: Predict the feasibility of reaction : 2Fe3  2I  2Fe2  I2
Given EoFe3|Fe2  0.77 V , Eol | l  0.54 V

2
Solution: Cathode: 2Fe3  2e  2Fe2 Reduction

Anode: 2I  I2  2e Oxidation
Cell Reaction: 2Fe3  2I  2Fe2  I2
EoCell  (0.77  0.54) V  0.23 V > 0 (Eocell  SRP of cathode – SRP of anode)
Illustration: Calculate Eocell of the cell made of electrodes
EoAg|Ag   0.80 V (oxidation)
EoMnO|Mn2  1.51 V (reduction)

4
Solution: Eocell  SRP cathode – SRP of anode  1.51  0.80  0.71 V
Illustration: Check the feasibility of following cell : Ag(s)  Ag (aq) ||Cu2(aq) |Cu(s)
Given: EoAg|Ag   0.80V , EoCu/Cu2  0.34 V
Solution: EoAg |Ag  0.80 V , EoCu2|Cu  0.34 V
Eocell  (0.34  0.80) V  0.46 V  0  not feasible
Illustration : Write the cell reaction and
find out the potential of the cell:
2 2
Zn(s) | Zn (aq), (1M) || Cu (aq), (1M) | Cu(s) . Given: E0Cu2 / Cu  0.35V; E0Zn2+ / Zn  0.76V
Solution: Anode: Zn  Zn2+ + 2e–

Cathode: Cu2+ + 2e–  Cu
––––––––––––––––––––––
Cell reaction: Zn + Cu2+  Zn2+ + Cu
E0cell  E0RP, Cu2 (aq)|Cu(s)  E0RP, Zn2 (aq)|Zn(s)  [0.35  (0.76)] V  1.11V
In chapter exercise – 03 (Gibb’s free energy and Cell potential)

Subjective:
1. The standard oxidation potentials E° for the half cell reactions are given,
Al (s)  Al+3 (aq) + 3e¯ E° = 1.66 V
Fe (s)  Fe+2 (aq) + 2e¯ E° = 0.41 V
E o of the cell reaction: 3Fe+2 (aq) + 2Al (s)  2Al+3 (aq) + 3Fe (s) will be?
2. The standard potentials E°, for the half reactions are:

Zn (s) = Zn+2 (aq) + 2e¯; E° = + 0.76 V
Fe (s) = Fe+2 (aq) + 2e¯; E° = + 0.41 V
The E o for the cell reaction: Fe+2 (aq) + Zn (s)  Zn+2 (aq) + Fe (s) will be?
3. The standard reduction potential for Fe+2 | Fe and Sn+2 | Sn electrodes are –
0.44 V and – 0.14 V respectively. For the cell reaction,
Fe+2 (aq) + Sn (s)  Fe (s) + Sn+2 (aq), the standard e.m.f will be?
4. If, MnO4– (aq) + 8H+ (aq) + 5e–  Mn+2 (aq) + 4H2O (l); E° = 1.51 V
MnO2 (s) + 4H+ (aq) + 2e–  Mn+2 (aq) + 2H2O (l); E° = 1.23 V
Then find the E o of the reaction: MnO4– (aq) + 4H+ (aq)+ 3e–  MnO2 (s)+ 2H2O (l)
Objective:
1. A cell reaction would be spontaneous if the cell potential and G are respectively:
(a) positive and negative (b) negative, negative
(c) zero, zero (d) positive, zero
2. Which of the following statement is correct?
(a) Ecell and G of cell reaction both are extensive properties.
(b) Ecell and G of cell reaction both are intensive properties.
(c) Ecell is an intensive property while G of cell reaction is an extensive property.
(d) Ecell is an extensive property while G of cell reaction is an intensive property.
+ 2+
3. For a cell given below, Ag|Ag || Cu | Cu
Ag+ + e–  Ag, E° = x and Cu2+ + 2e–  Cu, E° = y. E° cell is

(a) x + 2y (b) 2x + y (c) y – x (d) y – 2x
4. The Ecell at 25°C for the following reaction is 1.50 V. Calculate the G in kJ at 25°C:
Cr(s)  3Ag  (aq)  Ag(s)  Cr3 (aq)
(a) –140.94 (b) –295 (c) –212 (d) –434.25

5. The E° for the following cell: In(s) | In  OH 3  aq  || SbO2–  aq  | Sb  s  is +0.34 V.
Using reduction potential E°=–1.0 V for the In  OH 3 | In(s) electrode, calculate the
reduction potential E° for the SbO2– (aq) | Sb(s) electrode.

(a) –1.34 (b) +0.66 (c) +0.82 (d) –0.66
6. What is the standard electrode potential for the reduction of HClO represented by
the reaction in aq solution: HClO  H  2e 
 Cl –  H2O
Given: Cr 2 
 Cr 3  e –  E  0.41 V
HClO  H  2Cr 2 
 2Cr 3  Cl–  H2O  E  1.80 V
(a) 1.39 (b) 1.54 (c) 1.22 (d) 0.90

7. When two half–cells of electrode potential of E1 and E2 are combined to form a cell of
electrode potential E3, then (when n1, n2 and n3 are no. of electrons exchanged in
first, second and combined half–cells):
E1n1  E2n2 E n E n
(a) E3 = E2 – E1 (b) E3 = (c) E3 = 1 1 2 2 2 (d) E3 = E1 + E2
n3 n3
8. Use the following E° for the electrode potentials, calculate G° in kJ for the indicated
reaction: 5Ce4  aq   Mn 2  aq   4H2O  l  
5Ce3  aq   MnO4 –  aq   8H  aq 
Given that: MnO4 –  aq   8H  aq   5e – 

 Mn 2  aq   4H2O  l   E  1.51 V
Ce4  aq   e – 
 Ce3  aq   E  1.61 V
(a) –9.65 (b) –24.3 (c) –48.25 (d) –35.2

9. Predict whether the following reactions are feasible?
I. Sn+4 + 2Fe+2  Sn+2 + 2Fe+3  Eο = 0.10 V, Eο = 0.77 V
Sn+4 /Sn+2 Fe+3 /Fe+2
II. 2Cu+1  Cu+2 + Cu  Eο = 0.52 V, Eο = 0.15 V

Cu+ /Cu Cu+2 /Cu+
(a) I only (b) II only (c) I and II (d) none of these
10. Find the standard cell potential involving the cell reaction
In+2 + Cu+2  In3 + Cu+, at 298 K.
Given: Eο = x1 V; Eο +3 = x2 V;Eο +2 = x3 V
Cu+2 /Cu+ In /In+ In /In+
(a) x1 + x3 – x2 (b) (x1 + x3 – 2x2)/3 (c) x1 + x3 – 2x2 (d) x1 + x3 + 2x2

11. In a simple electrohcemical cell, which is in standard state, half cell reactions with
their appropriate oxidation potentials are
Pb (s) – 2e–  Pb+2 (aq); E° = +0.13 volt
Ag (s) – e–  Ag+ (aq); E° = –0.80 volt
Which reaction is feasible?
(a) Pb+1 (aq) + Ag (s)  Ag+ (aq) + Pb (s) (b) Pb+2 (aq) + 2Ag (s)  2Ag+ (aq) + Pb (s)
(c) Ag+ (aq) + Pb (s)  Ag (s) + Pb+1 (aq) (d) 2Ag+ (aq) + Pb (s)  2Ag (s) + Pb+2 (aq)
12. Given:
2Br–  Br2 + 2e–; E° = –1.09 V
I2 + 2e–  2I–; E° = 0.54 V
Fe+2 + 2e–  Fe; E° = –0.44 V
Which of the following reactions will not be spontaneous?
(a) Fe + Br2  FeBr2 (b) Fe + I2  FeI2
(c) I2 + 2Br–  2I– + Br2 (d) Br2 + 2I–  2Br– + I2
ANSWER KEYS
Que. 1 2 3 4 5 6 7 8 9 10 11 12
Ans. a c c d d a b c b c d c
4. Dependence of potential (emf) of a Cell on Concentration
4.1 Nernst equation:
The free-energy change for a reaction is given by: G  G  RT lnQ
Here Q is the reaction quotient. The reaction quotient has the form of the equilibrium
constant, except that the concentrations and gas pressures are those that exist in a
reaction mixture at a given instant.
Substituting G = – nFEcell & G0 = – nFE0cell , we get,  nFEEcell  nFEE0cell  RT lnQ
RT 2.303RT
Ecell  Ecell
0
 ln Q  Ecell  Ecell
0
 log Q
nF nF
At standard condition: T = 298 K, R =8.314 J/(molK), F = 96500 C
0.059
Ecell  E0cell  log Q
n
0.059
At equilibrium  ECell =0  and Q = keq  E0cell  log k eq
n
Illustration: Can you explain how the potential of cell changes as the cell operates?
Solution: As the reaction occurs in the voltaic cell, the concentrations of products increase
and the concentrations of reactants decrease. Therefore, Q and log Q increase. The second
term in the Nernst equation, (0.0592/n) log Q, increases, so that the difference E 0cell –
(0.0592/n) log Q decreases. Thus, the cell emf, E cell, becomes smaller. Eventually the cell
emf goes to zero, and the cell reaction comes to equilibrium.
Illustration: Calculate the cell potential for the Galvanic Cell: Zn(s) | Zn2+ (0.01 M) || Cu2+ (0.1
M) | Cu(s).
EoCell  0.34 V
[Zn 2 ] 0.01
Solution: The net reaction is Zn(s) + Cu2+ (x2)  Zn2+ (x1) + Cu(s)  Q  2
=  101
[Cu ] 0.1
0.059
Ecell  E0cell  log101  0.34 V  1 V  1.34 V
2
Illustration : Calculate the standard e.m.f. of the reaction: Fe3+ + 3e–  Fe(s) E 30 = ?
Given Fe3+ + e–  Fe2+ E10 = 0.771V and Fe2+ + 2e–  Fe(s) E 02 = – 0.44V
Solution: Fe3+ + e–  Fe2+ E10 = 0.771V
G10  nFEo1  (1)(F)(0.771V)  0.771V
Fe2+ + 2e–  Fe(s) E 02 = – 0.44V

G02  nFEo2  (2)(F)(0.44)  0.88FV
Fe3+ + 3e–  Fe(s) E 30 = ? (This reaction can be obtained by addition the above two)
G30  (3)(F)(E3o )  3FE3o
G30  G10  G02  3FE3o  0.771F  0.88F  0.109F
0.109
or E3o   V  0.036 V
3
4.2 Concentration Cells
In concentration cell, the two electrodes are of the same material and they are dipping in
the solutions of their respective ions at different concentrations.
Example: Zn(s) | Zn2+ (C1) || Zn2+ (C2) | Zn(s).
Let‟s understand the functioning of above mentioned concentration cell.
Zn | Zn2+ (C1) || Zn2+ (C2) | Zn

Oxidation half cell Zn  Zn2+ (C1) + 2e– E0OP  0.76V
Reduction half cell Zn2+ (C2) + 2e–  Zn E0RP  0.76V
––––––––––––––––––––––––––––––––––––
Net Cell reaction Zn2+ (C2)  Zn2+ (C1) E0cell  0.00V
––––––––––––––––––––––––––––––––––––
0.0591  C1  0.0591 C
E cell  Ecell
0
 log    E cell  log 2  ECell > 0 if C2 > C1
2  C2  2 C1
4.3 Standard hydrogen electrode: Here the inert electrode is present in contact with the gas
at 1 atm pressure (unless specified) and its ions in the solution e.g. Hydrogen gas
electrode, etc.
H2 (g)
(a)
(at1atm)
Pt
H3O  (aq) 
Solution of H(aq ) ion
(1M)
[Acid solution]
H   1M
Hydrogen Electrode
The nature of inert electrode should be such that, when the external voltage is changed
even by small amount from the equilibrium value, the reaction will proceed one way or the
other. Most suitable electrode is platinum with fine coat of platinum powder or platinum
black.
Representation of SHE
For anode : Pts  |H2 g  (1 tm)|Haq  1M||
Re action : H2 (g)  2H (aq)  2e (oxidation) : E0H |H  0
2
 2
[H ]
Reaction quotient  Q  and n f  2 . Here concentration of H+ or [H  ] should be
PH2 (g)
taken in Molar and partial pressure of H2 (g) or PH2 (g) should be taken in bar or atm (1 bar
≈ 1 atm)

For cathode: ||H(aq ) (1M)|H2(g) (1atm)  Pt (s)
Re action : 2H (aq)  2e  H2 (g) (Redction) : E0H |H  0

2
PH2 (g)
Reaction quotient  Q  and n f  2
[H  ]2
The reduction potential (and hence oxidation potential also) of hydrogen electrode at
standard condition is taken to be zero.
Note:
1. No matter, with whatever set of stoichiometric coefficients, one balances the reaction, the
potential remains the same.
2. SRP all other electrodes 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 and using the equation:
ECell  EoRe duction potential of Cathode  EoRe duction potential of Anode
0
Diagram: Represents how the reduction potential of Zinc electrode is measured.

e– V
Zn (rod) H2(g)
Zn2+ 1M
(1M)
Illustration: The hydrogen electrode is dipped in a solution of pH = 3 at 25°C and pressure of

hydrogen gas is 1 bar. The reduction potential of the electrode would be
PH
 H 2  g  : Q  2 2 and n f  2
Solution: 2H  (aq)  2e – 
[H ]
0 0.059 (PH )  0.059 1 


Ecell = Ecell  log 22 = 0  log 3 2  V=  0.177 V
2 [H ] 
 2 [10 ]  
Illustration: Calculate the value of Ecell for following concentration cell?

Pt | H2 (1 bar) | HCl (0.01) || HCl (0.1) | H2 (1 bar)|Pt
Solution: Net Cell reaction : H2 (g)Anode  2H (aq)Cathode 
 H2 (g)Cathode  2H (aq)Anode
(0.1 M)2 1 bar 0.059
Q  102  Ecell  ECell
o
 log102  0.059 V
(0.01 M)  1 bar
2
2
Brain Teaser : Write the expression of ECell for the following Concentration Cell.
Pt |Cl2 (g), 1 bar | Cl– (C1) || Cl– (C2)| Cl2 (g), 1 bar | Pt
0.0591 C
Answer: E cell  log 2
2 C1
In chapter exercise – 04 (Nernst Equation)
Subjective:
1. Represent the cell in which the following reaction takes place and calculate

E(cell) if E(cell)  3.17V . Mg(s)  2Ag  (0.0001 M)  Mg2 (0.13 M)  2Ag(s)
2. Calculate the emf of the cell or Ecell in which the following reaction takes place
Ni(s)  2Ag  (0.002M)  Ni2 (0.160M)  2Ag(s) . 
Given that: Ecell  1.05V
3. Write the Nernst equation and calculate emf of the following cells at 298 K:
(For this question, use the standard reduction potential data of required electrode
from the electrochemical series given in the booklet)
(i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)| Pt(s)
(iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2(g) (1 bar)|Pt(s)
(iv) Pt(s)|Br2(l)|Br–(0.010 M)||H+(0.030 M)|H2(g) (1 bar)|Pt(s).
4. Calculate the reduction potential for the following half cells at 25°C
(i) Mg|Mg 2 (1 104 M); E0  2.36V
Mg|Mg2
(ii) Cl2 |Cl (2 105 M); E0  1.36V

Cl2|Cl
5. The standard reduction electrode potential of Cu|Cu2+ is –0.34 volt. At what

concentration of Cu2+ ions will this electrode potential be zero?
6. Calculate the potential of hydrogen electrode in contact with a solution whose pH is
10.
7. Calculate the equilibrium constant of the reaction

Cu(s)  2Ag  (aq)  Cu2 (aq)  2Ag(s) ; Ecell  0.46V
8. The cell in which the following reaction occurs:
3  2 
2Fe (aq)  2I (aq)  2Fe (aq)  I2(s) has Ecell  0.236 V at 298K. Calculate the standard
Gibbs energy and the equilibrium constant of the cell reaction.

Objective:
1. The value of the reaction quotient, Q, for the cell
+3
Cr (s) | Craq (0.1M) | | Cu+2
aq (0.5M) | Cu (s) is:
(a) 12.5 (b) 0.08 (c) 0.20 (d) 5.0

2. The Nernst equation giving dependence of electrode potential on concentration is
M+n (aq) + ne–  M (s)
2.303 RT [M] 2.303 RT [M+n ]
(a) E = E°+ log +n (b) E = E°+ log
nF [M ] nF [M]
2.303 RT 2.303 RT
(c) E = E°  log [M+n ] (d) E = E°  log [M+n ]
nF nF
3. If the pressure of hydrogen gas is increased from 1 atm to 100 atm, keeping the
hydrogen ion concentration constant at 1 M, the reduction potential of the hydrogen
half–cell is at 25°C will be
(a) 0.059 V (b) –0.059 V (c) 0.295 V (d) 0.118 V
4. The reduction potential of hydrogen electrode at pH = 10 and 25°C is
(a) 0.059 volt (d) zero volt (c) –0.59 volt (d) –0.059 volt
5. Electrode potential for Mg electrode varies according to the equation
0.06 1
E  Eo  log The graph of E 2 vs log[Mg 2 ] is
Mg2 |Mg Mg2 |Mg 2 2
[Mg ] Mg |Mg
EMg2+|Mg
EMg2+|Mg
(a) (b)
log[Mg2+] log[Mg2+]
EMg2+|Mg
EMg2+|Mg
(c) (d)
log[Mg2+] log[Mg2+]
6. The nature of curve E°cell vs log Kc is:
(a) straight line (b) parabola (c) hyperbola (d) elliptical curve
7. Which of the following is (are) correct about Gibb‟s Free energy?
(a) G = H – TS and G < 0 for reaction to be spontaneous
(b) G > 0 indicates that the reaction is spontaneous.
(c) G < 0 implies KC < 1
(d) G < 0 implies KC = 1.
8. For the reaction: 2A (s) + B+2 (aq)  2A+ (aq) + B (s), Nernst equation for the Ecell is
RT [A+ ] RT [A+ ]2
(a) E = E°  ln +2 (b) E = E°  ln
F [B ] 2F [B+2 ]
RT [A+ ] RT [A+ ]
(c) E = E°  ln (d) E = E°  ln +2
F [B+2 ] F [B ]
9. The emf of the cell: Tl|Tl+(0.001 M)||Cu+2 (0.01 M)|Cu is 0.83 V. The emf of this
cell could be increased by
(a) increasing the concentration of Tl+ ions
(b) increasing the concentration of Cu+2 ions
(c) increasing the concentration of both
(d) none of the above
10. Two Daniell cells were set up: One with 1 M ZnSO4 and 1 M CuSO4, the other with 2
M ZnSO4 and 2 M CuSO4. Their emf‟s are E1 and E2 respectively. Then
(a) E1 = 2E2 (b) E2 = 2E1 (c) E2 = 4E1 (d) E1 = E2
11. The e.m.f. of the following galvanic cells:
(I) Zn | Zn+2 (1M) | | Cu+2 (1M) | Cu
(II)Zn | Zn+2 (0.1M) | | Cu+2 (1M) | Cu
(III) Zn | Zn+2 (1M) | | Cu+2 (0.1M) | Cu
(IV) Zn | Zn+2 (0.1M) | | Cu+2 (0.1M) | Cu
are reprsented by E1, E2, E3 and E4. Which of the following statement is true?
(a) E1 > E2 > E3 > E4 (b) E3 > E2 > E1 > E4
(c) E3 > E1 = E4 > E2 (d) E2 > E1 = E4 > E3
12. Which cell will measure standard reduction potential of copper electrode?
(a) Pt(s)| H2 (g, 0.1 bar)| H+(aq.1 M)|| Cu2+(aq.1M) Cu
(a) Pt(s)| H2 (g, 1 bar)| H+(aq.1 M)|| Cu2+ (aq.2 M) Cu
(c) Pt(s)| H2 (g, 1 bar)| H+(aq.,1 M)|| Cu2+ (aq.1 M) Cu
(d) Pt(s)| H2 (g, 1 bar)| H+(aq.0.1 M)||Cu2+(aq.1M) Cu
RT
13. The nernst equation E  E – ln Q , indicates that the Q will be equal to
nF
equilibrium constant Kc when:
(a) = E° (b) RT/nF = 1 (c) E = zero (d) E° = 1
14. The equilibrium constant for the following general reaction is 1030. Calculate E° for
the cell at 298 K.
2X2 (s) + 3Y+2 (aq)  2X2+3 (aq) + 3Y (s)
(a) +0.105 V (b) +0.2955 V (c) 0.0985 V (d) –0.2955 V
Answer Key
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. b d b c b a a c b d d c c b
5. Types of Electrodes
The various types of electrodes used and the chemical reactions which take place are:
5.1 Gaseous electrode: SHE is an example of gaseous electrode. Here the inert electrode is
present in contact with the gas at 1 atm pressure (unless specified) and its ions in the
solution e.g. Hydrogen gas electrode, etc. It is denoted as
1
H+ | H2 (1 atm) | Pt and the chemical reaction is H+ + e–  H2(g).
2
H2 (g)
(a)
(at1atm)
Pt
H3O  (aq) 
Solution of H(aq ) ion
(1M)
[Acid solution]
H   1M
Hydrogen Electrode
5.2 Meta-Soluble salt Electrode: Here the metal electrode dips in a solution containing its
ions and the metal electrode takes part in chemical reaction. Reactivity of the metal
should be intermediate otherwise the reactive metals will react with water and cannot act
as electrodes. The example is the copper electrode dipping in copper sulphate solution. It
is denoted as Mn+ | M in general and in particular Cu2+ (c) | Cu and c is the
concentration. The chemical reaction is
Cu2+ + 2e–  Cu(s).
Cu Rod.
[CuSO4 ]  1M
5.3 Metal-Insoluble Salt Electrode: In this half cell, a metal coated with its insoluble salt is
in contact with a solution containing the anion of the insoluble salt.
Construction:
AgCl Ag rod
aq. solution of
AgCl
Undissolved AgCl
Half cell reaction:
(a) If it act as anode : If it is normal silver electrode than.
Ag(s)  Ag  (aq)  e …(i)
But solution have Cl (aq) ion so Ag  (aq) and Cl (aq) form precipitate of AgCl(s)
Ag  (aq)  Cl (aq)  AgCl s  …(ii)
Overall half cell reaction at anode [adding eq. (i) and (ii)].
Ag(s)  Cl (aq)  AgCl(s)  e …(iii)
(b) If it ac as cathode: 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 [adding eq. (i) and (ii)].
AgCl(s)  e  Ag(s)  Cl (aq) …(iii)
Cell representation:
Anode: Ag(s)|AgCl(s)|Cl (aq)||  EoAg(s)|AgCl(s)|Cl (aq )
Cathode: ||Cl (aq)|AgCl(s)|Ag(s)  EoCl (aq )|AgCl(s)|Ag(s)
Relation between EoCl (aq )|AgCl(s)|Ag(s) and EoAg  (aq )|Ag(s)
If a cell is constructed using metal – metal soluble salt and metal – metal insoluble salt
electrode.
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     Ag   & Ecell  0

a c
o
But Ecell  Ecell 
0.059
log
 AgCl(s)
1  Ag   Cl 
 c  a
0.059 1
At equilibrium  0  Eocell  log
1  Ag  Cl 

 c  a
Ksp
For solubility: AgCl(s)  Ag  (aq)a  Cl (aq)a  Ksp   Ag   Cl   [Cl ] 
a a [Ag  ] a
0.059  Ag  
 a
0 Eocell  log [At equilibrium the concentration of  Ag     Ag   ]
1  Ag   Ksp
 a c
 a
0.059 1 0.059
Eocell  log  Eocell   log Ksp
1 Ksp 1
0.059 1
As, Eocell  Eocathode  EoAnode  EoAg  /Ag  ECl
o

/AgCl/Ag
 EoAg  /Ag  ECl
o

|AgCl|Ag
 log
1 Ksp
0.059
EoCl /AgCl/Ag  EoAg  /Ag  log Ksp
1
0.059
Example: Pb|PbSO (s)|SO2 ||Pb2 |Pb(s)  EoSO2|PbSO |Pb  EPb
o
2
|Pb
 log Ksp
4 4 4 4 2
Illustration: Calculate the Ksp of AgI if E0I |AgI|Ag  0.151V and E0Ag+ |Ag  0.7991V
0.059
Solution: EoI|AgI|Ag(s)  EoAg  (aq )|Ag(s)  log K SP  [Cl ]
1
Ksp  1016.1  7.94 1017
Illustration: Consider the cell at 25C : Ag(s) | AgBr(s) | Br–(aq) || Cl (aq)|AgCl(s)|Ag
If K sp of AgBr and AgCl are 5 1013 and 1010 respectively for what ratio of concentration of
Br  (aq) and Cl (aq) would be emf be equal to zero.
Solution: Eocell  EoCl /AgCl/Ag  EoBr /AgBr/Ag
 0.059 
 EoAg  /Ag  log Ksp  AgCl   EoAg  /Ag  0.059log Ksp  AgBr  
 1   
0.059 Ksp  AgCl 

 Ecell  0.059 log Ksp  AgCl   log Ksp  AgBr   0.059log
1 Ksp  AgBr 
 
Anode : Ag  Br  AgBr  e
Cathode : AgCl  e  Ag  Cl 
______________________________
Br   AgCl(s) 
 
 Cl  AgBr(s)
o 0.059  Cl 
E cell  Ecell  log   
1  Br 
0.059 Ksp  AgCl  0.059  Cl  

log  log   
1 Ksp  AgBr  1  Br 
Ksp  AgCl   Cl   Br   Ksp  AgBr  1

  so,    
Ksp  AgBr   Br  Cl  Ksp  AgCl 200

 
5.4 Calomel Electrode:
It is metal – insoluble salt type electrode. A calomel cell consists of a platinum electrode
Hg 2Cl2 )
dipping into mercury in contact with calomel (dimercury (I) chloride
and potassium chloride solution.
Usually the solution is saturated with potassium chloride.
In standard calomel electrode: [Cl ] =1 M = 1 N
As anode:
2Hg( )  Hg 22 (aq)  2e 
Reactions: Hg 22 (aq)  2Cl   Hg 2Cl2 (s)
_______________________________
2Hg( )  2Cl  (aq)  Hg 2Cl2 (s)  2e 
Cell representation: Pt(s)|Hg()|Hg2 Cl2 (s)|Cl (aq)||
RT
ECl /Hg o
 ECl   n Cl  = 0.246 V at 25C
2Cl2 /Hg /Hg 2Cl2 /Hg F
As Cathode:
Hg 22  2e  Hg()
Reactions : Hg 2Cl2  Hg 22 (aq)  2Cl  (aq)
____________________________
Hg 2Cl2 (g)  2e   Hg()  2Cl 
Cell representation: ||Cl (aq)|Hg 2 Cl2 |Hg()|Pt(s)
5.5 Thermodynamics of the Cells:
The e.m.f. of the cell is related to free energy by equation  G = –nFE

 G   G   E   E 
Now  T   S   T   nF  T   S  S  nF  T 
 P  P  P  P
 E 
The enthalpy of the cell reaction will be: H = G + TS = nFE  TnF  
 T P
Where, G = Free energy change, H = Enthalpy change & S = entropy change during
operation of cell.
E
= Temperature coefficient of cell.
T
Note: The heat effects in the system can be calculated as follows. If the process is irreversible
(i.e. by mixing the reactants together), heat flow to the system can be given by the reaction
H = QP. If the process is reversible the heat flow to system is given by QP = TS.
Illustration: The standard potential of the following cell is 0.23 V at 15C and 0.21 at 35C.
Pt|H2 (g)|HCl(aq)|AgCl(s)|Ag(s)
(i) Write the cell reaction.

(ii) Calculate H, S for the cell reaction by assuming that these quantities remain
unchanged in the range 15C to 35C.
(iii) Calculate the solubility of AgCl in water at 25C. Given standard reduction potential of
the Ag  / Ag couple is 0.80 V a 25C.
 dE  0.21  0.23
Solution:  dT    1  103 volt deg 1 .
 P 20
S  96500 103 J/K /mol.  96.5 J/K /mol.
(i) Cell reaction: H2  2AgCl(s)  2H  2Ag(s)  2Cl
(ii) S  96.5 J/K /mol.  22195  H  288  S
 20265  H  288  S  S  96.5 J/K /mol.  H  49987 J/mol.
(iii) Cl / AgCl / Ag,
Ksp
Ag  (C)  e  Ag, C 
1
0.0591 1
0.22  0.80  log  C  Ksp  1.53 1019
1 C
Solubility  KSP  1.24 105 M.
In chapter exercise – 05 (Types of electrodes)
Objective:
1. What is the SRP for S2 |CuS|Cuhalf  cell ?
Given: Ksp (CuS)  1035 and E  0.34V
Cu2|Cu
(a) 1.034V (b) 1.0V (c) –0.694V (d) 0.694V
2. Given the following standard electrode potentials, the Ksp for PbBr2 is
 
PbBr2 (S)  2e  Pb(s)  2Br (aq); E°=–0.248V
Pb2 (aq)  2e  Pb(s); E  0.126V
(a) 7.4 105 (b) 4.9 1014 (c) 5.2 106 (d) 2.3 1013
3. Given the data at 25°C,

Ag + I–  AgI + e–; E° = 0.152 V
Ag  Ag+ + e–; E° = –0.800 V
What is the value of log Ksp for AgI?
(a) –8.12 (b) +8.612 (c) –37.83 (d) –16.13
dEcell
4. The temperature coefficient, of the emf i.e,  0.00065 volt deg–1 for the cedd
dT
Cd|CdCl2(1M)|AgCl(s)|Ag at 25°C. Calculate the entropy changes S298K for the cell
reaction,
Cd  2AgCl  Cd  2Cl  2Ag
(a) –105.5 JK–1 (b) –150 JK–1 (c) –75.7 JK–1 (d) –125.5 JK–1
ZnSO4 CuSO4
5. The potential of the Daniell cell, Cu was reported by Buckbee,
1(M) (1M)
Surdzial and Metz as E  1.1028 – (0.64110–3 )T  (0.72 10–5 )T2 , where T is the cesium
temperature. Calculate S° for the cell reaction at 25°C
(a) –45.32 unit (b) –34.52 unit (c) –25.43 unit (d) –54.23 unit
Answer Keys
Que. 1 2 3 4 5
Ans. c a d d d
6. Electrolysis and Electrode Reactions:
The process of decomposition of an electrolyte on passing electricity on electrical current
through its aqueous solution or through its molten state. The cell used for this processes
is called an electrolytic cell.
i e–
cathode anode
B A 
Elecrolyte(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 neutralized after
accepting electrons from the cathode.
Actions will be attracted towards Anode and will get neutralised after releasing extra (–ve)
charge.
Cathode: B  e  B
Anode: A   A  e
Net reaction: B  A   B  A

The electrodes, like platinum, which only transfer electrons to and from the solutions are
termed as “inert electrodes”. The “reactive electrodes” are those which participate
chemically into the electrode reactions.
Illustration: Write the product at anode and cathode by electrolysis of molten NaCl.
Solution: Electrolysis of molten NaCl:
Anode: 2Cl  Cl2  2e
Cathode: Na   e  Na
Over all reaction: 2Na   2Cl  2Na  Cl2 (g)
Illustration: Write the product at anode and cathode by electrolysis of molten PbBr2.
Solution: Electrolysis of Molten PbBr2 :
1
Anode: Br   Br2 (g)  e
2
Cathode: Pb2  2e  Pb(s)
Over all reaction: Pb2  2Br  Pb  Br2 (g)
6.1 Preferential discharge theory:
In case two ore more types of positive and negative ion area 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.
Example: Cation having highest reduction potential is discharged first at cathode:
(Last) K   Ca 2  Na   Mg 2  Al3  Zn2  Fe2  H  Cu2  Ag   Au3 (First)
Example: Anion having highest oxidation potential is discharged first at anode.
     
(Last) SO2
4  NO3  OH  Cl  Br  I (First)
6.2 Electrolysis of different substance in aqueous solution:

[A] Electrolysis of water:
To make water conducting, little H2SO4 is added into it.
Species present in solution H ,OH ,SO24 ,H2O
Possibilities of reactions at Anode:

(i) 4OH  O2  2H2O  4e EoOP  0.40 V (Conc of OH is very less so this
reaction will not be considered)

(ii) SO24  S2O82  2 e EoOP  2.05 V
(iii) 2H2O  O2  4H  4e EoOP  1.23 V (This reaction will take place)
[Rule - Whenever there are many anions/species which are competing to get oxidized at
anode, than species with maximum OP, will get oxidized preferentially]
Since in this solution OH ions are negligible, so water will get oxidised.
Anode: 2H2O  O2  4H  4e o

ESRP  1.23
Possibilities of reactions at Cathode:

(i) 2H  2e  H2 EoSRP  0.0V
(ii) 2H2O  2e  H2 (g)  2OH EoSRP  0.83 V
[Rule - Whenever there are many anions/species which are competing to get reduced at
cathode, than species with maximum RP, will get reduced preferentially]
Since H+ concentration is negligible, hence water will get reduced.
Cathode: 2H2O  2e  H2 (g)  2OH
Overall Recation:
Anode: 2H2O  O2  4H  4e
 
Cathode: 2H2O  2e  H2 (g)  2OH
Adding them: 2H2O  O2  2H2
[B] Electrolysis of aqueous Solution of NaBr:

Species present in solution Na  ,Br  ,H ,OH ,H2O
Cathode: Possible reaction

(i) Na   e  Na EoSRP  2.71
(ii) 2H2O  2e  H2 (g)  2OH EoSRP  0.83 V (This reaction take place)
Anode: Possible reaction

(i) 2Br   Br2 (g)  2e EoSOP  1.08 V (This reaction take place)
(ii) 2H2O     O2 (g)  4H  4e EoSOP  1.23 V
2H2O  2Br   Br2 (g)  H2 (g)  2OH
Note: The SRP value of Na is much less than H2O that‟s why we can‟t obtain Na from NaBr (aq).
[C] Electrolysis of Brine Solution (Conc NaCl):
Na+(aq) + e–  Na(s) E0 = –2.71V

2H2O(l) + 2e–  H2(g) + 2OH–(aq) E0 = – 0.83V (This reactions takes place)
Under standard conditions, you expect H2O to be reduced in preference to Na+, which agrees
with what you observe. Hydrogen is evolved at the cathode.
2Cl–(aq)  Cl2(g) + 2e– –E0 = –1.36V

2H2O(l)  O2(g) + 4H+(aq) + 4e –E0 = – 1.23V
Note: 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.
Now if If Cl― is oxidized at anode then

Potential of external battery required (Ecell)= | SRP of cathode – SRP of anode |
= |―0.83―1.23|=2.06 V
Now if H2O is oxidized at anode then
Potential of external battery required (Ecell)= | SRP of cathode – SRP of anode |
| 0.83  1.23|| 2.06| 2.06 V = |―0.83―1.36 |= 2.19 V
So at over potential, kinetically Cl2 production is favoured.
Net reaction:
2H2O(l) + 2e–  H2(g) + 2OH–(aq) (cathode)

2Cl–  Cl2(g) +
(aq) 2e– (anode)
–––––––––––––––––––––––––––––––––––––––––
2H2O(l) + 2Cl–(aq)  H2(g) + Cl2(g) + 2OH–(aq)
Because the electrolysis started with sodium chloride, the cation in the electrolyte solution is
Na+. When you evaporate the electrolyte solution at the cathode, you obtain sodium hydroxide
NaOH. (The process is also called Chlor – Alkali process as it produces Cl2 and NaOH (Alkali)
[D] Electrolysis of aqueous Na2SO4:

Anode:
(i) SO24  S2O82  2 e EoOP  2.05 V
(ii) 2H2O  O2  4H  4e EoOP  1.23 V (This reaction will take place)
Note: If the concentration, of acid is high then: Oxidation of SO24 to S2O82 takes place at
over potential.
Cathode:
(i) 2H  2e  H2 EoSRP  0.0V (This reaction takes place)
(ii) 2H2O  2e  H2 (g)  2OH EoSRP  0.83 V
Illustration: Write the Products of electrolysis of aq copper sulphate using platinum electrode.
Solution: Electrolysis of aq. Solution of CuSO4 :
Species present in solution Cu2 ,SO24 ,H ,OH ,H2O
Cathode: Reaction possibilities:

(i) Cu2  2e  Cu E  0.34 (This reaction takes place)
(ii) 2H2O  2e  H2  2OH (aq) E  0.83 V
Anode: Reaction possibilities:

(i) 2H2O  O2  4H  4e o
EOX  1.23 V (This reaction takes place)
(ii) SO24  S2O82  2 e EoOP  2.05 V
Over all reaction 2H2O  2Cu2  2Cu  O2  4H
Illustration: Explain what will happen if of aq copper sulphate is electrolyzed using copper
electrodes.
Solution: Anode Possibilities :
(i) SO4  not possible
(ii) 2H2O  O2  4H  4e E0  1.23 V
2 
(iii) Cu  Cu  2e EoOx  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
Diagrammatically it can be shown:
Cu Cu
aq.CuSO4
[Cu2 (aq)]
Brain Teaser: How will the concentration of [Cu 2 (aq)] change if aq CuSO4 is electrolyzed using
copper electrodes.
Ans: It will remain constant
Illustration: What will happen if Aq AgNO3 is electrolyzed using Ag anode and Iron cathode.
Solution: Anode Possibilities: 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 EoRP  0.83 V
Hence, Silver will get deposited at iorn. The phenomena is called electroplating.
Diagrammatically it can be shown
Anode
Cathode
Ag or Au Fe
rod
Layer of Ag or Au
In chapter exercise – 06 (Electrolysis)
Subjective:
1. Consider the following diagram in which an electrochemical cell is coupled to an electrolytic
cell. What will be the polarity of electrodes „A‟ and „B‟ in the electrolytic cell?
2. A galvanic cell has electrical potential of 1.1V. If an opposing potential of 1.1V is applied to
this cell, what will happen to the cell reaction and current flowing through the cell?
3. How will the pH of brine (aq. NaCl solution) be affected when it is electrolysed?
4. When acidulated water (dil.H2SO4 solution) is electrolysed, will the pH of the solution be
affected? Justify your answer.
Objective :
1. In the electrolysis of aqueous sodium chloride solution which of the half cell reaction will
occur at anode? (Don‟t consider the case of over potential)

(a) Na+ (aq) + e– Na (s); ECell = –2.71V

(b) 2H2O(l)  O2(g) + 4H+(aq) + 4e– ; ECell = ―1.23V

(c) H+ (aq) + e– H2 (g); ECell = 0.00 V

(d) Cl– (aq) Cl2 (g) + e– ; ECell = ― 1.36 V
1.[b]
7. Faradays law of Electrolysis:
7.1 Faraday’s First Law: The mass (W) of an ion discharged during electrolysis is
proportional to the quantity of charge passed (Q).
 W Q   W  C  t or W = Z  C  t
Where, Q = Current in amperes (c) × times in sec. (t)
Z (unit g ) is constant, called electrochemical equivalent of the ion deposited and is

C
equal to mass of substance discharged when a current of 1 ampere is passed for 1 second
(i.e. Q = 1).
Illustration: Calculate the value of Z for an ion Mn  

 M , if molar mass of metal M is Mw
Solution: 1 F charge = = 96514.8C  96500C
Mn   n e 
M
For above reaction: n 96500 C charge will deposit Mw gram of metal
Mw
1C charge will deposit gram of metal
n  96500
Mw M  1 E
Hence Z    w  
n  96500  n  96500 96500
E = Equivalent mass of metal, n = moles of electron involved during reaction or change in
oxidation number.
Brain Teaser: Calculate the value of electrochemical equivalent of Cu for Reaction Cu 2  Cu .
Atomic mass of copper = 63.5 amu.
63.5 g
Ans:
2  96500 C
Illustration: How many columbs of charge are required for following reduction?
(i) 1 mole of Cu2 to Cu (ii) 1 mole of MnO4 to Mn2
Solution: (i) Q  96500  2C (2 mole of e  ) = 2 F of charge
(ii) MnO4  8H  5e  Mn2  4H2O (Q  5  96500 C  5F)
Illustration: How many grams of Cu will get deposited by passing 2 Ampere for 30 minites in aq.
CuSO4 and what will the weight of O2 produced at anode.
Solution: Possible reaction

Cathode: Cu2  2e  Cu
Anode: 2H2O  O2  4H  4e
Calculation of weight of Cu:
2 mole of e  deposits 1 mole of Cu.

 2  96500 C charge deposits = 63.5 g of Cu
 63.5 
 2  30  60 C charge deposits =   30  60  2  g = 1.18 g of Cu
 2  96500 
(Calculate of weight of O2
4 mole e  liberates (1 mole O2) 32 g of O2
 4  96500 C charge liberates (1 mole O2) 32 g of O2
 32 
 3600 C charge deposits   3600  g of O2
 4  96500 
7.2 Faraday’s Second Law: When the same quantity of electricity is passed through
different electrolytes, the masses of different ions liberated at the electrodes are directly
proportional to their electrochemical equivalents or equivalent weights.
W2 E1
For same amount of charge passed  W  E w  W1  E1 , W2  E 2  
W2 E 2
7.3 Some commercial cells
The commercial cells are actually portable source of electrical energy. These cells are also known
as Batteries.
Types of Commercial Cells: There are mainly two types of commercial cells.
(a) Primary Cells: These cells cannot be longer period of time because they are not
chargeable. Some common examples of primary cells are:
i) Dry cell and

ii) Mercury Cell
i) Dry Cell: It is used in torches, toys and in other electronic devices. Leclanche cell is
the compact form of the dry cell.
In this cell zinc cylinder acts as an anode. The cylinder is filled with the paste of NH4Cl
and little amount of ZnCl2 in the form of paste in water. A graphite rod surrounded by
a black paste of MnO2 and carbon powder acts as a cathode.
The cathodic reaction of the cell is represented as
MnO2 + NH4+ + e–  MnO(OH) + NH3
And the anodic reaction is Zn  Zn2+ + 2e–
It gives voltage of approximately 1.2 to 1.5V
Since, the NH4Cl in slightly aqueous medium is acidic, it will corrode the Zn and the
cell stops its functioning. Due to the corrosion and the consumption of Zn in the
process, this cell cannot be reused.
ii) Mercury Cell: It consists of Zn anode and HgO(s) as a cathode. The electrolyte of this
cell is a paste of KOH and ZnO.
The anodic reaction of the cell: Zn(Hg) + 2OH–  ZnO(s) + H2O + 2e–
And the cathodic reaction is HgO(s) + H2O + 2e–  Hg(l) + 2OH–
The voltage of the mercury cell is 1.35V. The cell shows constancy in its potential
throughout its life. This cell is used in small electrical circuits e.g., watches, hearing
aids etc.
(b) Secondary Cells: They are rechargeable by passing direct current in them, and,
therefore, they can be used again and again. These cell are also known as accumulators
or storage cells.
Most common accumulators are Lead Accumulators and Nickel Cadmium Accumulators.
Lead Accumulators: In lead accumulators three to six voltaic cells are connected in series
to get 6 to 12 volt.
The anode of this cell is made of spongy lead and cathode is a grid of lead packed with
PbO2. The electrolyte used in the cell is 38% H 2SO4 by weight having a density of 1.30
g/ml. When the Pb plates are placed for sometimes, a deposit of PbSO4 is formed on them.
The cell (voltaic) is represented as:
Pb | PbSO4 || H2SO4(aq) | PbSO4 | PbSO2 | Pb
 PbSO4 + 2e–

Pb(s) + SO42–(aq) 
 PbSO4(s) + 2H2O
2e– + PbO2(s) + 4H+(aq) + SO42–(aq) 
 PbSO4(s) + 2H2O (overall reactions)
Pb(s) + PbO2(s) + 2H2SO4(aq) 
It is clear from the net cell reaction that H2SO4 is consumed during the operation of the
cell and its density regularly decreases. When the density of the H2SO4 solution falls below
1.2g/ml, the recharging of the battery is required.
Recharging of the Cell: When D.C. passed directly in this battery, the reactions of its
voltaic cells are reversed and this will slowly increase the density of the H2SO4 solution.
The recharging reaction is represented as: 2PbSO4(s) + 2H2O  Pb(s) + PbO2(s) + 2H2SO4
The discharging process of the storage cell is based on the principles of electrochemical
cell, whereas the charging process is based upon the principles of electrolytic cells.
7.4 Fuel Cell

In these cells fuel can be supplied continuously during the operation of the cell.
Example : 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.)
Net Reaction: H2 (g)  O2 (g)  2H2O(l). E  1.22V
In chapter exercise – 07 (Faraday’s law of Electrolysis)

Subjective:
1. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is
the mass of copper deposited at the cathode?
2. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many
electrons would flow through the wire?
3. Consider the reaction: Cr2O72  14H  6e  2Cr3  8H2O
What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O72 ?
4. How much charge is required for the following reductions:
(i) 1 mol of Al3+ to Al.
(ii) 1 mol of Cu2+ to Cu.
(iii) 1 mol of MnO4– to Mn2+.
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.
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 Fe2O3.
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?
Objective :
1. How many electrons are there in one coulomb of electricity?
(a) 6.023 × 1023 (a) 1.64 × 10–24 (c) 6.24 × 1018 (d) 6.24 × 10–24
2. How many coulombs are provided by a current of 0.010 mA in the calculator battery that
can operate for 1000 hours?
(a) 1.0 (b) 10 (c) 0.010 (d) 36
3. In the electrolysis of CuSO4 solution, how many grams of Cu are plated out on the cathode
in the time that it takes to liberate 5.6 litre of O2 (g), measured at STP, at the anode?
(a) 31.75 (b) 14.2 (c) 4.32 (d) none of these
4. In the commercial perparation of aluminium, aluminium oxide (Al 2O3) is electrolysed at
1000°C. How many coulombs of electricity are required to give 54 kg of aluminium? Assume
the cathode following reaction:
Al+3 + 3e–  Al
(a) 17.3 × 108 (b) 3.21 × 107 (c) 1.82 × 104 (d) 57.9 × 107
5. When molten lithium chloride (LiCl) is electrolysed, lithium metal is formed at the cathode. If
current efficiency is 75% then how many grams of lithium are liberated when 1930 C of
charge pass through the cell:
(Atomic weight: Li = 7)
(a) 0.105 (b) 0.120 (c) 0.28 (d) 0.240
6. How many minutes are required to deliver 3.21 × 106 coulombs using a current of 500 A
used in the commercial production of chlorine?
(a) 8.3 (b) 5.3 × 104 (c) 6420 (d) 107

7. Passage of a current for 548 seconds thorugh a silver coulometer results in the deposition of
0.746 g of silver. What is the current (in A)?
(a) 1.22 (b) 1.16 (c) 1.07 (d) 1.00
8. Electrolysis can be used to determine atomic masses. A current of 0.550 A deposits 0.55 g of
a certain metal in 100 minutes. Calculate the atomic mass if n = 3:
(a) 100 (b) 45.0 (c) 48.25 (d) 144.75
9. Beryllium occurs naturally in the form of beryl. The metal is produced from its ore by
electrolysis after the ore has been converted to the oxide and then to the chloride. How many
grams of Be (s) is deposited from a BeCl2 solution by a current of 5.0 A that flows for 1.0h?
(Atomic weight: Be = 9)
(a) 0.840 (b) 1.68 (c) 1.42 (d) 1.08
10. How many minutes will it take to plate out 5.0 g of Cr from a Cr 2(SO4)3 solution using a
current of 1.50 A? (Atomic weight: Cr = 52.0)
(a) 254 (b) 309.3 g (c) 152 (d) 103
11. Calculate the current (in mA) required to deposit 0.195g of platinum metal in 5.0hours from
a solution of PtCl6–2: (Atomic weight: Pt = 195)

(a) 310 (b) 31 (c) 21.44 (d) 5.36
12. How many Faradays are required to reduce 0.25 g of Nb (V) to the metal?
(a) 2.7 × 10–3 (b) 1.3 × 10–2 (c) 2.7 × 10–2 (d) 7.8 × 10–3
13. One gram metal M+3 was discharged by the passage of 1.81×1022 electrons. What is the
atomic weight of the metal?
(a) 33.35 (b) 133.4 (c) 66.7 (d) none of these
14. When during electrolysis of a solution of AgNO3, 9650 coulombs of charge pass through the
electroplating bath, the mass of silver deposited on the cathode will be

(a) 1.08 g (b) 10.8 g (c) 21.6 g (d) 108 g
15. How much time is required for complete decomposition of 4 moels of water using 4 ampere?
(a) 3.86 × 105 s (b) 1.93 × 105 s (c) 96500 s (d) 48250 s
16. In the electrolysis of aqueous NaCl, what volume of Cl 2 (g) is produced in the time that it
takes to liberate 5.0 L of H2 (g)? Assume that both gases are measured at STP:
(a) 5.0 (b) 2.50 (c) 7.50 (d) 10.0
17. Aluminium oxide may be electrolysed at 1000°C to furnish aluminium metal.
(atomic mass = 27 amu; 1 Faraday = 96,500 coulombs) The cathode reaction is
Al3+ + 3e–  Al. To prepare 5.12 kg of aluminium metal by this method would require
(a) 5.49 × 101 C of electricity (b) 5.49 × 104 C of electricity
(c) 1.83 × 107 C of electricity (d) 5.49 × 107 C of electricity

18. The quantity of charge required to obtain one mole of aluminium from Al2O3 is ___________.
(a) 1F (b) 6F (c) 3F (d) 2F
Answer Key
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. c d a d a d a c a b c b d b b
Que. 16 17 18
Ans. a d c
8. Electrolytic Conductance:
8.1 Types of conductors: (A) Electronic conductors & (B) Electrolytic conductors
(A) Electronic Conductors : Current flows because of flow of electrons. On increasing
temperature (T), resistance (R) increases for such conductors.
(B) Electrolytic Conductors : These are solutions of electrolytes (WA, SA, WB, salt solution).
Current flows due to flow of ions. On increasing temperature (T), resistance (R) decrease
in such conductors because more charge carrier ions are produced.
8.2 Factors effecting electrolytic conductance :
(i) Nature of he electrolyte: Strong electrolyte gives better conduction.
(ii) Nature of he solvent : Polar solvent favors conduction more than non – polar solvent.
(iii) Concentration of electrolyte.
(iv) Temperature: On increasing temperature (T), conductivity increases.
We will discuss in detail about these factors in later section.
8.3 Terminology
8.3.1 Specific conductance: The resistance (R) of a metallic conductor is directly

proportional to its length () and inversely proportional to its cross-sectional area (a), i.e.,
  1 1 
R  R =     …(1)
a a  R a
Where  is a constant depending upon the nature of the material and is called specific
resistance or resistivity of the material.
The reciprocal of the resistance is called conductance (C) and similarly, the reciprocal of
specific resistance is called specific conductance or conductivity (k)
1 1  l a l
   k  C  C  k  (  Cell cons tan t )
 R a a l a
When R = 1 cm and a = 1 cm2.

Thus, specific conductance (k) is the conductance of solution in which electrodes plates
are 1 cm apart and have 1 cm2 cross-sectional area. In other words, it is the conductance
of 1 cc of the solution.
Units:
Resistance: Ohm or  Conductance: mho or –1 or or S (Siemens)
Specific resistance: Ohmcm or  cm Specific conductance: ohm–1cm–1 or –1 cm–1 or S cm–1
8.3.2 Molar Conductance (  M )
The conductance of solution kept between the electrodes at unit distance apart and having area
of cross – section large enough to accommodate sufficient volume of the solution
that contains 1 mole of electrolyte.
1000  k
M 
Molarity
In above equation : Unit of  M :  cm mol and that of molarity = mol/L
–1 2 –1
8.3.3 Equivalent conductance : Equivalent conductance of a solution is defined as

conductance of all the ions produced by 1 equivalent of the electrolyte dissolved in that
volume contained when electrodes are 1 cm apart and area of the electrodes is enough to
accommodate all electrolyte.
1000  k
 eq 
Normality
In above equation : Unit of  eq :  cm eq and that of Normality = eq/L
–1 2 –1
Note:  eq and  M are related as:  M = n  eq , n = n-factor of electrolyte.

1
Illustration: conductivity of N KCl at 298 K is  0.001765 1cm1 and resistance of cell
50
containing this solution is 100. Calculate the cell constant. Also find out equivalent
conductivity of above solution.
Solution: (i) Calculation of cell constant
 1    
 C    Cell constant      K  R   0.001765 100 cm―1  0.1765 cm―1
a R a a C a
(ii) Calculation of equivalent conductivity of solution
  100
eq 
N
; 
eq  0.001765 1 cm1  1000
1
 50 cm 3
/eq
 17.65  5 1cm2 eq 1  88.251cm2eq 1
Brain Teaser: Find equivalent and molar conductance of 0.01 M solution of K 2SO4 whose s
pecific conductance is 1.26  10–3 –1 cm–1.
Ans:  eq = 63 –1 cm2 eq–1 ,  M 1.26  102 –1 cm2 mol–1
Brain Teaser: The specific conductivity of 0.1 N KCl solution at 20°C is 0.0212 ohm –1 cm–1.
This solution was found to offer resistance of 55 ohm. Find cell constant of the
conductivity cell. If a solution of 1.0 M AB, a uni-univalent electrolyte offers a resistance
of 25 ohm, using the same conductivity cell, find its equivalent conductance.
Ans: Cell constant = 1.166 cm–1  eq = 66.66 ohm–1 cm2
In chapter exercise – 08 (Electrolytic Conductance)
Subjective:
1. Define conductivity and molar conductivity for the solution of an electrolyte.
2. Resistance of a conductivity cell filled with 0.1 mol L–1 KCl solution is 100 . If the
resistance of the same cell when filled with 0.02 mol L–1 KCl solution is 520 , calculate the
conductivity and molar conductivity of 0.02 mol L–1 KCl solution. The conductivity of 0.1
mol L–1 KCl solution is 1.29 S/m.
3. The electrical resistance of a column of 0.05 mol L–1 NaOH solution of diameter 1 cm and
length 50 cm is 5.55 × 103 ohm. Calculate its resistivity, conductivity and molar
conductivity.
4. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm –1. Calculate its molar
conductivity.
5. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500
What is the cell constant if conductivity of 0.001M KCl solution at 298 K is 0.146 × 10 –3 S
cm–1.
Objective:
1. Cell constant is maximum in case of a:
(a) wire of length 100 cm and area 100 cm.
(b) wire of length 10 cm and area10 cm.
(c) one centimeter cube of a material.
(d) equal in all cases.
2. Which quantity is temperature independent?

(a) Resistivity (b) Conductivity (c) Cell constant (d) Cell potential
3. 500 mL of an aqueous solution contains 0.1 mol of the solute AB; if its specific conductance
is x S cm–1, its molar conductance will be ........... S cm2 mol–1.
(a) 10x (b) 5000x (c) x (d) 200x
4. Reciprocal of siemen is:

(a) volt (b) ohm (c) ampere (d) coulomb
5. When a certain conductivity cell was filled with 0.01 M solution of KCl, it had a resistance of
160 ohm at 25°C, and when filled with 0.005 M NaOH, it had a resistance of 190 ohm. If
specific resistance of KCl solution is, 700 ohm-cm, specific conductance (ohm–1 cm–1) of
NaOH solution is:
(a) 0.00120 (b) 0.00170
(c) 0.00180 (d) 0.00190
Answer Key
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. d c b b d
9. Effect of dilution on electrolytic conductance:
9.1 Variation of conductance with dilution:

(i) Varition of κ : On dilution (decreasing concentration),  (specific conductance of
solution decreases).
(ii) Varition of λ eq / λ M : eq or M increases on dilution, because effect of volume
increment is greater than effect of decrement in .

9.2 Variation of λ eq / λ M of a solution with concentration:
(i) Strong electrolyte :


M  M
Practical value
 cM
weak electrolytes
c (mole litre1 )1/2
The above graph is experimentally observed and has been interpreted mathematically by
“Debye Huckle Onsagar” equation at low concentrations for strong electrolyte.

cM  M b c [b is a constant and depends on stoichiometry of
electrolyte]
 o
M or M  molar conductivity at infinite dilution or zero concentration
CM or M  molar conductivity at any concentration.

 o
In case of Strong electrolytes, we can calculate M or M by extrapolation of their straight
line variation of  M with concentration .

(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 weak electrolyte is also 100% dissociated so have higher values of

eq or M.
 0
So in case of weak electrolytes we can not calculate M or M by
extrapolation because of sharp increase in  M in lower concentration range.
9.3 Kohlrausch Law of independent migration of ions:
At infinite dilution when the dissociation of electrolyte is complete, each ion makes a
definite contribution towards the molar or equivalent conductivity of electrolyte,
irrespective of the nature of the other ion with which it was associated.
Or
At infinite dilution each ion makes a definite contribution towards molar or equivalent
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.
Mathematically we can conclude:

Equivalent conductivity :

 eq (electrolyte)  c  a (C+ & a― represents cation and anion respectively)
  
aq(NaCl)  Na   
Cl
  
aq(BaCl)  Ba 2  
Cl

aq(AlCl 3)
 Al3  Cl



aq (Al2 (SO4 )3 )  Al3  SO

2
4
Molar conductivity :
0M  m 0c  n 0a  [m & n are no of cations and anions present in one
formula unit of the electrolyte]

0M(NaCl)  0Na   0Cl
0M(BaCl2 )  0Ba2  2 0Cl
0M(AlCl3 )  0Al3  3 0Cl
0M(Al2 SO4  )  2 0Al3  3 SO

0
2
3 4
9.4 Application of Kohlrausch Law:

(A) Calculation of λ 0M of weak electrolytes:
0M(CH3COOH)  0CH COO  0H

3
0M(CH3COONa )  0CH COO  0Na 

3
0M(HCl)  0H  0Cl
0M(NaCl)  0Na   0Cl
0M(CH3 COOH)  0
M(CH3 COONa)
 0
M(HCl) 0
 M(NaCl)
Illustration: If molar conductivity it  dilute of Ba(OH)2, BaCl2 and NH4Cl are 523.28, 280.0,
129.8 1cm2mole1. Calculate molar conductivity at  dilute of NH4OH.

  

(2MNH4Cl
 MBa(OH)  MBaCl )
Solution: M NH4OH  2 2
2
2  129.8  523.28  280.0
 1cm2mole1. = 246.44 1cm2mole1.
2
Brain Teaser: For the strong electrolytes NaOH, NaCl and BaCl 2, the molar ionic
conductances at infinite dilution are 248  10–4, 126.5  10–4and 280.0  10–4 s m2 mol–1,
respectively. Calculate  0m for Ba(OH)2.
Ans: 523.2  10–4 S m2 mol–1
Brain Teaser: 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 1cm2mol1.
(B) Calculation of degree is dissociation and K eq of weak electrolytes (dissociation
contants):
Let  Cm &  m are molar conductivity at concentration C and at  dilution respectively
 cm c2
Then, degree of dissociation,    K eq  [For Uni-univalent HA type
 0m 1   
electrolyte]
Illustration: The molar conductivity of CH3COOH at 298 and concentration of 0.1 M is 5.20
1cm2 mol1 , then calculate  at 0.1 M. Given: M


[H ]
 349.80 1cm2 mol 1 &

M [CH COO ]
 40.9 1cm2 mol1 .
3
Solution: 0M(CH3COOH)  0CH COO  0H  (349.8  40.9) 1cm2 mol1  390.7 1cm2 mol1
3
5.20 5.20
 1 (at concentration = 0.1 M) =   100  1.3%
390.7 390.7
Brain Teaser: In the above question, calculate  at 0.02 M concentration of acetic acid if molar
conductivity at 0.02 M is 49.2 1cm2 mol1 .

Ans: 12.5 %
(C) Determination of solubility of sparingly soluble salt: The specific conductivity of a

saturated solution of the test electrolyte (sparingly soluble) made in conductivity water is
determined by the method as described above. From this the specific conductivity of
conductivity water is deducted. The molar conductance of the saturated solution is taken
to be equal to  0m as the saturated solution of a sparingly soluble salt is extremely dilute.
Hence from equation (4).
1000
 0m = ,
C
Where C is the molarity of solution and hence the solubility.
Illustration: The sp. Cond. Of a saturated solution of AgCl at 25C after subtracting the sp.
Conductance of conductivity of water is 2.28 106 mho cm1. Find the solubility product

at AgCl at 25C. AgCl  138.3 S cm2 mol1 
1000  2.28  106 Scm1
Solution: K AgCl  2.28  106 Scm1, 138.3 S cm2 mol 1 
So lub ility
S  1.65 105 mol L1  Ksp  S  2.72 1010 M2

2
Brain Teaser: The specific conductance of a saturated solution of AgCl at 25°C after
subtracting the specific conductance of water is 2.28  10–4 S m–1. Calculate the solubility of
AgCl in gram per dm3 at this temperature. The molar ionic conductances of Ag + and Cl– ions
are 73.3  10–4 and 65.0  10–4 Sm2 mol–1, (Atomic mass of Ag: 108 and Cl: 35.5)
Ans: 1.80  10–3 g dm–3
Illustration: If observed conductivity of pure water at 25C is
 5.54 108 1cm1 and 0H  349.8 S cm2 mol1; 0OH  198.5 S cm2 mol1. Then
calculate K w of water .
Solution: oH2O  oH  oOH = 548.3 S cm2 mol1
1000 1000
oM(H2 O)     5.54  108 
molarity molarity (Concentration of dissociated H2O molecules )
5.54  108 Scm1  1000

548.3 S cm2 mol1   H2Odissociate  1.01 107 M
H2Odissociated
 H   1.01  107 M  K w  H  OH   1.01 1.01 1014  1.02 1014 at 25C
In chapter exercise – 09 (Variation of electrolytic Conductance with dilution)
Subjective:
1. Solutions of two electrolytes „A‟ and „B‟ are diluted. The  m of „B‟ increases 1.5 times while
that of A increases 25 times. Which of the two is a strong electrolyte? Justify your answer.
2. In an aqueous solution how does conductivity of electrolytes change with addition of water?
3. Why on dilution the  m of CH3COOH increases drastically, while that of CH3COONa
increases gradually?
4. Calculate  m for CaCl2 and MgSO4 from the data given in Table. We know from Kohlrausch
law that
Ion °/(S cm2mol–1) Ion  °/(S cm2mol–1)
H+ 349.6 OH¯ 199.1
Na+ 50.1 Cl¯ 76.3
K+ 73.5 Br¯ 78.1
Ca2+ 119.0 CH3COO¯ 40.9
Mg2+ 106.0 SO42– 160.0
5.  m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1 respectively. Calculate Å
for HAc.
6. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 S cm–1. Calculate its
dissociation constant if  m for acetic acid is 390.5 S cm2 mol–1.
7. Why does the conductivity of a solution decrease with dilution?
8. The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2 mol–1. Calculate its
degree of dissociation and dissociation constant. Given 0 = 349.6 S cm2 mol–1 and
M,(H )
0 = 54.6 S cm2 mol–1

M, (HCOO )
9. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar

conductivity and if M for acetic acid is 390.5 S cm2 mol–1, what is its dissociation
constant?
Question based on graph:
10. The molar conductivity of KCl solutions at different concentrations at 298 K are given below:
c/mol L–1  m /S cm2 mol–1
0.000198 148.61
0.000309 148.29
0.000521 147.81
0.000989 147.09
Show that a plot between Em and c1/2 is a straight line. Determine the values of Em and A
for KCl.
11. The conductivity of sodium chloride at 298 K has been determined at different
concentrations and the results are given below:
Concentration [M] 0.001 0.010 0.020 0.050 0.100
102 ×  [S m–1 ] 1.237 11.85 23.15 55.53 106.74
Calculate  m for all concentrations and draw a plot between  m and c½. Find the value
of  m
Objective:
1. In the variation of  m with 
C ,  m  m  
 a  bm  C , a and b are called:
(a) van der Waals‟ constant (b) Debye-Huckel constants

(c) Onsager constants (d) critical constants
2. 0mH2O is equal to _______________.
(a) 0m(HCl)  0m(NaOH)  0m(NaCl) (b) 0m(HNO3 )  0m(NaNO3 )  0m(NaOH)
(c) 0m(HNO3 )  0m(NaOH)  0m(NaNO3 ) (d) None of these
3. om(NH4OH) is equal to ______________.
(a) 0m(NH4OH)  0m(NaOH)  (NaCl)

0
(b) 0m(NH4Cl)  0m(NaOH)  (NaCl)
0
(c) 0 0 0
m(NH4Cl)  m(NaCl)  (NaOH) (d) 0 0 0
m(NaOH)  m(NaCl)  (NH4Cl)
4. Following are some facts about electrolytic conduction:

I:  m decreases with increase in C
II: For weak electrolytes, there is rapid increase in the degree of ionisation with dilution
and  m or eq increases rapidly in lower concentration range.
III:  
m can be obtained by extrapolation to C  0 for all kinds of electrolyte. Correct
statements are:
(a) I, II, III (b) I, III (c) I, II (d) II, III
5. 
AgCl (A weak electrolyte) can be obtained:
(a) by extrapolation of the graph  and C to zero concentration.
(b) by known value of   of AgNO3, HCl and HNO3.

(c) both (a) and (b)
(d) none of the above.
6. For pure water degree of dissociation of water is 1.9 ×10–9 

m H

 
= 350 S cm2 mol–1.
 
 2
m OH = 200 S cm mol
–1.
hence, molar conductance of water is:
(a) 1.045 ×10–6 S cm2 mol–1. (b) 1.045 ×10–9 S cm2 mol–1.
(c) 1.045 ×10–10 S cm2 mol–1. (d) 1.045 ×10–14 S cm2 mol–1.
7. Given the following molar condictivities at 25°C:, HCl, 426 1 cm2 mol–1; NaCl, 126 1
cm2 mol–1; NaC (sodium crotonate), 83 1 cm2 mol–1.What is the ionization constant of
crotonic acid? If the condictivity of a 0.001 M crotonic acid solution is 3.83×10–5 1 cm–1?
(a) 10–5 (b) 1.11 × 10–5 (c) 1.11 × 10–4 (d) 0.04
8. The ionization constant of a weak acid is 1.6×10–5 and the molar conductivity at infinite
dilution is 380×10–4 S m2mol–1. If the cell constant is 0.01 m–1 then conductance of 0.01
M acid solution is:
(a) 1.52 × 10–5 S (b) 1.52 S (c) 1.52 × 10–3 S (d) 1.52 × 10–4 S
Answer Key
Que. 1 2 3 4 5 6 7 8
Ans. b a b c b a b b
SOLUTION
In chapter exercise – 01 (Introduction to electrochemical cell)
Subjective:
1. An element (generally a metal rod) in contact with its ions in aqueous solution, is called
electrode. Example – Zinc rod dipped in ZnSO4(aq) solution.
2. Device which converts chemical energy of a redox reaction into electrical energy.
3. Zn(s)|Zn2+(aq)|| Ag+(aq)|Ag(s)
(i) Anode, i.e., zinc electrode will be negatively charged.
(ii) The current will flow from silver to copper in the external circuit.
(iii) At anode: Zn(s)  Zn2 (aq)  2e
At cathode: Ag  (aq)  e  Ag
4. Cu|Cu2+||Ag+|Ag
Objective:
1.[D] AgNO3 + NaCl  AgCl + NaNO3. There is no change in oxidation stae of any ion/element.
This will not form an electrochemical cell.
2.[C] Removal of salt bridge leads to break in circuit which means zero potential for
electrochemical cell.
3.[B] An electrochemical cell stops working after some time because „electrode potential of both
the electrodes becomes equal‟.
4.[A] In an electrochemical process, a salt bridge is maintain electrical neutrality in each

solution
5. [B] In a Galvanic cell electron flows from anode to cathode outside the cell.
6. [D]
Current is carried by both cation and anions, usually in different fraction, During the
passage of electricity through the solution of an electrolyte.
7. [D]
Zn (s)  Zn+2 (aq) + 2e–
Cd+2 (aq) + 2e–Cd (s)
--------------------------------------------------
Zn (s) + Cd+2 (aq)  Cd (s) + Zn+2 (aq)
8. [B]
In cell representation oxidation rection is written on left side of salt bridge and ions ar
just before and after the salt bridge.
Zn | Zn+2 || Ag+ | Ag
9. [C]
In chapter exercise – 02 (Electrode Potential)

Subjective:
1. The electrical potential difference set up between the metal and its ions in the is
called electrode potential or the electrode potential may be simply defined as the
tendency of an electrode to lose or gain electrons when it is in contact with of its
own ions.
2. EoMn |M  1 V  EoM|Mn  1 V
EoMn |M  Reduction potential  Mn   n e 
M
 Mn   n e
EoM|Mn  Oxidation potential  M 
3. The standard reduction potential (SRP) values of different electrodes arranged in the
decreasing order is called electrochemical series.
4. For a metal to have higher reducing strength, its tendency to oxidize itself should be
higher and hence its oxidation potential should be higher. So let‟s represent to oxidation
potential of these metals:
EoLi|Li  3.05 V, EoK|K  2.93 V, EoBa|Ba 2  2.91 V, EoZn|Zn 2  0.76 V, EoAg|Ag  0.8 V
So order of oxidation potential and hence reducing strength : Li > K > Ba > Zn > Ag
Objective:
1. (c)
The metal whose oxidation potential is highest or reduction potential is least will displace
other metals from their salt solutions. Here „B‟ has least reduction potential.
2. (d)
Since copper lies below Al in the series of reactivity of metals given, so no reaction will
take place.
3. (a)
Since „A‟ has least reduction potential. So, it is strongest reducing agent and can displace
rest of all.
4. (b)
Since copper lies above in electrochemical series, so it will reduce the Ag + and get oxidised
giving blue coloured solution. The cell reaction is:
0 +1 +2 0
Cu (s) +2 Ag NO3 (aq)  Cu(NO3 )2(aq) + 2 A g (s)
5. (d)
Since it has large negative reduction potential, so, A – will act as strong reducing agent so
it will get oxidised readily.
6. (a)
By electrochemical series, we can see that reduction potential of Al is less than that of
Mn, Cr and Fe but greater than that of K. Hence K cannot be produced on reduction of its
oxide by aluminium.
7. (c)
Metal placed above in electrochemical series replaces the other from their salt solutions.
Copper lies below the lead, lead lies above Ag and Ag lies below the Cu.
The order of decreasing reducing character of the three metals is Pb, Cu, Ag
In chapter exercise – 03 (Gibb’s free energy and Cell potential)

Subjective:
1. Al+3 (aq) + 3e–  Al (s) E°red = –1.66 V
Fe+2 (aq) + 2e–  Fe (s) E°red = –0.41 V
The cell reaction is: 3Fe2+ (aq) + 2Al (s)  2Al3+ (aq) + 3Fe (s)
Here Fe acts as cathode and Al as anode.
 Eοcell = Eοcathode  Eοanode = (–0.41) – (–1.66) = +1.25 V
2. Zn+2 (aq) + 2e– = Zn (s); E°red = –0.76 V
Fe+2 (aq) + 2e– = Fe (s); E°red = –0.41 V
Now, the cell reaction is: Fe+2 (aq) + Zn (s)  Zn+2 (aq) + Fe (s)
In this Fe acts as cathode and Zn as anode.
 E°cell = E°cathode – E°anode=(–0.41) – (–0.76) = +0.35 V
3. Fe+2 (aq) + Sn (s)  Sn+2 (aq) + Fe (s)

Here anode is Sn and cathode is Fe.
 Eοcell = Eοcathode ο
 Eanode = (–0.44) – (–0.14) = –0.30 V
4. For the given reactions,
(i) MnO4–(aq) + 8H+ (aq) + 5e–  Mn+2 (aq) + 4H2O (l); ΔG1ο =  5F (1.51) =  7.55 F
(ii) MnO2 (s) + 4H+ (aq) + 2e–  Mn+2 (aq) + 2H2O (l); ΔGο2 =  2F (1.23) =  2.46 F
(iii) MnO4– (aq) + 4H+ (aq)+ 3e–  MnO2 (s)+ 2H2O (l); ΔGο3 =  3F Eο  /MnO
MnO4 2
From above three reactions it is clear that (iii) can be obtained by the operation (i) – (ii)
 ΔGο3 = ΔG1ο  ΔGο2  3F Eο  /MnO = –7.55 F + 2.46 F = –5.09 F
MnO4 2
5.09 F
 Eο  /MnO = = +1.696 V
MnO4 2 3 F
Objective:
1. [A] Positive and negative.
2.[C]
Ecell is intensive while r G is extensive
3. [C]
Ecell  (E°)OP  (E°)R P = – x + y = y – x
4. [D] G =― nFEcell  ―396485  1.5 J = ―434250 J = 434.25 kJ
5. [D] Ecell =  E°R P  E°OP  0.34 = (E°)  /Sb+  1.0

SbO2
 (E°)  (aq)/Sb  0.34  1.0 = –0.66 V.

SbO2
6. [A]
HClO(aq.) + H+ (aq) + 2Cr2+(aq)  2Cr3+ (aq) + Cl (aq) + H2O(l) +1.8 V
2Cr3+ (aq) + 2e  2Cr2+ (aq) – 0.41 V
2Cr2+ (aq)  2Cr3+ (aq) + 2e + 0.41V
HClO (aq) + H+ (aq) + 2e  Cl (aq) + H2O(l) E°
Ecell =  E°OP   E°R P  + 1.8 = + 0.41 + E°  E° = 1.39 V
7. [B]
(G)cell  (G)1st electrode  (G)2nd electrode  – n3 F E3 = – n1 F E1 – n2 F E2
n1 E1 + n2 E2
 E3 =
n3
8. [C]
5Ce4+(aq.) + 5e  5Ce3+(aq.) E° = +1.61 V
Mn2+ (aq.) + 4H2O(l)  MnO4 (aq.) + 8H+(aq.)+5e E° =  1.51 V
5Ce+4 (aq.) + Mn+2 (aq.) + 4H2O(l)  5Ce+3 (aq.) + MnO4 (aq.) +8 H+ (aq.)
E°cell = Eanode
 
+Ecathode n = 2  = – 1.51 + 1.61 = 0.1V.
O.P. R.P.
G° =  nF E°cell = – 5 × 96500 × 0.1 = – 48.25 KJ.

9. [B]
For 1st reaction  Ecell  (  0.77 + 0.10) =  0.67 V < 0 Not feasible
For 2nd reaction  Cu+  e  Cu E° = 0.52 V
Cu2+  e  Cu+ E° = 0.15 V
 0.52 + 0.15 
Cu2+  2e  Cu E° =   V = 0.67/2 = 0.335 V
 2 
2Cu2+  3e  Cu+  Cu
 0.15 + 2 × 0.335  (0.15 + 0.67)V

E° =   V = = (0.82/3) = 0.273 V  feasible reaction.
 3  3
10.[C] To get the required equation:In+2 + Cu+2  In3 + Cu+ from the given equations:
Cu2+ + e  Cu+ E° = x1 V ... (1)
In3+ + 2e  In+ E° = x2V ... (2)
In2+ + e  In+ E° = x3 V ... (3)
1st substract equation (2) from equation (3)  Equation (3) + {―Equation(2)}
In2+ + e  In+    (3)
In+  In3+ + 2e    (2)
In2+  In3+  e
Now add equation (1) in the above obtained equation:

In2+  In3+  e
Cu2+ + e  Cu+    (1)
In+2 + Cu+2  In3 + Cu+ Equation (4) nf =1

(G)4 = (G)1  (G)3  (G)2  – 1F x = – 1F x1 – 1F x3 + 2 F x2  x = x1  x3  2x2
2 
11 [D] Pb(s)  Pb (aq.)  2e E o
Pb(s)|Pb2
 0.13 V (OP)  E o
Pb2 |Pb(s)
 0.13 V (RP)
Ag (s)  Ag  (aq.)  e EoAg(s)|Ag  0.8 V (OP)  EoAg |Ag(s)  0.8 V (RP)
Checking option [B]

Cell reaction: Pb2 (aq.)  Ag (s)  Pb(s)  Ag  (aq.)  Pb – cathode and Ag-Anode
Ecell  [(E°)cathode  (E°)Anode ]RP  0.13V  0.8V  0  Not feasible
Checking option [D]

Cell reaction: 2Ag+ (aq) + Pb (s)  2Ag (s) + Pb+2 (aq)  Ag – cathode and Pb-Anode
Ecell  [(E°)cathode  (E°)Anode ]RP  0.8V  (0.13V)  0.93 V  0  feasible
Similarly other options can also be checked.
12 [C]
(a) Fe + Br2  FeBr2
Ecell  EOP
 
 ER P = (0.44 + 1.09) > 0
(b) Fe + I2  FeI2
Ecell  EOP
 
 ER P = (0.44 + 0.54) > 0
(c) I2  2Br   2I + Br2
Ecell  EOP
 
 ER P = (– 1.09 + 0.54) < 0 Not spontaneous
(d) Br2  2I  2Br  + I2
Ecell  (1.09  0.54) > 0
In chapter exercise – 04 (Nernst Equation)

Subjective:
1. The cell can be written as
Mg|Mg2+(0.130M)||Ag+(0.0001M)
 RT [Mg 2 ]
Ecell  Ecell  ln
2F [Ag  ]2
0.059V 0.130
 3.17V  log  3.17V  0.21V  2.96V
2 (0.0001)2
2. Applying Nernst equation to the given cell reaction,
2
 0.0591 [Ni ] 0.0591 0.160
Ecell  Ecell  log  2
 1.05V  log
n [Ag ] 2 (0.002)2
0.0591
 1.05  log(4  104 )
2
0.0591
 1.05  (4.6021)  1.05  0.14V  0.91V
2
3. (i) Mg | Mg+2 (0.001 M) | | Cu+2 (0.001 M) | Cu (s)

The half–cell reactions are:
Mg (s)
+2
Mg (aq) +2e


( Anode )
Cu
+2
(aq) + 2e

Cu ( Cathode)
+2 +2
Mg (s)+ Cu (aq) Mg (aq)+ Cu (s) (Net cell
reaction)
Applying Nernst equation,
ο 0.0591 [Mg +2 ]
Ecell = Ecell  log
n [Cu+2 ]

= Eο
Cu+2/Cu
 Eο
Mg+2/Mg   0.0591
2
log
[0.001]
[0.0001]
=(0.34)  (  2.37) 
0.0591
2
log10
0.0591
=2.71   2.68 V
2
(ii) Fe (s) | Fe+2 (0.001 M) | | H+ (1 M) | H2 (g, 1 bar) | Pt (s)

Fe (s)  Fe+2 (aq) + 2e– (Anode)
2H+ (aq) + 2e–  H2 (g) (Cathode)
Fe (s) + 2H+ (aq)  H2 (g) + Fe+2 (aq) (Net cell
reaction)
ο 0.0591 [Fe+2 ]PH2

Applying Nernst equation, Ecell = ECell  log
n [H+ ]2
0.0591 (0.001) (1) 0.0591

= (Eο +  Eο ) log =(0.0  (0.44))  log103
H /H2 Fe+2 /Fe 2 (1)2 2
0.0591
= 0.44  3 = 0.52865 V  0.53 V
2
(iii) Sn (s) | Sn+2(0.050M) || H+(0.020 M) | H2 (g, 1 bar) | Pt(s)
Sn (s) Sn+2 (aq) + 2e– Anode
2H+ (aq) + 2e– H2 (g) Cathode
Sn (s) + 2H+(aq) H2 (g) + Sn+2 (aq) (Net cell
reaction)
ο 0.0591 PH [Sn2 ]
Ecell = Ecell  log 2 + 2
n [H ]

= Eο +
H /H2
 Eο
Sn+2 /Sn   0.0591
2
log
(1)(0.050)
(0.020) 2
0.0591
= (0  (0.14))  log125 0.14 – 0.06 = 0.08 V
2
(iv) Pt | Br2 (l) | Br– (0.010 M) | |H+ (0.030 M) | H2 (g, 1 bar) | Pt (s)
2Br   aq   Br2 l   2e 
2H  aq   2e  H2  g 
2Br   aq   2H  aq   Br2 l   H2  g 
ο 0.0591 PH 0.0591 1
Ecell = Ecell  log  2 2  2 =(Eο +  Eο  ) log
n [H ] [Br ] H /H2 Br2 /Br 2 (0.030) (0.010)2
2
0.0591  1 
= (0  1.07)  log  8  = (–1.07 – 0.208 ) V= –1.278 V
2  9  10 
4. (i) Mg 2  2e 


 Mg (reduction)
0.0591 1 4  0.591
E  E  log( )  2.36   2.4782V
Mg2|Mg Mg2|Mg 2 1  10 4 2
1  
(ii) Cl2  e  Cl (reduction)
2
0.591
E  E  log[Cl ]
Cl2,Cl Cl2 ,Cl n
0.0591
 1.36  log(2  105 )  1.6377V
1
5. Cu2  2e 
 
 Cu,E  0.34vlt,
0.0591 1
E  E  log
Cu2  ,Cu Cu2  ,Cu 2 [Cu2 ]
0.0591
 E  log[Cu2 ]
2
0.0591
 0  0.34  log[Cu2 ]
2
or log[Cu2 ]  11.5059  12.4941
Taking antilog, [Cu2 ]  3.12 1012 M
1
6. For hydrogen electrode, H  e  H2
2
0.0591 1
E 1 E 1  log 
H , H2 H , H2 n [H ]
2 2
0.0591 1
0 log 10 (pH  10 means [H ]  1010 M)
1 10
 0.059110  0.591V
 0.059V
7. E(cell)  log KC  0.46V or
2
0.46V  2
log KC   15.6  KC  3.92 1015
0.059V
8. 2Fe3  2e  2Fe2 or 2I  I2  2e
Hence, for the given cell reaction, n=2.

rG  nFEcell

 2  96500  0.236J = –45.55kJ mol–1.
r G
r G  2.303RT log KC or KC 
2.303RT
45.55 kJ mol1
  7.983
2.303  8.314  103 kJK 1  298K
 KC  Antilog (7.983)=9.616 107
Objective:
1 [B]
2
2Cr(s) + 3Cu+2 (aq.)  2Cr+3 (aq.) + 3Cu(s)  Q = (0.1) = 0.08
0.5 M 0.1 M (0.5)3
2 [D]
2.303RT 1 2.303RT
E = E°  log +n  E = E°  log[Mn+n ]
nF [M ] nF
3 [B]
H+ (aq) + e–  1/2 H2 (g)
0 0.059 (PH2 )1/2

1 [H ]
0 0.059 (100)1/2
1 1
0.059 (100)1/2
Ecell = 0.00  log =  0.059 V
1 1
4 [C]
H+ (aq) + e–  1/2 H2 (g)
0 0.059 (PH2 )1/2

1 [H ]
0.059 (1)1/2
Ecell = 0.00  log 10 (since pH=10 so[H+]=10–10)
1 10
Ecell = –0.59
1
5 [B] Lets take the reduction of Mg2+: Mg 2 (aq)  2e 
 Mg(s)  Q
Mg 2
PV 8.21 atm  3 L

mol of O3    1 mol
0.059 R  T 0.0821 L  atm  300 K
E Cell  E Cell
o
 log Q 
nf mol  K
1 mol of O3 contains 3 mol oxygenatom
0.059
E  Eo  log[Mg 2 ]
Mg2 |Mg Mg2 |Mg 2  X 
 Y   C   m 
Hence, plot of E Vs log[Mg 2 ] will be linear with positive slope and intercept =
Mg2|Mg
E°.
6 [A]
G° =  2.303 RT log KC  nF E°cell
2.303 RT
E°cell  log KC  y = mx  Straight line passing through origin.
nF
7 [A] G <0 indicates that reaction is spontaneous.
8 [C]
2A(s) + B+2(aq.)  2 A+ (aq.) + B(s)

2
 A+ 
 E cell 
 E°cell  
RT
2F
ln  
B+2 
 
 A+ 
RT °  
E=E  × 2 ln
2F B+2 
 
RT [A+ ]
 E = E°  ln
F [B+2 ]
9 [B]
2 Tl (s) + Cu+2 (aq.)  2 Tl+ (aq.) + Cu(s)

0.01 M 0.001 M
E°cell = 0.83 V.
2
 Tl+ 
0.059
 E cell  E°cell  log  
2 Cu +2
 
By increasing the concentration of Cu2+ the emf of this cell could be increased.
10 [D]
Nerst equation for Daniel cell
Zn(s) + Cu+2 (aq) 

 +2
 Cu(s) + Zn (aq)
 Zn+2 
0.059
 E cell   E°cell  log  
n Cu 
2+
 
0.059
E1  E°  log 1/1
2
 E1  E°
0.059 2
E2  E°  log
2 2
 E2  E°
So E1  E2
11 [D]
 Zn2+ 
0.059
Ecell  E°cell  log  
2 Cu2+ 
 
0.059 1
(I) E1  E°cell  log    E°cell
2 1
0.059  0.1  0.059
(II) E2  E°cell  log  °
  Ecell 
2  1  2
0.059  1  0.059
(III) E3  E°cell  log  °
  Ecell 
2  0.1  2
0.059  0.1 
(IV) E4  E°cell  log  °
  Ecell
2  0.1 
E2  E1 = E4 > E3
12 [C]
For standard electrode potential, [Cu2+] = 1M
13 [C]
RT
E = E°  log Q
nF
At equilibrium Q = KC
and E = Zero
14 [B]
0.059 0.059
E° = log Keq.  log 1030 = + 0.295 V
n 6
In chapter exercise – 05 (Types of electrodes)
Objective :
1[C]
One design a cell in which the half cell reaction is
CuS(s)  2e  
 2
 Cu(s)  S (aq)
 2  
so, Cu(s)  Cu  2e G1
CuS  2e 

 2 
 Cu(s)  S (aq) G2
 2 2 
CuS(s)  Cu (aq)  S (aq) G3
From G3  G1  G2
0.0591
E 2   E  log Ksp
S CuS|Cu Cu2Cu 2
0.0591
 0.34  log(1035 )  0.694V
2
2[A]
3 [D]
 + 
Ag I(s)  Ag (aq) + I(aq)
Ag I(s) + e  Ag(s) + I (aq) – 0.152 V
Ag(s)  Ag+ (aq) + e – 0.800 V
(G)1  (G)2  (G)3
– 2.303 RT log ksp = + 1.F (0.152) + 1.F (0.8)

0.952F  0.952
log ksp =  =   16.13
2.303 RT 0.059
dEo
4 [D] So  n f F  2  96500C (0.00065 Volt deg 1 )  125.45J K 1
dT
dEo d
5 [D] So  n f F  2  96500  {1.1028 – (0.64110 –3 )T  (0.72  10–5 )T 2 }
dT dT
So  2  96500  {– (0.64110–3 )  2  (0.72 10–5 )T}
So  2  96500  {– (0.64110–3 )  2  (0.72 10–5 )  25} = ―54.233 unit.
In chapter exercise – 06 (Electrolysis)
Subjective:
1. In the electrochemical cell, zinc acts as a negatie pole while copper acts as a
positive pole. Hence, electrode „A‟ will have negative polarity while electrode „B‟ will
have positive polarity.
2. No current will flow and the reaction stops.
3. When aqueous NaCl solution is electrolysed, H2 is liberated at cathode, Cl2 at anode
and NaOH is formed in the solution. Hence, pH of the solution will rise.
4. pH of the solution will not be affected as [H+] will remain the same. This is because
the amount of H+ ions reduced is compensated by the H+ ions produced by
oxidation of H2O.
 
At cathode : 2H  2e  H2 ,
1
At anode : H2O  O2  2H  2e .
2
Objective:
1.[b] Oxidation occurs at anode. As (b) has higher oxidation potential than (a), (b)
occurs.
In chapter exercise – 07 (Faraday’s Law of Electrolysis)

Subjective:
1. t=600s charge=current ×time = 1.5A×600 s = 900C
According to the reaction: Cu2+(aq) + 2e¯ = Cu(s)
We require 2Fe or 2 × 96487 C to deposit 1 mol or 63 g of Cu.
For 900C, the mass of Cu deposited =(63g mol–1×900C)/(2 × 96487C mol–1) = 0.2938g.
2. Q(coulombs)=1 (ampere) × t (sec.)
= (0.5 ampere) × (2 × 60 s) = 3600C.
A flow of 1F, i.e., 96500C is equivalent to flow of 1 mole of electrons, i.e., 6.02×1023
electrons.
 3600C is equivalent to flow of electrons
6.02  1023
  3600  2.246  1022 electrons.
96500
3. From the given reaction, 1 mol of Cr2O27 ions require 6F
= 6×96500C = 579000C of electricity for reduction to Cr3+.
4. (i) Al+3 (aq) + 3e–  Al (s)
It is clear that to reduce one mole of Al+3, 3 moles of electrons are required.
 Q = 3 mole of e–= 3 Faraday = 3 × 96500 C =289500 C =2.895 × 105 C
(ii) Cu+2 (aq) + 2e–  Cu (s)

Just as above,
Q = 2 mole of e–= 2 Faraday = 2 × 96500 = 193000 = 1.93 × 105 C
(iii) MnO4– (aq) + 8H+ (aq) + 5e–  Mn+2 (aq) + 4H2O (l)
For this, Q = 5 mole of e– = 5 Faraday = 5 × 96500C = 482500C = 4.825 × 105 C
Q 20
5. (i) Eq. of e– = Eq. of Ca  =  Q= 1 × 96500 C = 1 F
96500 40 /2
Q 40 40
(ii) Eq. of e– = Eq. of Al  =  Q=  96500 C = 4.44 F
96500 27 /3 9
6. (i) The oxidation reaction of water is:
2H2O (l)  4H+ (aq) + O2 (g) + 4e–
Since 2 mole of H2O liberates one mole of O2, hence half moles O2 will be liberated by
one mole of H2O.
Q 1
Now, Eq. of e– = Eq. of O2  =  4  'n' factor for O2 = 4
96500 2
Q= 2 × 96500 C = 193000 C = 1.93 × 105 C
(ii) Oxidation reaction FeO to Fe2O3 is:
+2 1 +3
FeO Fe2O3
2
Total change in oxidation number of Fe = 1/2 (2 × 3) – 2 = +1
„n‟ factor for FeO = 1
Q
Now, Eq. of e– = Eq. of FeO  =1  1
96500
Q = 96500 C = 9.65 × 104 C
5  20  60 m 5  20  60  58
7. Eq. of e– = Eq. of Ni  =  m= = 1.803 g
96500 58.7/2 96500  2
Objective:
1. [C]
Charge on one electron = 1.6 × 10–19 C.
1
No. of electron in 1 C charge = = 6.24 × 1018 electrons.
1.6 × 1019
2. [D]
q = it = (0.01 × 10–3 A) × (1000 × 60 × 60 sec)= 36 C.
3. [A]
1
H2O(l)  2H+ (aq.) + O2(g) + 2e
2
w 5.6
equivalents of Cu = equivalents of O2 liberated  2 × =4× w = 31.75
63.5 22.4
g.
4. [D]
54000/27 q/96500
Mole of Al/1 = Mole of electron/3  =  q = 57.9 × 107 C
1 3
5. [A]
Mole of Li/1 = Mole of electron/1
w/7 1930 × 0.75/96500

= , w = 0.105 g.
1 1
6. [D]
q 3.21 × 106 3.21 × 106

q = it  t = = sec. = min.  t = 107 min.
i 500 500 × 60
7. [A]
q = it = (548.i) C
Ag+ (aq.) + e  Ag(s).
0.746 548 × i
moles of Ag / 1 = moles of e– / 1 =  i = 1.22 A
108 96500
8. [C]
Let the metal ion is M+3 and the atomic mass is x g.
M+3 (aq) + 3e–  M (s)
0.55 0.55 × 100 × 60

mole of metal M (s) / 1 = mole of electron / 3  =  x = 48.25
x 96500  3
g/mol.
9. [A]
BeCl2 + 2e  Be + 2Cl
w 5 × 1 × 60 × 60
mole of Be / 1 = mole of electron / 2 =  w = 0.84 g
9 96500  2
10. [B]
Cr+3 (aq) + 3e–  Cr (s)
mole of Cr / 1 = mole of electron / 3

5 1.5 × t(sec.) 37115.38
 =  t= sec. = 309.3 min.
52 96500  3 2
11. [C]
Pt+4 (aq.) + 4e  Pt(s)
0.195 (5 × 60 × 60 × i)
mole of Pt / 1 = mole of electron / 4  =  i = 21.44 mA.
195 96500  4
12. [B]
Nb+5 (aq) + 5e–  Nb (s)
0.25 mole of electron

mole of Nb / 1 = mole of electron / 5 =
96 5
Mole of electron = 1.3 × 10–2.
Charge of one mole electron = 1 faraday
13. [D]
M+3 (aq) + 3e–  M (s)
mole of metal M / 1 = mole of electron / 3
1 1.81 × 1022
Let x g is the atomic mass of metal.  =  x = 99.83 g/mol
x 6.023 × 1023  3
14. [B]
Equivalents of Ag deposited = equivalents of electron.
9650
1 × w/108 = 1 × w = 10.8 g.
96500
15. [B]
1
H2O(l)  2H+ (aq.) + O2(g) + 2e
2
4×t
mole of H2O / 1 = mole of electron / 2  4 =  t = 1.93 × 105 sec.
96500  2
16. [A]
1
Cl (aq.)  Cl2(g) + e ... (1)
2
1
H2O(l) + e  H2(g) + OH (aq.) ... (2)
2
Mole of Cl2 Mole of H2

= [Since number of electron furnished by Cl –(aq) = number of
1/2 1/2
electron captured by H2O]
V(L) 5
2×  2× V=5L
22.4 22.4
17. [D]
5.12 × 103 /27 q/96500

Mole of Al/1 = Mole of electron/3  =  q = 5.49 × 107 C.
1 3
18. [C]
Al2O3  2Al, i.e.,2Al3  6e  2Al or Al3  3e  Al.
Hence to obtaine one mole of Al, charge required = 3F.
In chapter exercise – 08 (Electrolytic Conductance)
Subjective:
1. Students must try this question.
2.
Given, c1  0.1mol L1, R1  100 , k1 1.29 S / m
c 2  0.02mol L1, R1  520 , k 2  ?
l
We know that, k  c 
A
l
k1  c1  ....(1)
A
l
k 2  c2  ....(2)
A
k 2 c2
from (1) and (2)  
k1 c l
c2 0.02
 k 2  k1   (1.29 S m1 )   0.258 S m 1
cl 0.1
So,
3
S ml 1m
(0.258 )  (1000  6 )
k  1000 m L 10 ml
Molar conductivity = M    129  104 S m2 mol –1
c mol
0.02
L
3. Given, R = 5.55  103 ohm, diameter = 1 cm, l = 50 cm, c = 0.05 mol L-1
Cross sectional Area (A) = 3.14  (0.5 cm)2 = 0.785 cm2 = 0.78510-4 m2
R =   l /A   = RA/l = 5.55103 ohm  0.785  10-4 m2 / 0.5 m = 0.87135 ohm-m
Conductivity (k) = 1/ = 1.147 S m-1
Molar Conductivity ( M ) = k  1000/c =
S 1000 ml 1m3
(1.147 ) (  6 )
m L 10 ml
1
 2.294  102 S m2 mol 1
0.05 mol L
S ml 1 cm3
(0.0248 )  (1000  )
k  1000 cm L 1 ml
4. Molar conductivity = M    124 S cm2 mol –1
c mol
0.2
L
l
5. Cell Constant = = R  k = 1500 ohm  0.146 10-3 S cm-1 = 0.219 cm–1
A
Objective:
1. [D]
l
Cell constant =
A
l 100 1
For [A] = cm  1 cm1
A 100
l 10 1
For [B] = cm  1 cm1
A 10
l 1
For [C] = cm1  1 cm1
A 1
Therefore, All have equal values of cell Constant.
2. [C] Every quantity is dependent on temperature except Cell constant.
Dis tan ce between electrode plate
Cell cons tan t 
Area of electrode plate
3. [B]
Given, k = x S cm-1
k  1000 x  1000
Molar conductivity =   5000 x
c (0.1 / 0.5)
4. [B], Inverse of Siemen is Ohm.
5. [D]
For KCl, c = 0.01 M, R = 160 ohm, k = 700 ohm–cm
For NaOH, c = 0.05 M, R = 190 ohm, k = ?
 l l R
R  Cell Cons tan t ( ) 
A A 
R R R 190 ohm
So, 1  2   2  1  2  700 ohmcm   831.25 ohm cm
1  2 R1 160 ohm
So, SpecificConducatnce  1 /  2  1.2  103 S cm 1
In chapter exercise – 09 (Variation Electrolytic Conductance with dilution)
1. Electrolyte „B‟ will be strong electrolyte because it is completely ionised and on dilution the
molar conductance will increase to the small extent due to increase in speed of ions only.
2. On the addition of water, number of ions per unit volume decreases and therefore
conductivity decreases.
3. In the case of CH3COOH, which is a weak electrolyte, the number of ions increase on
dilution due to an increase in degree of dissociation.
CH3COOH + H2O  CH3COO-(aq.) + H2O.
4. 0M(Ca Cl2 )  0Ca2  2 0Cl = 119.0 + 2  76.3 = 271.6 S cm2 mol–1
0M(MgSO4 )  0Mg2  0SO 2 = 106.0 + 160.0 = 266 S cm2 mol–1

4
5. 0M(HAc)  0HCl  0NaAc  0NaCl = 425.9 + 91.0 – 126.4 = 390.5 S cm2 mol–1
6.
ml 1cm3
( 4.95 10 5 Scm1 ) 1000 ( )
k  1000 L 1ml
m   1
 48.15 Scm2 mol 1
C 0.001028 mol L
Given,  m  390.5 Scm mol 1
0 2
m 48.15
Therefore,   0
  0.123
m 390.5
c2
Therefore, K a   c2  0.001028  (0.1232 ) 1.56 105 mol L–1
(1   )
7. Conductivity of an electrolyte depends on number of ions per unit volume, which decreases
with the dilution of electrolyte. That‟s why conductivity of a solution decrease with dilution.
8. Given, c  0.025mol L1 , M  46.1 S cm2 mol1
0 0 0 2 1
 M (HCOOH)       349.6  54.6  404.2 S cm mol
M (H ) M (HCOO )
M 46.1
Therefore, deg ree of dissociation ()    0.114
0M 404.2
c2
Therefore, K a   c2  0.025  (0.1142 )  3.25 104 mol L–1
(1   )
9.Given, conductivity (k) = 7.896 × 10–5 S cm–1 , c = 0.00241 M

k  1000 7.896 105 1000
Molar conductivity = M    32.76 S cm2 mol –1
c 0.00241
M 32.76
Therefore, deg ree of dissociation ()    0.084
0M 390.5
c2
Therefore, dissociation cons tan t (K a )   c2  0.00241  (0.0842 ) 1.7 105 mol L–1
(1  )
Question based on graph:
10. m   o  b c
m
148.6  mo  b 0.000198 ........(1)
Similarly, 148.29  m  b 0.000309 ........(2)

o
Solving eq. (1), (2)
We get  mo = 150.0 S cm2 mol–1
And b = 91.24 S cm2 L0.5 mol-1.5
k  1000 1.237 102 1000

11. M   12370 S m2 mol –1 . Similarly for other values of k and c.
c 0.001
Concentration/M 0.001 0.010 0.020 0.050 0.100
102 × /S m–1 1.237 11.85 23.15 55.53 106.74
Conductivity ( M ) 12370 11850 11575 11106 10674
Objective:
1. [B]
2. [A]
3. [B]
4. [C], I, II are true for all kinds of electrolytes. But III is true only for the strong electrolytes.
For weak electrolytes extrapolation don‟t work.
5. [B]
6. [A], Given  = degree of dissociation = 1.9 ×10–9
Given,  
  –1   2
m H = 350 S cm mol ,  m OH = 200 S cm mol
2 –1  
m  H2O  m H
So,   
  
 
m OH = 350 + 200 = 550 S cm mol
2 –1
m  H2O
Molar Conductance =    = 1.9 ×10–9 550 S cm2 mol-1 = 1.045 10-6 S cm2 mol-1
7. [B]
Given,   1 2
m  HCl   426  cm mol
–1
 1 2
m  NaCl   126  cm mol
–1
 1 2
m  NaA   83  cm mol
–1
   
m  HA    m  NaA    m  HCl    m  NaCl 
= 83 + 426 – 126 = 383 1 cm2 mol–1

Given, Conductivity (k) = 3.83×10–5 1 cm–1
So, Molar Conductivity  k  1000 (3.83 10 –5 1 cm –1 ) 1000

M  HA     38.3 1 cm2 mol 1
c  0.001 mol L 1
M  HA  38.3
Then, degree of dissociation () =   0.1
 383
M  HA 
2 2
Ionization Constant = K  c  0.001  0.1  1.11  105
a
(1  ) (1  0.1)
8. [B]

Given, Molar Conductivity at infinite Dilution M  380 104 S m2mol1
Cell Constant = l/A = 0.01 m-1, c = 0.01 M
c2 0.001  2
Ionization Constant = Ka    1.6  105    4  102
(1  ) (1  )
degree of dissociation () = M  M

 0.04

M 380  10 S m2mol1
4
 M  380 104 S m2mol1  0.04  1.52 103 S m2mol1

3
So, Conductivity (k) = M  c  1.52  10  0.01M 1.52 108 S m–1
1000 1000
Conductivity (k) = cell constant  conductance
So, Conductance = conductivity/cell constant = 1.5210-8/0.01 = 1.5210-6 Ω-1

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Electrochemistry Page No.

JEE ADVANCED SYLLABUS

Example: A zinc rod, dipped in a solution of ZnSO4 (aq)

A copper rod, dipped in a solution of CuSO4 (aq)

1.2 Electrochemical or Voltaic or galvanic cell: It is a system consisting of electrodes, in

Anode () Cathode (+)

1.3 Cell Notation:

(iii) Concentration of the electrolytes in the anode and cathode is written in

Illustration: Represent the following cell based on reactions given.

Illustration: Writing the cell Reaction from the Cell Notation

a) Anode half reaction: Tl(s)  Tl+(aq) + e–,

Cathode half reaction: Sn2+(aa) + 2e–  Sn(s)

b) Anode half reaction: Zn(s)  Zn2+(aq) + 2e–.

In chapter exercise – 01 (Introduction to electrochemical cell)

At cathode: Reduction: Mn  (aq)  ne 

E Zn 2  Reduction potential of zinc electrode = ―0.76 V

2.2 Electrochemical series:

better oxidizing agent among KMnO4 and K 2Cr2O7 ?

Solution: MnO4  Mn2 : because it has higher reduction potential.

Solution: Zn  Zn2  2e SOP = 0.76 V

Cu  Cu2  2e SRP = + 0.34 V

Mg  HCl(aq)  MgCl2  H2

Cu  HCl(aq)  no reaction

E oMn |M & E oM|Mn .

3. What do you mean by electrochemical series?

following metal in order of their reducing strength.

3. Gibb’s free energy and Cell potential:

3.1 Relation between Gibb’s free energy and cell potential:

where , n = number of e– involved in cell (electrode) reaction

F = Faraday‟s constant = change on 1 mole of e–  1.6  1019 C   6.022  1023

2Zn2  4e  2Zn(s) E  0.79 V , G  4  96500   0.79 

So G of various reactions can be added or substracted to get G of resultant reaction,

Solution: (i) Cu2  2e  Cu , Eo  0.337 V , G10  n1FE10 (n1  2)

(ii) Cu2  e  Cu E  0.153 V , Go2  n2FE20 (n2  1)

Target Cu  e  Cu , E03  ? Go3  n3FE3o (n3  1)

 FEo3  2F  0.337  F  0.153  Eo3  0.521

Solution: MnO4  Mn2  5e E1o  1.51 (i)

MnO2  Mn2  2e Eo2  1.23 (ii)

Target : MnO4  MnO2  3e E3o  ? (iii)

EoH| H  0 , G o2 = ―n2F(0 V) = ―2 F(0 V)

Eo3  ? , G 3o = ―n3F Eo3  G 3o = G1o + G o2

n3FE3o  (n1FE1o )  (n 2 FEo2 )  E3o  E1o  Eo2 = 0.34 (As n1  n 2  n 3  2 )

Illustration: Predict the feasibility of reaction : 2Fe3  2I  2Fe2  I2

Given EoFe3|Fe2  0.77 V , Eol | l  0.54 V

Solution: Cathode: 2Fe3  2e  2Fe2 Reduction

Cell Reaction: 2Fe3  2I  2Fe2  I2

Illustration: Calculate Eocell of the cell made of electrodes

EoAg|Ag   0.80 V (oxidation)

EoMnO|Mn2  1.51 V (reduction)

Solution: Eocell  SRP cathode – SRP of anode  1.51  0.80  0.71 V

Given: EoAg|Ag   0.80V , EoCu/Cu2  0.34 V

Solution: EoAg |Ag  0.80 V , EoCu2|Cu  0.34 V

Eocell  (0.34  0.80) V  0.46 V  0  not feasible

Solution: Anode: Zn  Zn2+ + 2e–

In chapter exercise – 03 (Gibb’s free energy and Cell potential)

2. The standard potentials E°, for the half reactions are:

Ag+ + e–  Ag, E° = x and Cu2+ + 2e–  Cu, E° = y. E° cell is