ELECTROCHEMISTR

Electrochemical cells
EMF
Measurement of EMF
Relation between EMF & free energy change of cell reaction
Electrode potential with reference to H-electrode
Electrodes
Determination of pH
Different types of cells

Electrochemical Cell & Galvanic Cell:

Electrochemical cell is a system or arrangement in which two electrodes are fitted in the
same electrolyte or in two different electrolytes, which are joined by a salt bridge.
Electrochemical cell is of two types.
(a) Electrolytic Cell
(b) Galvanic Cell or Voltaic Cell

Electrolytic Cell: It is a device in which electrolysis (chemical reaction involving

oxidation and reduction) is carried out by using electricity or in which conversion of
electrical energy into chemical energy is done.
Galvanic Cell: The device used to convert the chemical energy produced on a red-ox
reaction into electrical energy is called an electrochemical cell or simply a chemical cell.
These are also called galvanic cells or voltaic cell after the names of Luigi Galvanic and
Alessandro Volta who were first to perform experiments on the conversion of chemical
energy into electrical energy.
In electrochemical cell, a spontaneous red-ox reaction is carried out in an indirect
manner and the decrease in free energy during chemical reaction appears as electrical
energy. An indirect red-ox reaction is such that reduction and oxidation processes are
carried out in two separate vessels called half-cells.
Daniel Cell: It consists of two half-cells. The left hand half-cell contains a zinc metal
electrode dipped in ZnSo4 solution. The half-cell on the right hand side consists of Cu
metal electrode in a solution of CuSo4. A salt bridge that prevents the mechanical
mixing of the solution joins the half-cells.
When the zinc and copper electrodes are joined by a wire the following observation are
made.
(a) There is flow of electric current through the external circuit.
(b) The Zn rod loses its mass while copper rod gains in the mass.
(c) The concentration of ZnSo4solution increases while the concentration of CuSo4
solution decreases.
(d) The solutions in both the compartments remain electrically neutral.
During the passages of electric current through external circuit, electrons flow from zinc
electrode to the copper electrode. At the zinc electrode, zinc metal is oxidized to zinc
ions, which go into the solution. The electrons released at the electrode travel through
the external circuit to the copper electrode where they are used in the reduction of Cu2+
ions to metallic copper which is deposited on the electrode.

Cell Reaction
Zn Zn2 2e (Oxidation So anode)
Cu 2 2e Cu (Reduction So cathode)
Net reaction Zn Cu 2 Zn2 Cu

At the zinc rod, oxidation occurs. So it is the anode of the cell and negatively charged.
Electrode Sign : The sign of the anode and cathode in the voltaic or galvanic cells are
opposite to those in the electrolytic cells.

Salt bridge and its function:

Salt bridge is usually an inverted U-tube filled with concentrated solution of inert
electrolytes. An inert electrolyte is one whose ions neither involved in any
electrochemical change nor do they react chemically with the electrolytes in two halfcells. Generally salts like KCl, KNO3, and K2SO4 etc. are used. For the preparation of
salt bridge, gelatin or agar-agar is dissolved in a hot concentrated aqueous solution of an
inert electrolyte and solution thus formed is filled in the U-tube. On cooling the solution
set in the form of a gel in the U-tube. The ends of the U-tube are plugged with cotton
wool as to minimize diffusion effects.
Function of salt bridge:
(a) It connects the solutions of two half cells and complete the cell circuit.
(b) It prevents transference or diffusion of the solutions from one half cell to the other.
(c) It keeps the solutions in the two half-cells, electrically neutral. In anodic half-cell,
positive ions pass into solution and there shall be accumulation of extra positive
charge in the solution around the anode, which will prevent flow of electrons from

anode. Similarly in the cathodic half cell accumulate around cathode due to
deposition of positive ions by reduction. To neutralize these ions, sufficient
numbers of positive and negative ions are provided by salt bridge. Thus salt bridge
maintains electrical neutrality of the solution.
(d) It prevents liquid-liquid junction potential i.e. the potential difference which arises
between two solutions when contact with each other.
Representation of Electrochemical Cell (Galvanic Cell)
(a) The anode (negative electrode) is written on the left hand side and cathode (positive
electrode) on the right hand side.
(b) The anode of the cell is represented by writing metal or solid phase and then the
metal ion present in the electrolytic cell. Both are separated by a vertical line or a
semicolon. For example
e.g. (i) Zn | Zn2 or Zn; Zn2
. Zn | ZnSO4 or Zn s | ZnSO4 0.1m

(ii) Pt, H 2 1atm |H + 0.1M .

(c) The cathode of the cell is represented by writing the cat-ion of the electrolyte first
and then the metal. Both are separated by a vertical line or semicolon.
Cu 2+ |Cu or Cu 2+ ;Cu or Cu 2+ 1m |Cu.

For gaseous electrode e.g. Cl- 1m |Cl2 1atm ,P|

(d) The salt bridge which separates the two half cells is indicated by two parallel
vertical line. For example the Daniel cell can be represented as
Zn s |ZnSo 4 aq ||CuSO 4 aq |Cu s
Anode Salt bridge

Q.

Cathode

Write down the reactions at the following two electrodes as well as the total cell reactions.
(i) Fe|Fe2+ ||Fe2+ -Fe3+ |P+
(ii)

Ans: (i)

Zn|ZnO2-2 , OH- ||Hg 2Os |Hg

Fe s Fe2 aq 2e

Fe3 e Fe2 2

Net reaction Fe s 2Fe3 3Fe2 aq

(ii)

At anode

Zn s +4OH- +2H2O ZnO22- +2e+4H2O

1
Hg 2 O+2e 2Hg+ O 2
2

1
Zn s 4OH 2 Hg 2O ZnO22 2 H 2O 2 Hg O2 g
2

Q.

Write the cell reactions and electrode half-reactions for the following cells:
(a) P | K3 Fe CN 6 , K 4 Fe CN 6 || CvCl3 aq | Cv
aq

Ans: At anode
At cathode

aq

Fe CN 4- Fe CN 3- +e 3
6
6

3+
Cr +3e Crs

Cr 3 aq 3 Fe CN 6
Q.
Ans:

3 Fe CN 6 Cr s

Cd | CdCl2 aq || HNO3 aq | H 2g , P+

Cd s Cd 2 2e
2H 2e H 2 g

Cd s 2H aq Cd 2 aq H 2 g

Q.
Ans:

Zn | ZnSO4 aq || AgNO3 aq | Ag

Zn s Zn2 aq 2e
Ag aq e Ag s 2

Zn s 2 Ag aq Zn2 aq 2 Ag s

Q.
Ans:

Cu | Cu 2 aq || Mn2 aq , H aq | MnO2 s , P
Cu s Cu 2 aq 2e
MnO2 s 4H 2e Mn2 aq 2H 2O e

Cu s MnO2 s 4H Cu 2 aq Mn2 aq 2H 2O

Q.

Pt0 | Fe3 aq , Fe2 aq || Sn4 aq , Sn2 aq | Pt

Ans: Fe2 Fe3 e 2

Sn4 2e Sn2

2Fe2 Sn4 2Fe3 Sn2

Q.

Pt , Cl2 g | HCl aq || K 2Cr2O4 aq , Ag 2CrO4 s | Ag

Ans: 2Claq Cl2 2e

Ag2CrO4 2e 2 Ag s CrO42 aq

Electrode Potential
When a metal is placed in a solution of its ions the metal acquires either a positive or
negative change with respect to the solution due to this. A definite potential difference is
developed between the metal and the solution. This potential difference is called
electrode potential.

For example when a plate of zinc placed in a solution having Zn2+ ions, it becomes
negatively charged with respect to the solution and thus a potential difference is set up
between zinc plate and solution. This potential difference is termed electrode potential
of zinc. Similarly when copper is placed in a solution having Cu2+ ions it becomes
positively charged with respect to the solution. A potential is setup between the copper
plate and the solution. The potential difference is established due to the formation of
electrical double layer at the interface of metal and the solution.
The development of negative charge (as on Zn plate) or positive charge (as on Cu plate)
can be explained as follows.

When a metal rod is dipped in its salt solution, two charges occur.
(a) Metal ions pass from the electrode into solution leaving an excess of electrons and
thus a negative charge on the electrode..
(b) Metal ions in solution gain electrons from the electrode leaving a positive charge on
the electrode.
Definition: The electrical potential difference setup between the metal and its ions in the
solution 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 solution
of its own ions.
The electrode potential is further termed as oxidation potential if oxidation takes place at
the electrode with respect to standard hydrogen electrode and is called reduction
potential.
If in the half-cell, the metal rod is suspended in a solution of one molar concentration
and the temperature is kept at 298K, the electrode potential is called standard electrode
potential, represented usually by E0.
Measurement of Electrode Potential
The absolute value of the electrode potential of a single electrode (called single
electrode potential) can not be determined because oxidation half reaction or reduction
half reaction cannot takes place. It can only be measured by using some electrode as the
reference electrode. The reference electrode used is the standard or normal hydrogen
electrode (SHE or NHE). So the electrode potential of a given electrode is measured by
connecting a standard hydrogen electrode through a salt bridge. The e.m.f of the cell is
measured either by a calibrated potentiometer or by a high resistance voltmeter.

In the standard hydrogen gas electrode, hydrogen gas at atmospheric pressure is passed
into 1M HCl at 298K in which a foil of platinum coated with platinum black (finely
divided platinum) remains immersed. The electrode is usually represented as
Pt , H 2 g | H 1m

Example: Determination of standard electrode potential of Zn / Zn2 electrode.

A cell comprising of a Zn electrode immersed in 1m ZnSO 4 solutions and standard
hydrogen is setup and connected to it through a salt bridge. Both the electrodes are
connected with a voltmeter as shown in figure.

FIGURE (Normal hydrogen electrode)

Effect of Electrolytic Concentration and temperature on the electrode potential:
(Nernst Equation)
Consider a general reaction M n aq ne M s
According to Law of Mass Action
According to Vant Hoffs reaction isotherm
0

G G RT 1n Q
M s
0

G G RT 1n
M naq

As M s 1

So G G 0 RT 1n

1
M naq

Since in a reversible reaction, the electrical energy produced at the expense of the free
energy change i.e G nFE, G o nFE o , where E and Eo are standard electrode
potential.
F Faradays of electricity = 96500 coulombs
n number of electrons involved in the cell reaction
So nFE nFE 0 RT 1n

1
M naq

RT
1
1n
nF
M n
2.303RT
1
E E0
log
nF
M n

or, E E 0

At 250C, T = 298K, F = 96500 coulomb, R = 8.314 JK1mole1

0.0591
1
E E0
log
n
M n

Electrochemical Series
By measuring the potential of various electrodes again at standard hydrogen electrode
(SHE), a series of standard electrode potential has been established. When the electrodes
(metals and non metals) in contact with their ions are arranged on the basis of the values
of their standard reduction potential or standard oxidation potential, the resulting series
is called the electrochemical or electromotive or activity series of the elements.
By international convention, the standard potential of electrodes are tabulated for
reduction half reactions, indicating the tendencies of the electrodes to behave as cathode
towards SHE. Those with positive Eo values for reduction half reactions do in fact act as
cathode vs SHE while those with negative Eo values of reduction half reactions behave
instead as anodes vs SHE.
Application of Electrochemical Series
1. Calculate the standard EMF of the cell: to be discussed under determination of e.m.f
2. To predict anode or cathode:
An electrode with higher oxidation potential (lower reduction potential) is taken as
cathode.
Example: Eo Zn /Zn =-0.76 - Anode
2+

E Cu 2+ /Cu=0.34V - Cathode

3. To test the feasibility of a reaction:

For example, let us consider the reaction
Cu+Zn 2+ Cu 2+ +Zn
E 0Cu 2 / Cu 0.34V

Given

E 0 Zn 2 / Zn 0.76V

For the above reaction to take place, Cu has to lose electron and Zinc has to gain
electron and this is only feasible only if oxidation potential of is more that that of
Zinc. But from the electrochemical series it has been found that oxidation potential of
Zn (0.76V) is more than that of Cu (-0.34V). So the above reaction is not feasible.
4. To predict the reactivity of the elements
(To compare the relative activities of metal)
Greater the oxidation potential of a metal, more easily it can lose electrons and hence
greater is it is reactivity. As a result, a metal with greater oxidation potential can

displace with lower oxidation potential from their salt solution. For example Zn can
displace Cu from it is salt solution.
Similarly the metals which are above hydrogen in electrochemical series can displace
hydrogen from mineral acids.
Cell Potential or EMF of a cell
Every galvanic or voltaic cell is made up of two half-cells, the oxidation half-cell
(anode) and the reduction half-cell (cathode). One of the electrodes must have a higher
electrode potential (higher tendency to lose electrons) than the other electrode. As a
result of this potential difference, the electrons flow from an electrode at a higher
potential to the electrode at a lower potential. The difference between the electrode
potentials of the two half-cells is known as electromotive force (EMF) of the cell or cell
potential or cell voltage.
The EMF of the cell or cell potential can be calculated from the values of electrode
potential of the two half cells constituting the cell.
(i) When oxidation potential of anode and cathode are taken into account
E ocell E o anode E ocathode

(ii) When reduction potential of cathode and anode are taken into account
E ocell E ocathode E o anode .
Effect of Electrolytic concentration and temperature EMF of a cell (Nernst
equation)
The electrode potential and the EMF of the cell depend upon the nature of the electrode,
temperature and the activities (concentrations) of the ions in solution. The variation of
electrode and cell potential with concentration of ions in solution can be obtained from
thermodynamic considerations.
For a general reaction
aA+bB
mM+nN occurring in the cell. According to Gibbs reaction isotherm, the Gibbs
free energy change is given by
G=G 0 +RT in Q

M N -------- (1)
in
a
b
A B
m

or G G RT
0

The decrease in free energy of a chemical reaction appears as electrical energy in an

electrochemical cell.
The electrical energy produced in a cell is given by nFEcell and nFE0cell.
0
So G nFEcell and G0 nFEcell
Putting these values in equation (1)

M N
nFEcell nFE RT 1n
a
b
A B
m
n
M N

RT
0
Ecell Ecell
1n
a
b
nF
A B
m
n
M N

2.303RT
0
Ecell Ecell
log
--------------- (2)
a
b
nF
A B
m

0
cell

The equation is known as Nernst equation.

At 250C,
T = 298K, R = 8.314JK-1mole-1 F = 96500coulaub
Equation (2) reduces to

M N
0.0591

log
a
b
n
A B
m

Ecell E

0
cell

Relation between Electrical energy and enthalpy of a cell reaction

(Temperature dependence of EMF)
According to Gibbs Heimholtz equation
G
G H T

T p
but G nFEcell

G
Ecell

nF

T p
T p
H
E
T cell
or, Ecell
nF
T p

Ecell

is known as temperature coefficient of EMF of the cell.

T p
E
(i) If cell 0 , the electrical energy will be equal to enthalpy of the reaction.
T p
E
(ii) If cell 0 , then EMF of the cell, then electrical energy increases with rise in temperature and
T p
the additional energy will be supplied to the cell by surrounding and if that is not possible the
temperature of the cell fall during its working.
E
(iii) If cell is <0 , then electrical energy will be less than the enthalpy of the reaction.
T p

The EMF of the cell Cd, CdCl2. 2.5 H2) (solid) || AgCl(s). Ag, in which the cell reaction is

5
CdCl2 . H 2O 2 Ag s is 0.6753V at 250C and 0.6915V at 00C. Calculate the
2
free energy change, H and G of the reaction at 250C.
Cd s 2 AgCl s

Ans:

The cell reaction requires 2 electrons, so

n=2
G nFE 2 96500 0.6753
130332.9 J
130.33 KJ
H
E
E
T

nF
T p

In this case, EMF decreases with increase in temperature i.e

E

is negative thus
T p

0.6915 0.6753
E

25K
T p

0.00065 VK 1 at atm pressure

H
0.6753V
298 0.00065VK 1
2 96500
H 167717 167.72 KJ
H G
123.8 JK 1
Again S
T
Determination of Equilibrium Constant from Standard EMF
0
G 0 RT 1nK nFEcell
0
2303RTLogK nFEcell

LogK

0
nFEcell
2.303RT

At 25o C log K

0
nEcell
0.0591

Determination of Equilibrium Constant from EMF

0
G0 RT 1nK nFEcell

C D
2.303RT
2.303RT
E
log K
log
a
b
nF
nF
A B
c

C D
0.0591
0.0591
log K
log
At 25 C E
a
b
n
n
A B
c

Q. Calculate the equilibrium constant of the reaction 2 Ag Zn

2 Ag Zn2 occurring in the

Zinc Silver cell at 250C when Zn 2 0.10 M and Ag 10M EMF of the cell is found to be
1.62 volt.
Zn 2
0.0591
0.0591
Ans: E
log K
log
2
n
n
Ag
0.0591
0.0591
0.10
1.62
log K
log
2
2
2
10

or, K 8.128 1052

Q. Consider the electrochemical cell Fe, Fe2 0.1M | Cd 2 0.001M Cd
(a)
Write the cell reaction
(b)
Calculate the EMF of the cell
E 0 Cd 2 / Cd 0.40V
(c)
Calculate equilibrium constant
E 0 Fe2 / Fe 0.448V
Ans:

Std. EMF = 0.091V

nFE 0
log K
0.643
2.303RH
K = 4.39d

Q. What ratio of Pb2 / Sn2 concentration is needed to reverse the following reaction?
Sn s Pb2 aq
Sn2 aq Pb s
E 0 Sn2 / Sn 0.136V E 0 Pb2 / Pb 0.126V
0
Ecell
E 0 Pb 2 / Pb E 0 Sn 2 / Sn

Ans:

0.126 0.136
0.01V

0
Ecell Ecell

Sn 2
0.0591
log 2
2
Pb

At equilibrium Ecell 0
So 0 0.01

Pb 2
0.0591
log 2
2
Sn

Pb 2
0.458
Sn 2
Pb 2
0.458 , cell reaction exists and it will be reversed when
Thus till
Sn 2

Sn 2
0.458
Pb 2

Alternative determination of G, S & H and Go, So & Ho

We know G nFE 0
Differentiating the above equation
G 0
E 0

nF

T p
T p

G 0
As S

T p
0

E 0
So S 0 nF

T p

Again H 0 G 0 T S 0
E 0
nFE 0 nFT

T p
E 0
H 0 nFE 0 nFT

T p

Q.

The
EMF
of
the
standard
Weston
cell
8
CdSO4 , H 2O s || CdSO4 sat , Hg 2 SO4 , Hg in which the cell reaction
3
8
8
Cd Hg Hg 2 SO4 H 2O
CdSO4 H 2O
3
3

written

as

Cd(Hg),

E 0
is 1.0185 V at 250C. Calculate G 0 , S 0 and H 0 for the reaction if
for the cell is
T p

5 105 VK 1

Ans:

G0 nFE 0 196531.93
196.53 KJ

E 0
5
S 0 nF
2 96500 5 10
T p

9.65 JK 1

H 0 G 0 T S 0
193656 J 193.656 KJ .

Application of EMF Measurement

Determination of pH by E.M.F measurements
1. By using Hydrogen electrode:
The potential of a hydrogen electrode in contact with its a solution of H+ ions involving the
reaction.
1
H+ +e
H2 (g) is given by
2
1
2.303RT
E = E0
log
[H ]
F
2.303RT
1
=
log
F
H
or, E = 0.0591 Ph
Thus the potential of a hydrogen electrode depends upon the pH of the solution with which it is
in contact. This can be determined by combining the hydrogen electrode with a reference
electrode, which may be

(i) Normal Hydrogen Electrode

In the standard hydrogen gas electrode, hydrogen gas at atmospheric pressure is passed into
1M HCl at 298K in which a foil of platinum coated with platinum black (finely divided platinum)
remains immersed. The electrode is usually represented as Pt , H 2 g | H 1m

The above half-cell is connected to a standard hydrogen electrode and the EMF of the cell is
determined by a potentiometer. The complete cell can be represented as

Pt, H2 (1atm), H+ (c = ?) || H+ (1M), H2 (1 atm), Pt

Ecell = ER - EL
= 0 ( 0.0591pH)
= 0.0591 pH
E
PH cell
0.0591
Limitations of Hydrogen electrode:

1. The hydrogen electrode is easily affected by compounds of Hg, As and S and oxidizing
agents like Fe+3, MnO4, Cr2O72 and consequently this electrode cannot be used in
solutions containing these ions.
2. It cannot be used in presence of ions of many meters.
3. It cannot be used in solutions containing redox system.
(ii) Calomel electrode

Figure

Construction: It consists of a tube in the bottom of cell is a layer of mercury, over which a
past of Hg + Hg2Cl2 is placed. The remaining portion of the cell is faced with a solution of
KCl. A Pt wire is dipped into Hg layer for electrical contact. The side tube is used for
making electrical contact with a salt bridge.
The calomel electrode can be represented as Hg, Hg2Cl2(s), KCl. The potential of calomel
electrode depends on the concentration of KCl.
0.1N 0.3335V
1N 0.2810V
Satd. 0.2422V
When hydrogen electrode containing solution of unknown concentration combined with
calomel electrode, the complete cell can be represented as
P , H 2 latn H c ? || KCl 0.1N or N or satd | Hg 2Cl2 , H
Ecell Ecalomel EH 2
Ecell 0.2422 0.0591 pH
0.2422 0.0591 pH
pH

Ecell 0.2422
0.0591

By Using Glass Electrode

2. By using Quihydrone Electrode:

The quinone and hydroquinone system involves the following reactions
Q + 2H+ + 2e QH2
Thus when a platinum electrode is immersed in a solution containing quinhydrone, a potential is
established which is given by

EQ EQ0

QH 2
2.303RT
log
2
2F
Q H

Q H
2.303RT
0
EQ
log
2F
QH 2
EQ0
E0 EQ0

Q 2.303RT log H 2
2.303RT
log

2F
2F
QH 2
Q 2.303RT log H
2.303RT
log
2F
F
QH 2

If Quinone and hydroquinone are taken in equimalar proportion Q QH 2

2.303RT
log H
F
2.303
RT
Then
EQ0
pH
F
250 C
EQ EQ0 0.0591 pH
EQ EQ0

since EQ0 0.6996V

so EQ 0.6996 0.059 pH
In order to determine the pH the quin hydrone electrode is combined with calomel electrode. The
complete cell can be represented as

Hg , Hg 2Cl2 , KCl satd || H uni.. , Q, QH 2 , P

Ecell Ecalomel EHQ

0.6996 0.0591 pH 0.2422
pH

0.6996 0.2422 Ecell

0.0591

It can not be used for solutions of pH more than 8 because in alkaline solution H2Q ionizes appreciably
as an acid and also get oxidized by O2.
Q.1 The potential of a hydrogen gas electrode in a solution of an acid of unknown strength is
0.29V at 298K as measured against NHF. Calculate pH of the solution.

pH

Ecell
0.29

4.9
0.0591 0.591

Q2. Find out the pH of a solution in a quinhydrone half-cell is coupled with standard
calomel electrode. The EMF of the combined cell was determined to be 0.123 at 250C. Ecalone
= 0.2415 and
BATTERIES
The device that stores chemical energy for latter release, as electricity is known as battery.
Or,
A battery is an electrochemical cell or several electrochemical cell connected in series that can be
used as a source of direct electric current at a constant voltage.
1.

Primary battery or primary Cells

The battery in which cell reaction is not reversible. When all or most part of the reactants have
been converted into products, no more electricity is produced and the cell becomes dead.

2.

Secondary battery or secondary cell

The cell reaction can be reversed by passing direct electric current in opposite direction. A
secondary battery can be used through a large number of cycles discharging or charging.

3.

Flow battery and fuel cell

In which the reactants, products and electrolyte passed through the battery i.e it is an simple
electrochemical cell that converts chemical to electrical energy.

Dry or Laclanche Cell : A cell without fluid components

The anode of cell is Zn container and carbon rod is the cathode.

Electrolyte is the mixture of NH4Cl, ZNCl2 and MnO2 to which starch added to make a thick paste
and avoid the leakage of the electrolyte.
Cell Reaction
At anode - Zn s Zn2 aq 2e
At cathode : Involves the reduction of MnO2 to a Mn2O3

2MnO2 H 2O 2e Mn2O3 2OH

OH Produced may react with NH4+ to form NH3 which may disrupt the current flow. This is prevented
by the reaction of NH3 (g) with Zn+2 to form complex Zn NH 3 2 Cl2
2 NH 4 OH NH 3 g H 2O

2 NH 3 Zn 2 2Cl Zn NH 3 2 Cl2

Total reaction at cathode

2MnO2 2 NH 4 Zn 2 2Cl 2e Mn2O3 Zn NH 3 2 Cl2 H 2O

Complete cell reaction:

2MnO2 2 NH 4 2Cl Zn s Mn2O3 Zn NH 3 2 Cl2 H 2O

Emf of the cell = I.5.V

Disadvantage:
(a) When current is drawn rapidly from it, products build upon the electrodes there by causing drop in
voltage.
(b) Since the electrolytic reduction is acidic so Zinc metal dissolves slowly thereby the cell run down
slowly even if it is not in use.
Use: Flash lights, transistors, calculators etc.
2.Alkaline battery
Improved from of dry cell in which NH4Cl is replaced by K OH. In this battery Zn powder is mixed with
KOH to get the gel.
A paste containing MnO2 surrounds graphite rod
At anode:

Zn s 2OH Zn OH 2 2e

At cathode:

2MnO2 H 2O 2e Mn2O3 2OH

________________________________

Zn s 2MnO2 s H 2O s Zn OH 2 s Mn2O3

Advantage:
(a) Zn does not dissolve as readily in a basic medium
(b) Alkaline battery maintains better its voltage as current down from it

(c) The life of alkaline battery is longer than dry cell since there is no corrosion of Zn
3. Ni-Cd (nicad) battery
Anode consists of Cd and cathode consists of a paste NiO(OH)
At anode : Cd s 2OH Cd OH 2 2e

(s)

At cathode : 2 NiO OH 2 H 2O 2e 2 Ni OH 2 2OH

________________________________________________
2 NiO OH Cd s 2H 2O s Cd OH 2 2Ni OH 2

The reaction can readily reversed because the reaction products Ni OH 2 and Cd OH 2
readily adhered to electrode surface.

It is recently developed portable rechargeable cell and its voltage is 1.4V.

Uses

Electronic Calculator
Electronic Flash Units.
Cordless electronic shavers

Lead Acid Storage Cell

A storage cell is one that can operate both as a voltaic cell and as an electrical cell. When
operates as a voltaic cell, it supplies electrical energy and being discharged. When being
recharged, it operates as an electrolytic cell.
Construction
One of the electrodes is made of lead and the other is made of Pb2 or a past of
PbO2 is pressed into a grid of Pb.

A number of Pb plates (-ve plates) and a number of PbO2 are connected parallel
in series.

The Pb plates are fitted in between the PbO2 plates.

Plates are separated by insulator likes strips of wood or glass fill.

The entire combination is dipped in 20 to 21H2SO4

Discharging: When operates as votaic cell

At anode: Pb s Pb 2e

Pb SO24 PbSO4
At cathode: PbO2 4H 2e Pb2 2H 2O

Pb SO42 PbSO4
______________________________________________

Netrealtio Pb PbO2 4H 2SO42 2PbSO4 2H 2O E.E

The voltage of each cell is about 2 value at a concentration of 21.4 1/0 H 2SO4 at 250C.
Charging:

At cathode: PbSO4

Pb SO 4

Pb 2e

At anode: PbSO4

Pb

Pb SO42

Pb 2H 2O PbO2 4H 2e
Net reaction

2PbSO4 2H 2O E.E Pb PbO2 4H 2SO42

Uses :

In electrical vehicles
Gas engine ignition
Telephone exchange
Train
Broad casting station
Automobiles
Power stations

Fuel Cell: The cell in which electric energy is produced without combustion of oxygen and a gas that
can be oxidized. It converts chemical energy of fuel directly into electrical energy.

It consists of two electrodes made of graphite impregnated with a catalyst (Pt, Ag or a metal oxide).
The electrodes are placed in an aqueous solution of KOH or NaOH. O2 and H2 are constantly bubbled
through cathode and anode respectively.

The electrodes used in fuel cell should have the following characteristics
(a) Be good conductor
(b) Good electron source or sinks
(c) Should not be consumed or deteriorated by electrolyte heat or electrode reaction.
(d) They must excellent catalyst for that reaction
At anode:

H2

2H 2e

2H 2OH

2H 2O

At cathode:
O2 2H 2O 4e
4OH
________________________________
2 H 2O
Net reaction: 2 H 2 g O2 g

Application:
(a) Auxiliary engine source in space vehicle. Submarines
(b) The weight of fuel battery for 15days in space is about 250kg.
(c) It produces H2O, which proved to be a valuable source of fresh water.
Characteristic of fuel cell
(a) They dont store chemical energy
(b) Reactants are to supply constantly, while products are removed constantly.

Q. The standard reduction potential for Cu 2 / Cu is 0.34V. Calculate the reduction potential at
pH = 14 for the above couple. K Sp for Cu OH 2 is 1.0 x 109.
Ans: For Cu OH 2 , KSp Cu 2 OH

If pH = 14, then H 1014

OH 1
KSp
Cu 2
1.0 1019
2
OH
0.0591
1
E E0
log
2
Cu 2

0.0591
log 11019
2
0.0591
0.34
19
2
0.2205
0.34

Q. Find the solubility product of a saturated solution of Ag 2CrO4 in water at 298K if the EMF of
the cell Ag/Ag+ (satd. Ag2CrO4 solution) || Ag+ (0.1m) | Ag is 0.164v at 298K.
Ans: Ag | Ag Ag 2CrO4 solution saturated || Ag 0.1m | Ag

Ecell

C
0.0591
log 2
n
C1

0.0591
0.1
log
1
C1

0.164 0.0591log
C1

0.1
C1

1.66 104 m

Ag 1.66 104 m
2

K Sp for Ag 2CrO4 Ag Cr2O42

Since Ag 1.66 104 m

1.66 104 m
So Cr2O4
2
1.66 104
4 2
K Sp = 1.66 10

= 2.287 10 12 mole3 lit 3

Q. Calculate the EMF of the cell

Pt , H 2 1atm

CH 3 COOH NH 4OH Pt , H 2
||
0.1m
0.01m 1atm

Ka for CH3COOH = 1.8 x 105 Kb for NH4OH = 1.8 x 105

CH 3COO H

CH 3COOH

Ka
Ka.C
C
1.8 105 0.1

H C C
Ans:

1.342 10 3 mole / lit

NH 4OH

NH 4 OH

OH C C

Ka
Kb . C
C

1.8 105 0.01

0.424 103 mole / lit
1014
H
2.359 1011 mole / lit
3
0.424 10

Ecell

C
0.0591
log 2
2
C1

0.0591
2.359 1011
log
1
1.342 103
0.04575V

Q. The EMF of the cell Zn s |1.0m Zn2 aq || Ag aq x m | Ag s at 250C is 0.805V and

is
T p
3.98 x 104 v/k. Calculate the enthalpy change at 250C.

E
H nFE nFT

T p
Ans:

nF T
E
T p

2 96500 298 3.98 104 0.805

178, 260 J mole 1 178.26 KJ mole 1

PREVIOUS YEAR QUESTION

OBJECTIVE TYPE

Q.1.

Which of the following relations between the standard free energy change G 0 and
0

E is correct?
(a) G 0 nFE 0

(b) G 0 nFE 0

ANS:

2003)
(b)

Q.2.

For a cell, the cell reaction is

(c) G 0 nE 0

(B.P.U.T-

Mg s Cu 2 aq Cu s Mg 2 aq
If the standard reduction potentials of Mg and Cu are 2.37V and 0.34V find the standard
EMF of the cell.
(B.P.U.T-2004)
ANS:
0
0
0
0
Ecell
Ecathode
Eanode
E Cu0 EMg

0.34 2.37 2.71V

Q.3.

Write down the net cell reaction for

Zn s | ZnO22 , OH | HgO s | Hg

(B.P.U.T-

2004)
ANS:

Zn s 2 H 2O 4OH ZnO22 4H 2O 2e
HgO s 2 H 2O 2e Hg H 2O 2OH

Zn s HgO s 2OH ZnO22 H 2O HgO s

Q.4.

Write the cell reaction in the dry cell.

2004)

(B.P.U.T-

ANS:
At anode:

Zn s Zn2 2e

At cathode:

2MnO2 s H 2O 2e Mn2O3 s 2OH

NH 4 aq OH aq NH 3 g H 2O 2

Zn s 2 MnO2 s 2 NH 4 aq 2Cl aq Zn NH3 2 Cl2 s

Zn s 2MnO2 s 2 NH 4 aq 2Cl aq
Mn2O3 s Zn NH 3 2 Cl2 s 2 H 2O s
Q.5.

Write down the cell reaction for

Pt , H 2 | H || CuCl2 | Cu
ANS:

H 2 g 2 H 2e
Cu 2 2e Cu s

(B.P.U.T-2005)

H 2 g Cu 2 aq 2H aq Cu s
Q.6.

Write down the cell reaction for

Pt , Hg , Hg2Cl2 , Cl , H , H 2 , Pt.

(B.P.U.T-2005)

ANS:

Hg s Hg 2 2e
Hg 2 2Cl Hg 2Cl2
2 H 2e H 2

Hg s 2H 2Cl Hg2Cl2 H 2
Q.7.

Write down the cell involving the reaction

ANS:

1
I2
Fe3 I
2
Fe2 | Fe3 || I 2 | I

Q.8.

For the electrochemical cell M | M || X | X .

Fe 2

(B.P.U.T-2006)

E 0 X / X 0.33V

E 0 M / M 0.44V

Since oxidation potential X is more than that of M, so the above reaction is

spontaneous.
ANS:

EM0 / M 0.44V

Ex0/ x 0.33V

Since oxidation potential x is more than that of M, so the above reaction is spontaneous.
(B.P.U.T-2006)
Q.9.

What is the overall reaction-taking place during the charging of lead acid storage cell?
(B.P.U.T-2006)

ANS:
At cathode:

At anode:

PbSO4 Pb 2 SO42
Pb 2 2e Pb

PbSO4 Pb 2 SO42
Pb 2 2 H 2O PbO2 4 H SO42 2e

2PbSO4 2H 2O Energy Pb PbO2 4H 2SO42

Q.10.

An electrochemical cell is discharged irreversibly at a finite rate. If G is the free

energy change for the discharge reaction and well is the total electrical work output of
the cell during the discharge process, which of the following relations will be true.
(B.P.U.T-2007)

ANS:

CuCl G

SUBJECTIVE TYPE
Q.1. Write down the reaction s at the following two electrodes as full cell reactions.
(a) Fe | Fe2 || Fe2 Fe3 | Pt
(B.P.U.T-2003)
ANS:

Fe Fe 2 2e
Fe3 e Fe 2 2

2Fe3 Fe 3Fe2
Q.2.

What is the EMF of the following cell at 250C?

Zn s | Zn2 0.01m ||Ag 0.1m | Ag s

(B.P.U.T-2004)

Given that the standard potentials of Zn s | Zn2 and Ag | Ag half cell are 0.76 and
0.80V respectively.
ANS:
At anode : Zn s Zn2aq 2e
At cathode: Agaq e Ag s 2

Zn s 2 Agaq Zn2aq 2 Ag s
0
0
Ecell
Eanode Ecathode
0.76 0.80

1.56V

Zn2aq
0.0591

Ecell E
log
2
2
Agaq

0.0591
0.01
1.56
log
2
2
0.1
0
cell

1.56

0.0591
log1
2

1.56

Q.3.

What are the reactions taking place when the storage cell is supplying electrical
energy.
(B.P.U.T-2004)

ANS:

When the storage cell supplies electrical energy, then it behaves as a voltaic cell. The
reactions taking place at anode and cathode as.
At anode :

PbSO4 Pb 2 SO42
Pb 2 SO42 PbSO4

At cathod :

PbO2 4 H 2e Pb 2
Pb 2 SO42 PbSO4

Net cell reaction : Pb PbO2 4H 2SO42 2PbSO4 2H 2O Energy

Q.4.

The EMF of the following cell is 0.445V.

Pt , H 2 1atm | H unknown || KCl satd . | HgCl2 | Hg .

Calculate the pH of the solution. (B.P.U.T-2005)

ANS:

The potential of hydrogen electrode involving the reaction H e

1
H 2 is given by
2

0.0591
1
at 250C
log

1
H
i.e. EH 2 0 0.0591 pH
or, EH 2 0.0591 pH
E E0

E.m.f of the cell is given by

Ecell Ecalomel EH 2
Ecell Ecalomel 0.0591 pH

Ecell Ecalomel
0.0591
0.445 0.2415

0.0591
3.45

pH

Q.5.

ANS:

The emfs of a cell are 0.35252V and 0.35333V at 250C and 200C respectively. If the
number of electrons involved in the overall reaction is two. Calculate G 0 and H 0 at
250C. (B.P.U.T-2005)

Ecell at 250 C Ecell at 200 C 0.35252 0.35333

Ecell

1.62 104V
T
5
5

p
0
0
G nFEcell
2 96500 0.35252
68 Kg
Again

H 0 G 0 T S 0 68 103 31.27
77318 J
77.318 KJ
Q.6.

The equilibrium constant for the reaction

Ag s Fe3 aq
Ag aq Fe2 aq is 0.335.
Find out the standard electrode potential of Fe3+, Fe2+ | Pt, if the standard reduction
potential of Ag+ | Ag is 0.799V.
(B.P.U.T-2005)

ANS:
For the above reaction the cell can be represented as

Fe2 | Fe3 || Ag | Ag
0
0
Ecell
E Ag
E 0 Fe3 / Fe 2

/ Ag

0.028 0.799 EFe3 / Fe2

0
EFe
0.799 0.028 0.771V
3
/ Fe

Q.7.

The standard reduction potential for Sn2 2e Sn and Sn4 4e Sn are 0.136 and
0.15V respectively. Calculate E0 and G 0 for Sn4 2e Sn2 .

Ans:

G0 1 nFE 0

Sn 4 4e Sn

4 96500 0.15
57.9 KJ / mole

Sn Sn 2 2e

2 96500 0.136
26.248 KJ / mole

Sn 4 2e Sn 2

G 0 G 0 G 0 57.9 26.248
1

84.148
E0
Q.8.
ANS:

G
84148

0.436volt
nF
2 96500
0

Write down the cell reaction involved in Nickel Cadmium cell.

At anode:

Cd s OH CdOH 2e
2

2 NiO s 2 H 2O 2e 2 NiOH 2OH

2

REVIEW QUESTIONS
Question 1
What is cell constant? Give its unit.
Answer:
The cell constant is the ratio of the distance between the parallel plates of the cell and the area of the electrode.
The unit of cell constant is cm1.
Question 2

What is electrode potential?

Answer:
The tendency of an electrode to lose or gain electrons, when it is in contact with its own ions is known as
electrode potential.
Question 3
What is oxidation potential?
Answer:
The tendency of an electrode to gain electrons, when it is in contact with solution of its own ions is known as
oxidation potential.
Question 4
What is reduction potential?
Answer:
The tendency of an electrode to lose electrons, when it is in contact with solution of its own ions is known as
reduction potential.
Question 5
What is electrochemical cell? How can you increase the value of reduction potential of an
electrode?
Answer:
A device used to convert the chemical energy produced in a red-ox reaction into electrical energy is known as
electrochemical cell.
The value of reduction potential of an electrode may be increased by increasing the concentration of metal ions
in contact with metal electrode or increasing the temperature.
Question 6
Why do electrochemical cells stop working after some time?

Answer:
An electrochemical cell produces electrical energy at the cost of red-ox reaction. When the red-ox reaction is
completed, the cell stops working, since it is now incapable of undergoing red-ox reaction any more.
Question 7
Why is hydrogen electrode not generally used in pH measurement?
Answer:
Hydrogen electrode is not generally used in pH measurement because

(i)
(ii)
(iii)

It is difficult to set up
It can not be used in red-ox systems
It can not be used in presence of Hg, As, S, Fe+3, MnO4, Cr2O3 etc.

Question 8
What is the difference between electrochemical cell and electrolytic cell?
Answer:
Electrochemical cell
Electrolytic cell
(i) Here the chemical energy is converted (i) Here, the electrical energy from an
to electrical energy
external source is used to bring about the
chemical change.
(ii) Here spontaneous redox reaction (ii) Here the redox reaction is nonoccurs
spontaneous and takes place only when
electrical energy is supplied from outside.
(iii) Here anode is assigned as negative (iii) Here anode is connected to the
and cathode is assigned as positive positive terminal and cathode to the
electrode.
positive terminal of battery.
(iv) Two electrodes are set up in two (iv) Two electrodes are set up in the same
different vessels.
vessel.
Example: Dry cell, lead storage battery.
Example: Changing lead storage.

Worked Out Examples

Electromotive Force
Example 1
Write down the individual electrode reactions and also the total cell reaction for each of the following cells
(a)
Pb PbSO4 (S),SO4 Cu ++ Cu

(b)

+ 2 Pt
Zn | Zn || H | H

Solution:

(a) The reduction potential value of Pb PbSO (S),SO = 0.3505V

4

The reduction potential value of Cu Cu 0.337

Hence Pb PbSO (S),SO is anode or negative electrode and Cu|Cu ++ is cathode or positive electrode.
4

By convention oxidation occurs in anode or negative electrode

Pb +SO4
PbSO4 + 2e

(1)

and reduction occurs in cathode or positive electrode

Cu 2 2e
Cu

(2)

By adding (1) and (2) we get the all reaction

Pb SO 4
PbSO 4 2e
Cu 2e
Cu
Cu Pb SO 4
Cu PbSO 4
(b) The reduction potential value of Zn|Zn -0.761V
The reduction potential value of H2 | H 0.000V
Hence Zn| Zn is anode or negative electrode and H2 | H is cathode or positive electrode.
By convention oxidation occurs in anode or negative electrode

Zn
Zn 2e

(1)

and reduction occurs in cathode or positive electrode

2H + 2e
H2

(2)

By adding (1) and (2) we get cell reaction

Zn
Zn 2 2e
2H + 2e
H2
Zn+2H +
Zn ++ +H 2
Example 2
Give the cell reactions of the following cells and calculate their standard e.m.f at 25C using the standard
reduction potential value
++
(a) Hg Hg 2 Cl 2 (S) Cl Cu Cu

(b) Pt Fe ++ - Fe +++ Cl- AgCl(S)Ag

Solution:
(a) Hg Hg Cl (S) Cl- Cu ++ Cu
2
2

The standard reduction potential value of Hg Hg 2 Cl 2 (S) Cl 0.268V

The standard reduction potential value of Cu Cu ++ = + 0.337V
The reduction potential value of both the electrode is positive but the value of Cu Cu is greater than the
value of Hg Hg 2 Cl 2 (S) Cl- .
So Hg Hg 2 Cl 2 (S) Cl- is the anode or negative electrode and Cu Cu is called cathode or positive electrode.

By convention oxidation occurs in anode or negative electrode

2Hg + 2Cl-
Hg2Cl2 + 2e

(1)

and reduction occurs in cathode or positive electrode

Cu 2e
Cu

(2)

By adding (1) and (2) we get the total cell reaction

2Hg+2Cl-
Hg 2 Cl2 + 2e
Cu 2e
Cu
2Hg 2Cl Cu
Hg 2Cl 2 +Cu
Hence
(Ereduction)

ECell = (Ereduction)

= (0.337 0.268) V
= 0.069V
++
+++
(b) Pt Fe -Fe

Cl- AgCl(S)Ag

The standard reduction potential value of Pt Fe ++ - Fe +++ = + 0.771V

The standard reduction potential value of Ag AgCl(S) Cl- = + 0.2223V
The reduction potential value of both the electrode is positive but the value of Pt Fe ++ -Fe +++ is greater than
that value of Ag AgCl(S) Cl- . So Ag AgCl(S) Cl- is anode or negative electrode and Pt Fe ++ - Fe +++ is
called cathode or positive electrode.

By convention oxidation occurs at anode or negative electrode

Ag + Cl-
AgCl + e

(1)

and reduction occur at cathode or positive electrode

Fe+++ + e
Fe++

(2)

By adding (1) and (2) we get the total cell reaction

Ag+Cl-
AgCl+e
Fe+++ +e
Fe ++
Ag+Cl- +Fe +++
AgCl+Fe ++
(Ereduction)

Hence ECell = (Ereduction)

+

= (0.771 0.223)V
= 0.5487V

Example 3
Calculate the potential of the following electrodes at 25C
(a) Ag Ag + (a=10-5 ) (oxidation)
(b) Pt Fe ++ -Fe +++ (reduction)

(a 0.1)

(a 0.01)

Solution:
(a) The electrode reaction (Oxidation) is

Ag
Ag + +e
E OX =E Ag Ag

RT aAg
ln

aAg

EAg Ag

RT
ln aAg [ aAg 1]

0.799 0.0592 log(105 ) E Ag Ag = - 0.799V

0.799 0.0592 5

0.799 0.2960
0.503V
(b)

Pt Fe Fe (reduction)

(a 0.1) (a 0.01)
The electrode reaction (reduction) is

Fe+++ + e
Fe++
Electrode potential E red E Fe++ -Fe+++

RT aFe
ln

aFe

0.771 0.0592 log

aFe
aFe

0 .1
0.01
100
0.771 0.0592 log
10

0.771 0.0592 log

0.771 0.0592
0.7118V 0.712 V
Example 4
Compute the cell potentials of the following

Cu Cu (a 0.01) Zn (a 0.1) Zn

Solution:

Cu Cu ( a 0.01) Zn ( a 0.1) Zn

The reduction potential value of Cu Cu ++ =+0.337 V

The reduction potential value of Zn Zn ++ =-0.761V
The electrode reaction (reduction) of the left hand electrode is

Cu ++ + 2e
Cu
The electrode potential E red ECu Cu

0.337

a
RT
ln Cu
2 aCu ++

0.0592
log aCu aCu 1
2

0.337 0.0296 log 10 2

0.337 0.0296 2
0.337 0.0592
0.2778 0.278V
The electrode reaction (reduction) of the right hand electrode is

Zn ++ + 2e
Zn
Hence electrode potential E red E Zn ++ Zn

a
RT
ln Zn
2 aZn ++

RT
ln aZn [ aZn 1]
2
0.0592
0.761
log aZn ++
2

E Zn

0.761 0.0296 log 101

0.761 0.0296
0.7906 V
Hence E Cell E reduction + - E reduction

(0.278 0.7906) V
1.0686 V.
Example 5
Construct electrochemical cell for the following reaction and then find out the standard free energy change
from their e.m.f

1
Cl 2 Br
2
Solution:

1
Br2 Cl
2

Reduction

1 2
Cl Br
2

1
Br2 Cl
2

Oxidation

Here

1
Cl2 + e
Cl
2

In this reaction chlorine (Oxidation number = 0) is reduced to Cl (oxidation number 1) , hence the positive
half will be the Cl2 Cl half cell i.e. (Pt) Cl2 Cl is cathode or positive electrode

1
2

Br2 e
Again Br
Here bromide (oxidation number = - 1) is oxidized to bromine (oxidation number = 0) hence the negative half
cell is Pt Br2 Br . The electrochemical cell where the given reaction occurs is represented as

Pt,Br2 Br Cl Cl2 (Pt)

The reduction potential value of Br2 Br 1.0652 V

The reduction potential value of Cl 2 Cl 1.359 V
The e.m.f. of the cell

ECell Ereduction Ereduction

(1.359 1.0652) V

= 0.2983 V

Standard free energy change

G nE
1 96500 0.2983 Joule
28351.7 Joules
2.83517 104 Joules .
Example 6
The e.m. f . of the cell Tl TlCl(S) KCl (m = 0.1) Hg 2Cl 2 (S) Hg is 0.73 volts and dE
is the cell reaction? Calculate H and G and for the reaction?

Solution:
Given cell

Tl TlCl( S ) KCl(m=0.1) Hg 2Cl2 (S) Hg

E Cell = 0.73V

As usual convention LHE is ve and RHE is +ve

Oxidation reaction at LHE( ve) : (Tl Tl e) 2
Reduction reaction at RHE (-ve) : Hg 2Cl2 + 2e = 2Hg + 2Cl

Total cell reaction: 2Tl Hg 2Cl2 2Tl 2Cl 2Hg

dT

7.5 104. What

or, 2Tl Hg 2Cl2 2 TlCl 2Hg

As cell emf is ve, so the reaction is spontaneous
Now we know, G n E Cell
where G free energy of the cell; n no. of electron involve = 2

F 96500 columb, ECell 0.73V

G 2 96500 0.73 Joule

140890 Joule 1.4 105 Joule

G
H G T

T P

We know

n E Cell T.n.

E E

Temp coeff

T T

140890 298 2 96500 7.5 10 4

140890 43135 .5
97754.5 Joule

9.77 104 Joule .

Example 7
At 25C and 1 atm, for the cell (Pt)H 2 HCl (0.1M) AgCl Ag . The
and dE

dT

1.8 104 Volt/C. Calculate G, H and S for the cell reaction.

Solution:
Anode:

H2 2Cl
2HCl 2e

Cathode : 2AgCl 2e
2Ag 2Cl
H 2 2AgCl
2HCl 2Ag
dE
= 1.810-4 volt/C; T=25C=298A
dT
Free energy change G nE
2 96500 0.35252 Joule
E all =0.35252V;

68036.36 Joule
68.036 KJ

Change in enthalpy H n T .

dE

E
dT

e.m.f = 0.35252 Volt

2 96500 298 1.8 104 0.35252 Joule

=193000 0.5364 0.35252 Joule
=193000 0.40616 Joule
= 78388.88 Joule
Change in entropy S n

dE
dT

2 96500 1.8 104 Joule

34.74 Joule
Example 8
For the cell H2 | HCl | AgCl, Ag E = 0.222V. If the measured e.m.f is 0.385 V. What is the PH of HCl

PH2 1atm

solution?

Solution:
The reaction in the cell
(pt) H2 (1 atm) | HCl | AgCl, Ag is
1
2

H2 + AgCl

Ag + HCl

RT
ln aHCl PH2 1atm

2RT
0
E cell =E cell

ln a a mean ionic activity

0
E cell =E cell

or,
or,

0
E cell =E cell
0.118 log a

or,

0
E cell =E cell
0.118 PH

or,

0.385 0.222 0.118PH

or,

PH 1.38

at 25C

log a log aH+ PH

Exercise
1. Derive the relation between the specific conductance and the equivalent conductance of a solution.
2. State Kohlrauschs law of independent migration of ions and its usefulness.
3. Explain the nature of conductometric titration curve when (any two)
(i)
CH3COOH by NH4OH
(ii)
CH3COOH by NaOH
(iii)
A mixture of HCl and CH3COOH by NaOH

(iv)
MgSO4 by Ba(OH)2
4. Define Galvanic cell? Give an example of Galvanic cell.
5. What do you mean by reversible and irreversible cells. Explain with suitable example.
6. Deduce thermodynamic expression of e.m.f. of a galvanic cell i.e. Nernst equation.
7. Derive the expression of the change of the following with EMF of the cell
(i) Gibbs free energy
(ii) Enthalpy
(iii) entropy.
8. Describe hydrogen half cell and derive the expression for potential the half cell. How pH of a solution is determined
through hydrogen half-cell.
9. Describe the construction and working principle of the Calomel electrode.

Problems
1. For the following cell write down the cell reaction and calculate the e. m. f at 250C
Pt| Tl+ (a = 0.5) | Tl+++ (a = 0.5) || Ce+++ (a = 0.8) | Ce++++ (a = 0.2) | Pt
E0Tl+++/Tl+ = 1.250 V and E0Ce++++/Ce+++ = 1.610 V
2. For the following cell write down the cell reaction and calculate the e. m. f at 25 0C
Pt| Fe+2 (a = 0.5), Fe+3 (a = 0.2)|| Cl- (a = 0.001) | AgCl | Ag
E0Fe+++/Fe++ = 0.771 V and E0AgCl/Ag = 0.222 V
3. For the following cell write down the cell reaction and calculate the e. m. f at 25 0C
Ag | Ag+ (a = 0.1) || Zn++ (a = 0.1) | Zn
E0Ag+/Ag = 0.799 V and E0Zn++/Zn = - 0.763 V
4. Construct electrochemical cell for the following reaction and then find out the standard free energy change from their
e.m.f.

2 Ag + + Cu
2 Ag + Cu +2
0
= 0.337 V
E 0Ag+ /Ag = 0.799 V , ECu
+2
/Cu

5. Construct electrochemical cell for the following reaction and then find out the standard free energy change from their
e.m.f.

Zn + 2H+ (aq)
Zn (aq) + H2 (g)
E0Zn+2 /Zn = 0.761V , E 0H + /H = 0 V
2

Q. The standard reduction potential for Cu / Cu is 0.34V. Calculate the reduction potential at
pH = 14 for the above couple. K Sp for Cu OH 2 is 1.0 x 109.
Ans: For Cu OH 2 , KSp Cu 2 OH
If pH = 14, then H 1014
OH 1
Cu 2

KSp
OH

1.0 1019

0.0591
1
log
2
Cu 2
0.0591
0.34
log 11019
2
0.0591
0.34
19
2
0.2205

E E0

Q. Find the solubility product of a saturated solution of Ag2CrO4 in water at 298K if the EMF of
the cell Ag/Ag+ (satd. Ag2CrO4 solution) || Ag+ (0.1m) | Ag is 0.164v at 298K.
Ans: Ag | Ag Ag 2CrO4 solution saturated || Ag 0.1m | Ag
Ecell

C
0.0591
log 2
n
C1

0.0591
0.1
log
1
C1

0.164 0.0591log
C1

0.1
C1

1.66 104 m

Ag 1.66 104 m
2

K Sp for Ag 2CrO4 Ag Cr2O42

Since Ag 1.66 104 m
1.66 104 m
2
2
1.66 10 4
K Sp = 1.66 10 4

So Cr2O4

= 2.287 10 12 mole3 lit 3

Q. Calculate the EMF of the cell
CH 3 COOH NH 4OH Pt , H 2
Pt , H 2 1atm
||
0.1m
0.01m 1atm
Ka for CH3COOH = 1.8 x 105 Kb for NH4OH = 1.8 x 105

CH 3COOH

CH 3COO H
Ka
Ka.C
C
1.8 105 0.1

H C C
Ans:

1.342 10 3 mole / lit

NH 4OH

NH 4 OH

OH C C

Ka
Kb . C
C

1.8 105 0.01

0.424 103 mole / lit
1014
H
2.359 1011 mole / lit
3
0.424 10

Ecell

C
0.0591
log 2
2
C1

0.0591
2.359 1011
log
1
1.342 103
0.04575V

E
Q. The EMF of the cell Zn s |1.0m Zn2 aq || Ag aq x m | Ag s at 250C is 0.805V and
is
T p
3.98 x 104 v/k. Calculate the enthalpy change at 250C.

E
H nFE nFT

T p

Ans:

nF T

T p

2 96500 298 3.98 104 0.805

178, 260 J mole 1 178.26 KJ mole 1

PREVIOUS YEAR QUESTION

OBJECTIVE TYPE
Q.1.

Which of the following relations between the standard free energy change G 0 and

ANS:

E 0 is correct?
(a) G 0 nFE 0
2003)
(b)

(b) G 0 nFE 0

(c) G 0 nE 0

(B.P.U.T-

Q.2.

For a cell, the cell reaction is

Mg s Cu 2 aq Cu s Mg 2 aq

If the standard reduction potentials of Mg and Cu are 2.37V and 0.34V find the standard
EMF of the cell.
(B.P.U.T-2004)
ANS:
0
0
0
0
Ecell
Ecathode
Eanode
E Cu0 EMg
0.34 2.37 2.71V

Q.3.

Write down the net cell reaction for

Zn s | ZnO22 , OH | HgO s | Hg

(B.P.U.T-

2004)
ANS:

Zn s 2 H 2O 4OH ZnO22 4H 2O 2e
HgO s 2 H 2O 2e Hg H 2O 2OH

Zn s HgO s 2OH ZnO22 H 2O HgO s

Q.4.

Write the cell reaction in the dry cell.

2004)

(B.P.U.T-

ANS:
At anode:

Zn s Zn2 2e

At cathode:

2MnO2 s H 2O 2e Mn2O3 s 2OH

NH 4 aq OH aq NH 3 g H 2O 2

Zn s 2MnO2 s 2 NH 4 aq 2Cl aq Zn NH 3 2 Cl2 s

Zn s 2MnO2 s 2 NH 4 aq 2Cl aq
Mn2O3 s Zn NH 3 2 Cl2 s 2 H 2O s

Q.5.

Write down the cell reaction for

Pt , H 2 | H || CuCl2 | Cu

(B.P.U.T-2005)

ANS:

H 2 g 2 H 2e
Cu 2 2e Cu s

H 2 g Cu 2 aq 2H aq Cu s
Q.6.

Write down the cell reaction for

Pt , Hg , Hg2Cl2 , Cl , H , H 2 , Pt.

(B.P.U.T-2005)

ANS:
Hg s Hg 2 2e
Hg 2 2Cl Hg 2Cl2
2 H 2e H 2

Hg s 2H 2Cl Hg2Cl2 H 2

Q.7.

ANS:

Write down the cell involving the reaction

1
Fe 2 I 2
Fe3 I
2
2
Fe | Fe3 || I 2 | I

Q.8.

For the electrochemical cell M | M || X | X .

(B.P.U.T-2006)

E 0 X / X 0.33V
E 0 M / M 0.44V
Since oxidation potential X is more than that of M, so the above reaction is spontaneous.
EM0 / M 0.44V
Ex0/ x 0.33V
ANS:
Since oxidation potential x is more than that of M, so the above reaction is spontaneous.
(B.P.U.T-2006)

Q.9.

What is the overall reaction-taking place during the charging of lead acid storage cell?
(B.P.U.T-2006)

ANS:
At cathode:

At anode:

PbSO4 Pb 2 SO42
Pb 2 2e Pb

PbSO4 Pb 2 SO42

Pb 2 2 H 2O PbO2 4 H SO42 2e

2PbSO4 2H 2O Energy Pb PbO2 4H 2SO42

Q.10.

An electrochemical cell is discharged irreversibly at a finite rate. If G is the free

energy change for the discharge reaction and well is the total electrical work output of
the cell during the discharge process, which of the following relations will be true.
(B.P.U.T-2007)

ANS: CuCl G

SUBJECTIVE TYPE
Q.1. Write down the reaction s at the following two electrodes as full cell reactions.
(a) Fe | Fe2 || Fe2 Fe3 | Pt
(B.P.U.T-2003)
ANS:
Fe Fe 2 2e
Fe3 e Fe 2 2

2Fe3 Fe 3Fe2

Q.2.

What is the EMF of the following cell at 250C?

Zn s | Zn2 0.01m ||Ag 0.1m | Ag s

(B.P.U.T-2004)

Given that the standard potentials of Zn s | Zn2 and Ag | Ag half cell are 0.76 and
0.80V respectively.
ANS:
At anode : Zn s Zn2aq 2e
At cathode: Agaq e Ag s 2

Zn s 2 Agaq Zn2aq 2 Ag s
0
0
Ecell
Eanode Ecathode
0.76 0.80

1.56V

Zn2aq
0.0591

Ecell E
log
2

2
Ag aq

0.0591
0.01
1.56
log
2
2
0.1
0
cell

1.56

0.0591
log1
2

1.56

Q.3.

What are the reactions taking place when the storage cell is supplying electrical energy.
(B.P.U.T-2004)

ANS:

When the storage cell supplies electrical energy, then it behaves as a voltaic cell. The
reactions taking place at anode and cathode as.
At anode :

PbSO4 Pb 2 SO42
Pb 2 SO42 PbSO4

At cathod :

PbO2 4 H 2e Pb 2

Pb 2 SO42 PbSO4

Net cell reaction : Pb PbO2 4H 2SO42 2PbSO4 2H 2O Energy

Q.4.

The EMF of the following cell is 0.445V.

Pt , H 2 1atm | H unknown || KCl satd . | HgCl2 | Hg .
Calculate the pH of the solution. (B.P.U.T-2005)

ANS:

The potential of hydrogen electrode involving the reaction H e

1
H 2 is given by
2

0.0591
1
at 250C
log

1
H
i.e. EH 2 0 0.0591 pH
or, EH 2 0.0591 pH
E.m.f of the cell is given by
Ecell Ecalomel EH 2
Ecell Ecalomel 0.0591 pH
E Ecalomel
pH cell
0.0591
0.445 0.2415

0.0591
3.45
E E0

Q.5.

ANS:

The emfs of a cell are 0.35252V and 0.35333V at 250C and 200C respectively. If the
number of electrons involved in the overall reaction is two. Calculate G0 and H 0 at
250C. (B.P.U.T-2005)
Ecell at 250 C Ecell at 200 C 0.35252 0.35333
Ecell

1.62 104V
T
5
5

p
0
G 0 nFEcell
2 96500 0.35252

68 Kg
Again
H 0 G 0 T S 0 68 103 31.27
77318 J
77.318 KJ

Q.6.

The equilibrium constant for the reaction

Ag s Fe3 aq
Ag aq Fe2 aq is 0.335.
Find out the standard electrode potential of Fe3+, Fe2+ | Pt, if the standard reduction
potential of Ag+ | Ag is 0.799V.
(B.P.U.T-2005)

ANS:

For the above reaction the cell can be represented as

Fe2 | Fe3 || Ag | Ag
0
0
Ecell
E Ag
E 0 Fe3 / Fe 2

/ Ag

0.028 0.799 EFe3 / Fe2

0
EFe
0.799 0.028 0.771V
3
/ Fe

Q.7.

The standard reduction potential for Sn2 2e Sn and Sn4 4e Sn are 0.136 and
0.15V respectively. Calculate E0 and G0 for Sn4 2e Sn2 .

Ans:

G0 1 nFE 0

Sn 4 4e Sn

4 96500 0.15
57.9 KJ / mole

Sn Sn 2 2e

2 96500 0.136
26.248 KJ / mole

Sn 4 2e Sn 2
G 0 G 0 G 0 57.9 26.248
1

84.148
E0

Q.8.
ANS:

G
84148

0.436volt
nF
2 96500
0

Write down the cell reaction involved in Nickel Cadmium cell.

At anode:

Cd s OH CdOH 2e
2

2 NiO s 2 H 2O 2e 2 NiOH 2OH

2

REVIEW QUESTIONS
Question 1
What is cell constant? Give its unit.
Answer:

The cell constant is the ratio of the distance between the parallel plates of the cell and the area of the
electrode.
The unit of cell constant is cm1.
Question 2
What is electrode potential?

Answer:
The tendency of an electrode to lose or gain electrons, when it is in contact with its own ions is known
as electrode potential.
Question 3
What is oxidation potential?
Answer:
The tendency of an electrode to gain electrons, when it is in contact with solution of its own ions is
known as oxidation potential.
Question 4
What is reduction potential?
Answer:
The tendency of an electrode to lose electrons, when it is in contact with solution of its own ions is
known as reduction potential.
Question 5
What is electrochemical cell? How can you increase the value of reduction potential of an
electrode?
Answer:
A device used to convert the chemical energy produced in a red-ox reaction into electrical energy is
known as electrochemical cell.
The value of reduction potential of an electrode may be increased by increasing the concentration of
metal ions in contact with metal electrode or increasing the temperature.
Question 6
Why do electrochemical cells stop working after some time?

Answer:

An electrochemical cell produces electrical energy at the cost of red-ox reaction. When the red-ox
reaction is completed, the cell stops working, since it is now incapable of undergoing red-ox reaction
any more.
Question 7
Why is hydrogen electrode not generally used in pH measurement?
Answer:
Hydrogen electrode is not generally used in pH measurement because
(iv)
It is difficult to set up
(v)
It can not be used in red-ox systems
(vi)
It can not be used in presence of Hg, As, S, Fe+3, MnO4, Cr2O3 etc.
Question 8
What is the difference between electrochemical cell and electrolytic cell?
Answer:
Electrochemical cell
Electrolytic cell
(i) Here the chemical energy is (i) Here, the electrical energy from an
converted to electrical energy
external source is used to bring about
the chemical change.
(ii) Here spontaneous redox reaction (ii) Here the redox reaction is nonoccurs
spontaneous and takes place only
when electrical energy is supplied
from outside.
(iii) Here anode is assigned as (iii) Here anode is connected to the
negative and cathode is assigned as positive terminal and cathode to the
positive electrode.
positive terminal of battery.
(iv) Two electrodes are set up in two (iv) Two electrodes are set up in the
different vessels.
same vessel.
Example: Dry cell, lead storage Example: Changing lead storage.
battery.

Worked Out Examples

Electromotive Force

Example 1
Write down the individual electrode reactions and also the total cell reaction for each of the
following cells

++
(a) Pb PbSO4 (S),SO4 Cu Cu

Zn | Zn || H | H 2 Pt

(b)

Solution:
(a) The reduction potential value of Pb PbSO 4 (S),SO 4 = 0.3505V
The reduction potential value of Cu Cu 0.337

++
Hence Pb PbSO 4 (S),SO
4 is anode or negative electrode and Cu|Cu is cathode or positive
electrode.
By convention oxidation occurs in anode or negative electrode

Pb +SO4
PbSO4 + 2e

(1)

and reduction occurs in cathode or positive electrode

Cu 2 2e
Cu

(2)

By adding (1) and (2) we get the all reaction

Pb SO 4
PbSO 4 2e
Cu 2e
Cu
Cu Pb SO 4
Cu PbSO 4

(b) The reduction potential value of Zn|Zn -0.761V

The reduction potential value of H2 | H 0.000V
Hence Zn| Zn is anode or negative electrode and H2 | H is cathode or positive electrode.
By convention oxidation occurs in anode or negative electrode
Zn
Zn 2e

(1)

and reduction occurs in cathode or positive electrode

2H + 2e
H2

(2)

By adding (1) and (2) we get cell reaction

Zn
Zn 2 2e
2H + 2e
H2
Zn+2H +
Zn ++ +H 2

Example 2
Give the cell reactions of the following cells and calculate their standard e.m.f at 25C using the
standard reduction potential value
(a) Hg Hg 2 Cl 2 (S) Cl- Cu ++ Cu
(b) Pt Fe ++ - Fe +++ Cl- AgCl(S)Ag
Solution:
(a) Hg Hg 2 Cl2 (S) Cl- Cu ++ Cu

The standard reduction potential value of Hg Hg 2 Cl2 (S) Cl 0.268V

The standard reduction potential value of Cu Cu ++ = + 0.337V
The reduction potential value of both the electrode is positive but the value of Cu Cu is greater than
the value of Hg Hg 2 Cl 2 (S) Cl- .
So Hg Hg 2 Cl 2 (S) Cl- is the anode or negative electrode and Cu Cu is called cathode or positive
electrode.
By convention oxidation occurs in anode or negative electrode

2Hg + 2Cl-
Hg2Cl2 + 2e

(1)

and reduction occurs in cathode or positive electrode

Cu 2e
Cu

(2)

By adding (1) and (2) we get the total cell reaction

2Hg+2Cl-
Hg 2 Cl2 + 2e
Cu 2e
Cu
2Hg 2Cl Cu
Hg 2Cl 2 +Cu

Hence
ECell = (Ereduction) (Ereduction)

= (0.337 0.268) V
= 0.069V
++
+++
(b) Pt Fe -Fe

Cl- AgCl(S)Ag

The standard reduction potential value of Pt Fe++ - Fe +++ = + 0.771V

The standard reduction potential value of Ag AgCl(S) Cl- = + 0.2223V

The reduction potential value of both the electrode is positive but the value of Pt Fe ++ -Fe +++ is greater
than that value of Ag AgCl(S) Cl- . So Ag AgCl(S) Cl- is anode or negative electrode and
Pt Fe++ - Fe +++ is called cathode or positive electrode.

By convention oxidation occurs at anode or negative electrode

Ag + Cl-
AgCl + e

(1)

and reduction occur at cathode or positive electrode

Fe+++ + e
Fe++

(2)

By adding (1) and (2) we get the total cell reaction

Ag+Cl-
AgCl+e
Fe+++ +e
Fe ++
Ag+Cl- +Fe +++
AgCl+Fe ++

Hence ECell = (Ereduction) (Ereduction)

+

= (0.771 0.223)V
= 0.5487V
Example 3
Calculate the potential of the following electrodes at 25C
(a) Ag Ag + (a=10-5 ) (oxidation)
(b) Pt Fe ++ -Fe +++ (reduction)
(a 0.1)

(a 0.01)

Solution:
(a) The electrode reaction (Oxidation) is
Ag
Ag + +e
E OX =E Ag Ag

RT aAg
ln

aAg

EAg Ag

RT
ln aAg [ aAg 1]

0.799 0.0592 log(105 ) E Ag Ag = - 0.799V

0.799 0.0592 5

 0.799 0.2960
0.503V
(b)

Pt Fe Fe (reduction)

(a 0.1) (a 0.01)

The electrode reaction (reduction) is

Fe+++ + e
Fe++

Electrode potential E red E Fe++ -Fe+++

RT aFe
ln

aFe

aFe

0.771 0.0592 log

aFe

0.771 0.0592 log

0 .1
0.01

0.771 0.0592 log

100
10

0.771 0.0592
0.7118V 0.712 V
Example 4
Compute the cell potentials of the following
Cu Cu (a 0.01) Zn (a 0.1) Zn

Solution:
Cu Cu ( a 0.01) Zn ( a 0.1) Zn
+

The reduction potential value of Cu Cu ++ =+0.337 V

The reduction potential value of Zn Zn ++ =-0.761V
The electrode reaction (reduction) of the left hand electrode is
Cu ++ + 2e
Cu

The electrode potential E red ECu Cu

0.337

a
RT
ln Cu
2 aCu ++

0.0592
log aCu aCu 1
2

0.337 0.0296 log 10 2

0.337 0.0296 2

 0.337 0.0592
0.2778 0.278V
The electrode reaction (reduction) of the right hand electrode is
Zn ++ + 2e
Zn

Hence electrode potential E red E Zn ++ Zn

a
RT
ln Zn
2 aZn ++

RT
ln aZn [ aZn 1]
2
0.0592
0.761
log aZn ++
2

E Zn

0.761 0.0296 log 101

0.761 0.0296
0.7906 V
Hence E Cell E reduction + - E reduction
(0.278 0.7906) V
1.0686 V.

Example 5
Construct electrochemical cell for the following reaction and then find out the standard free energy
change from their e.m.f
1
1
Cl 2 Br
Br2 Cl
2
2
Solution:

Reduction

1 2
Cl Br
2

1
Br2 Cl
2

Oxidation

Here

1
Cl2 + e
Cl
2

In this reaction chlorine (Oxidation number = 0) is reduced to Cl (oxidation number 1) , hence the
positive half will be the Cl2 Cl half cell i.e. (Pt) Cl2 Cl is cathode or positive electrode
1
Br2 e
Again Br
2
Here bromide (oxidation number = - 1) is oxidized to bromine (oxidation number = 0) hence the

negative half cell is Pt Br2 Br .

represented as
Pt,Br2 Br Cl Cl2 (Pt)

The electrochemical cell where the given reaction occurs is

The reduction potential value of Br2 Br 1.0652 V

The reduction potential value of Cl2 Cl 1.359 V
The e.m.f. of the cell

ECell Ereduction Ereduction

(1.359 1.0652) V

= 0.2983 V

Standard free energy change

G nE
1 96500 0.2983 Joule
28351.7 Joules
2.83517 104 Joules .

Example 6

e.m. f .

dE

7.5 104. What is the cell reaction? Calculate H and G and for the reaction?

dT

of

the

cell

Tl TlCl(S) KCl (m = 0.1) Hg 2Cl 2 (S) Hg

The

Solution:
Given cell
Tl TlCl( S ) KCl(m=0.1) Hg 2Cl2 (S) Hg

E Cell = 0.73V

As usual convention LHE is ve and RHE is +ve

Oxidation reaction at LHE(ve) : (Tl Tl e) 2
Reduction reaction at RHE (-ve) : Hg 2Cl2 + 2e = 2Hg + 2Cl

Total cell reaction: 2Tl Hg2Cl2 2Tl 2Cl 2Hg

or, 2Tl Hg 2Cl2 2 TlCl 2Hg

As cell emf is ve, so the reaction is spontaneous

Now we know, G n E Cell
where G free energy of the cell; n no. of electron involve = 2
F 96500 columb, ECell 0.73V
G 2 96500 0.73 Joule
140890 Joule 1.4 105 Joule

We know

G
H G T

T P

is

0.73

volts

and

 n E Cell T.n.

E E

Temp coeff

T T

140890 298 2 96500 7.5 10 4

140890 43135 .5
97754.5 Joule

9.77 104 Joule .

Example 7
At 25C and 1 atm, for the cell (Pt)H 2 HCl (0.1M) AgCl Ag . The
Volt and dE

dT

e.m.f = 0.35252

1.8 104 Volt/C. Calculate G, H and S for the cell reaction.

Solution:
Anode:

H2 2Cl
2HCl 2e

Cathode : 2AgCl 2e
2Ag 2Cl
H 2 2AgCl
2HCl 2Ag
dE
= 1.810-4 volt/C; T=25C=298A
dT
Free energy change G nE
2 96500 0.35252 Joule
E all =0.35252V;

68036.36 Joule
68.036 KJ

dE

Change in enthalpy H n T .
E
dT

2 96500 298 1.8 104 0.35252 Joule

=193000 0.5364 0.35252 Joule
=193000 0.40616 Joule
= 78388.88 Joule
Change in entropy S n

dE
dT

2 96500 1.8 104 Joule

34.74 Joule

Example 8
For the cell H2 | HCl | AgCl, Ag E = 0.222V. If the measured e.m.f is 0.385 V. What is the PH of
HCl solution? PH2 1atm

Solution:
The reaction in the cell
(pt) H2 (1 atm) | HCl | AgCl, Ag is
1
Ag + HCl
2 H 2 + AgCl
RT
ln aHCl PH2 1atm

2RT
0
E cell =E cell

ln a a mean ionic activity

0
E cell =E cell

or,
or,

0
E cell =E cell
0.118 log a

or,

0
E cell =E cell
0.118 PH

or,

0.385 0.222 0.118PH

or,

PH 1.38

at 25C

log a log aH+ PH

Exercise
1. Derive the relation between the specific conductance and the equivalent conductance of a solution.
2. State Kohlrauschs law of independent migration of ions and its usefulness.
3. Explain the nature of conductometric titration curve when (any two)
(i)
CH3COOH by NH4OH
(ii)
CH3COOH by NaOH
(iii)
A mixture of HCl and CH3COOH by NaOH
(iv)
MgSO4 by Ba(OH)2
4. Define Galvanic cell? Give an example of Galvanic cell.
5. What do you mean by reversible and irreversible cells. Explain with suitable example.
6. Deduce thermodynamic expression of e.m.f. of a galvanic cell i.e. Nernst equation.
7. Derive the expression of the change of the following with EMF of the cell
(i) Gibbs free energy
(ii) Enthalpy
(iii) entropy.
8. Describe hydrogen half cell and derive the expression for potential the half cell. How pH of a solution is
determined through hydrogen half-cell.
9. Describe the construction and working principle of the Calomel electrode.

Problems

1. For the following cell write down the cell reaction and calculate the e. m. f at 250C
Pt| Tl+ (a = 0.5) | Tl+++ (a = 0.5) || Ce+++ (a = 0.8) | Ce++++ (a = 0.2) | Pt
E0Tl+++/Tl+ = 1.250 V and E0Ce++++/Ce+++ = 1.610 V
2. For the following cell write down the cell reaction and calculate the e. m. f at 250C
Pt| Fe+2 (a = 0.5), Fe+3 (a = 0.2)|| Cl- (a = 0.001) | AgCl | Ag
E0Fe+++/Fe++ = 0.771 V and E0AgCl/Ag = 0.222 V
3. For the following cell write down the cell reaction and calculate the e. m. f at 250C
Ag | Ag+ (a = 0.1) || Zn++ (a = 0.1) | Zn
E0Ag+/Ag = 0.799 V and E0Zn++/Zn = - 0.763 V
4. Construct electrochemical cell for the following reaction and then find out the standard free energy change
from their e.m.f.

2 Ag + + Cu
2 Ag + Cu +2
0
= 0.337 V
E 0Ag+ /Ag = 0.799 V , ECu
+2
/Cu

5. Construct electrochemical cell for the following reaction and then find out the standard free energy change
from their e.m.f.

Zn + 2H+ (aq)
Zn (aq) + H2 (g)
E0Zn+2 /Zn = 0.761V , E 0H + /H = 0 V
2