1

3. Electrochemistry
Electrochemistry is the study of conversion of chemical energy of redox reaction into electrical energy
(electrochemical cell) and electrical energy into chemical energy (electrolytic cell) (non-spontaneous redox reaction)

Electrochemical cells or Galvanic cells or voltaic cells
The cell that converts the chemical energy of a spontaneous redox reaction into electrical energy.
Eg: Daniell cell.

Daniell cell
This cell converts the chemical energy of a spontaneous redox reaction into electrical energy and has an
electrical potential equal to 1.1 V when concentration of Zn
2+
and Cu
2+
ions is unity.
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)



1. In a galvanic cell, the half-cell in which oxidation
takes place is called anode and it has a negative
potential.
2. The other half-cell in which reduction takes place
is called cathode and it has a positive potential.
3. Electrons flow from negative electrode (anode)
to positive electrode (cathode) in the external circuit.
4. The direction of current flow from cathode to
anode.
5. Inner circuit is completed by the flow ions
through the salt bridge.
(i) Cu
2+
+ 2e
-
Cu (reduction half reaction)
(ii) Zn Zn
2+
+ 2e
-
(oxidation half reaction)
Overall reaction:
Zn
(s)
+ Cu
2+
(aq)
Zn
2+
(aq)
+ Cu
(s)


Function of salt bridge:
Salt bridge is the inverted U tube, contains an inert electrolytic solution-KCl,KNO
3
,NH
4
NO
3
1. To maintain electrical neutrality of the solution in the two half cell.
2. To complete the electrical circuit by allowing the ions to flow from one solution to the other without mixing the
two solutions.

Representation of Galvanic cell


Left (Loss of electrons) Salt Bridge Right (gain of electrons)
Anode Cathode
Oxidation Reduction
Negative Positive
(LOAN)

M (s) M
n+
(conc) M
n+
(conc) M (s)


2

Electrode potential- A potential difference develops between the electrode and the electrolyte which is called
electrode potential.

Standard electrode potential E
0
. The electrode potential of a metal electrode when the concentrations of all
the species involved is unity.

Cell potential (unit- volts) Or Electromotive force (emf) of the cell . The cell potential is the difference between
the electrode potentials of the cathode and anode. It is also called emf of the cell, when no current is flowing through
the cell.
E
cell
= E
right
E
left
: or E
cell
= E
cathode
E
anode


Std cell potentials E
0
cell
= E
0
cathode
E
0
anode

Note: The electrode with higher reduction potential E
0
is reduced, acts as cathode.
The electrode with lower reduction potential E
0
is oxidised, acts as anode.

Q. Write the half cell reactions and depict the cell for the cell reaction.
Cu(s) + 2Ag
+
(aq) Cu
2+
(aq) + 2Ag(s)
Half- cell reactions: Cathode(reduction): 2Ag
+
(aq) +2e

2Ag(s)
Anode (oxidation): Cu(s)Cu
2+
(aq) + 2e

Cu(s) l Cu
2
+(aq) ll Ag+ (aq) l Ag(s)
E
cell
= E
right
E
left
= E
Ag
+
Ag
E
Cu
2+

Cu


Standard hydrogen electrode (SHE)
*Standard hydrogen electrode is the reference electrode whose electrode
potential E
0
is zero. The electrode potential of other electrodes is measured
with respect to it.
*The standard hydrogen electrode consists of a platinum electrode coated
with platinum black. The electrode is dipped in 1M acidic solution (HCl)
and pure hydrogen gas at 1 bar pressure is bubbled through it.
*It represented by Pt(s) H
2
(g) H
+
(aq).
*The reaction is H
+
(aq) + e

1/2 H
2
(g)


Measurement of Electrode potential
At 298 K, a cell is constructed by taking standard hydrogen electrode as anode (reference half-cell) and the other
half-cell as cathode, the emf of the cell gives the electrode potential of the other half-cell. E

anode
for SHE is zero.
E
0
cell
= E

cathode
E

anode

E
0
cell
= E

cathode
0 = E

cathode


Measurement of Electrode potential of Cu
2+/
Cu electrode.
At 298 K, a cell is constructed by taking SHE as anode and the other half-cell Cu
2+/
Cu as cathode, the emf of the
cell gives the electrode potential of the Cu
2+/
Cu half cell. E

anode
for SHE is zero.
E
0
cell
= E

cathode
E

anode

E
0
cell
= E

cathode
0 = E

cathode =
0.34V .
The measured emf of the cell : Pt(s) H
2
(g, 1 bar) H
+
(aq, 1 M) Cu
2+
(aq, 1 M) Cu is 0.34 V

Measurement of Electrode potential of Zn
2+
Zn electrode.
At 298 K, a cell is constructed by taking SHE as anode and the other half-cell Zn
2+
Zn as cathode, the emf of the
3

cell gives the electrode potential of the Zn
2+
Zn half cell. E

anode
for SHE is zero.
E
0
cell
= E

cathode
E

anode

E
0
cell
= E

cathode
0 = E

cathode = --
0.76 V.
The measured emf of the cell : Pt(s) H
2
(g, 1 bar) H
+
(aq, 1 M) Zn
2+
(aq, 1M) Zn is -0.76 V.

The emf of the Daniell cell
Anode : Zn(s) Zn
2+
(aq, 1 M) + 2 e

Cathode: Cu
2+
(aq, 1 M) + 2 e

Cu(s)
The overall reaction of the cell is Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
Emf of the cell = E

cell
= E

R
E

L
= 0.34V ( 0.76)V = 1.10 V
Note: Metals like platinum or gold are used as inert electrodes. They do not participate in the reaction but provide
their surface for oxidation or reduction reactions and for the conduction of electrons.

Nernst equation:
For the electrode reaction: M
n+
aq)
+ ne M
(s)

Electrode potential at any concentration is
E
(Mn+/M)
= E

(Mn+/M)
2.303RT log 1 , concentration of solid M is taken as unity ,
nF [M
n+
]
E
(Mn+/M)
= E

(Mn+/M)
0.059 log 1
n [M
n+
]
R is gas constant (8.314 JK mol
1
), F is Faraday constant (96487 C mol
1
), T is temp in kelvin
For a reaction,
E
(cell)
= E

(cell)
2.303RT log [product] Consider only ions
nF [reactant]
substituting the values of R, F and T = 298 K , n= no. of e- involved
E
(cell)
= E

(cell)
0.059 log [product]
n [reactant]
Q. For the reaction: Cu
2+
(aq, 1 M) + 2 e

Cu(s)
E
(Cu2+/ Cu)
= E

(Cu2+/ Cu )
0.059/2 log 1/[Cu
2+
]

Q. For the reaction: Zn(s) Zn
2+
(aq, 1 M) + 2 e

E
(Zn2+/ Zn)
= E

(Zn2+/ Zn )
0.059/2 log 1/[Zn
2+
]

Q. For the reaction: Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
E
(cell)
= E

(cell)
2.303RT/nF log[Zn
2+
]/[Cu
2+
]
E
(cell)
= E

(cell)
0.059/2 log [Zn
2+
]/[Cu
2+
]
E(cell) depends on the concentration of both Cu
2+
and Zn
2+
ions. It increases with increase in the concentration of
Cu
2+
ions and decrease in the concentration of Zn
2+
ions

Q. Ni(s) Ni
2+
(aq) Ag
+
(aq) Ag
The cell reaction is Ni(s) + 2Ag
+
(aq) Ni
2+
(aq) + 2Ag(s)
The Nernst equation can be written as
E
(cell)
= E

(cell)
2.303 RT/2F log [Ni
2+
]/[Ag
+
]
2

E
(cell)
= E

(cell)
0.059/2 log [Ni
2+
]/[Ag
+
]
2


Relationship between equilibrium constant Kc and standard cell potential E

(cell)
.
E

(cell)
= 0.059/n log K
C
At equilibrium there is no change in the concentration of Cu
2+
and Zn
2+
ions, voltmeter
gives zero reading. E
(cell)
= 0
4

Relation between E
(cell)
and Gibbs Energy or max.work done by a galvanic cell

r
G
0
= -nFE
0
(cell)


Relation between Gibbs energy
r
G
0
and equilibrium constant Kc

r
G = - 2.303RT log Kc



Resistance R = l/A where R= resistance, l =length, A= area of cross section, (Greek, rho)=, resistivity.
SI unit of = ohm metre ( m or cm)

Conductance, G. The inverse of resistance R, is called conductance, G.
G = 1/R = A/ l = k A/l
G=k A/l
SI unit of conductance is siemens, S and is equal to ohm
1
(also known as mho) or
1
.

Conductivity k (kappa) : The inverse of resistivity, called conductivity (specific conductance).
The SI units of conductivity k are S m
1
or S cm
1
.

Relation between resistance R, conductivity k and cell constant G *
R k = G*

Metallic or electronic conductance Electrolytic or ionic conductance:
(1)Conductance due to the movement of electrons.
(ii) it decreases with increase of temperature because
kernels starts vibrating which hinder the flow of
electrons).
(iv) the composition of the metallic conductor
remains unchanged.

i) Conductance of electricity by ions
(v) it increases with the increase of temperature
because dissociation increases and no. of ions increases)
(vi) Passage of direct current change its composition
due to electrochemical reactions.

Measurement of the Conductivity of Ionic Solutions
Q. State the problems faced while measuring the conductivity of ionic solutions and explain how to overcome
these problems.
Unknown resistance can be measured using a Wheatstone bridge. For measuring the resistance of an ionic solution
we face two problems
.(i) Passing direct current (DC) changes the composition of the solution which is solved by using an alternating
current (AC) .
(ii) A solution cannot be connected to the bridge like a metallic wire or other solid conductor which is solved by
using a conductivity cell.

Q. Define conductivity of a solution. How does conductivity of solution vary with concentration of electrolyte
(dilution) ?
The conductivity of a solution at any given concentration is the conductance of one unit volume of solution kept
between two platinum electrodes with unit area of cross section and at a distance of unit length. [G = A /l = (both
A and l are unity)]

Conductivity always decreases with decrease in concentration both, for weak and strong electrolytes.
Reason: The number of ions per unit volume that carry the current in a solution decreases on dilution.

5

Q. Define molar conductivity of a solution. How does molar conductivity of solution vary with concentration
of electrolyte (dilution) ?
Molar conductivity of a solution can be defined as conducting power of all the ions produced by dissolving
one mole of an electrolyte in solution. (or)
Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution
containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of unit
length. Therefore,

m
= A /l = V Since l = 1 and A = V ( volume containing 1 mole of electrolyte)

* Molar conductivity increases with decrease in concentration ( on dilution).
Reason :The total volume(V) of solution containing one mole of electrolyte also increases.(decrease in is
more than compensated by increase in its volume).

*Variation of
m
for

strong electrolytes

m
increases slowly with dilution for strong electrolytes
Reason: Strong electrolytes are completely ionized in solution at all concentrations. On dilution, the ions move
apart due to the decrease in interionic attractions and mobility of ions increases.

*Variation of
m
for

weak electrolytes (acetic acid)
On dilution, m increases steeply for weak electrolyte.
Reason: On dilution, the degree of dissociation increases and consequently the number of ions in total volume
of solution that contains 1 mol of electrolyte increases and mobility of ions increases.

Q. Relation between conductivity and molar conductivity
Molar conductivity ,m = 1000
molarity
m = 1000 or m = 1000
M c
unit of m =S cm
2
mol
1
, =S cm
1
,molarity= mol/L

Q. Define Limiting molar conductivity (m).
Limiting molar conductivity (m) is the molar conductivity when concentration of solution approaches
zero. (Or) molar conductivity at infinite dilution.
In case of strong electrolytes,
m
can be obtained by extrapolation of
m
to zero concentration.

m
=
m
A c
12

If we plot
m
against c
1/2
, we obtain a straight line with intercept
m

and slope = A.
In case of weak electrolytes,
m
can be obtained from Kohlrauschs law
of independent migration of ions.

Kohlrausch law of independent migration of ions.
The law states that limiting molar conductivity of an electrolyte can be represented as the sum of the
individual contributions of the anion and cation of the electrolyte.
In general, if an electrolyte on dissociation gives v
+
cations and v

anions then its limiting molar conductivity is

given by:
m
=
+

+
+

Here,
+
and

are the limiting molar conductivities of the cation and anion respectively.
Applications of Kohlrausch law
6

(i) to calculate m for weak electrolyte.

(ii) to determine dissociation constant of weak electrolyte K
a
=c
2
/(1 )
where c is the concentration
(iii) To calculate the degree of dissociation for weak electrolyte =
m
/ m

Quantitative Aspects of Electrolysis--Faradays Laws of Electrolysis
1. Faradays First Law
The amount of chemical substance deposited (m) at any electrode during electrolysis by a current is proportional to
the quantity of electricity (Q) passed through the electrolyte.
m= Z Q = Z I t = At.mass x I x t Z = Electrochemical equivalent ( At. Mass / n F ) , Q = It
n F

2. Faradays Second Law
When same quantity of electricity is passed through different electrolytic solution connected in series, the
amounts of different substances produced at the electrodes are proportional to their chemical equivalent
weights
(Eq. wt = Atomic Mass of Metal Number of electrons required to reduce the cation).
m
1
/ m
2
= Eq. wt
1
/ Eq wt
2
; Eq. wt = At. Mass / n
Mass Cu deposited/ Mass of Ag deposited = Equivalent mass of Cu/Equivalent mass of Ag
The amount of electricity (or charge) required for oxidation or reduction ,Q = n F
Q = Massx nF/ Molar.mass (n = no. of electrons, F = Faraday, 96500Cmol
-1

Ag
+
(aq) + e Ag(s) Q = n F= 1x 96500C
Mg
2+
(l) + 2e

Mg(s) Q = n F= 2x 96500C
Al
3+
(l) + 3e

Al(s) Q = n F= 3 x 96500C

Products of Electrolysis
Note: The species with higher reduction potential E
0
is reduced, acts as cathode.
The species with lower reduction potential E
0
is oxidised, acts as anode.

1.Electrolysis of aqueous sodium chloride solution During the electrolysis of aqueous sodium chloride solution,
the products are NaOH, Cl
2
and H
2
.
At the cathode there is competition between the following reduction reactions:
Na
+
+ e

Na ; E

(Cell)
=2.71V
H
2
O + e

12H
2
+ OH

;E

(Cell)
=0.83V
The reaction with higher value of E

is preferred at the cathode during electrolysis is:

H
2
O + e

12H
2
+ OH

At the anode the following oxidation reactions are possible:
Cl

12 Cl
2
+ e

E
0
cell = 1.36 V
2H
2
O O
2
+ 4H
+
+ 4e

E
0
( cell )
= 1.23 V
The reaction at anode with lower value of E

is preferred and therefore, water should get oxidised in preference to

Cl

. On account of overpotential of oxygen,

Cl

12 Cl
2
+ e

is preferred.

7

Thus, the net reactions may be summarised as:
Cathode: H
2
O + e

12 H
2
+OH

; Anode: Cl

12 Cl
2
+ e

Net reaction: NaCl + H
2
O Na
+
+ OH

+ 12H
2
+ 12Cl
2


Q. E
0
for the oxidation of Cl

ions is more positive than that of water, even then in the electrolysis of aqueous
sodium chloride, why is Cl

oxidised at anode instead of water?

Oxidation of water to O
2
at anode requires overpotential.

Predict the Product of Electrolysis
Electrolyte Cathode (High E
0
value) Anode (Low E
0
value - Oxidised)
1. Aq. NaCl
NaCl +H
2
O NaOH + 12H
2
+
12Cl
2

H
2
(H
2
O + e

12 H
2
+OH

)

Cl
2
(Cl

12 Cl
2
+ e

) Due to
overpotential, O
2
will not be liberated.
2. Molten NaCl Na (Na
+
+ e

Na) Cl
2
( Cl

12Cl
2
+e

)
3. Aq CuSO
4
soln(Cu electrode) Cu (Cu
2+
+ 2 e

Cu) Cu
2+
(Cu Cu
2+
+ 2 e

)
4.Aq AgNO
3
soln(Ag electrode) Ag (Ag
+
+ e

Ag) Ag
+
( Ag Ag
+
+ e

)
5.Aqueous CuCl
2
using Pt
electrode
Cu (Cu
2+
+ 2 e

Cu) Cl
2
(Cl

12 Cl
2
+ e-

)
Due to overpotential, O
2
will not be
liberated. (oxidation of H
2
O to O
2
at
anode requires overpotential )
6.Aq AgNO
3
soln (Pt electrode) Ag (Ag
+
+ e

Ag) O
2
(2H2O O
2
+ 4H
+
+ 4e

)
7.Dilute H
2
SO
4
( Pt electrode) H
2
(H
+
+ e

12 H
2
) O
2
(2H
2
O O
2
+ 4H
+
+ 4e

)
8. Conc. H
2
SO
4
(Pt electrode) H
2
(H
+
+ e

12 H
2
) S
2
O
8
2
(2SO
4
2
S
2
O
8
2
+ 2e

)
Battery
Any battery may have one or more than one electrochemical cell connected in series used as a source of
electrical energy where the chemical energy of the redox reaction is converted into electrical energy

Types of batteries.
Primary Batteries : In the primary batteries, the electrode reaction occurs only once and after use over a period of
time battery becomes dead and cannot be reused again. Eg: Dry cell, Mercury cell.
Secondary batteries: A secondary cell after use can be recharged by passing current through it in the opposite
direction so that it can be used again. A good secondary cell can undergo a large number of discharging and
charging cycles Eg: lead storage battery, Nickel-Cadmium storage cell.

Dry cell / Leclanche cell It is used commonly in our transistors and clocks.
Anode: A zinc container
Cathode : A carbon (graphite) rod surrounded by powdered manganese dioxide and carbon.
Electrolyte: A moist paste of ammonium chloride (NH
4
Cl) and zinc chloride (ZnCl
2
) is filled in the space between
the electrodes.
Anode: Zn(s) Zn
2+
+ 2e

Cathode: MnO
2
+ NH
4
+
+ e

MnO(OH) + NH
3

Complex formed: [ Zn (NH
3
)
4
]
2+
.
Dry cell does not have definite life because NH
4
Cl being acidic corrodes the Zn container, even when not in use.

Mercury cell, It is suitable for low current devices like hearing aids, watches, etc.
Anode: Zinc mercury amalgam
Cathode: A paste of HgO and carbon.
Electrolyte: A paste of KOH and ZnO.
8

Anode: Zn(Hg) + 2OH

ZnO(s) + H
2
O + 2e

Cathode: HgO + H
2
O + 2e

Hg(l ) + 2OH

Overall reaction : Zn(Hg) + HgO(s) ZnO(s) + Hg(l )

Advantage: The cell potential remains constant during its life as the overall reaction does not involve any ion
in solution whose concentration can change during its life time.

Lead storage battery : It is commonly used in automobiles and invertors.
Anode: A lead anode
Cathode: Lead dioxide (PbO
2
)
Electrolyte: A 38% solution of sulphuric acid.
Anode: Pb + SO
4
2
PbSO
4
+ 2e

Cathode: PbO
2
+ SO
4
2
+ 4H
+
+ 2e

PbSO
4
+ 2H
2
O
Overall cell reaction (when it is in use): Pb +PbO
2
+2H
2
SO
4
2PbSO
4
+ 2H
2
O
On charging: 2PbSO
4
+ 2H
2
O Pb+PbO
2
+2H
2
SO
4


Nickel- cadmium cell has longer life than the lead storage cell but more expensive to manufacture.
Overall reaction during discharge is: Cd +2Ni(OH)
3
CdO +2Ni(OH)
2
+H
2
O

Fuel cell
Galvanic cells that are designed to convert the energy of combustion of fuels like hydrogen, methane,
methanol, etc. directly into electrical energy are called fuel cells. Eg: H
2
-O
2
fuel cells.
Eg: H
2
-O
2
fuel cells which uses the reaction of hydrogen with oxygen to form water. The cell was used for
providing electrical power in the Apollo space programme.

Cathode: O
2
+ 2H
2
O + 4e

4OH

Anode: 2H
2
+ 4OH

4H
2
O + 4e

Overall reaction: 2H
2
+ O
2
2 H
2
O
Advantages:
1. Continuous source of energy: The cell runs continuously as long as the reactants (fuels) are supplied. There is no
electrode materials to be replaced.
2. High efficiency:
3. Fuel cells are pollution free
Corrosion:

Anode: 2 Fe 2 Fe
2+
+ 4 e


Cathode: O
2
+ 4 H
+
+ 4 e

2H
2
O
Overall reaction : 2Fe+O
2
+ 4H
+
2Fe
2+
+ 2 H
2
O
Atmospheric oxidation:
2Fe
2+
+ 2H
2
O + O
2
Fe
2
O
3
+ 4H
+


9

Mechanism of rusting of iron:
Corrosion of iron occurs in presence of water and air. Corrosion is an electrochemical phenomenon. At a
particular spot of an object made of iron, oxidation takes place and that spot behaves as anode.
Anode: 2 Fe 2 Fe
2+
+ 4 e


Electrons released at anodic spot go to another spot on the metal and reduce oxygen in presence of H
+.
This spot
behaves as cathode.
Cathode: O
2
+ 4 H
+
+ 4 e

2H
2
O
Overall reaction : 2Fe+O
2
+ 4H
+
2Fe
2+
+ 2 H
2
O
The ferrous ions are further oxidised by atmospheric oxygen to ferric ions which come out as rust in the form of
hydrated ferric oxide(Fe
2
O
3
. x H
2
O) .
Atmospheric oxidation: 2Fe
2+
+ 2H
2
O + O
2
Fe
2
O
3
+ 4H
+


Prevention of corrosion.
(i) painting, greasing. (ii) coating the metal with Zn, tin.(iii) Cathodic protection: Iron article is conneted with more
active metals like Mg or Zn. Mg will be oxidized and it protect the iron.

Q. Alkaline medium inhibits rusting of iron?.
Rusting of iron takes place in presence of H+ ions. Alkaline medium neutralizes the H+ ions and thereby
inhibits rusting.

Q. Rusting of iron is quicker in saline water .Why?
In saline water, dissociation of H
2
O is more. There is more H+ ions, hence quicker the rusting.

Q What would happen if protective tin coating over an iron bucket is broken in some places?
Fe is more reactive (less E
0
value) than tin, Fe is oxidized and undergo rusting.

Q. Iron does not rust even if zinc coating is broken in a galvanized pipe. Why?
Zinc is more reactive (less E
0
value) than Fe, Zn is oxidized and undergoes corrosion, prevent iron from rusting.
Q. Depict the galvanic cell in which the cell reaction is Cu + 2Ag
+
2Ag + Cu
2+

Cu|Cu
2+
|| Ag
+
|Ag
Q. Write the Nernst equation for the cell reaction in the Daniel cell. How will the E
Celll
be affected when
concentration of Zn
2+
ions is increased?
. Zn + Cu
2+
Zn
2+
+ Cu E
Cell
= E
Cell

(0.059/2) log [Zn

2+
]/[Cu
2+
]
E
Cell
decreases when concentration of Zn
2+
ions, [Zn
2+
] increases.

Reader Exercises - Example
3.1 Represent the cell in which the following reaction takes place
Mg(s) + 2Ag
+
(0.0001M) Mg
2+
(0.130M) + 2Ag(s) Calculate its E
(cell)
if E

( cell )
= 3.17 V.
MgMg
2+
(0.130M)Ag
+
(0.0001M)Ag
E
(cell)
= E

( cell )
0.059 /n log [Mg
2+
]/[Ag
+
]
2

=3.17 V 0.059V/2 log 0.130/(0.0001)
2
= 3.17 V 0.21 V = 2.96 V.

3.2 Cal. the equilibrium constant :Cu(s) + 2Ag
+
(aq) Cu
2+
(aq) + 2Ag(s) E
( cell )
= 0.46 V
E

(cell)
= 0.059 /n log K
C

0.059 /2 log K
C
= 0.46V
log K
C
= 0.46 V 2/0.059V = 15.6
K
C
=antilog 15.6 = 3.92 10
15


10

3.3 The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy
for the reaction:Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s)
Solution
r
G

= nFE
0
(cell)

n = 2, F = 96500 C mol
1
and E
( cell )
= 1.1 V
Therefore,
r
G

= 2 1.1V 96500 C mol

1
= 21227 J mol
1


3.4 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. Conductivity of 0.1 mol L
1
KCl soln is 1.29S/m.

3.5. 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 10
3
ohm. Calculate its resistivity, conductivity and molar conductivity.
A = r
2
=3.14 x 0.5
2
= 0.785 cm
2
; l = 50 cm
R = l/A or = RA/l = 5.55 10
3
0.785 cm
2
/50 cm = 87.135 cm
Conductivity = = 1/ = (1/87.135) S cm
-1
=0.01148 S cm
-1

Molar conductivity,
m
= ( 1000 ) / c = 0.01148 1000 / 0.05 = 229.6 S cm
2
mol
1


3.7. Calculate
m
for CaCl
2
and MgSO
4
from the data given in Table 3.4

m(CaCl)
=
Ca
2+
+ 2
Cl

= 119.0 S cm
2
mol
1
+ 2(76.3) S cm
2
mol
1
= (119.0 + 152.6) S cm
2
mol
1
= 271.6
S cm
2
mol

m(MgSO4
) =
Mg
2+
+ 2
SO
2
4
= 106.0 S cm
2
mol
1
+ 160.0 S cm
2
mol
1
= 266 S cm
2
mol
1
.

3.8.
m
for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm
2
mol
1
respectively. Cal. for HAc.

(HAc)
=
(HCl)
+
(NaAc)

(NaCl)
= (425.9 + 91.0 126.4 ) S cm
2
mol
1
= 390.5 S cm
2
mol
1
.

3.9 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 cm
2
mol
1
.

m
= /c =4.9510
5
S cm
1
/0.001028 mol L
1
1000cm
1
/ L =48.15 cm
2
mol
1

=
m
/
m
=48.15 S cm
2
mol
1
/390.5 S cm
2
mol
1
= 0.1233
= c
2
/(1- ) 0.001028 mol L
1
(0.1233)
2
/ 1- 0.1233 = 1.78 10
5
mol L
1


3.10. A solution of CuSO
4
is electrolysed for 10 minutes with a current of 1.5 amperes. What is the
mass of copper deposited at the cathode?
t = 10x60= 600 s charge = current time = 1.5 A 600 s = 900 C
Cu
2+
(aq) + 2e

= Cu(s) n = 2.
Mass of Cu deposited = z I t =(63 g mol
1
1.5 x 600 C)/(2 96500 C mol
1
) = 0.2938 g.

Intext Questions
3.1 How would you determine the standard electrode potential of the system Mg
2+
|Mg?
3.2 Can you store copper sulphate solutions in a zinc pot?
3.3 Consult the table of standard electrode potentials and suggest three substances that can
oxidise ferrous ions under suitable conditions
3.4 Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.
3.5 Calculate the emf of the cell in which the following reaction takes place
Ni(s) + 2Ag
+
(0.002 M) Ni
2+
(0.160 M) + 2Ag(s) Given that E

(Cell)
= 1.05 V
3.6 The cell in which the following reaction occurs:
2Fe
3+
( aq ) + 2I

( aq ) 2Fe
2 +
( aq ) + I
2
( s ) has E
cell
= 0.236 V at 298 K. Calculate the standard
Gibbs energy and the equilibrium constant of the cell reaction.
3.7 Why does the conductivity of a solution decrease with dilution?
3.8 Suggest a way to determine the
m
value of water.
11

3.9 The molar conductivity of 0.025 mol L1 methanoic acid is 46.1 S cm
2
mol
1
. Cal its degree of
dissociation and dissociation constant. Given (H
+
)=349.6 Scm
2
mol
1
and (HCOO

) = 54.6 S cm
2

mol


3.10 If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons
would flow through the wire?
3.11 Suggest a list of metals that are extracted electrolytically.
3.12 Consider the reaction: Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
3+
+ 8H
2
O
What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr
2
O
7
2
?
3.13 Write the chemistry of recharging the lead storage battery, highlighting all the materials that
are involved during recharging.
3.14 Suggest two materials other than hydrogen that can be used as fuels in fuel cells.
3.15 Explain how rusting of iron is envisaged as setting up of an electrochemical cell.

Exercises
3.1 Arrange the following metals in the order in which they displace each other from the solution
of their salts.Al, Cu, Fe, Mg and Zn.
3.2 Given the standard electrode potentials, K
+
/K = 2.93V, Ag
+
/Ag = 0.80V, Hg
2+
/Hg = 0.79V,
Mg
2+
/Mg = 2.37 V, Cr
3+
/Cr = 0.74V Arrange these metals in their increasing order of reducing
power.
3.3 Depict the galvanic cell Zn(s)+2Ag
+
(aq) Zn
2+
(aq)+2Ag(s) takes place. Show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.
3.4 Cal. the standard cell potentials of galvanic cell in which the following reactions take place:
(i) 2Cr(s) + 3Cd
2+
(aq) 2Cr
3+
(aq) + 3Cd
(ii) Fe
2+
(aq) + Ag
+
(aq) Fe
3+
(aq) + Ag(s)
Calculate the
r
G

and equilibrium constant of the reactions.

3.5 Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)|Mg
2+
(0.001M)||Cu
2+
(0.0001 M)|Cu(s)
(ii) Fe(s)|Fe
2+
(0.001M)|| H
+
(1M)|H
2
(g)(1bar)| Pt(s)
(iii) Sn(s)|Sn
2+
(0.050 M)||H
+
(0.020 M)|H
2
(g) (1 bar)|Pt(s)
(iv) Pt(s)|Br
2
(l )|Br

(0.010 M)||H
+
(0.030 M)| H
2
(g) (1 bar)|Pt(s).
3.6 In the button cells widely used in watches and other devices the following reaction takes
place:
Zn(s) + Ag
2
O(s) + H
2
O(l ) Zn
2+
(aq) + 2Ag(s) + 2OH

(aq) Determine
r
G
0
and E
0
for the reaction.
3.7 Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their
variation with concentration.
3.8 The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm
1
. Calculate its molar
conductivity.
3.9 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 298K is 0.146 10
3
S cm
1
.
3.11 Conductivity of 0.00241 M acetic acid is 7.896 10
5
S cm
1
. Calculate its molar0 conductivity
and if
m
for acetic acid is 390.5 S cm
2
mol
1
, what is its dissociation constant?
3.12 How much charge is required for the following reductions:
(i) 1 mol of Al
3+
to Al. (ii) 1 mol of Cu
2+
to Cu. (iii) 1 mol of MnO

4
to Mn
2+
.
3.13 How much electricity in terms of Faraday is required to produce
(i) 20.0 g of Ca from molten CaCl
2
. (ii) 40.0 g of Al from molten Al
2
O
3
.
3.14 How much electricity is required in coulomb for the oxidation of (i) 1 mol of H
2
O to O
2
. (ii) 1
mol of FeO to Fe
2
O
3
.
12

3.15 A solution of Ni(NO
3
)
2
is electrolysed between platinum electrodes using a current of 5
amperes for 20 minutes. What mass of Ni is deposited at the cathode?
3.16 Three electrolytic cells A,B,C containing solutions of ZnSO
4
, AgNO
3
and CuSO
4
,
respectively are connected in series. A steady current of 1.5 amperes was passed through them
until 1.45 g of silver deposited at the cathode of cell B. How long did the current flow? What mass
of copper and zinc were deposited?
3.17 Using the standard electrode potentials given in Table 3.1, predict if the reaction between the
following is feasible:
(i) Fe
3+
(aq) and I

(aq) (ii) Ag
+
(aq) and Cu(s) (iii) Fe
3+
(aq) and Br

(aq) (iv) Ag(s) and Fe

3+
(v) Br
2
(aq)
and Fe
2+
(aq)
3.18 Predict the products of electrolysis in each of the following:
(i) An aqueous solution of AgNO
3
with silver electrodes.
(ii) An aqueous solution of AgNO
3
with platinum electrodes.
(iii) A dilute solution of H
2
SO
4
with platinum electrodes.
(iv) An aqueous solution of CuCl
2
with platinum electrodes.

Formula

Std cell potentials E
0
cell
= E
0
cathode
E
0
anode
E

(cell)
= 0.059/n log K
C

Std gibbs free energy,
r
G
0
= -nFE
0
(cell

r
G = - 2.303RT log Kc
R = l/A Conductance, G=k A/l
R k = G*, cell constant (l/A) Molar conductivity,
m = 1000 or m = 1000
M c
unit of m =S cm
2
mol
1
, =S cm
1
,
molarity= mol/L
m
1
/ m
2
= Eq. wt
1
/ Eq wt
2
Eq. wt = At. Mass / n
m= Z Q = Z I t = At.mass x I x t
n F
Q = It Z = At. Mass / n F
The amount of electricity (or charge) required
for oxidation or reduction ,Q = n F
Q = Massx nF/ Molar.mass
n = no. of electrons, F = Faraday, 96500Cmol
-1

Dissociation constant, K
a
=c
2
/(1 ) Degree of dissociation, =
m
/ m
Nernst Equation
For the electrode reaction: M
n+
aq)
+ ne M
(s)

Electrode potential at any concentration is
E
(Mn+/M)
= E

(Mn+/M)
2.303RT log 1 , concentration of solid M is taken as unity ,
nF [M
n+
]
E
(Mn+/M)
= E

(Mn+/M)
0.059 log 1
n [M
n+
]
R is gas constant (8.314 JK mol
1
), F is Faraday constant (96487 C mol
1
), T is temp in kelvin
For a reaction,
E
(cell)
= E

(cell)
2.303RT log [product] Consider only ions
nF [reactant]
substituting the values of R, F and T = 298 K , n= no. of e- involved
E
(cell)
= E

(cell)
0.059 log [product]
n [reactant
13