UNIT (3)

ELECTRO CHEMISTRY

P -1
1.(a)Define molar conductivity of a substance and describe how for weak and
strong electrolytes, molar conductivity changes with concentration of solute. How
is such change explained? .
(2009,2012, Delhi - 2012)
Ans : Molar conductivity : the conductivity of a solution having one mole of
electrolyte, placed between two electrodes separated by 1 cm apart and having
area of cross section as 1 cm.
Molar conductivity increases sharply for weak electrolyte with decrease in
concentration because both number of ions as well as mobility of ions increases
with dilution.i.e. decrease in concentration where as in case of strong
electrolyte , it increases slightly on dilution because number of ions do not
increase appreciably where as mobility of ions increases.
(b) Define conductivity & limiting molar conductivity of an electrolyte. Discuss
the variation of conductivity with concentration.
Ans : When a solution is placed between two electrodes which is 1 cm apart
and having area of cross section 1 squre cm then it is called conductance.
Geater the number of ions, more is the conductance. On dilution, number of
ions per unit volume decreases,hence conductivity decreases.
When concentration approaches zero, the molar conductivity is known as limiting
molar conductivity and is represented by the symbol m .
2. State the relationship amongst the cell constant of a cell, the resistance of the
solution in the cell and the conductivity of the solution. How is molar conductivity
of a solute related to the conductivity of its solution?
(2009,2011,2012)

Cell constant = specific conductance x observed resistance

m

=kx

1000
C

where C = molar concentration of solution , k =

conductivity
3.What type of a cell is the lead storage battery? Write the anode and the
cathode reactions and the overall reaction occurring in a lead storage battery
while operating.(2009,2010,2011,2012)
Ans : Lead storage battery is a secondary battery .The cell reactions when the
battery is in use are given below:
At Anode

Pb(s) + SO(aq) PbSO(s) + 2e

At Cathode

PbO(s) + SO(aq) + 4H+(aq) + 2e PbSO(s) + 2HO (l )

i.e., overall cell reaction consisting of cathode and anode reactions is:
Pb(s)+PbO(s)+2HSO(aq) 2PbSO(s) + 2HO(l)
On charging the battery the reaction is reversed i.e. PbSO(s) deposited on the
electrode (anode and cathode )is converted back into Pb & PbO and HSO is
regenerated.
4. (a)Suggest two materials other than hydrogen that can be used as fuels in
fuel cells.
P -2
(b) write its one important characteristic.
(c) What is sacrificial protection of Iron .
(d) Metallic and electrolytic conductor
(e)Two difference between electro chemical cell & electrolytic cell .
(f) Two difference between E.M.F. & potential difference .

1
2

Metallic conductor
Flow of electricity takes place
without the decomposition of
material
Flow of electricity is due to flow of
electron
Electro chemical cell
It converts chemical energy into
electrical energy
Anode &cathode are immersed in
two separate compartments
joined by a salt bridge.
E.M.F.
It is the difference of potential
between two electrodes when no
current is flowing through the
circuit.
It is responsible for the flow of
steady current through the circuit.

Electrolytic conductor
Flow of electricity takes place by the
decomposition of material
Flow of electricity is due to flow of
ions.
Electrolytic cell
It converts electrical energy into
chemical energy
Both the electrodes are immersed in
same solution.
Potential difference
It is the difference of potential
between two electrodes when
current is flowing through the circuit.
It is not responsible for the flow of
steady current through the circuit.

5. Corrosion is essentially an electrochemical phenomenon. Explain the reactions

occurring during corrosion of iron kept in an open atmosphere.
(2009)
Ans : The mechanism of rusting an Iron is explained with the help of
Electrochemical theory.Water layer present on the surface of iron dissolve CO of

air and gives Carbonic acid (HCO)

HCO

2 H + CO

This solution work as an electrolyte. In the presence of H ion Fe atoms

undergoes oxidation at any spot. This spot will work as anode.
At Anode: 2 Fe (s) 2 Fe(aq) + 4 e

E(Fe/Fe) = 0.44 V

These electrons reach another spot H ions and dissolved oxygen take up these
electrons and this place work as cathode.
At Cathode : O(g) + 4 H(aq) + 4 e 2 HO (l )
=1.23 V

EH/ O / H O

The overall reaction being:

2Fe(aq) + 2HO(l) + O(g) FeO(s) + 4H(aq)
FeO
rust)

+ x HO

FeO . xHO (hydrated ferric oxide called

P-3

6. State Kohlrausch law of independent migration of ions. Write an expression for

the molar conductivity of acetic acid at infinite dilution according to Kohlrausch
law.
(2010)
Ans : Ans : The law states that molar conductivity at infinite dilution( limiting
molar conductivity )of an electrolyte is equal to the sum of molar conductivity of
anions and cations respectively.
m for acetic acid = mCHCOO + mH.
Application :
ions

To calculate m for any electrolyte from the of individual

7. Predict the products of electrolysis in each of the following: (i) An aqueous

solution of AgNO with silver electrodes. (ii) A dilute solution of HSOwith
platinum electrodes. (iii) An aqueous solution of CuCl with platinum electrodes
(iv) Aqueous NaCl solution .
par
t
(i)

cathode
Ag

anode
Ag

Reaction at cathode & anode

Ag + e

Ag

Ag

Ag

4OH

Ag +e
(ii)

Ag

Ag + e

2HO(l) + O(g) +4e

(iii)

2 H + 2e

2HO(l) + O(g) +4e

4OH

Cu

Cl

(iv)

Cu + 2e

Cu

2Cl

Cl + 2e
Na

Cl

Cl

(v)

Na + e

Na

2Cl

2Cl

Cl + 2e

(vi)

2 H + 2e
Cl + 2e

8. Give reasons:
(i)Rusting of iron is faster in saline water than in ordinary water.
Ans- Saline water contains NaCl. This NaCl helps water to dissociate into H and
OH. Greater the number of H ion ,quicker will be rusting.
(ii)An electrochemical cell stops working after sometime.
Ans- Due to the decrease of concentration of Anodic half cell and increase of
concentration in cathodic half cell,the reduction potential in anodic half cell
decreases and cathodic half cell increases. But at a certain time, it becomes
equal and so flow of current is stopped.
(iii) Porous plate or salt bridge is not required in a lead storage cell.
Ans- Porous plate or salt bridge is required, when oxidising agent and reducing
agent is in liquid state.But in lead storage battery, the oxidising agent (PbO),
reducing agent (Pb) as well as product of redox reaction (PbSO) are solid.Hence
Porous plate or salt bridge is not required
(iv) Direct current is not used in measuring electrolytic conductance.
It is because direct current causes electrolysis of the electrolytic solution due to
which concentration near the electrode changes.
(v) A mercury cell gives constant voltage through out its life
P -4
Ans- The over all reaction of this cell does not contain any ion in
solution.Hence,concentration remains same and therefore voltage.
9. Formulate the Galvanic cell in which the following reaction takes place :
Zn + Ag

Zn + 2Ag

(2008)
State : (i) Which one of its electrodes is negatively charged .

(ii) The reaction taking place at each of its electrode .

(iii) The carriers of the current within this cell . Ans : From Ag to Zn .
(iv) The carrier of the current inside and outside the cell.
Ans : Inside the cell , current is carried by ions and outside the cell , current is
carried by electrons
where n = number of total electrons involved in cell reaction.
(8) At equilibrium , Q = K

and E = 0 i.e. no flow of current .

NUMERICALS
1. (i) The conductivity of a 0.20 M solution of KCl at 298 K is 0.0248 S cm.
Calculate its molar conductivity.
Ans
: 124.0 S cm mol
(2008)
(ii) The molar conductivity of a 1.5 M solution of an electrolyte is found to
be 138.9 S cm mol . Calculate conductivity of this solution. Ans : 0.208 S
cm
(2012)
(iii)The resistance of a conductivity cell containing 0.001 M KCl solution at 298
K is 1500 . What is the cell constant if the conductivity of 0.001 M KCl solution
at 298 K is 0.146 10 S cm?
Ans : 0.219
(2008 , Delhi -2012)
(iv) The electrical resistance of a column of 0.05 M NaOH solution of diameter 1
cm and length 50 cm is 5.55

10 ohm. Calculate its resistivity , conductivity

and molar conductivity.

Ans:

87.135 cm ,0.01148 S cm, 229.6 S cm

mol(2012)
2.(i) Conductivity of 0.00241 M acetic acid solution is 7.896

105

S cm.

Calculate its molar conductivity in this solution. If m for acetic acid be 390.5 S
cm mol, what would be its dissociation constant? Ans : 32.8 S cm mol,

Ka

= 1.86 10

(2008)

(ii)
3.(i) How many mercury moles would be produced by electrolysing 0.10 M
[Hg(NO)] solution with a current of 2 ampere for 3 hours
[Hg = 200.6 g mol-I]
Ans : 0.11
(2010)

P -5
(ii)Three electrolytic cells A, B and C containing solutions of zinc sulphate, silver
nitrate and copper sulphate respectively, are connected in series. A steady
current of 1.5 ampere was passed through them until 1.45 g of silver was
deposited at the cathode of cell B. How long did the current flow? What mass of
copper and what mass of zinc were deposited in the concerned cells?
(Atomic masses of Ag = 108, Zn = 65.4, Cu = 63.5)
Ans : 14.4 mt , 0.426 gram , 0.438 gram
(2008)
4. (i) Calculate the cell voltage for the following Voltaic cell which is set up at
25C :
(a)

Ag (0.001 M) | Ag and Cu (0.10 M) | Cu

E cell

= 0.46 V )

Ans: 0.3125 V
(2009,2012)
(b)Al | Al (0.001 M) and Ni | Ni (0.50 M) [

N i 2 +/
E

= 0.25 V ,

E Al / Al

- 1.66 V ]
Ans : 1.4602 V
(2009)
(c) Pt(s)|Br(l)|Br(0.010 M)||H(0.030 M)| H(g) (1 bar)|Pt(s).
(ii) Calculate the potential for half-cell containing 0.1 M
Cr(aq) ,and 1.0 x

Cr 2 O7

104

E = 1.315 V

K 2 Cr 2 O7 (aq) , 0.2 M

M H (aq) . The half cell reaction is :

(aq) + 14 H+ (aq) + 6e-

2Cr (aq) + 7HO(l)

Ans

: 0.782V
and the standard electrode potential is given as E = 1.33 V
(2011)
(iii) A Voltaic cell is set up at 25C with the following half cells Al(0.001 M)
and Ni (0.50M) . Write an equation for the reaction that occurs when the cell
generates an electric current and determine the cell potential. (Given E Ni/Ni
= - 0.25 V E Al/ Al = - 1.66 V)
Ans : 1.88V
(2011)

(iv) Calculate the cell potential , E at 25C for the cell if the initial concentration
of Ni(NO) is 0.1 molar and the initial concentration of AgNO is 1.0 molar .
+/ Ag

Ag

(Given E Ni/Ni = - 0.25 V ,

1.08V

= 0.80V , Log 10 = 1)

Ans :

(2012)

(v) A strip of Nickel metal is placed in a 1 molar solution of Ni(NO) and a

strip of Silver metal is placed in a 1 molar solution of AgNO . An
electrochemical cell is created when the two solutions are connected by a salt
bridge and the two strips connected by wires to a voltameter .
Write the balanced equations for the overall reactions occurring in the cell and
+/ Ag

calculate cell potential . (Given E Ni/Ni = - 0.25 V ,

Ans : E = 1.08 V

Ag

= 0.80V)

(2012)

(vi) Calculate the potential of H electrode in contact with a solution whose pH is

10.
Ans : E = 0.591V
P -6

r G for the reaction :

(vii) Calculate the equilibrium constant and

(a) Fe (s) + Cd (aq)

Cd2 +/Cd
E

= - 0. 40 V ,

Fe(aq) + Cd(s)

E Fe /Fe

= -0.44 V ]

Ans : 22.57

(20O9)
(b) Ni(s) + 2Ag(aq) Ni(aq) + 2Ag(s)
(2011)

E = 1.05 V

( 1 F = 96500 C mol)

Ans : 202.65 KJmol

(c) In a button cell , widely used in watches , the following reaction takes place
:
Zn(s) + AgO(s) + HO

Zn(aq) + 2Ag(s) + 2 OH(aq)

Z n2+ /Zn
E

= - 0.76 V ,

A g +/ Ag
E

= +0.80 V] Ans : 3.08

KJ/mol ( Delhi 2012)

5. (i) One half cell in a voltaic cell is constructed from a silver wire dipped in
silver nitrate solution of unknown concentration. Its other half-cell consists of a
zinc electrode dipping in 1.0 M solution of Zn (NO). A voltage of 1.48 V is
measured for this cell. Use this information to calculate the concentration of
silver nitrate solution used.
Ans : 0.04 M
[

Z n2+ /Zn
E

= - 0.76 V ,

A g +/ Ag
E

= +0.80 V]

(2009)
(ii) A copper-silver cell is set up. The copper ion concentration is 0.10 M. The
concentration of silver ion is not known. The cell potential when measured was
+/ Ag

0.422 V. Determine the concentration of silver ions in the cell. (Given

= 0.80V ,

E Cu

/Cu

Ag

= 0.34V) (2010)

Cathodic half cell reaction :

2Ag + 2e

2Ag

E =

0.80 V
Anodic half cell reaction:

Cu

2e

Cu

0.34 V
................................................................................................................................
................................................................
Net cell reaction

2Ag + Cu

Cu E = 1.14 V

Let [ Ag] = x M

Q=

2+
Cu

+
Ag

[ Ag ]2 .

(0.1)
(x)

2Ag +

0.0591
n

According to Nernst equation : E = E

Or

Or

0.422 = 1.14

0.1
x

0.0591
2

= Antilog 24.3

log

0.1
x

log Q

i.e. log

Hence x = 7.1 x

0.1
x

102

= 24.3

M.

6.Calcualte mfor acetic acid.

Given that m (HCl) = 426 S cm mol , m (NaCl) = 126 S cm mol
m (CHCOONa) = 91 S cm mol
(2010)
Solution : m(CHCOOH = mCHCOONa
P -7
=

91

m NaCl + m HCl

126 + 426 = 391 Scm mol .

7. Two half cell reaction of an electrochemical cell are given below : (2011)
MnO + 8H + 5e

Sn (aq) 2e

Mn + 4HO

4 +

Sn

(aq)

E = + 1.51 V ;

E = + 0.15 V

Construct the redox equation from the two half cell reactions and predict if this
reaction favours the formation of reactants and products shown in the equation .
Ans : net cell reaction : 2MnO + 16H + 5 Sn (aq) --------> 2 Mn + 8HO +
(aq)

4+
5 Sn

E = 1.66V

Since E of cell is positive . So reaction will take place in forward direction .

8.(i) How much charge is required for the following reductions:
(a) 1 mol of MnO to Mn (b) 40.0 g of Al from molten AlO (c) 1 mol of
FeO to FeO.
Ans : (a) 482500 C (b) 424600 C (c) 96500 C