PART A ( Answer Key)

1.

Mention the differences between electrochemical cell and electrolytic cell.

Difference in electrolytic cell and galvanic cell

Electrolytic cell

Galvanic cell

1. Conversion of electrical energy into

chemical energy

1. Chemical energy into electrical energy

2. The anode carries positive charge vice

versa.

2. The anode carries negative charge Vice

versa.

3. Electrons are supplied to the cell from

the external power supply.

3. Electrons are drawn from the cell.

4. Not a spontaneous reaction. Eocell is 4. Spontaneous reaction. Eocell is +ve,

ve, then the process is nonspontaneous Ex. then the process is spontaneous. eg.
electroplating
Corrosion

2.

Calculate the single electrode potential for magnesium in 0.5 M MgSO4

solution at 25 C. (Given EMg2+/Mg = - 2.37 V)

Mg--------

Mg2+

+ 2 e-

E Mg, Mg2+ = Eo Mg, Mg2+ - 0.0592 / 2 log 0.5

= 2.37+0.0089
= 2.379 V
3.

Define standard electrode potential with an example.

Standard electrode potential (Eo): The measure of tendency of an electrode to lose or gain
electrons, when it is contact with a solution of its own salt of 1 molar concentration at 25o C is
known as standard electrode potential.

4.

When does the electrochemical cell become a standard cell?

A standard cell is one which is capable of giving constant and reproducible e.m.f., and has a
negligible temperature-coefficient of the e.m.f.

5.

Which is a better reducing agent: Li or Na? Give reason.

(Given ELi+/Li = -3.05 V and ENa+/Na = -2.71 V)

Li is a better reducing agent; Li has lower standard reduction potential than Na.
Li undergoes oxidation easily than Na and releases electrons for reduction more readily.
6.

Construct a cell with Fe and Mg at standard conditions and calculate the emf
developed. (EFe/Fe2+ = +0.44 V and EMg2+/Mg = -2.37 V)

Mg/ Mg 2+ // Ag+/Ag
Eo cell = Eo c - Eo a
Eo cell = -0.44+2.37 =1.93 V
7.

Can 1 M CuSO4 solution be stored in a vessel made of Nickel?

(ECu/Cu2+ = -0.34 V and ENi2+/Ni = +0.25 V)

No, CuSO4 cannot be stored in Ni vessel.

Ni is more anodic and undergoes oxidation. Ni vessel dissolves in CuSO4 solution .
8.

Emf of Daniel cell is 1.08 V at 25 C. Calculate the free energy change associated
with it.

G = - nFE = -2x69500x1.08 =-208440 J/mol

PART B
A cell is formed by dipping Zn rod in 0.1M Zn2+ solution and Ag rod in
0.0M Ag+ solution. The standard reduction potentials of Zn and Ag are and

+0.80V

calculate

the

respectively.
emf

of

the

Write
cell.

the

cell

Also

find

representation,
the

cell

equilibrium

0.76V

reactions

constant

for

and
the

reaction.........(1+2+3+2)

a. Cell Reprasentation: Zn/Zn2+ // Ag+/Ag

Cell reaction: Zn + Ag+

--------
Zn2+ +

Eo cell = 0.8 + 0.76 =1.56 V

Ecell = Eo cell - 0.0592 / 2 log 0.1/(10)2
Ecell = 1.6488 V
Go = - nFEo = - RTlnK
Ln K = 2 x 96500 x 1.56 / 8.314x 2.303
Ln K = 301080 /8705.84 = 52.77
K = antilog 52.77 = 5.8884 x 1052

------------- 1 mark
Ag

------------ 2 marks
------------- 1 mark

-------------- 2 marks

--------------- 2 marks

What is electrochemical series? Explain in detail its applications with examples..(2+8)

ELECTROCTREMICAL SERIES: The arrangement of elements in the increasing order of their

std. reduction electrode potential.
Application of electrochemical series
1. Relative ease of oxidation or reduction can be predicted

The metals on the top with ve reduction pot. Can more easily undergo oxidation & act as
anode.

Ex. Zn = -0.76 V favours oxidation reaction

While the metals at the bottom with +ve reduction. Pot. has great tendency to undergo
reduction & act as cathode

Ex. Cu = +0.34 V favours reduction reaction.

2. Cell representation can be predicted

A galvanic cell formed by two half cells with 2 diff. metals.
From EMF series, the metal which is undergoing oxidation or reduction can be predicted
The electrode undergoes oxidation (anode) is written at left
The electrode undergoes reduction (cathode) is written at right

Salt bridge is written in between these two electrodes with in the double line

Ex. For Danial cell with Zn and Cu electrodes

The cell representation
Zn / Zn2+ // Cu2+ / Cu
The cell reaction can also be written
Anodic reaction:
Zn (s)

Zn2+ (aq) + 2 e

Cathodic reaction:
Cu2+ (aq) + 2 e -

Cu (s)

The net reaction:

Zn (s) + Cu 2+ (aq)

Zn 2+ (aq) + Cu (s)

3. Calculation of Std emf (Eocell) of the cell

Oxidn Half cell|| Redn half cell

Eocell= Eocathode Eoanode
Ex. Standard e.m.f (Eocell) of Danial cell
Eocell = EoCu EoZn = +0.34 (-0.76) = +1.1 V
OR
Eocell = Eooxid + Eored

= +0.76 + 0.34 = + 1.1 V

4. Calculation of standard free energy (Go) and equilibrium constant

(Keqm)

Go = - nFEo
Keqm :
Go = - RT ln Keqm
- nFEo = - RT ln Keqm
Eo = __RT_ 2.303 log Keqm
nF
log Keqm = nEo / 0.0592

at 25o C

Keqm = Antilog [nEo / 0.0592]

5. The spontaneity or feasibility of the cell reaction can be predicted
Spontaneity of the redox reaction can be predicted from the e.m.f value of complete cell
reaction.
If Eocell = + ve, Go = - ve, since Go = - nFEo The reaction is feasible.
If Eocell = - ve , Go = + ve. Then the reaction is not feasible.
6. Hydrogen liberating tendency of the metal can be predicted
The metal with low reduction potential will displace H2 from an acid solution.
Zn+ H2SO4

ZnSO4 + H2

The metal with +ve potential will not displace H2 from an acid solution
Ag + H2SO4

no reactn

7. Replacing tendency of a metal (M) by another M:

The metals with low reduction potential undergo oxidation and pass into the solution and the M
ion with high red. potential undergo reduction and get deposits on electrode. Zn, Ni undergo
dissolution in CuSO4 solution and will displace Cu from solution.

8. Corrosion tendency of M:
The metals higher in the series are anodic or more reactive and they are more prone to corrosion.
The metals lower in the series are noble metals and they are less prone to corrosion.