Sri Chaitanya Narayana IIT Academy

Chemistry_Electrochemistry

Sri Chaitanya Narayana IIT Academy

Sri Sarvani Educational Society
COMMON CENTRAL OFFICE_MADHAPUR_HYD

CHEMISTRY : ELECTROCHEMISTRY

Assignment-2
1)
Match the following :Column-I
(A) For a galvanic cell, the Ecell = 0 (p)
(B) The charge carried by
(q)
(C)

electrons
During discharge of
storage battery

(D)

lead(r)

Column-II
19300 coulombs
The cell reactions are at
equilibrium
2F

(s)

2 moles of H2SO4 are consumed

(t)

Cell reactions are reversed

2)
The

chlorate

ion

can

disproportionate

in

basic

solution

according

. The equilibrium concentration of the

a solution initially at 0.1 M in chlorate ion is
(

to

the

reaction

ions resulting from

then a is _______

and
).
PARAGRAPH FOR QUESTION NO 28 - 30

. Following technique is adopted to check suspected drunk drivers. Read the passage and answer the
questions at the end of it.
When suspected drunk drivers are tested with a Breathalyzer, the alcohol (ethanol) in the exhaled breath is
oxidized to ethanoic acid with an acidic solution of potassium dichromate:
The Breathalyzer measures the colour change and produces a meter reading calibrated in terms of blood
alcohol content.
3)
Colour of the testing solution changes from:
4)
If the standard half-cell potential for reduction of ethanoic acid to ethanol is 0.06 V and that of reduction
of
to
1) 1.39 V

is 1.33 V, then
of the reaction taking place in alcohol meter is:
2) 1.27 V
3) -1.39 V
4) -1.51 V

5)
What is the value of E for the reaction when the concentrations of ethanol, ethanoic acid,
are 1.0 M and the pH is 4.00 ?
1) 0.31 V
2) -1.01 V
3) 1.64 V
4) 0.95 V
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PARAGRAPH FOR QUESTION NO 6 8

One of the nicest application of reduction potential is the prediction of the products of reaction
involving elements having several oxidation states. Consider the reaction of iodine with permanganate
in acid solution. The pertinent diagram is shown below

6)
What are species which are unstable towards disproportion
7)
When the reaction between and
carried out with iodide in excess, then the products of the
reaction are
8)
To the acidic permanganate solution, iodide solution is added drop
wise the products of reaction are
1)
2)
3)
4)
PARAGRAPH FOR QUESTION NO 9 11
85.5ml of 0.672 Normal solution of Sodium bromate was prepared. Half cell reaction is
The driving force
diminishes to zero on the way to equilibrium, just as in any other spontaneous
process. Both
and the corresponding cell potential
are zero when the redox reaction comes
to equilibrium.
The Nernst equation for the redox process of the cell may be given as
The key to the relationship is the standard cell potential E0, derived from the standard
free energy change as :
9)
The equilibrium constant Kc for the reaction :
Will be :
10)
The value of the reaction quotient Q, for the cell

is

11)
The standard emf of the cell,
in which the cell reaction is 0.6195 V
at 00C and 0.6753 V at 250C. The value of
of the reaction at 250C is.
12.
A hydrogen electrode placed in a buffer solution of NaCN and HCN in the mole ratio of X : Y and Y :
X has an oxidation electrode potential values E1 and E2 volts respectively at 25C. The pKa value of
HCN is
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(A)

13.

14.

E1 E 2

(B)

E1 E 2

Chemistry_Electrochemistry

0.118
0.118
E

E
E
1 2
2 E1
(C)
(D)
0.118
0.118
The e.m.f. of the cell
Cd (s) + Hg2+ (aq) Cd+2 (aq) + Hg
is given by E = 0.6708 1.02 104 (T 25 V) where T is the temperature in C and E in volts. The
entropy change for the reaction is
(A) 19.69 J deg1
(B) 129.3 kJ
(C) 19.69 kJ deg1
(D) 9.85 J deg1

If E MnO4 / Mn 2 1.51V and E MnO2 /Mn 2 1.23V , then E MnO4 /MnO2 is

(A) +0.28 V
(B) 0.28 V
(C) + 0.74 V
(D) + 1.69 V

15.

A graph is plotted between Ecell of quinhydrone half cell and pH of solution. Intercept is 0.699 V. At
what pH, Ecell will become 0.492 V?
(A) 3.5
(B) 4.2
(C) 7
(D) 10

16.

Calculate the cell EMF in mV for

Pt | H 2 1atm | HCl 0.01M | AgCl(s) | Ag(s) at 298 K

Given : G f (AgCl) = 109.56 kJmol1 and G f (H+ + Cl)(aq) = 130.79 kJ mol1

(A) 456 mV
(B) 654 mV
(C) 546 mV
(D) none of these

17.

At what

Br

does the following cell have its reaction at equilibrium?

CO32
Ag(s) | Ag 2CO3 s | Na 2CO 3 aq || KBr(aq) | AgBr(s) | Ag(s)

Given : Ksp = 8 1012 for Ag2CO3 and Ksp = 4 1013 for AgBr
(A) 1 107
(B) 2 107
(C) 3 107
(D) 4 107
18.

19.

Calculate the EMF of the cell at 298 K

Pt | H2 (1 atm) | NaOH (xM), NaCl (xM) | AgCl (s) | Ag (Given E Cl /AgCl/ Ag 0.222V )
(A) 1.048 V
(B) 0.04 V
(C) 0.604 V
(D) emf depends on x and cannot be determined unless value of x is given

Consider the cell Ag Ag x, C1 Ag y, C 2 Ag. Given that C2 = 10C1 and that x and y are degrees
y
of dissociation in AgNO3 solution of concentrations C1 and C2 in the two half cells, then log in
x
terms of the emf E of the cell at 298 Kelvin will be
E
E
1
(A)
(B)
0.059
0.059
E
E
1
(C)
(D)
.
0.059
0.118

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20.

Chemistry_Electrochemistry

The standard reduction potentials of some half cell reactions are given below :
2
PbO 2 4H 2e
E 1.455V
Pb 2H 2O
2
MnO 4 8H 5e
Mn 4H 2O

E = 1.51 V

3
Ce 4 e
Ce
H 2 O 2 2H 2e
2H 2O
Pick out the correct statement :

(A) Ce+4 will oxidize Mn+2 to MnO 4

E = 1.61V

(C) H2O2 will oxidize Mn+2 to MnO 4

E = 1.71 V

(B) MnO 4 will oxidize Pb to PbO2

(D) PbO2 will oxidize Mn+2 to MnO 4

21.

Identify the incorrect statement (s)

(A) In the spontaneous chemical reaction of a galvanic cell, electrons flow from the cathode to the
anode.

(B) In the equation E cell E RHS E LHS , the E RHS and E LHS are the standard reduction potentials.
(C) Doubling the coefficients in a chemical reaction will square the value of Keq will double G and

will double E cell .

(D) Salt Bridge is essential for all types of cells.

22.

Consider the cell Ag | AgBr | KBr (0.01 M) | | KCl (1M) | AgCl | Ag with EMF 0.059 V. Conclusion
inferred may be
(A) The ratio of the simultaneous solubilities of AgCl and AgBr in pure water is 1000
(B) It is concentration cell
(C) Change in concentration of KCl will not affect EMF.
(D) KSP (AgCl) > KSP (AgBr)
PARAGRAPH FOR QUESTION NO 23 - 25

Comprehension:
The potential of an electrode when each species involved in it exists in the standard state is called its standard
potential. The standard reduction potential of a couple is the measure of its tendency to get reduced. A series
obtained by arranging the various couples in order of their decreasing standard potential is called
electrochemical series. Any of the two couples of this series joined together gives an electrochemical cell in
which reduction occurs at the electrode which occupies the higher position. The standard potential of
hydrogen electrode is taken to be zero by convention.
Given below are the sequence of halfreactions (acidic media) with relevant E0 values in volt at 298K.

0.560
2
0.95
MnO
MnO

2.26 MnO

Mn 3 1.50 Mn 2 1.18 Mn
4
4
2
0
Also given some more E 298 data are:

Fe 2

23.

24.

0.44

Fe (s)

The E0 for MnO

4
(A) 1.054V
(C) 5.27V

0.036

Fe3

Mn 2 is equal to

(B) 1.506V
(D) 7.53V

The value of E0 of reaction:

MnO 4 5Fe 2 8H

Mn
2 5Fe
3 4H 2O
(A) 0.734V
(B) 0.282V
(C) 4.498V
(D) Cant be calculated as concentrations of species are not given.

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25.

Chemistry_Electrochemistry

For the all

Fe(s) | Fe2+ (0.1M) || 100 mL 0.3M HA (pKa =5.2)
mixed with 50 mL 0.4M NaOH | H2 (1 atm), Pt
RT
0.059V and log1020 = 1.3) is equal to
the Ecell at 298 ( 2.303
F
(A) 0.15V
(B) +0.185V
(C) 0.44V
(D) +0.145V

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ELECTROCHEMISTRY 2 KEY & HINTS

1. A- Q ; B-P,R; C- P,R,S ; D- T 2.2

3.3

7.2

13.A 14.D

18.A

8.1

9.1
19.C

10.4

11.1 12.A

20.A,B,C

21.A,B,C,D

4.2

5.4

6.3

15.A 16.A

22.A,B,D

23.B

17.B
24.A

25.D

1)
Hint) Conceptual.
2)
Hint) 2
3)
Hint)
is orange changing to
4)
Hint)

5)
Hint)

6)
Hint)For disproportion of a species its successive reduction potential should be greater than
previous education potential.
7)
Hint)
As,
oxidizes to , it will be absorbed by present in the mixture forms
8)
Hint)
The products of the reaction must be stable in presence at
is not formed as
oxidize it to

and

is also not formed only

is formed.

9)

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Hint)

10)
Hint)

11)
Hint)

12.

13.

16.

17.

0.059
1
log 0.059 pH I
1
H
I

x
= 0.059 pKa1 log
y

E1 =

E2 = + 0.059 pHII = 0.059 pka log

x

E E2
pKa = 1
.
0.118
E
E
S nF here 1.02 104 V degree1
T P
T P
= 2 96500 ( 1.02 104)
= 19.69 Jdeg1.
Cell Reaction : H2 + 2AgCl 2Ag + 2H+ + 2Cl

G cell reaction 2 130.79 2 109.56 42.46 kJ mol1

42460

0.220V
E cell
2 96500
0.059
1
Ecell = +0.220 + 2 log
4
= 456 mV.
0.01

Ag+ (cathod)

1e

Ag anode

K sp AgBr / Br
0.059
Ecell = Ecell + 1 log
K sp Ag 2 CO3 / CO3

18.

Br
CO3

2 10 7 .

1
H 2 AgCl
1e H Ag Cl
2

Ecell = 0.22 +
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0.059
1
log
1
H Cl
.
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19.

20.
22.

Chemistry_Electrochemistry

Cell reaction : Ag (y, C2) Ag (x, C1)

0.059
y C2
10 y
log
0.059 log
E=
.
1
x C1
x
y
E
log
1 .
x 0.059

For 2Mn2+ + 5PbO2 + 4H+ 5Pb + 2MnO4 + 2H2O E = 1.455 1.51 = negative.
Reaction is not fissible.
The cell can be represented as
K sp AgBr
K sp AgCl

| Ag
||
Ag
Ag | Ag+

Cl

Br

Net reaction : Ag C Ag A
+

Ecell = 0.059 log

K sp AgCl

K sp AgBr

K sp AgCl 0.01
1 K sp AgBr

10
103
0.01

Let the simultaneous solubilities of AgCl and AgBr and x and y moles / litre respectively.

AgCl (s) Ag Cl
x y

Ag Br
AgBr (s)
y
x y

Ksp (AgCl) = x y x

Ksp (AgBr) = x y y

24.

K sp AgCl

x
103
y

K sp AgBr
Thus, the simultaneous solution of AgCl is 103 times the simultaneous solution of AgBr.
MnO 4
3 MnO 42 ;
E 0 0.56V

MnO 24
2e
MnO 2

MnO 2 ;
Mn 3 ;

E0

2.26V

E0

0.95V

Mn 3
e Mn 2 ;
E 0 1.50V

MnO 4
5e

25.

Mn 2 ;

E0

0.56 2 2.26 0.95 1.50

= 1.506V
5

Fe2 2e

Fe;
E
0
0.44V
Fe

Fe3 3e;
E 0 0.036V

Fe 2

Fe3

e;

E0

(0.44) 3(0.036)
= 0.772V
1

0
0
E 0cell = E MnO4 ,8H ,Mn 2 E Fe3 ,Fe 2

= 1.506 (+0.772)
= +0.734V

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