Electrochemistry Neeraj Swarnkar

SAMCQ

1. H
2
(g) and O
2
(g), can be produced by the electrolysis of water. What total volume (in
L) of O
2
and H
2
are produced at STP when a current of 30 A is passed through a
K
2
SO
4
(aq) solution for 193 min.?
(a) 20.16 (b) 40.32 (c) 60.48 (d) 80.64

2. The standard EMF of Mn | Mn
2+
electrode is +1.18 V at 25C. The
2
Mn(s)|Mn(OH) (s)|OH
E

is (Given
Mn(OH)
2
sp
K = 2 10
13
and log 2 = 0.3)
(a) 1.56 V (b) 1.18 V (c) 0.805 V (d) none of these

3. The standard reduction potential of a silver chloride electrode is 0.2 V and that of a
silver electrode is0.79V. The maximum amount of AgCl that can dissolve in 10
6
L of
a 0.1 M AgNO
3
solution is
(a) 0.5mmol (b) 1.0 mmol (c)2.0mmol (d) 2.5mmol

4. Twolitre solution of a buffer mixture containing 1.0 MNaH
2
PO
4
and 1.0 M Na
2
HPO
4

is placed in two compartments (one litre in each) of an electrolytic cell. The platinum
electrodes are inserted in each compartment and 1 .25 A current is passed for 212
min. Assuming electrolysis of water only at each compartment, what will be the sum
of pH in both compartment after passage of above charge? pK
a
for H
2
PO
4
- = 2.15.
(a) 4 (b) 4.3 (c) 4.6 (d) 4.9

5. In an analytical determination of arsenic, a solution containing arseneous acid,
H
3
AsO
4
, KI and a small amount of starch is electrolysed. The electrolysis produces
free I
2
from I
-
ions and the I
2
immediately oxidises the arseneous acid to hydrogen
arsenate ion, HAsO
4
2-
.
I
2
+ H
3
AsO
3
+ H
2
O



2I
-
+ HAsO
4
2-
+ 4H
+
When the
oxidation of arsenic is complete, the free iodine combines with the starch to give a
deep blue colour. If during a particular run, it takes 65.3 s for a current of 10.5 mA to
give an end point (indicated by the blue colour), how many gram of arsenic are
present in the solution? (As = 75)
(a) 0.266 mg (b) 0.0266 g (c) 0.1266 g (d) 0.1266 mg

6. KCl cannot be used as a salt bridge for the cell
Cu(s) | CuSO
4
(aq) || AgNO
3
(aq) | Ag(s)
because
(a) CuCl
2
gets precipitated (b) Cl
2
gas is evolved
(c) AgCl gets precipitated (d) none of the above

7. The reduction potential for the metal M in following species is given below :


M M MO MO MO
dV cV bV
2
aV
3

Here d > c > b > a
Which of the following is correct :
(a)
3
MO

will not disproportionate (b)

2
MO

will disproportionate.
(c)M will disproportionate. (d)All are correct.

8. Conducting power of an electrolyte depends on
(a) nature of electrolyte (b) Concentration of solution
(c) Temperature (d)All are correct

MAMCQ
9. The values of E
0
of some reactions are given
I
2
+ 2e

2I

E
0
= 0.54 volts
Sn
+4
+ 2e

Sn
2+
E
0
= 0.152 volts
Cl
2
+ 2e

2Cl

E
0
= 1.36 volts
Fe
+3
+ e

Fe
2+
E
0
= 0.76 volts
Ce
+4
+ e

Ce
3+
E
0
= 1.6 volts
Hence
(a) Fe
3+
oxidizes Ce
+3
(b) Ce
4+
can oxidize Fe
2+
(c) Sn
2+
will reduce Fe
3+
to Fe
2+

(d) Cl
2
will be liberated from KCl by passing I
2
.

10. Which of the following cell(s) can act as concentration cell:
(a)Pt, H
2
(P
1
)|HCl(aq.)|H
2
(P
2
), Pt
(b)Ag|AgCl(s), KCl(aq.)||Ag
+
(aq.)
|Ag
(c)Pt, H
2
(P
1
)| OH

(aq.)
||H
+
(aq)
|H
2
(P
1
), Pt
(d)PtH
2
(P
1
)|H
+
(aq)
|O
2
(P
2
), Pt

11. The metal(s) which can not be obtained by electrolysis of its aqueous solution is
(a) Au (b) Al (c) Cu (d) Zn

12. Molar conductivity of an electrolyte increases with increase in temperature due to
(a) Increase in average kinetic energy of solution
(b) Increase in effective degree of ionization.
(c) Weakening of interionic attraction so ions become more free to move
(d) Decrease in viscosity of solution

13. For a solution of an electrolyte at a particular concentration and temperature, which
of the following is not the function of cell constant?
(a) Specific conductance (b) Molar conductance
(c) Equivalent conductance (d) Conductance

14. A test for completeness of electrodeposition of Cu from a solution of
( )
2
Cu aq
+
is to
add
3
NH
( ) aq . A blue colour signifies the formation of the complex ion

Cu NH
3
( )
4
2+

K
f
=1.110
13
( )
. 250mLof
( )
4
0.1MCuSO aq is electrolysed with a
3.512 A current for 1368 s. A sufficient quantity of
( )
3
NH aq is added to complex
any remaining
2
Cu
+
and to maintain a free
| |
3
NH 0.10M = .
NOTE :

Cu NH
3
( )
4

+2
is detectable at concentration greater than
5
1 10 M

,


(a) Blue colour will appear
(b) In the solution conc. of complex is

4 10
4
M
(c) In the solution

Cu
+2

= 3.6x10
13

(d) No blue colour will appear

INTEGAR TYPE
15. The potential of Pt, Hg
(l)
Hg(I) nitrate (0.01M) Hg(I) nitrate (0.1M) Hg
(l)
, Pt
is y x 10
-2
V.The value of y is--------------------
given,
RT
2.303 0.06
F
=
16. For following cell, calculate value of E
cell
in multiple of

10
2
volts
( ) ( ) ( ) ( ) ( ) ( ) ( )
2 4 4 3 2
Pt s H 1atm NH Cl 0.2M , NH OH 0.1M NaHCO 0.1M H 1atm Pt s
Also given
k 4
b
P of NH OH 4.7 = for
2 3
H CO
6 10
a a
1 2
K 10 , K 10

= =

14
w
K 10

=
10
log 2 0.3 =
RT
2.303 0.06
F
=


COMPREHENSION-1
A hydrogen electrode, Pt, H
2
( 1atm) 30 ml HA (weak acid) is set up at 298k. The
electrolyte solution is titrated with a strong base BOH and the potential of the
electrode is measured at different volumes of BOH added. The following data is
observed

BURETTEREADING (in mL) E of hydrogen electrode (in Volts)
(volume of BOH added)
10 -0.4068
15 -0.4356
30 -0.7620
(Take 2.303RT/F = 0.06; log2 = 0.3; log3 = 0.48; log5 = 0.7)

17. The initial pH of (before addition of BOH) of HA solution is
(a) 4.74 (b) 3.65 (c) 3.74 (d) 3.89

18. The potential of hydrogen electrode at equivalence point of titration is
(a) -0.5958V (b) -0.6024V (c)-0.5934V (d)-0.42V

COMPREHENSION-2

The overvoltage is a polarization potential associated with the electrochemical
processes occurring at the electrode surface. This effect is particularly important
when the product of electrolysis is a gaseous one. The difference between the voltage
actually required for an electrode half reaction to occur, and that expected
theoretically is termed as over voltage.

Electrode Overvoltage Electrode Overvoltage
Pt (platinized) 0.00 Ni 0.21
Pt (smooth) 0.09 Cd 0.48
Au 0.02 Sn 0.53
Ag 0.15 Pb 0.64
Cu 0.23 Zn 0.70
Fe 0.08 Hg 0.78


19. Overvoltage depends on
(a) Nature & physical state of electrode employed
(b) The physical state of the substance deposited
(c) Current density employed
(d) All of these

20. Potential difference required for liberation of
2
H at cathode (platinised- platinum
electrode) is from 1M
2 4
H SO solution is 0.48 V. The discharge potential of
2
H for
same solution at Zn electrode
(a) 0.48 V (b) 1.08 V (c) 0.7 V (d) 1.18 V

21. Given

0
Na Na
E 2.71V
+
=
0
Cl Cl
2
E 1.36V

= +

0
H O,OH H
2 2
E 0.83V

=
0
O H , H O
2 2
E 1.23V
+
= +
In electrolysis of aq. NaCl, water gets reduced at cathode and from
0
E values
given here it appears water will get oxidize at anode. But Cl
-
gets oxidize at anode
hence value of over potential of oxygen evolution should be greater than
(a) 1.23 V (b) 0.1 V (c) 0.13 V (d) 1.36 V

COMPREHENSION-3
For the next four questions refer to the following illustrations in which 1.0 M
solution and strips of metal shown below:


(I) A strip of metal D was inserted into each solution. Reactions occurred
in solutions containing A
2+
and C
2+
ions.
(II) Metal B reacted with solutions containing D
2+
and E
3+
ions. It was not
tested in other solutions.
(III) Metal C does not react with any of the solutions.

22. If metal A were placed in each solution, a reaction would be expected in
(A) solutions containing C
2+
ions only
(B) solutions containing B
+
, C
2+
and D
2+
only
(C) solutions containing C
2+
, D
2+
and E
3+
only
(D) solutions containing B
+
, D
2+
and E
3+
ions only


3 3
E(NO ) (aq)
23. For the metal A to E, a possible decreasing order of their oxidizing strength is
(A) A > B > C > D > E (B) C > A > E > D > B
(C) E > D > C > B > A (D) B > E > D > A > C

24. If the answer of the above question is assumed to be perfectly correct, all of the
following combinations of metal-metal-ion solution represents non-spontaneous
conditions except
(A) E D(NO
3
)
2
(B) A E(NO
3
)
3
(C) A C(NO
3
)
2
(D) C E(NO
3
)
2


25. Assuming that none of the metals A E produces H
2
(g) when dissolved in HCl, if the
above mentioned beakers are connected in series, molar ratio in which metals A E
deposited respectively.
(A) 1 : 1 : 1 : 1 : 3 (B) 2 : 2 : 2 : 2 : 3 (C) 3 : 3 : 3 : 3 : 2 (D) 3 : 3 : 3 : 3 : 1

COMPREHENSION-4
The next three questions relate to the illustrated apparatus below:

Half-cell E
o
(V at 25
o
C) Molar masses
Ni
2+
+ 2e
-

Ni 0.25 V Ni = 60
Pb
2+
+ 2e
-

Pb 0.13 V Pb = 207
Ag
+
+ e
-

Ag + 0.80 V Ag = 108
26. When the voltmeter is connected between Ni and Pb electrodes, it reads 0.12 V. After
0.10 mol of electrons have passed through the voltmeter, the mass of Ni electrodes
will be
(A) 6 grams greater (B) 3 grams greater (C) 6 grams less (D) 3 grams less

27. Based on the information above, in which cases would a spontaneous reaction be
expected to take place between the metal and the solution paired with it?
(I) Pb(s) Ag
+
(aq) (II) Ag(s) Ni
2+
(aq) (III) Pb(s) Ni
2+
(aq)
(IV) Ag(s) Pb
2+
(aq) (V) Ni(s) Pb
2+
(aq)
(A) I and II only (B) I and V only (C) II and V only (D) I, III and IV

28. If Ni/Ni(NO
3
)
2
and Ag/AgNO
3
half-cells are connected to a battery, what minimum
voltage would be required to reverse the cell reaction
Also given : At 25
o
C
2H
2
O + 2e
-

H
2
(g) + 2OH
-
; E
o
= 0.828 V
4OH
-

O
2
+ 2H
2
O + 4e
-
; E
o
= 0.40 V
(A) 1.05 V
(B) less than 1.05 V
(C) greater than 1.05 V
(D) the cell is not reversible i.e., water oxidizes before Ag start oxidizing



MATRIX MATCH

29. If following solution electrolysed using the inert electrodes gases liberated are

Column I Column - II
A
2 4
Na SO
P
2
Cl
B
4
ZnSO
Q
2
O
C HCl R
2
H
D
2 4
Ag SO
S
2
SO


30. Match Matrix
+
o
-10
Ag /Ag E = 0.8, Ksp(AgCl) = 10
| |
|
\ .
.
COLUMN I COLUMN - II
(A) Pt|H
2
(0.1 bar)| H
+
(0.1 M)|| H
+
(1 M) | H
2
(0.01 bar)| Pt P. Concentration cell
(B) Ag |AgCl (KCl, 0.1 M) ||Ag
+
(0.01M) | Ag Q. E
cell
> 0
(C) Cu| Cu
2+
(0.1 M)|| Cu
2+
(0.01 M)| Cu R. E
0
cell
= 0 but cell is
working
(D) Pt|Cl
2
(1 bar) | HCl (0.1 M)|| NaCl (0.1 M) Cl
2
(1 bar) | Pt S. non working condition






























ANSWER KEY

Que. 1 2 3 4 5 6 7
Ans. c a b b a c d
Que. 8 9 10 11 12 13 14
Ans. d bc abc bd abcd abc abc
Que. 15 16 17 18 19 20 21
Ans. 3 6 c a d d c
Que. 22 23 24 25 26 27 28
Ans. a b c c d b d

29.

AQ, R; BQ, R;CP, R; DQ

30. A P, Q, R; B Q; C P,S; D P,S