1.

TOPIC :ELECTROCHEMISTRY
(C) 2. (A) 3. (B) 4, A
6.
(A) 7. (A) 8. (A) (D)
11. (B) 12. (A) 13. (D) 14, (C 15. D
16. (A,C) 17. (C,D) 18. (C,D) 19. (B,) 20.

21. (D) 22. (A) 23. (A) -p, q, t;(B) -q:(C)-q. s, t, (D)-,t
24. 06 25. 2 26. 2 27. 22.
29. 3 30. 5
 RT
1. E° = 2FIn k
2. If pH are not same, then E0,
"cell as this cell can be taken as concentration cell.
3 In alkaline solutionas soon as Fe2* charges to Fe, it acquires OH to forn ppt. of Fe(OH), This prornotes
oxidation of Fe2* to Fe.

4. 2.303 RT Zn2+
cell
2F log Cu2
0.059 1
1.18 = log
2 [cu2']
1
40 =l0g
[Cu]= 1040
Cu21
X= 40

5. From the first reaction, we conclude

From the second reaction,we conclude

Ea <Ex2
EwW <Eie
From the third reaction,we conclude
ExX
Hence,
EwW <EyYa <Exe
6. In galvanic cell, reaction is spontaneous. But in electrolytic cell, reaction is non-spontaneous in the
absence to external battery.

7. NO, +
3H,0" +
Hg, 2Hg² + HNO, + 4H,0
t=t 0.3mole

Cathode : NO, + 3H,0* + 2e ’ HNO, + 4H,0

0.6mole 0.3mole
Total charge = 0.6 mole = 0.6 F= 0.6 x 96500C
Q=i x t= 10 x t= 0.6 x 96500
0.6×96500
t= sec = 0.6 x 96500 sec = 1.6 hour.
10

8. Anode Zn ’ Zn?* +2e

Cathode 2H' + 2e ’ H, =0-(-0.76) = 0.76 V
Cell: Zn + 2H' H, + Zn
 0.059 0.01x1
0.701 078- Iog
H°]= 10M
NaOH required is O.0tmole 0.4 gms.
Kg for AgCl= 10 (0.1) = 10
0.059
EAA +0.80 + log10 0 0.21 V

,-0.0591 log(H')
10. H(aq) +e;
-0.0691 log 1 /(CI
(8) Ag(s) +Chag) Agcl(s) +e

+ 2H* + 2e, (ell -0.0591 log[H']

(C)
(ell
-0.0691 log [Ag']
(D) Ag(s) ’Ag*(aq):
of B varies with ditferent nature of electrolyte e.g., NaCi (Na'Cl ), Mgo (Mg. 0), MgCI,
2
11. The value
(Mg, 2cH),etc
AgNO, is 3 x 10- M.
12. The solubility of AgBr in presence of 10-* molar and[NO,}= 10 m
Therefoe (Br]= 3 x 10 m, (Ag']= 4 x 104 m'
Therefore K NR-t Ag* + ^NO, 39 Sm-1

[Au(CN)I Certainy according tospontaneity and availability substance will be reduced.

14. +Zn Reduction
[Ag(CN),I
2 =-0.31-(-1.26) = 0.95V
E
EO Aj -0.60 -(-1.26) = 0.66 \V
As EOAgl21 > EAu<zn
Hence, Ag complex will be reduced first:
Mole of Ag in 500 L= 500 x 0.0030 = 1.5 mol
Mole of Au in 500 L=500 x 0.010= 1.5 mole
40
2¬
Mole of Zn in 40 g = 65.38 = 0.61 mol

2[Ag(CN)] + Zn ’ (Zn(CN),J + 2Ag

1 molof zinc reacts with 2 molof Ag() or Au(l), 0.61 mol of zinc reacts with 1.2 mol [Ag(CN),!
Remaining [Ag(CN),J =1.5-1.2= 0.3 mol
[Ag(CN),] will not be reduced as zinc gets over.
Hence, concentration of [Au(CN),J,reaction get over =0.003 x3=0.009 M(due to evaporation to one- hra)
0.3x3
Concentration of [Ag(CN),J when reaction gets over = = 0.0018 M
500

15. Cell reaction is : Fe(s)+ Ni,o,(s) ’ 2NiO(s) + FeO(s); E°ooll = 1.27 V.

AG° =- 2 x 96500 x 1.27
29
If NiO(s) and Fe(s) are present initially, then the cellreaction is not feasible.
30
76. In galvanic cell, reaction is spontaneous. Butin electrolytic cell, reaction is non-spontaneous in the absence
of external battery.
Anode is negative in galvanic cell, but it is positive in electrochemical cell.
17. (B)Cobalt has lesser SRP thand cadmium.
(C)There are cases, when standard potential decrease on increasing concentration of electrolyte.
(D)Only hydrogen electrode has 0.0 Vas SRP.
 195 JEE Advanced PacKage
18. Cellreaction is 2Ag +Hg,Cl,(s) ’ 2AgCl+2Hg() in claculateion of Q.
taken
Ecal is independent of Ci-. Hg,CI,(s) and AgCi(s) are not
19. Species are Ni", SO, s,o,, H,0.
At anode
Only H,0 can get oxidized.
2H,0 ’ 0,+ 4H* +4e
At cathode:
N2* + 2 ’ Ni(s)

20 x 28950
20. Total charge = 96500 = 6F

Mole of Br, formed=2

Mole of CI, formed= 1.
1
[CH]
21. Eoe =EsoP -0.06 log rr-i ESoP +0.06 log
Eop « log [CH
22. H, +Hg,CI, 2Hg + 2C+ 2H*

Eel = cr /Hg,Cl, /Hg -H*/H,

0.06 log [H (12
2

0.67 = EOCIr /Hg,CiI, /Hg +0.06 pH

0.67 = ECr /Hg,CI, /Hg +0.06 x 6.5

0.28 = E crr /Hg,Cl, /Hg

electrodes. So, given cell is a concentration cell.
23. (A) Both cathode and anode are Hydrogen
0.059 =-0.059 x log 0.2 (>0).
So, 1 \o910 (Hlc
0.059 0.059
= 1.57 log,, 10(>0)
(B) Ec(Eg 2 logo (Ag* 2

0.059
(C) Eca =[E*n-Epo 2 log,oHö xPD
0.059 (0.1)' x0.001
=0-(-0.01) - 2 log,0 (0.01)x 0.1 = 0.01 V(>0)
have the
value 1, so, E = E, and it can be said that Cell will
Since the expression of log upon solving haselectrodes.
same emf as the one made up of standard
after diluting each electrode solution to double
Also the expression of log will have the same value even
cell.
volume. So, it would not affect emf of
0.059 [ci]
(D) E Eo cal 1 lo90 (Br
0.059 Ksp [AgCij 0.059 [CI]
1 log,o Ksp [AgBr] 1 lo90 [Br
0.059 (10-10) 0.059 (0.1)
=0
=
1 log,o (5x10) 1 log,o (5x10")
So, cellreaction is at equilitbrium.
Also, upon diluting the electrode solutions to double volume, both Eo cell and expression of log will remain
unchanged. So, E, willremain zero and thus, no change in emf of cell would occur.
24. (a) H, &O, in (a), (b), (e), (i)
In. (d) H, and Fe at cathode and 0, at anode.
In. (h)Cl at anode and H, at cathode.
Elt 63.5 xlx 3600 |0.536A
W= ZQ = ZIt = 0.635 = 2x 96500
25. F

0.547-0.536
% error= -x100 =2%
0.536
965
26. Q= x 60 x 60 x 2
36

Moles of e= F 2.
Ag* + e ’Ag Moles of Ag = 2
2x 108
Mass of Ag =2 x 108 g Volume of Ag = 10.8 = 20 cm

X
20 = 100 x X=2
10

1000 x(Kso -kH,o)

27. 10=

1000 x(3.4-2.02)x 105

138 =

S=1x 10-5 Ans.

28. 1=Ec = E°cal

0.059 [Ag*
2 Iog
8
0.059
2 =E = E 2
log
(Zn2)
0.059
4 = Em = Ecel 2 log
29. 2Cu*1 ’ Cu +Cu+2
2Cu+1 + 2e ’ 2Cu
Cu-2e Cu*2

2Cu+1 ’ Cut2+ Cu

E° 2x0.521+2(-0.337) =0.184
2
As E° for disproportionation is positive, so
Cu'
E°
cutCu Which means, it has higher tendencydisproportionate
to go to Cu. dio
Cu' is less stable than Cu2* as it has higne

30. CH, + 10OH

configuration is highly stable.
Co+7H,0 +8e
48.25 x 3600 x 1
No. of Faradays required =
96500
1
Hence mol. of CH, required = 8 48.25 x 3600 x 1
volume of CH, =5.04 L.
96500