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TARGET : PRE-MEDICAL 2025 PHYSICAL CHEMISTRY
ELECTROCHEMISTRY
1.
+3
Initial equivalent of Cr = M × V × V.F. 7.
+ +2
Mg(s) + 2Ag (aq)  Mg (aq) + 2Ag(s)
250
⇒ 0.2 × × 3 ⇒ 0.15 0.0591 [Mg +2 ]
1000 Ecell = E°cell – log
n [Ag + ]2
Final equivalent of
0.0591 (2 × 10−2 )
250 Ecell = 3.17 – log
+3
Cr = 0.1 × × 3 ⇒ 0.075 2 (10−3 )2
1000
0.0591
Left equivalent of Ecell = 3.17 – × 4.3
2
Cr = 0.15 – 0.075 ⇒ 0.075
+3
= 3.17 – 0.129
equivalent weight × I × t = 3.04 volt
w=
96500 ∆G° = – nF E°cell
96.5 × t = –2 × 96500 × 3.17

®
0.075 =
96500 = –611.8 kJ
t = 75 sec. [Mg2+ ]
Q= = 20000
2. NaCl + 4H2O → NaClO4 + 4H2 [Ag+ ]2
–1 +7 Q = 20000
Change in oxidation no. of NaClO4 (V.F.) = 8 8. Cu+2 + 2e– → Cu
Molecular wt. of NaClO4 = 122.5 g/mole 0.0591 1
Ered = E°red – log
1000 2 [Cu +2 ]
Mol of NaClO4 = = 8.16
122.5 on increasing [Cu+2]↑ Ered↑
No. of Faradays = 8.16 × 8 ⇒ 65.3  66 therefore order of S.R.P. Q>R>S>P
[Link]. × Q
∆G 10. W=
5. % efficiency of a cell = × 100 96500
∆H
[Link]. × Q
−nFE cell (a × b × c) × d =
84 = × 100 96500
∆H
(Area × Thickness) × d
−2 × 96500 × E cell
84 = × 100 31.7 × Q
−285 × 103 –2
(10 × 10 × 10 ) × 8.94 =
96500
Ecell = 1.24 volt
8.94 × 96500
1 Q= ⇒ 27172 C
6. H+ + e– → H2(g) (1 atm) 31.7
2
11. According to nernst equation
At 1 atm pressure
0.0591 [Mg +2 ]
0.0591 (1) 1/2 Ecell = E°cell = log
Ered = E°red – log n [Ag + ]2
1 1
0.0591 (0.120)
Ered = E°red = 0 Ecell = 3.17 – log
2 (10−4 )2
At 100 atm pressure
Ecell = 2.96 volt
1/2
1 0.0591 (100) 12. e.m.f. of cell will not be zero because acetic acid
E=
red E 0red − log
1 1 is weak electrolyte (Acid) which is not completely
1 0
E red =E red
– 0.0591 ionised.
13. Stronger is reductant. weaker is its conjugate
E1red = 0 – 0.0591 ⇒ – 0.0591
oxidant and vice-versa.

HS Your Target is to secure Good Rank in Pre-Medical 2025 [ 21 ]

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PHYSICAL CHEMISTRY TARGET : PRE-MEDICAL 2025
14. 20. For H2 – O2 Fuel cell
E = 0.50
o
ClO3− → ClO − n1 = 4 1 ∆G10 2H2 + 4OH– → 4H2O + 4e–
+5 +1

1 O2 + 2H2 O + 4e − → 4OH −
ClO − → Cl2 n2 = 1 E 2o = 0.40 ∆G20
+1 2 0 2H2 + O2 → 2Η 2 O (2mole)
1
Cl2 → Cl − n3 = 1 E 3o = 1.36 ∆G03 required no. of faraday for two mole H2O = 4
2 0 −1

ClO3− → Cl − n= 6
o
E =? ∆G04 = ? required no. of faraday for one mole H2O = 2
+5 −1

21.
+ –
∆G° = ∆G10 + ∆G20 + ∆G30 4H2O  4H + 40H

nE° = n1E10 + n2E20 + n3E30 At anode 4OH– → 2H2O + O2(g) + 4e–

4 × 0.50 + 1 × 0.40 + 1 × 1.36
E° = ⇒ 0.63 volt 1 mole (22.4 L)
6
At cathode 4H+ + 4e– → 2H2 (g)
15. If same quantity of electricity is passed then
+2
equivalent of Cu = equivalent of Cu
+
(2 × 22.4 ltr)

®
 W   W  total volume of the gas = VO2 + VH2
 [Link]  = 
 Cu+2  [Link] Cu+
WCu+2 WCu+ = 67.2 ltr.
=
22.
–6
[Link]. / 2 [Link]. / 1 Given Ka = 25 × 10
WCu+2 1
= M = C = 0.01
WCu+ 2
ΛC = 19.6 S.cm2 eq–1
−5
k × 1000 4.95 × 10 × 1000
16. Λ ∞M = ⇒ = 50 for weak acid
M 99 × 10−5
ΛC 50 ΛC
Ka = cα but α =
2
⇒α= = = 0.125 Λ∞
Λ∞ 400
17. According to debye huckel onsagar equation Ka ka Λ
α= = c
ΛC = Λ∞ – b C C C Λ∞

260 = Λ∞ – b 0.25 ...(1) 25 × 10−6 19.6

=
0.01 Λ∞
250 = Λ∞ – b 1 ...(2)
eqn (1) – eqn (2) Λ∞ = 392 S cm2 eq–1
than 10 = 0.5 b 23. Ag+ + e– → Ag(1 mole)
b = 20
3 mole → 3 mole Ag
on putting value in eqn(1)
Cu + 2e → Cu(1 mole)
+2 –

260 = Λ∞ – 20 × 0.5
3
Λ∞ = 270 3 mole e– → mole Cu
2
18. Oxidising power ∝ SRP
Au + 3e → Au (1 mole)
+3

19. Fe + e → Fe
+3 – +2

Molar ratio
n
According to nernst eq
Ag : Cu+2 : Au
+3

+2
0.0591 [Fe ]
Ered = E ored − log 3
1 [Fe +3 ] 3 : : 1
2
1.5
Ered = 0.770 – 0.0591 log 6 : 3 : 2
0.015
Ered = 0.77 – 0.12 ⇒ 0.652

[ 22 ] Your Target is to secure Good Rank in Pre-Medical 2025 HS