SA 19 20 XII Chemistry Unit-1

Physical Chemistry UNIT 1
1. Answer (2)
Total 4 alternate corners, 4 alternate edges and 2 alternate faces are present in a cubic unit cell.
1 1
Number of ‘A’ atoms =  4 
8 2
1
Number of ‘B’ atoms =  4  1
4
1
Number of ‘C’ atoms =  2  1
2
Hence, formula of unit cell = A1/2BC and simplest formula of compound is AB2C2.
2. Answer (2)
Orthorhombic crystal system has simple, body centred, end centred and face centred unit cell.
3. Answer (4)
4. Answer (4)
Only Ba forms body centred structure, Ca and Sr forms face centred structure while Be forms hexagonal close
packed structure.
5. Answer (3)
NM (2) (20 g mol1)
= = = 9.11 × 105 gm–3 = 0.91 g cm–3
 2  452  10   6.023  10 
3
a3NA 12
m/ 3 23
mol 1
6. Answer (3)
7. Answer (2)
In Fe3O4, O2– ions form the ccp lattice, one Fe2+ is present in octahedral void. While Fe3+ ions are equally
distributed in between octahedral and tetrahedral voids. So, only 12.5% tetrahedral voids are occupied.
8. Answer (1)
9. Answer (1)
10. Answer (4)
All the correct statements.
11. Answer (1)
12. Answer (1)
1
Number of ‘A’ atoms =  8  1
8
1
Number of ‘B’ atoms =  6  3
2
1
Number of ‘C’ atoms =  12  1  4
4
After passing tetrad axis, 2 face atoms and 1 body atom is removed. Now,
1
Number of ‘A’ atoms =  8  1
8
1 1
Number of ‘B’ atoms =  6   2  2
2 2
Number of ‘C’ atoms = 4 – 1 = 3
Hence, formula of unit cell is AB2C3.
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2 Physical Chemistry Success Achiever (Part-II) (Solutions)
12a. Answer (1) (AIEEE 2011)

8
ZA 
8
5
ZB 
2
So formula of compound is AB5/2.
i.e., A2B5
13. Answer (3)

In Frenkel defect, ions occupy the interstial site like interstitial defect and create a vacancy in the lattice site
like vacancy defect. So, it is the combination of vacancy as well as interstitial defect.
13a. Answer (3) [JEE (Main)-2018]

In Frenkel defect, cation is dislocated from its normal lattice site to an interstitial site.
14. Answer (2)

15. Answer (1)
In case of BCC structure,
3a
r  r–  (a = cell edge length, r+ + r– = inter ionic distance)
2
3  3.5
r  r– 
2
r+ + r– = 3.031 Å

—
Cl
– Cl
—
Cl –
Cl
+
Cs
—
Cl –
Cl
— Cl
Cl
2rCl  2rCs  3 a
3a
rCl  rCs 
2
16. Answer (3)

17. Answer (4)
In a cubic crystal, 9 plane of symmetry, 13 axis of symmetry and 1 centre of symmetry is present.
18. Answer (3)
1 1
Number of O2– ions = 8  6  4
8 2
Success Achiever (Part-II) (Solutions) Physical Chemistry 3
Number of metal ions = 1  2 3

(12.5% T.V ) ( 50% O.V.)
Hence, formula of metal oxide is M3O4.

19. Answer (2)
The length of face diagonal = a 2
= 80 2
So, a = 80 pm (a = cell edge length)
In NaCl type structure,
a 80
r  r    40 pm
2 2
a 361
r=   127.6 pm
2 2 2 2
19b. Answer (2) [JEE (Main)-2017]
In FCC, one of the face is like A
By ABC,
a
2a2 = 16r2
1 2 C B
 r2  a
8
1
 r a
2 2
a
Distance of closest approach = 2r =
2
20. Answer (4)
Body diagonal of cube = 3 a = (1.732) (387 pm) = 670.3 pm
2 (r+ + r–) = 670.3 pm

670.3
r+ = pm – 181 pm = 154 pm
2
21. Answer (3)
Factual type.
22. Answer (2)

CrO2 is strongly attracted towards magnetic field so it is ferromagnetic.
23. Answer (1)

For fcc,
ax 2 (x = cell edge length)
a
x
2
3
 a  a3

Volume of fcc unit cell =  
 
 2 2 2
24. Answer (2)
The length of body diagonal is a 3 . Two tetrahedral voids are present on each body diagonal at the distance
a 3
.
2
25. Answer (3)
The simplest unit of hcp structure is hexagon. Other statements are correct.
26. Answer (4)
For bcc,
a 3 5 3
r   2.165 Å
4 4
r = 216.5 pm

Edge length of BCC is 4.29 Å.
In BCC,
4
edge length = r
3
4
4.29 = r
3
4.29
r= 3  1.86 Å
4
27. Answer (2)

28. Answer (3)
Total 4 body diagonals are present in a cube. 1 middle tetrahedral void is present on each body diagonal is
common for all. So, total number of tetrahedral voids are 9.
29. Answer (1)
rNa 
From r  0.75
K
rNa  0.75 rK  …(i)
rNa 
Putting the value of rNa in  0.55 then we get
rCl –
0.75 rK 
 0.55
rCl–
rK  0.55
  0.733
rCl– 0.75
2(rK   rCl– ) 2(0.733  1)

So, 2(r   r – )  2(0.55  1)  1.118
Na Cl
(Side for unit cell for KCl = 2(rK   rCl– ) , Side for unit cell for NaCl = 2(rNa  rCl– ))
30. Answer (4)

All statements are correct for fluorite structure.
31. Answer (4)
1 mole AlCl3 develops 2 mole of cation vacancies in the doping in NaCl.
10 5
Number of cation vacancies = 2   6.023  10 23 = 1.2046 × 1017
100
32. Answer (3)
In this defect, some Fe2+ ions are converted into Fe3+ ions. Due to charge balance number of Fe atoms
decrease. Hence, it is found as Fe0.95O not FeO.
33. Answer (2)
Both Al3+ ions are present in octahedral voids. Other statements are correct.
34. Answer (3)
In the unit cell of NaCl, Na+ ions are present in octahedral voids and Cl– ions are present on ccp lattice. When
one body diagonal plane is placed in the unit cell, then 4 corner ions, 2 edge ions, 2 face ions and 1 body
ions are removed. Now,
1  1
Number of Na+ ions = 4    2  1  2
 4  2
1 1  1
Number of Cl– ions = 4    2   4   2
2 8  2
Hence, simplest formula is NaCl.

35. Answer (2)
37.46 a13 a 37.46

  1 3  1.103
27.94 a32 a2 27.94
36. Answer (3)

Fact
37. Answer (2)
Volume of any lattice is
V = abc(1 – cos2– cos2– cos2– 2cos cos cos)1/2
V1 = Vtetragonal = a2c
(because a = b  c,  =  =  = 90°)
3
V2 = Vhexagonal = a2c 
2
(because a = b  c,  =  = 90°,  = 120°)
V1 2
 
V2 3
38. Answer (1)

MnO2 has rutile structure.
39. Answer (4)
Reverse osmosis involves moment of solvent particles through semipermeable membrane from concentrated
solution to dilute solution.
40. Answer (3)
For isotonic solution C1 = C2 (at constant temperature).
41. Answer (1)
98 1000  1.6
N=   32
49 100
42. Answer (2)
9.1 × 10–31 kg = 1 e–
1 
 1 kg = e
31
9.1 10
∵ 6.023 × 1023 e– = 1 mole
1  1 1
 e  
31 23 31
9.1 10 6.023  10 9.1 10
 Number of moles (n) = 0.018 × 108 = 1.8 × 106 moles
n
 Molarity = v
2
1.8 106
M=
0.5
M = 3.6 × 106 M.
43. Answer (4)
According to Raoults law for non-volatile solution.
PB  P  A  solute 
  xA  
PB B  solvent 
and in Ostwald Walker process
PB  P loss in weight of solvent


PB gain in weight of CaCl2 .
44. Answer (4)
45. Answer (1)
Elevation in boiling point is inversely proportional to molecular length of solute.
46. Answer (4)
47. Answer (2)
meq of HCl = meq of NaOH
Mass
 1000  NVml …(i) (N = 0.5 N, V = 100 ml)
Eq mass
mass of HCl  1000

∵ molality = M.m  mass of solvent (g)
 g  1000
5    
 Eq mass  w
g
  1000  w  5 …(ii)
Eq mass
from eq. (ii) to (i)
N  0.5 N 
 w × 5 = 0.5 × 100  
 V  100 ml 
w = 10 g.
(mass of solvent )
48. Answer (3)
a3Na
M=
N
(1.984 gcm3 )(630  10 10 cm)3 (6.023  1023 mol1)

=
4
= 74.7 g mol–1
49. Answer (1)
50. Answer (2)
51. Answer (3)
52. Answer (3)
53. Answer (1)
nRT
Osmotic pressure () =
v
i1n1RT i2n 2RT
 1 = and 2 =
v v
  = 1 + 2
 i1n1RT   i2n 2RT 

 =  v    v 
   
and v1 + v2 = v
 i1n1  i2n 2 
 =  v
RT

 
T  ini in2 
  
v v v 
 i1n1  i2n 2 
 
or  =  v  v RT .
 1 2 
54. Answer (4)
54a. Answer (2) [JEE(Main)-2016]
18
pº –ps nsolute 18
  180 
ps nsolvent 178.2 17.82
18
At normal boiling point of water V.P. = pº = 760 torr
760 – ps 18
 
ps 1782
or, 1800 ps = 760 × 1782

ps = 752.4 torr
55. Answer (2)
PB  P in A  A  solute 
 …(i)  
PB in A  nB B  solvent 
∵ solution is concentrated
P°B = 760 mm-Hg P = 750 mm-Hg
5.85
nA = = 0.1 mole
58.5
180
nB = = 10 moles
18
 
for AB  A  B
1   
 i=1+
 from equation (i)
760  750 0.1(1   )


760 (1   )0.1  10
1 0.1(1   )
 (dilute solution)
76 10
100
1+=
76
 = 0.315.
56. Answer (3)
Solution will be ideal and for ideal solution Hmix. = 0.
57. Answer (3)
3
Al 2 (SO 4 ) 4  2Al  3SO 4 2
2 moles
1 mole 3 moles
nsolute
Molality = w  1000
solvent
 w 
d  v 
 
n  w  250  1
3=  1000  w  250 g 
250  1
 
 
3
n= mole
4
According to above equation,
∵ 1 mole of Al2SO4 producing 2 moles of Al3+
3 2 3 3
 mole of Al2SO4 producing  = mole
4 1 4 2
3 23 23
 Number of Al3+ ions =  6.023  10  9.03  10 ions.
2
58. Answer (2)

For MgCl2,  = 50% i.e. 0.5
2 
MgCl2  Mg  2Cl
1   2
 i1 = 1 + 2
i1 = 1 + 1
i1 = 2
for CH3COOH,  = 50% i.e. = 0.5
1
CH3 COOH  (CH3 COOH)2
1 
2

2

i2 = 1  Total value of
2
i2 = 1 – 0.25 i = i1 + i 2
i2 = 0.75 i = 2 + 0.75
i = 2.75
59. Answer (1)
60. Answer (3)
61. Answer (3)
Addition of acid in to water is exothermic and H < 0 then solution will be non ideal showing negative deviation.

Ethanol has H-Bonding, n-heptane tries to break the H-bonds of ethanol, hence, V.P. increases. Such a
solution shows positive deviation from Raoult's Law.
62. Answer (3)

At –56.6°C, solid and liquid are in the same phase.
63. Answer (1)
Vapour pressure does not changes with enthalpy.
64. Answer (2)
65. Answer (2)
Solvent is the component which have same physical state as that solution.
66. Answer (3)
3 
For AlCl3  Al  3Cl
1   3
 i1 = 1 + 3 ( = 100%)
i1 = 4
 
NaCl  Na  Cl
1   
i=1+ ( = 100%)
i=2
 1 = i1RT
2 = i2cRT
1 i
 1
 2 i2
1 4

2 2
 1 : 2 = 2 : 1.
67. Answer (1)

The solution which shows maximum freezing point must have minimum number of solute particles.
(1) [Co(H2O)6]Cl3  [Co(H2O)6]3+ + 3Cl–, i = 4
(2) [Co(H2O)5Cl]Cl2  H2O  [Co(H2O)5Cl]2+ + 2Cl–, i = 3
(3) [Co(H2O)4Cl2]Cl  2H2O  [Co(H2O)4Cl2]+ + Cl–, i = 2
(4) [Co(H2O)3Cl3]  3H2O  [Co(H2O)3Cl3], i = 1
So, solution of 1 molal [Co(H2O)3Cl3]  3H2O will have minimum number of particles in aqueous state.
Hence, option (4) is correct.
68. Answer (1)
Hvap = Lv × M.m = 540 × 18 = 9720 cal/mole.
69. Answer (3)
 xA …(i)  
From Eqn (i)

xA xA
m = x  55.55 xA  1
B 0.054
xA  1 
3 = x  55.55 x A 1   1
B  0 . 054 
xA 1
xA 
xB = 0.054 19.5
xA
 xB  …(i) xA = 0.05
0.054
∵ xA + xB = 1 P°B – P = xA × P°B
P°B – P = 0.05 × 760 = 38.97 mm-Hg.
Vapour pressure of pure acetone P°A = 185 torr

Vapour pressure of solution, PS = 183 torr
Molar mass of solvent, MA = 58 g/mole
P°A – PS nB
as we know =
PS nA
185 – 183 WB MA
 = ×
183 MB WA
2 1.2 58
 = ×
183 MB 100
1.2 58
 MB = × ×183
2 100
= 63.68 g / mole
70. Answer (3)

71. Answer (1)
SO2 + NaOH  NaHSO3
meq. of NaOH = meq of NaHSO3
g
NV   1000(NaHSO 3 )
(NaOH) eq mass
g
0.1 1 100   1000
104
 gNaHSO  1.04 g (mass of NaHSO )

3 3
 For the calculation of lowering of vapour pressure
 xA  
1.04
PB  P
 104
 PB 36 (dilute solution)
18
PB  P 0.01
 
PB 2
0.01
 (P°B – P) =  1 (atm)
2
P  P
B = 0.005 atm
(lowering of vapour pressure)
72. Answer (2)
RT0 2
Kb 
1000 Hv
2
2  (373)
Kb 
 9.72 3
1000   10
18
Kb = 0.52° mole/kg
 Tb = Kb × m
Tb = 0.52 × 0.1 = 0.052°.

73. Answer (2)
1
C 6H5 COOH  C H COOH
1 
n 6 5
1

n

 i = 1  
n
 1   100%
i = 1   1    
 n    1 
 1
 i = 1  1   …(i)
 n 
Tf (obserbed)
i=
Tf (calculated)
Tf
 i …(ii)
Kfm
12.2  1000
m=
122  100
m = 1 molal
0.93
 i=
1.86  1
1
i=
2
Putting the value of ‘i’ in equation (i)
 1
i  1  1  
 n
1  1
 1  1  
2  n
n = 2.
74. Answer (2)

For MX2 salt
Van’t Hoff factor = 1 + 2 = 2
 = 0.5
75. Answer (3)

Tb = Kbm
 logTb = logKb + logm log  Tb
y = mx + c
 m=1 (tan = 1,   = 45°) log m
76. Answer (4)

Solute solvent interaction is equal to solute-solute and solvent-solvent interaction.
77. Answer (4)
For dilute solution
nA
xA ~ n (nA + nB ~ nB)
B
PB  P in A
   ix A .
PB nB
78. Answer (2)

For isotonic solution
A = B
 CART = CBRT
CA = CB.
79. Answer (2)
P A x A
x A 
( vapour phase )
P A x A  PB x B
50  0.5
 xA =
50  0.5  100  0.5
25
xA =
75
 xA = 0.33.
80. Answer (3)
The solution which flow into the blood stream are of the same osmotic pressure as that of blood otherwise
due to difference in osmotic pressure blood cells may swell and burst.
81. Answer (2)
Partial pressure of water
R.H   100
Saturated partial pressure of water
82. Answer (2)
Fact
83. Answer (3)
P  XA PA0  XBPB0
84. Answer (3)

2A
A2
3A
A3
1 0 
 1 
1  3
2
 2
 i  1  i  1
2 3
1 2 1
 1   0.5  1    0.33
2 3 3

0.2 / 60
0.45 = i(5.12)  1000
20
 i = 0.527
 CH3COOH2

2CH3 COOH
1–  
2

 i  1–
2

 0.527 = 1 –
2

 = 0.473
2
  = 0.946
 % association = 94.6%
85. Answer (2)
8.314   383.7  92
2
RTb2 M1
Kb   Hv  = 34 kJ mol–1
1000Hv 1000  3.32  103
86 Answer (2)
i = 5 for K4[Fe(CN)6) and i = 5 for Mohr salt.

Tf = i Kfm
i for Na2SO4 is 3(100% ionisation)
0.01
Tf = 3 × 1.86 ×
1
Tf = 0.0558 K
  i CRT
C2H5OH  1  0.500  R  T  0.5 RT
Mg3 (PO4 )2  5  0.100  R  T  0.5 RT
KBr  2  0.250  R  T  0.5 RT
Na3PO4  4  0.125  RT  0.5 RT
87. Answer (4)

88. Answer (2)
G1 = – 2Fx1, G2 = + x2F, G3 = – FE°
G3 = – G1 – G2 = – (– 2Fx1) – (x2F) = – FE°
E° = (x2 – 2x1) V
3+ E0 = ? 2+ E0 = – 0.439 V
Fe (1)
Fe (2)
Fe
E0 = – 0.036 V
(3)
G01 + G02 = G03

 – n1E01 – n2E02 = – n3E03
 – E0 + 2 × 0.439 = +3 × 0.036
 E0 = +0.77 V
89. Answer (3)

Ksp = 4x3, (x is solubility of Ag2CrO4)
[Ag+] = 2x
0.0591 1
E = 0.80 – log
1 2x
90. Answer (2)
AgNO3 will react with copper.
91. Answer (3)
Standard free energies of reactant and product are same.
Go = 0
92. Answer (4)
93. Answer (4)
Value of ‘n’ is not given.
94. Answer (4)
2.303 RT
E= – log Q
nF
2H+ 
 H2
PH2
Q=
[H ]2
95. Answer (4)
96. Answer (4)
Fact.
97. Answer (2)
Only H2O is electrolysed.
98. Answer (4)
Change in oxidation number of N is 6
22.4
 Veqv = = 3.73 L
6
99. Answer (1)
2H2O + 2e–  H2 + 2OH– ...(i)
2H2O  O2 + 4H+ + 4e– ...(ii)
2x
From (i) 1 mol of H2 = 22.4 LH2 is obtained by 2 units xL of H2  units costing Rs.x
22.4
hence, 1 units costs = Rs. 11.2
from (ii) : 22.4 L at NTP costs = 4 units
= 4 × 11.2
xL costs = 2x
100. Answer (3)
NO2 NO
2e– +  
nf 2
n=2
gram Eq = n × mole = 2 × 0.5 = 1

1 Eq nitro benzene require 1 F
1
 Net charge = = 1.25 F
0 .8
101. Answer (2)
It is 2.26 V.
102. Answer (1)

The cell can be formed as Fe|Fe3+; OH–|Fe(OH)3(s)|Fe
The electrode reactions can be written as
Fe(s)  Fe3+ + 3e–
Fe(OH)3(s) + 3e–  Fe(s) + 3OH–
Overall reaction is i.e., by adding
i.e. E° = E0 – E0
OH– /Fe(OH)3 /Fe Fe2  /Fe
E0 can be calculated if we know E° and E° can be calculated as follows

OH– /Fe(OH)3 /Fe
0.0591 0.0591 (–36.4)

E° = log10 –36.4 
0.3 3
 0.75V
EOH–/Fe(OH)3 /Fe = –0.75 – 0.036 = –0.786 V
103. Answer (2)
Eocell = EFe
o
2
/ Fe
– E oCr  3 / Cr
104. Answer (2)

Li has maximum reducing power.
105. Answer (3)
WAg WMg
=
E Ag EMg
106. Answer (3)
BaSO4 = (C1 – 2C2 + C3)
M 0.01
K= = (C1 – 2C2 + C3) ×
1000 1000

According to Debye Huckle onsager equation,
C    A C
Here A = B
 C     B C
107. Answer (2)

Pb(s) + CaC2O4(s)  PbC2O4(s) + Ca+2 + 2e–
108. Answer (2)
Temperature coefficient becomes minimum.
109. Answer (3)
Example : Pt | Sn+2, Sn+4
110. Answer (1)
0.0591
E = Eo – log [H+]2 = Eo + 0.0591 × pH
2
E1 – E2 = 0.0591 [(pH)1 – (pH)2]
111. Answer (2)
After electrolysis aqueous NaCl is converted into aqueous NaOH
0.250  35  60
The quantity of electricity passed = F = 5.44 × 10–3 F
96500
The number of equivalents of OH– ion formed = 5.44 × 10–3
5.44  10 –3
 Molarity of NaOH =  1.36  10 –2
0.4L
 POH = –log (1.36 × 10–2) = 1.87
 pH = 12.13
112. Answer (3)
G
=
H
3
CH3OH(l) + O (g)  CO2(g) + 2H2O(l)
2 2
Greaction = Gproducts – Greactant
= [–394.4 – 2 × 237.2] – [–166.2]
= –702.6 kJ
G
We know, efficiency of a fuel cell,    100
H
–702.6
=  100
–726
97%
113. Answer (2)
M C 2
= ,K=
 1– 
114 Answer (2)
– +
CHCOOH + H2O CH3COO + H3O
c 48.15
x (degree of ionisation) =  =  0.1232
0 390.7
cx2 1.0283  10 –3  (0.1232)2

Ka(ionisation constant) = = = 1.78 × 10–5
(1– x) (1– 0.1232)
Current = conductance × potential difference
1000  conductance  cell constant

Equivalent conductance c =
normality
1000  conductance  0.50cm–1

97.1 (ohm–cm2equiv–1) =
0.1(equivalent cm–3 )  1.50
 conductance = 0.02913 ohm–1

 current = 0.02913 × 5 = 0.1456 A

For 0.2 M solution
R = 50 
 = 1.4 S m–1 = 1.4 × 10–2 S cm–1
1 1
    cm
 1.4  10 2
l
Now, R  
a
l R
   50  1.4  10 2
a 
For 0.5 M solution

R = 280 
=?
l
 50  1.4  10 2
a
l
 R
a
1 1 l
  
 R a
1 1
  =  50  1.4  10 2 =  70  10 2 = 2.5 × 10–3 S cm–1
280 280
  1000 2.5  10 3  1000

Now, m  = = 5 S cm2 mol–1 = 5 × 10–4 S m2 mol–1
M 0.5
115. Answer (3)
dE S
=
dT nF
116. Answer (3)
Order of deposition, Br– > OH– > N O3– > F–
117. Answer (1)
E > 0, Q < 1.
1
H  e – 
 H2
2
Apply Nernst equation

1
0.059 PH 2
E0 log 2
1 [H ]
0.059 21/2
E log
1 1
Therefore E is negative.
118. Answer (4)

E = Z × 96500
119. Answer (1)
Fact.
120. Answer (3)
Electrons released from Fe move towards impurity.
121. Answer (1)
122. Answer (2)
Cell is used for prepation of NaOH.
123. Answer (4)
1 Eq of H2O will evolve 11.2 L H2 and 5.6 L O2 at NTP.
124. Answer (3)
No relation with reactions.
125. Answer (2)
1
H2O  O + 2e–, H2O2  O2 + 2e–
2 2
B2H6 + 3O2  B2O3 + 3H2O
27.66 of B2H6 = 1 mole of B2H6 which requires three moles of oxygen (O2) for complete burning
6H2O  6H2+ 3O2 (On electrolysis)
Number of faradays = 12 = Amount of charge
12 × 96500 = i × t
12 × 96500 = 100 × t
12  96500
t second
100
12  96500
t hour
100  3600
t = 3.2 hours
126. Answer (1)

wq
127. Answer (3)
electrolys is 1
NaH    Na  H2 (g)
2
( cathode) anode

On electrolysis only in case of Ca2+ salt aqueous solution H2 gas discharge at Cathode.
Case of Cr
At cathode : Cr3+ + 2e–  Cr
So, Cr is deposited.
Case of Ag
At cathode : Ag+ + e–  Ag
So, Ag is deposited.
Case of Cu
At cathode : Cu2+ + 2e–  Cu
Case of Ca2+
1
At cathode : H2O + e–  H + OH–
2 2
128. Answer (1)

E
w= ×i×t
96500
129. Answer (4)
0.0591 [Cu 2 ]1
E1 – E2 = log
2 [Cu  2 ] 2
130. Answer (2)

Go = – nF Eocell = – 2 × 96500 × 1.10 J
131. Answer (4)
1
H2

+
H +e
–
2
K = [H+] = C1
E = E° – 0.0591 logC1
E decreases if C1 increases.
1
Cl–

Cl2  e
–
2
1 1
K 
– C2
[Cl ]
E = E° + 0.0591 logC2
E increases if C2 increases.

Ag +
Ag + e
–
K = C3
E = E° – 0.0591logC3
E decreases if C3 increases.
132. Answer (2)
133. Answer (4)
For spontaneous cell reaction, E > 0.
For Cr3+, E°Cr 3+ /Cr O2– = – 1.33 V

2 7
For Cl–, E°Cl– /Cl = – 1.36 V

2
For Cr, E°Cr/Cr 3 = 0.74 V
For Mn2 , E°Mn2 /MnO – = – 1.51 V

4
Positive E° is for Cr, hence it is strongest reducing agent.
134. Answer (1)
G3 = G°1 + G°2

–n3E°3 = – n1E°1 – n2E°2
+3E°3 = 2 × 1.26 – 1 × 0.336
E°3 = 0.728 V
135. Answer (2)

Cu does not react with dilute H2SO4.
136. Answer (2)
E
w= ×it
96500
 127 
 
 1 
10 = × i × 60 × 60
96500
i = 2.11 A
137. Answer (2)
It requires no gaseous reactant.
138. Answer (1)
Eo = +0.22 – 1.36 = –1.14 V
1
0.059
 E  Eo 
1

log PCl2 2
–w max = G = –nFE = (–1) (–1.14) × 96500 × 10–3
=110 kJ mol–1
139. Answer (4)

2 × 1.6 × 10–19C is carried by 1 molecule of Zn2+
1
 2 × 10–5 C is carried by =  2  105
2  1.6  1019
1 1
 14
 moles
1.6  10 N0
1

1.6  6.023  1014  1023
= 10–10
140. Answer (2)
1000 sp.conductance
0 (BaSO4 ) 
conc.(Normality)
1000  8  10 –5
Normality =
400
Normality
Molarity =  10 –4 M
2
Ksp = S2 = 10–8 M2
141. Answer (3)
Eºcell  EºCu2 /Cu – EºCr3 /Cr = 0.34 – (– 0.74) = +1.08 V
142. Answer (4)

E  0.5208 V
Cu /Cu
+ –
Ag Ag + e ; E°Ag/Ag+ = –0.80V
– –
AgI+e Ag + I ; E°I– / AgI/Ag+ = –0.15V
Ag + I–
+
AgI E°Cell = –0.95V
K = [Ag+] [I–] = Ksp
0.0591
ECell = log K sp
1
–0.95
 log K sp
0.0591
Ksp = 8.42 × 10–17
143. Answer (2)
0.059   D  
Ecell  0.003  log     0 at equilibrium
2  H  
  D  
0.006  0.059log   
 H  
 D    D
0.102  log       100.102 1.2
 H   H 
144. Answer (3)
145. Answer (3)
146. Answer (1)
The fraction of collision with sufficient energy i.e., e – E a / RT becomes unity only at Ea = 0.
147. Answer (4)
2.303  a 
k= log  
t a–x 
at time (t/2) seconds
0.6932 2.303  a 
 log  
t ( t / 2) a– x 
0.6932  a 
 log  
2  2.303 a– x 
 a 
log    0.15
a– x 
 a 
   1.413
a– x 
a = 1.413a – 1.413x
0.413a = 1.413x
x 0.413

a 1.413
0.413
% fraction of element decayed =  100 = 29%
1.413
148. Answer (1)
1
t 1/ 2 & where n is order of reaction
n –1
a
for zero order reaction n = 0

t1/2 & a
149. Answer (4)
On decreasing the volume of vessel the to half conc. of A and B are increased by factor of
2 times.
 Rate will be increased by a factor of 4 times

Rate = k[A] [B]
150. Answer (2)

For the completion of 75% reaction 2 half life requires.
 2 t1/2 = 50
t1/2 = 25 mins
ln 2
t1/2 =
k
2.303  0.301
 k=
6.93
2.303  a 
log 
 a – 0.99a 
Also, t =
k
2.303  1 
 t = 2.303  0.301  6.93 log  0.01 = 46.05 minutes
151. Answer (3)

Rate = k[0.1]m [0.2]n = 2 × 10–3 …(i)
m n –3
k[0.1] [0.4] = 4 × 10 …(ii)
k[0.2]m [0.2]n = 2 × 10–3 …(iii)
dividing equation (i) by (ii)
n
1  1
 n=1
2  2 
dividing equation (i) by (iii)

m
 1
2 1 m=0
 
 Rate = k[A]0 [B]

2A  B  C  D
1 d[A] d[B] d[C] d[D]

Rate of Reaction =   
2 dt dt dt dt
Let rate of Reaction = k[A]x[B]y
d[C]
Or,  k[A]x [B]y
dt
Now from table,
1.2 × 10–3 = k [0.1]x[0.1]y ...(i)
1.2 × 10–3 = k [0.1]x[0.2]y ...(ii)
2.4 × 10–3 = k [0.2]x[0.1]y ...(iii)
Dividing equation (i) by (ii)
1.2  10 3 k[0.1]x [0.1]y

 
1.2  10 3 k[0.1]x [0.2]y
y
 1
 1  
2
 y0
Now Dividing equation (i) by (iii)
1.2  10 3 k[0.1]x [0.1]y

 
2.4  10 3 k[0.2]x [0.1]y
1 x
 1  1
 2  2
   
 x 1
d[C]
Hence = k[A]1[B]0 .
dt
152. Answer (3)

Temperature cofficient is the ratio of rate constant when the temperature differ by 10°
75 32 K
65 16 K
55 8K
45 4K
35 2K
25° K
Since the value of rate constant will be increased by 32 times therefore the rate will be increased by 32 times.
153. Answer (1)
t1/2  a
t1/2 = ka
log t1/2 = log k + log a
y = c + mx
m=1
  = 45°
154. Answer (3)
k = A e –Ea / RT
when Ea = 0
The k = A, it means rate constant is independent of temperature
 k rate constant at 330 K will be 4.5 × 105 s–1
155. Answer (1)
x 10
k= for zero order reaction = = 10
t 1
20
In second case k = = 10
2
30
In third case k = = 10
3
Since rate constant (k) is equal in each case therefore reaction follows the zero order mechanism.
156. Answer (1)
k1
Value of k1 is the least, therefore the conversion A  B is the slowest and rate determing step of the
reaction.
157. Answer (4)

r1 = k[A] – 1st order reaction
r2 = k[A]2 – 2nd order reaction
r3 = k[A]3 – 3rd order reaction
When the rate constant k is same for three reaction it is clear that
r1 = r2 = r3 when [A] = 1
r1 > r2 > r3 when [A] < 1
r1 < r2 < r3 when [A] > 1
158. Answer (3)
Ea
Energy
P
H
R z
Reaction progress
It is clear from the graph that Ea should be greater than H.

159. Answer (2)
Since the half life of first order reaction is independent of initial conc.
160. Answer (4)
At intersection of two curve the concentration of A and B are equal (i.e., half of the reactant converted into
products) therefore it represent the half life of A.
161. Answer (2)
Rate = k[A][B]2 since [A] is taken in excess therefore its concentration remain almost constant
 Rate = k[B]2 k × [A] = k
 Order of reaction = 2
162. Answer (2)
Positive catalyst increases the rate of chemical reaction by lowering of activation energy of system.
163. Answer (2)
k = A e –Ea / RT
Ea
ln k = ln A –
RT
y = c + mx
Ea
Slope of graph = –
R
164. Answer (1)
A (g)  2 B (g)  C (g)

t  0 PA  90 0 0
t  t 90 – x 2x x
After time t 90 + 2x = 180

x = 45
2.303 90
k= log
10×60 90 – 45
0.6932
= 10×60
= 1.155 × 10–3 s–1

Assume the order of reaction with respect to acetaldehyde is x.
Condition-1 :
Rate = k[CH3CHO]x
1 = k[363 × 0.95]x
1 = k[344.85]x ...(i)
Condition-2 :
0.5 = k[363 × 0.67]x
0.5 = k[243.21]x ...(ii)
Divide equation (i) by (ii),

x
1  344.85 
   2  (1.414)x
0.5  243.21 
 x=2
165. Answer (1)

166. Answer (3)
Heat of the reaction H = Ea f – Eab
 H = x
and the activation energy of reverse reaction is also x.
167. Answer (2)
Rate = k[NO2] 2
Rate of reaction is independent of concentration of CO.
168. Answer (2)
Rate of reaction = [A]a
[A]I = 2.2 M r1 = 2.4 M s–1
2 .2 2 .4
[A]II = = 1.1 M r2 = 0.6 or
2 4
On reducing the conc. of A to half the rate of reaction is decreased by 4 times.
169. Answer (2)
170. Answer (1)
Rate constant depends only on temperature.
171. Answer (1)

172. Answer (3)
Rate = k[ester] [H+ ]
K H2SO 4  K [H  ]H2SO 4
KHCl = K[H+] HCl
Since [H+] is obtained from H2SO4 is more than HCl therefore K H2SO4  K HCl .
173. Answer (3)

Since concentration of increases time to time but not linearly.
174. Answer (1)
1 d [I– ] d [I ]
–  2
2 dt dt
d [I– ] 0.5 – 0.46

  0.004 M min –1
dt 10
d [I2 ]
 0.002 M min –1
dt

0.693
Rate = K[H2O2] =  0.05
25
1 0.693
Rate of formation of H2O2 =   0.05 = 6.93 × 10–4 mol min–1
2 25
175. Answer (2)

Rate = k[A]
8.75 × 10–5 = k(0.5)
k = 17.5 × 10–5 s–1 = 1.75 × 10–4 s–1
176. Answer (4)
Since the concentration of H2O2. If (first order reaction) decreases with the time as (at = a0 e –kt ) therefore graph
(4) is correct.
177. Answer (2)
t = 144 = 1.44 × 100
1
= 1.44 t1/2, tav =

1
=

1
N N ·
e = 0  0 e  e
t
N N
N0
 N=
e
178. Answer (4)
2.303 a 2.303
t= log = 2
k a  0.99a k
2.303  2
t=
k
 1
t = 2.303  2 ·  = 4.604 tav = 4.6
k 
179. Answer (2)
K 2Ea  K 2Ea 1.0  10 2  60  3.0  10 2  70

Ea  = = 67.5 kJ mol–1
K 2  K a 1.0  10 2  3.0  10 2
180. Answer (3)
Rate = k[A]x [B] y
R = k[A]x [B]y …(i)
R
= k[2A]x [2B]y …(ii)
2
R
= k[2A]x [B]y …(iii)
4
Dividing equation (ii) by (iii)
2 = [2] y
y=1
dividing equation (i) and (iii)
x
 1
4 =   x = –2
2
181. Answer (2)
CA  2, CB  4
182. Answer (3)

1
t1/ 2  n –1
a
t1/2 × an – 1 = constant
 n=2
183. Answer (3)
0.6932
t1/2 =
k
2.303 100 2.303

t = log  log1000
k 0 .1 k
6.909
=
k
 t = 10 t1/2

ln 2
t1/2 =
k
2.303  0.301
 k =
6.93
2.303  a 
log 
 a – 0.99a 
Also, t =
k
2.303  1 
  6.93 log 
 0.01
t =
2.303  0.301
= 46.05 minutes
184. Answer (3)
k2
 e(E1 – E 2 ) / RT
k1
E1 – E 2 2
  2 .5
RT 2 10 – 3  400
k2
 e 2 .5
k1
k 2  e 2 .5 k 1
185. Answer (1)
At very high conc. of NH3
1 + k2 [NH3 ] k2 NH3
k 1[NH3 ]
rate =  constant
k 2 [NH3 ]
This follows the zero order kinetics therefore rate is independent of conc. of NH3 .
186. Answer (3)
A (g)  2 B (g)  C (g)

initial pressure P0 0 0
After reaction P0 – P 2P P
total pressure after the reaction

P0 – P + 2P + P = Pt
 2P = Pt – P0
 Pt – P0  2.303  P0  P0 2.303  2 P0 
P =   = log   = 2.303 log = log  
 2  t  0  t  0  P – P0  t  3 P0 – P 
 P –P   t 
P –  t 

  2 
187. Answer (2)

After the expiry of 40 mins the reactant A decomposes to 75% therefore
A (g)  B (g)  C (g)

Initial pressure 400 0 0
 3 3 3
After t  40 mins 4001–  400  400 
 4 4 4
 total pressure of reaction mixture
 3 3 3 3
= 400 1–   400   400  = 400  400  = 400 + 300 = 700 mm of Hg
 4 4 4 4
188. Answer (1)

Let N0 and N be the number of atoms of the radioactive substance present at the start and after 5 minutes
respectively rate of disintegration at the start = N0 = 275 and the rate of disintegration after 5 minute = N
N0 475
= 270 dividing both, 
N 270
N0
Or,  1.76
N
2.303 N
We know that   log10 0
t N
2.303
 log10 1.76 = 0.113 minute–1
5
0.693 0.693
Half life period =   6.1 minute
 0.113
189. Answer (4)
7500  0.012 0.35
Weight of radioactive potassium =  = 0.0315 g
100 100
0.693 Weight

Activity = t1/2 Atomic weight  Avogadro’s number
0.693 0.0315
Activity = 9
  6.023  1023 = 4.81  105 dpm
1.3  10  365  24  60 40
190. Answer (2)
k1 2.5 10 –3 2.5 10 –3 10 2 25

% of y = 100 =  100 = –2 = = 16.66%
k1  k 2 – 3
2.5 10  1.25 10 – 2 1.50 10 1.50
% z = 100 – 16.66 = 83.34%
191. Answer (2)

K1
Cyclohexene
Bicyclohexane
K2
Methyl cyclopentene
K1 1.26  104
Percentage of cyclohexene =  100 =  100 = 77%
K1  K 2 1.26  104  3.8  10 5
 % of methyl cyclopentene = 23%
192. Answer (2)
kf = 4 × 10–4
kb = 2 × 104
kf 4 10 –4
keq =  4
 2 10 – 8
kb 2 10
193. Answer (1)
k 500  A e –Ea / R  500 …(i)
k 400  A e –(Ea – 20 ) / 400 R …(ii)

from equation (i) and (ii) we get
Ea (E – 20)
– – a
500 R 400 R
– 4 Ea = – 5 Ea + 100
Ea = 100 kJ mol –1

–Ea /RT
k1 = Ae 1
–Ea /RT
k2 = Ae 2
1
k2 Ea – Ea2 
e RT 1
k1 =
k Ea – Ea2 10  103
ln 2 = 1 = 4
k1 RT 8.314  300
194. Answer (4)

Rate = k[N2O5 ]
2.4 × 10–5 = 3 × 10–5 [N2O5 ]
2 .4
[N2O5 ] =  0 .8
3
195. Answer (1)
The rate constant of the decay is
0.693 0.693
K 
t1/2 22
If K1 and K2 are the rate constants of the reactions leading to 222Th and Fr223, respectively we have
0.693
K1 + K2 =
22
K1 2

K 2 98
On solving for K1 and K2 we get
K2 = 0.03087–1y–1
K1 = 0.00063–1y–1
196. Answer (4)
  N 
 ln  N 
   N0  24  N  48 g
t  t1
 
2
.  0
 ln 2  N
0
197. Answer (4)
0.693 2.303 4 1
9
 log
4.5  10 t 4
2.303  4.5  109 10

t log 3
0.693 2
2.303  4.5  109

=  0.1
0.693
= 1.445  109 years

198. Answer (4)
Rate = k[A]n
r1 = k[A]n
8r1 = k 4n.[A]n
 2n = 3  n = 1.5
199. Answer (3)
X is intermediate.
200. Answer (2)
K1E1  K 2E2 102  60  3  102  70

Ea  
K1  K 2 102  3  102
= 67.5 kJ mol–1
201. Answer (4)
x ap
Apply  . At high P, 1 + bp  bp.
m 1+ bp
202. Answer (3)

Based on definition of peptization.
203. Answer (3)
Size of clay particles is greater than 100 nm.
204. Answer (4)
The size of crystalline particles are very small as compare to diameter of pores of membrane.
205. Answer (2)
Fluorescein and Eosin are examples.
206. Answer (1)
207. Answer (3)
208. Answer (3)
209. Answer (3)
Higher the critical temperature higher the adsorption of gas.
210. Answer (4)
211. Answer (4)
Catalyst decreases activation energy hence rate constant increases.
Ea
–
K  Ae RT
A
K Ea
e RT
As Ea decreases, K increases.
Hence rate of reaction increases.
212. Answer (4)
213. Answer (2)
Colloids of metal and their sulphides are prepared by special methods not by simple mixing.
214. Answer (3)
Lyophilic colloids not easily coagutated and are highly stable.
215. Answer (3)
Kraft temp. = Temp. above which micell is formed.
216. Answer (2)
217. Answer (3)
Brownian motion is zig-zag motion responsible for stabilisation of colloids and it prevent the colloidal particle
to settle down.
218. Answer (2)
2AuCl3 + 3HCHO + 3H2O 
 2Au(sol) + 3HCOOH + 6HCl
219. Answer (2)
Cellulose is a polymer having very large particle size.
220. Answer (3)
Fauzasite is natural, Na56[(AlO2)56(SiO2)136]  250 H2O.
221. Answer (2)
Chemisorption is irreversible.
222. Answer (3)
KI KI
AgNO3  AgI  [AgI] I—
223. Answer (2)
For adsorption, S < 0, H < 0, G < 0.

Physisorption is an exothermic process with H –20 kJ/mol
224. Answer (3)

More contact with catalyst, faster rate of hydrogenation.
225. Answer (4)
In Bergious process Fe2O3 is used as catalyst.
226. Answer (1)
Brownian movement is independent to nature of solute.
227. Answer (2)
Due to very high difference between refractive indices of dispersed phase and dispersion medium.

For Tyndall effect refractive index of dispersion phase and dispersion medium must differ significantly.
Secondly, size of dispersed phase should not differ much from wavelength used.
228. Answer (1)

Proteins in acidic medium is positively charged and in basic medium, negatively charged. Au and CdS are
negatively charged.
229. Answer (4)
4 
Z=
D
230. Answer (1)
Ferric hydroxide is positively charged colloid.
231. Answer (1)
Gold numbers
Potato starch = 25
Gum Arabic = 0.15
Haemoglobin = 0.03
Gelatin = 0.001
232. Answer (4)
Both emulsions show different properties in given tests.
233. Answer (2)

It can describe only physisorption.
234. Answer (2)
It is an example of induced catalysis.
235. Answer (1)
Micelle formation takes place only above a certain temperature, hence, H = +ve
236. Answer (1)
Fact
237. Answer (4)
Fact
238. Answer (1)
Fact
239. Answer (3)
 E
S  nF   2  96500  1.5  104 = 28.95 JK–1 mol–1
  T  P


SA 19 20 XII Chemistry Unit-1

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SA 19 20 XII Chemistry Unit-1

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Physical Chemistry UNIT 1

12a. Answer (1) (AIEEE 2011)

13. Answer (3)

13a. Answer (3) [JEE (Main)-2018]

14. Answer (2)

15a. Answer (3) [JEE (Main)-2014]

16. Answer (3)

Number of metal ions = 1  2 3

Hence, formula of metal oxide is M3O4.

The length of face diagonal = a 2

19a. Answer (1) (AIEEE 2009)

19b. Answer (2) [JEE (Main)-2017]

In FCC, one of the face is like A

20. Answer (4)

Body diagonal of cube = 3 a = (1.732) (387 pm) = 670.3 pm

2 (r+ + r–) = 670.3 pm

22. Answer (2)

22a. Answer (1) [JEE (Main)-2016]

23. Answer (1)

ax 2 (x = cell edge length)

24. Answer (2)

26a. Answer (3) (AIEEE 2012)

26b. Answer (1) [JEE (Main)-2015]

27. Answer (2)

rNa  0.75 rK  …(i)

2(rK   rCl– ) 2(0.733  1)

30. Answer (4)

Hence, simplest formula is NaCl.

37.46 a13 a 37.46

36. Answer (3)

38. Answer (1)

and in Ostwald Walker process

PB  P loss in weight of solvent

mass of HCl  1000

from eq. (ii) to (i)

48. Answer (3)

(1.984 gcm3 )(630  10 10 cm)3 (6.023  1023 mol1)

 i1n1RT   i2n 2RT 

54a. Answer (2) [JEE(Main)-2016]

At normal boiling point of water V.P. = pº = 760 torr

or, 1800 ps = 760 × 1782

55. Answer (2)

 from equation (i)

760  750 0.1(1   )

56. Answer (3)

Solution will be ideal and for ideal solution Hmix. = 0.

57. Answer (3)

According to above equation,

∵ 1 mole of Al2SO4 producing 2 moles of Al3+

58. Answer (2)

for CH3COOH,  = 50% i.e. = 0.5

61a. Answer (1) (AIEEE 2009)

62. Answer (3)

63. Answer (1)

Vapour pressure does not changes with enthalpy.

64. Answer (2)

65. Answer (2)

67a. Answer (4) [JEE (Main)-2018]

68. Answer (1)

Hvap = Lv × M.m = 540 × 18 = 9720 cal/mole.

69. Answer (3)

From Eqn (i)

69a. Answer (2) [JEE (Main)-2015]

Vapour pressure of pure acetone P°A = 185 torr