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Solutions to Selected Questions for Revision | Physical Chemistry-II

1. Aq, r : B  r, s ; Cr, t ; Dp, s

In cubic cell axial lengths a = b = c
Refer to text for calculation of total number of atoms present in unit cell.
2. [A - p, s ; B - p, q ; C - q ; D - q, r]
(A) Simple cubic and FCC belong to the same crystal system and have a = b = c and       90
(B) Cubic and rhombohedral are two crystal systems where a = b = c and     

(C) Cubic and tetragonal are two crystal systems

(D) Hexagonal and monoclinic are two crystal systems and two crystallographic angles are equal
3.(A)

4.(D)

5.(ABC)

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6.

7.

8.

9.

10.

 4 3  4 3
 zeff  rA    z eff  rB 
 3 A  3 B
11.(C) P.F.  3
a
2  rA  rB   3a
4 4 4
1 rA3 
3 3
 
 8rA3 9 
3  
 2  rA  2rA   3a  2 3rA  a  P.F.  3

8 3 3rA 83 3 2 3

P.F   100  90%
2 3

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M X
12.(3.00) CCP OHV (octahedral void)
4 4
X  4 3  3 1  3 (Anion)
M  4  3 1  1  1 (Cation)

13.

14.

15.

16.

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17.

HgI 2  2KI 
 K 2 HgI 4
18.(B) When H gI2 is added to KI :
Moles 0.05 0.1 0.05
 0.05moles of HgI 2 are required for its complete reaction with KI
Thus, as HgI 2 is being added, number of solute molecules will decrease causing Tf to decrease  [Causing
Tg to increase]. When whole of KI has been converted to K 2 HgI 4 , further addition of HgI2 doesn’t change the Tg
since it is a sparingly soluble salt.
0.7 7
19.(2) 0.7  2  K f  0.2  Kf  
0.4 4

Hg  CN 2  mCN   Hg (CN)m
m2
0.1 0.2 0
0  0.2  0.1m  0.1
Now, Molarity of K   0.2 M ; Molarity of CN    0.2  0.1m  M ; Molarity of complex  0.1 M
0.53  K f  0.2  0.2  0.1m  0.1  K f  0.5  0.1m 
7
 0.53   0.5  0.1m   2.1  3.5  0.7m  0.7m  1.4  m  2.
4
20.(C) At a particular temperature as intermolecular forces of attraction increases, vapour pressure decrease.
So intermolecular forces of attraction of X < Y < Z.
21.(BD)

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 Z represent vapour pressure of pure liquid L and as  L  1 , the given graph is merging with ideal graph
of p L . Hence Option (C) is correct
 Since, vapour pressure of liquid L(pL ) is higher than the ideal values so L-M interactions are weaker than
L-L & M-M interactions. Hence Option (B) is correct choice.
22.(0.05) Case : 1
For solvent X
Solute: NaCl
Molality: m1
i2
Tb  (362  360)  2 (from graph)
1
Tb  i(m)(K b ) x  2  (2)(m)(K b ) x …………..(1) ; (K b ) x 
m1
Fro solvent Y
Solute : NaCl
Molality : m2
i2
Tb  (368  367)  1 (from graph)
Tb  i m(K b ) y
1
1  (2)(m1 )(K b ) y …………..(2) ; (K b ) y 
2m 2
Dividing (1) by (2)
2 2 m1 (K b ) x

1 2 m 2 (K b ) y
(K b ) x
2 ……(3)
(K b ) y
Case : 2
For solvent X:
Solute : Non volatile
Molality : m 2
i  ix
Tb  3a ; Tb  i x m(K b ) x
3a  i x m2 (K b ) x ………(4)
For solvent Y:
Solute : Non volatile
Molality : m2
i  iy
Tb  a ; Tb  i y m(K b ) y
a  i y m 2 (K b ) y ………(5)
Dividing (4) by (5)
3a i x m (K b ) x ix (K b ) y 3
 ;  3 
a i y m (K b ) y iy (K b ) x 2
ix 3
Now 
iy 2

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In solvent Y:
2S 
 S2
1 1
0.7 2  0.7 1.3
(1  0.7) 0.7 / 2 ; i y  1   
2 2 2
In solvent X:
2S 
 S2
1 1
 
1  ; ix  1 
2 2
i x 3 (1  0.5) 3 (1  0.5) 3  1.3
  2   2 ;  (1  0.5 )    0.05
iy 2 1.3 2 1.3 4
Higher the no. of particles, higher is the elevation in B.P.

23.

24.

25.

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26.

27.

28.

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29.

30.

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31.

E
 a
32.(A) k  A e RT

k v/s Ea k v/s T(C)

If Ea  k If T  k
Hence both graphs are correct
33. t1/2 = 21.2 min , k = 3.26 ×10-2 min -1
k
A  Product
(i) A 
B k
(ii) B  Product
Ea  10 
For (i)    ln 2
R  300  310 
E a (i)
 E a (i)  9300 ln 2  53.6 kJ  E a (ii)   26.8 kJ
2
At 310 K t1/2 (i) = 30 min
 Rate of (ii) = 2 rate of (i)  t1/2 (ii) 15min
Now for reaction (ii):
 k (310)   t1/2 (300)  E a (ii)  10 
ln  B   ln    
 k B (300)   t1/2 (310)  R  300  310 
 t (300)  ln 2
 ln  1/2   t1/2 (300)  21.2 min
 15  2
ln 2 0.693
 k B (300)    3.26  102 min 1
t1/2 21.2
34.(AC) K  P  Z e  Ea RT
(According to Arrhenius equation)
A
K  A e Ea RT
 P
Z
According to collision theory, P value is generally less than unity but for some reactions P is greater than one and
for such reactions, observed rate is greater than rate predicted from Arrhenius equation.
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For a reaction with P value greater than 1, implies that the experimentally determined value of frequency factor
(A) is higher than that predicted by Arrhenius equations and such reactions proceeds rapidly without the use of a
catalyst.

35.

36.

37.

38.

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39.

40.

41.

42.

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44.

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45.

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46.

47.

48. (i) – (B), (ii) – (D), (iii) – (D)

49.(B) W  Z. Q  Z  W / Q  g / coulomb

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1
50.(B) H   e  
 H2
2
0.5mol H 2  11200cc H 2  1F
1F
1.12cc H 2   1.12  9.65C
11200
Q  it  9.65  i  1  i  9.65A
51.(C) Opposite charges attract each other. Hence on mixing coagulation of two sols may be taken place.
52.(D) Fact

53.(A) Let the weight of acetic acid initially be W1 in 50 ml of 0.06N

W1  1000
0.06   W1  0.18g  180mg
60  50
After an hour, the strength of acetic acid = 0.042 N
W2  1000
0.042   W2  0.126g  126mg
60  50
So the amount of acetic acid adsorbed per 3g = 180 – 126 = 54 mg
54
Amount of acetic acid adsorbed per g   18mg
3
54.(B) Easily liquefiable gases (i.e., with higher critical temperature) are readily adsorbed as van der Waal’s forces are
stronger near the critical temperature.

103  10
55.(A) Number of particles  NA
103
103  10
Total area = Area covered by one particle × number of particle 0.24 = Area  3
 6  1023
10
20 2
Area  4  10 cm
(a) edge length  2  1010 cm  2 pm

56.(C) Mass of fatty acid = 0.027g ; Density = 0.9 g/cc

0.027
Volume of fatty acid   0.03cm3
0.9
2
Area of plate  r 2  3  10   300cm2
Volume of fatty acid = area of plate × height of fatty acid layer
0.03
0.03cm 3  300  h  h cm  10 4 cm  106 m
300
*57.(BCD)
 M   e  , O 2  e  
Reaction on metal surface M   O 2 This is an example of chemisorption.

58.(D) Impurities affect surface tension appreciably. It is observed that impurities which tend to concentrate on surface of
liquids compared to its bulk lowers the surface tension.
Substances like soaps (CH 3 (CH 2 )11 SO3 Na  ) decrease the surface tension sharply and those like alcohol
(CH 3OH, CH3CH 2 OH) lowers the surface tension slightly. Inorganic impurities present in bulk of a liquid such
as KCl tend to increase the surface tension.
*59.(BC)
(a) cloud is an aerosol in which liquid is dispersed phase and gas is dispersion medium. Whereas emulsion is
liquid in liquid system.
(b) higher the critical temperature of a gas, greater the amount of gas adsorbed thus, ethane will be
adsorbed to a greater extent then nitrogen.

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(c) Adsorption is an exothermic process, thus enthalpy decreases during this process. On adsorption, the
randomness of adsorbate molecules decreases, thus entropy decreases.
(d) Brownian motion of colloidal particles depends on the size of the particles as well as on viscosity of the
solution.
60.(C) Molar conductivity decreases with concentration till CMC
& further decreases rapidly beyond CMC.

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