EXERCISE I

Q.1 For an ideal binary liquid solution with PA > PB , which relation between XA (mole fraction of A in liquid
phase) and YA(mole fraction of A in vapour phase) is correct?
YA X A YA X A
(A) YA < YB (B) XA > XB (C) Y  X (D) Y  X
B B B B
Q.2 Mole fraction of A vapours above the solution in mixture of A and B (XA = 0.4) will be
[Given : PA = 100 mm Hg and PB = 200 mm Hg]
(A) 0.4 (B) 0.8 (C) 0.25 (D) none of these
Q.3 The exact mathematical expression of Raoult’s law is

P 0  Ps n P 0  Ps N P 0  Ps n P 0  Ps
(A)  (B)  (C)  (D) =n×N
P0 N P0 n Ps N P0

Q.4 A mixture contains 1 mole of volatile liquid A ( PA =100 mm Hg) and 3 moles of volatille liquid
B ( PB = 80 mm Hg). If solution behaves ideally, the total vapour pressure of the distillate is
(A) 85 mm Hg (B) 85.88 mm Hg (C) 90 mm Hg (D) 92 mm Hg
Q.5 Which of the following aqueous solution will show maximum vapour pressure at 300 K?
(A) 1 M NaCl (B) 1 M CaCl2 (C) 1 M AlCl3 (D) 1 M C12H22O11
Q.6 The Van’t Hoff factor for a dilute aqueous solution of glucose is
(A) zero (B) 1.0 (C) 1.5 (D) 2.0
Q.7 The correct relationship between the boiling points of very dilute solution oif AlCl 3 (T1K) and
CaCl2 (T2K) having the same molar concentration is
(A) T1 = T2 (B) T1 > T2 (C) T2 > T1 (D) T2  T1
Q.8 A 0.001 molal solution of a complex [MA8] in water has the freezing point of –0.0054°C. Assuming
100% ionization of the complex salt and Kf for H2O = 1.86 km–1, write the correct representation for
the complex
(A) [MA8] (B) [MA7]A (C) [MA6]A2 (D) [MA5]A3
Q.9 The vapour pressure of a solution of a non-volatile electrolyte B in a solvent A is 95% of the vapour
pressure of the solvent at the same temperature. If the molecular weight of the solvent is 0.3 times the
molecular weight of solute, the weight ratio of the solvent and solute are
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0
Q.10 At a given temperature, total vapour pressure in Torr of a mixture of volatile components A and B is
given by
PTotal = 120 – 75 XB
hence, vapour pressure of pure A and B respectively (in Torr) are
(A) 120, 75 (B) 120, 195 (C) 120, 45 (D) 75, 45
Q.11 Assuming each salt to be 90 % dissociated, which of the following will have highest boiling point?
(A) Decimolar Al2(SO4)3
(B) Decimolar BaCl2
(C) Decimolar Na2SO4
(D) A solution obtained by mixing equal volumes of (B) and (C)
Q.12 The vapour pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute was added to
the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the solvent if
decrease in vapour pressure is 20 mm of Hg
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8

Q.13 Elevation of boiling point of 1 molar aqueous glucose solution (density = 1.2 g/ml) is
(A) Kb (B) 1.20 Kb (C) 1.02 Kb (D) 0.98 Kb

Q.14 What will be the molecular weight of CaCl2 determined in its aq. solution experimentally from depression
of freezing point?
(A) 111 (B) < 111 (C) > 111 (D) data insufficient

Q.15 1.0 molal aqueous solution of an electrolyte A2B3 is 60% ionised. The boiling point of the solution at 1
1
atm is ( K b( H 2O)  0.52 K kg mol )
(A) 274.76 K (B) 377 K (C) 376.4 K (D) 374.76 K

Q.16 Which of the following plots represents an ideal binary mixture?

(A) Plot of Ptotal v/s 1/XB is linear (XB = mole fraction of 'B' in liquid phase).
(B) Plot of Ptotal v/s YA is linear (YB = mole fraction of 'A' in vapour phase)
1
(C) Plot of P v/s YA is linear
total

1
(D) Plot of P v/s YB is non linear
total

Q.17 Pressure over ideal binary liquid mixture containing 10 moles each of liquid A and B is gradually decreased
isothermally. If PAo =200 mm Hg and PBo =100 mm Hg, find the pressure at which half of the liquid is
converted into vapour.
(A) 150 mm Hg (B) 166.5 mm Hg (C) 133 mm Hg (D) 141.4 mm Hg

Q.18 The lowering of vapour pressure in a saturated aq. solution of salt AB is found to be 0.108 torr. If vapour
pressure of pure solvent at the same temperature is 300 torr. Find the solubility product of salt AB
(A) 10–8 (B) 10–6 (C) 10–4 (D) 10–5
Q.19 Which of the following represents correctly the changes in thermodynamic properties during the formation
of 1 mol of an ideal binary solution.

(A) (B) (C) (D)

Q.20 FeCl3 on reaction with K4[Fe(CN)6] in aqueous solution gives blue

colour. These are separated by a semipermeable membrane AB as
shown. Due to osmosis there is
(A) blue colour formation in side X.
(B) blue colour formation in side Y.
(C) blue colour formation in both of the sides X and Y.
(D) no blue colour formation.
 EXERCISE II

OBJECTIVE

Q.1 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74% [JEE 1999]

Q.2 In the depression of freezing point experiment, it is found that

(I) The vapour pressure of the solution is less than that of pure solvent.
(II) The vapour pressure of the solution is more than that of pure solvent.
(III) Only solute molecules solidify at the freezing point.
(IV) Only solvent molecules solidify at the freezing point.
(A) I, II (B) II, III (C) I, IV (D) I, II, III [JEE 1999]

Q.3 During depression of freezing point in a solution, the following are in equilibrium
(A) liquid solvent-solid solvent (B) liquid solvent-solid solute
(C) liquid solute-solid solute (D) liquid solute-solid solvent [JEE 2003]

Q.4 A 0.004 M solution of Na2SO4 is isotonic with a 0.010 M solution of glucose at same temperature. The
apparent degree of dissociation of Na2SO4 is
(A) 25% (B) 50% (C) 75% (D) 85% [JEE 2004]

Q.5 The elevation in boiling point, when 13.44 g of freshly prepared CuCl2 are added to one kilogram of
water, is [Some useful data, Kb (H2O) = 0.52 kg K mol–1, mol. wt. of CuCl2 = 134.4 gm]
(A) 0.05 (B) 0.1 (C) 0.16 (D) 0.21 [JEE 2005]

SUBJECTIVE
Q.6 A very small amount of a nonvolatile solute (that does not dissociate) is dissolved in 56.8 cm3 of benzene
(density 0.889 g cm3), At room temperature, vapour pressure of this solution is 98.88 mm Hg while
that of benzene is 100 mm Hg. Find the molality of this solution. If the freezing temperature of this
solution is 0.73 degree lower than that of benzene. What is the value of molal freezing point depression
constant of benzene? [JEE 1997]

Q.7 A solution of a nonvolatile solute in water freezes at 0.30°C. The vapor pressure of pure water at
298K is 23.51mmHg and Kf for water is 1.86 degree/molal. Calculate the vapor pressure of this solution
at 298K. [JEE 1998]

Q.8 To 500 cm3 of water, 3×10–3 kg of acetic acid is added. If 23% of acetic acid is dissociated, what will
be the depression in freezing point ? Kf and density of water are 1.86 K kg–1 mol–1 and 0.997 g cm–3
respectively. [JEE 2000]

Q.9 The vapour pressure of two miscible liquids (A) and (B) are 300 and 500 mm of Hg respectively. In a
flask 10 mole of (A) is mixed with 12 mole of (B). However, as soon as (B) is added, (A) starts
polymerising into a completely insoluble solid. The polymerisation follows first-order kinetics. After 100
minute, 0.525 mole of a solute is dissolved which arrests the polymerisation completely. The final vapour
pressure of the solution is 400 mm of Hg. Estimate the rate constant of the polymerisation reaction.
Assume negligible volume change on mixing and polymerisation and ideal behaviour for the final solution.
[JEE 2001]
Q.10 Match the boiling point with Kb for x, y and z, if molecular weight of x, y and z are same.[JEE 2003]
b.pt. Kb
x 100 0.68
y 27 0.53
z 253 0.98

Q.11 1.22 g of benzoic acid is dissolved in (i) 100 g acetone (Kb for acetone = 1.7) and (ii)100 g benzene
(Kb for benzene = 2.6). The elevation in boiling points Tb is 0.17°C and 0.13°C respectively.
(a) What are the molecular weights of benzoic acid in both the solutions?
(b) What do you deduce out of it in terms of structure of benzoic acid? [JEE 2004]

Q.12 72.5 g of phenol is dissolved in 1 kg of a solvent (kf = 14) which leads to dimerization of phenol and
freezing point is lowered by 7 kelvin. What percent of total phenol is present in dimeric form?
[JEE 2006]
 ANSWER

EXERCISE I

Q.1 C Q.2 C Q.3 C Q.4 B Q.5 D Q.6 B Q.7 B

Q.8 C Q.9 B Q.10 C Q.11 A Q.12 C Q.13 D Q.14 B
Q.15 D Q.16 C Q.17 D Q.18 C Q.19 C Q.20 D

EXERCISE II

Q.1 B Q.2 C Q.3 A Q.4 C

Q.5 C Q.6 0.1452, 5.028 K m –1

Q.7 23.44 mm Hg Q.8 0.229 Q.9 1.0 × 10–4

Q.10 Kb(x) = 0.68, Kb(y) = 0.53, Kb(z) = 0.98

Q.11 (a)122, (b) It means that benzoic acid remains as it is in acetone while it dimerises in benzene
O H O
as C C
O H O
Q.12 35% phenol is present in dimeric form