SOLUTIONS 43

EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION

3 –3
1. To 500 cm of water, 3.0 × 10 kg of acetic acid is added. If
23% of acetic acid is dissociated, what will be the Sol. For isotonic solutions, they must have same
concentrations of ions,
depression in freezing point? Kf and density of water are
–1 –1 –3 Therefore, 0.004 i(Na 2SO4 )  0.01
1.86 K kg mol and 0.997 g cm , respectively. (2000)
Ans. (0.228 K) 0.01
 i=
Sol. Mass of water = 500 × 0.997 g = 498.5 g 0.004
Also Na 2SO4  2Na + +SO42- i
Also CH 3COOH CH 3 COO   H  1-α 2α α 1+2α
1   
 i  1  2  2.5
 i  l    1.23 α  0.75  75%
3 1000
 Tf  ik f .m  1.23 1.86    0.228K
60 498.5 5. 1.22 g of benzoic acid is dissolved in 100 g of acetone and
100 g of benzene separately. Boiling point of the solution
2. During depression of freezing point in a solution the in acetone increases by 0.17ºC, while that in the benzene
following are in equilibrium (2003) increases by 0.13ºC; Kb for acetone and benzene is 1.7 K
–1 –1
(a) liquid solvent, solid solvent Kg mol and 2.6 K kg mol respectively. Find molecular
(b) liquid solvent, solid solute weight of benzoic acid in two cases and justify your
(c) liquid solute, solid solute
answer. (2004)
(d) liquid solute, solid solvent
Ans. (122;244)
Ans. (a)
Sol. During freezing, liquid solvent solidify and solid solvent Sol. (i) ΔTb =K b .m 2
remains in equilibrium with liquid solvent. 1.22 1000
 0.17  1.7  
M 100
 M  122
3. Consider the three solvents of identical molar masses. 1.22 1000
Match their boiling point with their kb values (2003) (ii) 0.13  2.6  
M 100
Solvents Boiling point kb values  M  244
X 100ºC 0.92 The above molar masses higher the value of Kb of a
Y 27ºC 0.63 solvent suggests that benzoic acid is monomeric in
acetone while dimeric in benzene.
Z 283ºC 0.53
Sol. Higher the values of K b of a solvent suggest that there is 6. The elevation in boiling point of a solution of 13.44g of
larger polarity of solvent molecules, which in turn implies CuCl2 in 1 kg of water using the following information will
higher boiling point due to dipole-dipole interaction. be ( Mol ec ul a r weight of CuCl 2 = 134.4 and
Therefore, the correct order of the three given solvents is –1
Kb = 0.52 K molal ) (2005)
Solvents Boiling point K b values
(a) 0.16 (b) 0.05
o
X 100 C 0.63 (c) 0.1 (d) 0.2
Y o
27 C 0.53 Ans. (a)
o
Sol.
Z 283 C 0.92
CuCl2  Cu 2  2Cl
t0 1mole 0 0
4. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. Degree
After ionisation 1   mole  mole 2 mole
of dissociation of Na2SO4 is (2004)
(a) 75% (b) 50% Thus number of particle after ionisation
(c) 25% (d) 85% 1     2  1  2
Ans. (a)
 44 SOLUTIONS

no.of particles after ionisation

i 8. When 20 g of naphthoic acid (C11H8O2) is dissolved in 50 g of
No.of particle beforeionisation –1
benzene (Kf = 1.72 K kg mol ), a freezing point depression of
1  2
(  on100% ionisation) 2K is observed. The Van’t Hoff factor (i) is (2007)
1 (a) 0.5 (b) 1
i3 (c) 2 (d) 3
Tb  K b  m  i Ans. (a)
Weight of CuCl2  20  1000
Sol. Molality=  × =2.325m
molecular weight of CuCl2  172  50
molality of CuCl2 
Weight of solvent 2
 T f = 2 = iK f .m  i   0.5
13.44 / 134.4 1.72  2.325
Molality   0.1m
1Kg
Tb  0.52  0.1 3
Tb  0.156  0.16o C Comprehension-I
Properties such as boiling point, freezing point and vapour
pressure of a pure solvent change when solute molecules
7. 75.2 g of C6 H5OH (phenol) is dissolved in 1kg of solvent
are added to get homogeneous solution. These are called
of kf = 14. If the depression in freezing point is 7K, then colligative properties. Applications of colligative
find the percentage of phenol that dimerises. (2006) properties are very useful in day-to-day life. One of its
Ans. (0075) examples is the use of ethylene glycol and water mixture
1000×K f ×WB as anti-freezing liquid in the radiator of automobiles.
Sol. Molar mass of solute (M B )= W ×ΔT A solution M is prepared by mixing ethanol and water.
A f
The mole fraction of ethanol in the mixture is 0.9
1000 14  75.2 Given, Freezing point depression constant of water
 MB 
1000  7 (k fwater )=1.86K kg mol -1
M B  150.4g per mol Freezing point depression constant of ethanol
Actual molar mass of phenol  94 g/mol (k ethanol )=2.0K kg mol-1
f
Calculated molar mass Boiling point elevation constant of water
Now, van’t Hoff factor, i = Observed molar mass
(k bwater )=0.52K kg mol -1
94 Boiling point elevation constant of ethanol
i   0.625
150.4 (k ethanol )=1.2K kg mol-1
b
Dimerisation of phenol can be shown as:
Standard freezing point of water = 273 K
2C 6 H 5 OH   C6 H 5 OH  2
Standard freezing point of ethanol = 155.7 K
1 0
Standard boiling point of water = 373 K
Initial: 1 0
Standard boiling point of ethanol = 351.5 K
α
At equilibrium: 1 - α + Vapour pressure of pure water = 32.8 mm Hg
2
α Vapour pressure of pure ethanol = 40 mm Hg
Total number of moles at equilibrium, i=1-α+
2 Molecular weight of water = 18 g mol1
α
i=1- Molecular weight of ethanol = 46g mol1
2
But i=0.625, thus, In answering the following questions, consider the
α α
solutions to be ideal dilute solutions and solutes to be
0.625  1   1  0.625 non-volatile and non-dissociative. (2008)
2 2
α  0.75 9. The freezing point of the solution M is
Thus, the percentage of phenol that dimerises is 75% (a) 268.7 K (b) 268.5 K
(c) 234.2 K (d) 150.9 K
 SOLUTIONS 45

Ans. (d) –1
kg mol ) is (2011)
Sol. In the given solution 'M', H 2 O is solute. –2 –2
(a) – 2.3 × 10 (b) – 5.7 × 10
0.1 –3 –2
Therefore, molality of H 2 O =  1000  2.4 (c) – 5.7 × 10 (d) – 1.2 × 10
0.9  46
Ans. (a)
 ΔT f =K ethanol  2.4  2  2.4  4.8
f Sol. van't Hoff factor (i)=4{3K + +[Fe(CN)6 ]3-
 T f =115.7 - 4.8=150.9 K
0.1 1000 1
Molality   
10. The vapour pressure of the solution M is 329 100 329
(a) 39.3 mm Hg (b) 36.0 mm Hg  T f =2=iK f .m
(c) 29.5 mm Hg (d) 28.8 mm Hg 1
Ans. (b)  4  1.86   2.3  10 2
329
Sol. PA  PAo x A  Tf = -2.3×10-2 o C
PAo  Ps (As % freezing point of water is 0 C )
o
 xB  x B mole fraction of solute 
PAo
40  Ps 14. For a dilute solution containing 2.5g of a non-volatile non-
 0.1 electrolyte solute in 100g of water, the elevation in boiling
40
point at 1 atm pressure is 2ºC. Assuming concentration of
Ps  36mm Hg
solute is much lower than the concentration of solvent,
the vapour pressure (mm of Hg) of the solution is (take Kb
11. Water is added to the solution M such that the mole fraction –1
= 0.76 K kg mol ). (2012)
of water in the solution becomes 0.9. The boiling point of
this solution is (a) 724 (b) 740
(a) 380.4 K (b) 376.2 K (c) 736 (d) 718
(c) 375.5 K (d) 354.7 K Ans. (a)
Sol. The elevation in boiling point is
Ans. (b)
Sol. Now ethanol is solute. n
ΔTb = K b .m; m = molality = 2 ×1000
0.1 w1
Molality of solute   1000  6.17
0.9  18 [n 2 =Number of moles of solute,
 ΔTb  6.17  0.52  3.20 w1 =weight of solvent in gram]
 ΔTb  373  3.2  376.2K n2
 2  0.76   1000
100
12. The Henry’s law constant for the solubility of N2 gas in
5 5
water at 298 K is 1.0 × 10 atm. The mole fraction of N2 in  n2 
19
air is 0.8. The number of moles of N2 from air dissolved in Also, from Raoult’s law of lowering of vapour pressure:
10 moles of water of 298 K and 5 atm pressure is
(2009) Δp n2 n
–4 –5
(a) 4.0 × 10 (b) 4.0 × 10 0
=x 2 =  2  n1  n 2 
–4 –6 p n1 +n 2 n1
(c) 5.0 × 10 (d) 4.0 × 10
Ans. (a) 5 18
 Δp=760× × =36 mm of Hg
19 100
Sol. The partial pressure of N2  0.8  5  4atm
 p=760-36=724 mm of Hg
P  KH x
4 15. 29.2% (w/W) HCl stock solution has density of 1.25 g
x  4  10 5
1 105 atm mL–1. The molecular weight of HCl is 36.5g mol–1. The
So, 10 mole of water contain volume (mL) of stock solution required to prepare a
4.0 104 200 mL solution 0.4 M HCl is (2012)
Ans. (0008)
13. The freezing point (inº C) of solution containing 0.1g of
K3[Fe(CN)6] (mol. wt. 329) in 100g of water (Kf = 1.86 K
 46 SOLUTIONS
As equalmolar solution of A&B
n solute
Sol. Molarity  Let both have I molar each
Vol.of solution
22.5 = PA0 xA +PB0 xB ...  2 
29.2 from (1)
n solute 
36.5
given PA0 =20
29.2  1.25
Molarity  PB0 =70
100
36.5 
1000 then from  2 

Molarity  10 M 22.5=20x A +70x B

M1V1  M 2 V2 22.5=20x A +70(1-x A )
10  V1  0.4  200 x A =0.95
Vl  8 mL
x B =0.05
x A 0.95
16. Benzene and naphthalene form an ideal solution at room = =19
temperature. For this process, the true statements is (are) xB 0.05
(2013)
(a) ΔG is positive (b) ΔSsystem is positive
(c) ΔSsurroundings =0 (d) ΔH=0 18. Mixture(s) showing positive deviation from Raoult’s law
at 35ºC is (are) (2016)
Ans. (b,c,d)
(a) carbon tetrachloride + methanol
Sol. When an ideal solution is formed process is spontaneous.
(b) carbon disulphide + acetone
According to Raoult’s law, for ideas solution
(c) benzene + toluene
H  0 (d) phenol + aniline
V Ans. (a,b)
mix  0
Sol. (a) CCl 4 +CH3 OH  Positive deviation from Rault’ss
Since there is no exchange of heat energy between system
and surrounding law have hydrogen bonding of methanol is broken by
CCl 4 .
Ssurrounding  0
(b) Mixture of polar and non-polar cause weak attraction
Ssystem   Ve hence show +ve deviation.
G  H  TS (c) C6 H6 +toluene  ideal solution
G   Ve (d) H-bonding between two, show -ve deviation

17. Liquids A and B form ideal solution over the entire 19. Pure water freezes at 273 K and 1 bar. The addition of 34.5
range of composition. At temperature T, equimolar g of ethanol to 500 g of water changes the freezing point
binary solution of liquids A and B has vapour pressure of the solution. Use the freezing point depression constant
45 Torr. At the same temperature, a new solution of A of water as 2 K kg mol -1. The figures shown below
and B having mole fractions xA and xB, respectively, represent plots of vapour pressure (V.P.) versus
has vapour pressure of 22.5 Torr. The value of x A/xB in temperature (T). [molecular weight of ethanol is 46 g mol-1]
the new solution is ............. . Among the following, the option representing change
(given that the vapour pressure of pure liquid A is 20 the freezing point is (2017)
Torr temperature T)
Ans. (19)
Sol. PT = PA0 xA +PB0 xB
1 1 (a)
45= PA0 × +PB0 ×
2 2
PA0 + PB0 = 90 ...(1)
 SOLUTIONS 47

21. The Mole fraction of urea in an aqueous urea solution

containing 900 g of water is 0.05. If the density of the
solution is 1.2 g/cm3, the molarity of urea solution
is_____. (Given data: Molar masses of urea and water
(b) are 60 g mol–1 and 18 g mol–1, respectively)
(2019/Shift-2)
Ans : 2.98
Sol : Mole fraction of urea in aqueous solution = 0.05
Let number of moles of solution is = 1 mole

(c)

n solute
molarity  V 1000
solution(in mL)
(d)
0.05  1.2 60
  1000   2.985
20.1 20.1
Ans. (c) Answer after rounding off = 2.98
Sol. T f  K f m
Answer after truncation = 2.98

34.5 22. 5.00 mL of 0.10 M oxalic acid solution taken in a conical

 2  3K
46  0.5 flask is titrated NaOH from a burette using
phenolphthalein indicator. The volume of NaOH required
Freezing point of H 2 O=273 K
for the appearance of permanent faint pink color is
Freezing point of solution =270 K tabulated below for five experiments. What is the
Option (c) shows depression of freezing point of 3K concentration, in molarity, of the NaOH solution ?
and V.P. of pure water is higher then V.P. of solution. (2020/Shift-1)
Exp. No. Vol. of NaOH (mL)
20. On dissolving 0.5 g of a non-volatile non-ionic solute 1 12.5
to 39 g of benzene, its vapor pressure decreases from 2 10.5
650 mm Hg to 640 mm Hg. The depression of freezing 3 9.0
point of benzene (in K) upon addition of the solute is 4 9.0
______ 5 9.0
(Given data: Molar mass and the molal freezing point Ans : (000.11)
depression constant of benzene are 78 g mol–1 and 5.12 Sol : No. of eq. of oxalic acid = No. of eq. of NaOH
K kg mol–1, respectively) (2019/Shift-1)
5.00  0.10 9.0  M
Ans : 1.02 or 2  1
1000 1000
P0  Ps n 
Sol :  i  solute  1
Ps n
 solvent   Molarity of NaOH solution  9  0.11M
650  640 0.5  78 23. Liquids A and B form ideal solution for all compositions
 1  MSolute  64gm of A and B at 25ºC. Two such solutions with 0.25 and
640 M  39
0.50 mole fractions of A have the total vapor pressures
0.5 1000 of 0.3 and 0.4 bar, respectively. What is the vapor
Tf  K f  m  5.12   Tf  1.02
64  39 pressure of pure liquid B in bar? (2020/Shift-2)
Ans : (000.20)
 48 SOLUTIONS

Sol : PT = PA0 X A + PB0 X B

0.3 = PA0 × 0.25 + PB0 × 0.75 …(i)

0.4 = PA0 × 0.5 + PB0 × 0.5 0.05V

Thus, the final solution has  BaCl2   = 0.025
0.8 = PA0 + PB0 ….(ii) 2V
0.05V
on solving eq n (i) & (ii) M and  Ba  NO3 2    0.025 M
2V
PA0 = 0.6, PB0 = 0.2 Thus, Tb '  Kb  i1 m1  i2 m2 

24. The boiling point of water in a 0.1 molal silver nitrate Tb '  0.5  3  0.025  3  0.025   0.5  3  0.05
solution (solution A) is xC. To this solution A. an  0.075C
equal volume of 0.1 molal aqueous barium chloride Tb '  100  0.075  100.075C
solution is added to make a new solution B. The Thus, difference in boiling points = 100.1 - 100.075
differnece in the boiling point of water in the two
= 0.025  2.5 102 C
solutions A and B is y  102 C. Thus, y = 2.5
(Assume, Densities of the solutions A and B are the
same as that of water and the soluble salts dissociate
completely. Use: molal elevation constant (Ebullioscopic
constant). kb  0.5 K kg mol 1 ; Boiling point of pure
water as 100C. )
The value of X is______. (2021)
Ans: 100.1
Sol.
AgNO3  Ag   NO3
Tb  i Kb. m  2   0.5   0.1
Tb  0.1C
Tb  100.1C

25. The boiling point of water in a 0.1 molal silver nitrate

solution (solution A) is xC. To this solution A. an
equal volume of 0.1 molal aqueous barium chloride
solution is added to make a new solution B. The
differnece in the boiling point of water in the two
solutions A and B is y  102 C.
(Assume, Densities of the solutions A and B are the
same as that of water and the soluble salts dissociate
completely. Use: molal elevation constant (Ebullioscopic
constant). kb  0.5 K kg mol 1 ; Boiling point of pure
water as 100C. )
The value of [y] is______. (2021)
Ans. 2.50
Sol. Since the densities of the given solutins is same as that
of pure water, we can assume molarlity = molarity Let
the volumes of both the solutions mixed = VL.