SOLUTIONS 31

EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS

Objective Questions I (Only one correct option] (c) 0.01 M (d) 0.001 M
Ans. (a)
1. In a solution of 7.8 g of benzene (C6H6) and 46 g of
1
toluene (C6H5CH3), the mole fraction of benzene is
(a) 1/6 (b) 1/5 Sol. M = 40 = 0.1M
(c) 1/2 (d) 1/3 0.25
6. Raoult's law states that for a dilute solution,
Ans. (a)
(a) the lowering of vapour pressure is equal to the mole
7.8 fraction of the solute
Sol. Number of moles of C 6 H 6 = = 0.1
78 (b) the relative lowering of vapour pessure is
46 proprotional to the amount of solute in the solution
Number of moles of C 6 H 5 CH 3 = = 0.5 (c) the relative lowering of vapour pressure is equal to
92
the mole fraction of the solute
Total moles = 0.6
(d) the vapour pressure of the solution is equal to the
0.1 1 mole fraction of the solvent
C6 H 6 = =
0.6 6 Ans. (c)
Sol. Raoult’s law state that the relative lowering of vapour
2. To 5.85 g of NaCl, one kg of water is added to prepare a pressure is equal to the mole fraction of solute.
solution. What is the strength of NaCl in this solution ?
(Molecular weight of NaCl = 58.5) Po  P
 XB
(a) 0.1 Normal (b) 0.1 Molal Po
(c) 0.1 Molar (d) 0.1 Formal Po = Pressure of pure solvent
Ans. (b) P = Partial pressre of solution
Sol. 5.85 of NaCl in 1kg. X B = mole fraction of solute
M WNaCl = 58.5g/mol 7. Which of the following pairs shows a negative deviation
from Raoult's law ?
 n  1 5.85 (a) Acetone–benzene (b) Acetone–ethanol
m= × =
 mw  mass of solution  kg  58.5×1 (c) Acetone–chloroform (d) Benzene–methanol
=0.1molal Ans. (c)
Sol. Acetone + chloroform A  B interactions are stronger
3. The formula weight of H2SO4 is 98. The weight of the than A-A and B-B interactions negative deviation.
acid in 400 ml of 0.1 M solution is 8. An azeotropic solution of two liquids has boiling point
(a) 2.45 g (b) 3.92 g lower than either of them when it
(c) 4.90 g (d) 9.8 g (a) shows negative deviation from Raoult’s law
Ans. (b) (b) shows no deviation from Raoult’s law
(c) show positive deviation from Raoult’s law
Sol. 400 ml×0.1M = 0.04 moles (d) is saturated
= 0.04×98 =3.92g Ans. (c)
Sol. In case of positive deviation from Raoult’s law, the
4. The molarity of a solution of Na2CO3 having 10.6 g in observed vapour pressure is greater than the ideal vapour
500 ml of solution is pressure and boiling point of azeotrope becomes lower
(a) 0.2 M (b) 2 M than either of pure liquid.
(c) 20 M (d) 0.02 M 9. If PA is the vapour pressure of a pure liquid A and the
Ans. (a) mole fraction of A in the mixture of two liquids A and B
Sol. Molarity = number of moles of solute in one litre of is x, the partial vapour pressure of A is :
solution.
(a) (1  x) PA (b) xPA
10.6
x 1 x
M = 106 = 0.2 M (c) (1  x) PA (d) PA
0.5 x
5. Molarity of a solution containing 1g NaOH in 250 ml of Ans. (b)
solution is
(a) 0.1 M (b) 1 M Sol. Partial pressure  mole fraction  pressure of pure liq.
 32 SOLUTIONS

x.PA WA M B 5×18
MA = = =178.2
10. Air contains O2 and N2 in the ratio of 1 : 4. The ratio of ΔP 15
Sol. × WB ×100
their solubilities in terms of mole fractions at atmospheric PB0 3000
pressure and room temperature will be (Given Henry’s
7 7
constant for O2 = 3.30 × 10 torr, for N2 = 6.60 × 10 torr) 14. The vapour pressure of benzene at a certain temperature
(a) 1 : 2 (b) 2 : 1 is 640 mm of Hg. A nonvolatile electrolyte solute
(c) 4 : 1 (d) 1 : 4 weighing 2.175 g is added to 30.08 g of benzene. If the
Ans. (a) vapour pressure of the solution is 600 mm of Hg, what is
the molecular weight of the solid substance ?
1 K O2 X O2 (a) 79.82 (b) 84.46
Sol. PT = K H X O2 = ×
4 K N2 X N2 (c) 59.60 (d) 49.50
Ans. (b)
1 1 X O2 X O2 1
= × = 2.175  78
4 2 X N2 X N2 2 MA = = 84.46
Sol. 40
11. The relative lowering of the vapour pressure is equal to ×30.08
600
the ratio between the number of
(a) solute molecules to the solvent molecules
15. Elevation in boiling point was 0.520C when 6 gm of a
(b) solute molecules to the total molecules in the
compound X was dissolved in 100 gm of water. Molecular
solution
(c) solvent molecules to the total molecules in the weight of X is (Kb of water is 0.52 K-kg/mol)
solution (a) 120 (b) 60
(d) solvent molecules to the total number of ions of the (c) 600 (d) 180
solute Ans. (b)
Ans. (b) moles of solute
Sol. According to Raoult’s law, the relative lowering of Sol. Tb  kb 
Mass of solvent(kg)
vapour pressure is equal to mole fraction of solute, i.e.,
the ratio of number of moles of solute to total number of 6
mole of all component in solution.
0.52 =0.52× M M =60
0.1
12. Vapour pressure of a solution of non-volatile solute is
(a) directly proportional to the mole fraction of the
solvent 16. The molal b.p. constant for water is 0.5130C kg mol–1.
(b) Independent of mole fraction of the solute When 0.1 mole of sugar is dissolved in 200 g of water,
(c) inversely proportional to the mole fraction of the the solution boils under a pressure of 1 atm at
solvent (a) 100.5130C kg/mol (b) 100.05130C kg/mol
(d) directly proportional to the mole fraction of the (c) 100.2560C kg/mol (d) 101.0250C kg/mol
solute Ans. (c)
Ans. (a) 0.1
Sol. For solution containing non-volatile solutes, the Sol.  Tb  0.513   0.256
0.2
Raoult’s law can be stated as, At a given temperature,
the vapour pressure of a solution containing non-volatile Tb =100.256o C kg/mol
solute is directly proportional to the mole fraction of the 17. The freezing point of a 0.05 molal solution of a non-
solvent. electrolyte in water is
(a) –1.860C (b) –0.930C
0
13. Vapour pressure of a solution of 5 g of non-electrolyte (c) –0.093 C (d) 0.930C
in 100 g of water at a particular temperature is 2985 N/ Ans. (c)
m2. The vapour pressure of pure water is 3000 N/m2, the Sol. Tf  k f  m
molecular weight of the solute is T f  1.86  0.05  0.096o C
(a) 60 (b) 120
(c) 178.2 (d) 380  freezing point   0.093O C
Ans. (c)
 SOLUTIONS 33

18. Calculate the molecular weight of a substance if the  1

freezing point of a solution containing 100 g of benzene i  1  1   
and 0.2g of the substance is 0.17 K below that of  n
benzene. The cryoscopic constant of benzene is 5.16 K On dimerization of acetic acid in benzene
kg mol–1. 2CH3COOH   CH3 COOH  2
(a) 70.46 (b) 85.66 2 moles of acetic acid associates into 1 mole of dimer
(c) 60.23 (d) 178.25
Ans. (c)  1
i  11   
moles of solute  2
Sol. T f  k f 
mass of solvent 
i 1
2
0.2
i is less than 1 for association.
0.17 = 5.16× M = 60.23
0.1
22. Which one has the highest boiling point ?
19. Which statement is incorrect about osmotic pressure
(), volume (V) and temperature (T) ? (a) 0.1 N Na2SO4 (b) 0.1 N MgSO4
(a) 1/v when T is constant. (c) 0.1 M Al2(SO4)3 (d) 0.1 M BaSO4
(b) T when V is constant. Ans. (c)
(c)  V when T is constant.
(d) V is constant when T is constant. Sol. Al2 (SO4 )3  2Al3+ +3SO42- =0.1M Al2 (SO 4 )3
Ans. (c) as the number of particles produced is maximum in 0.1M
n Al2(SO4)3 the elevation in boiling point will be maximum
Sol. π=CRT,π  at const T.
v 23. Which of the following aqueous solutions has the
20. A plant cell shrinks when it is kept in highest boiling point ?
(a) Hypotonic solution (a) 0.1 M KNO3 (b) 0.1 M Na3PO4
(b) A hypertonic solution
(c) 0.1 M BaCl2 (d) 0.1 M K2SO4
(c) A solution isotonic with cell sap
Ans. (b)
(d) Water.
Sol. more ions more will be ‘i’ more will be colligative
Ans. (b)
properties.
Sol. Hypertonic solutions have higher osmotic pressure, so 24. The freezing point of equimolal aqueous solutions will be
plant cell in hypertonic solution loses water. highest for
21. The van't Hoff factors i for an electrolyte which
(a) C6H5NH3Cl (aniline hydrochloride)
undergoes dissociation and association in solvents are
respectively (b) Ca(NO3)
(a) greater than 1 and greater than 1 (c) La (NO3)3
(b) less than 1 and greater than 1 (d) C6H12O6 (glucose)
(c) less than 1 and less than 1 Ans. (d)
(d) greater than 1 and less than 1
Sol. C6 H5 NH3 Cl:i =2; Ca  NO3  2 :i = 3;
Ans. (d)
Sol. La(NO3 )3 : i = 4; C6 H12 O6 : i =1;
observed number of moles of solute Lower the value of i , smaller will be the depression in
Van ' t Hoff factor 'i '  freezing point, higher will be the freezing temperature, if
Normal number of moles of solute molalities are equal. Hence, glucose solution will have
Relation between the degree of dissociation and van’t highest freezing temperature.
Hoff factor - 25. 0.01 M solution each of urea, common salt and Na2SO4
are taken, the ratio of depression of freezing point is
i   n  1    (a) 1 : 1 : 1 (b) 1 : 2 : 1
(c) 1 : 2 : 3 (d) 2 : 2 : 3
KCl on dissociation KCl  K   Cl , yields 2 ions Ans. (c)
i= 1+ Sol. Van’t hoff factors of Urea =1, common salt
for dissociation i is greater than 1
=2  Na , Cl 
 
For assciation the relation becomes
Na 2SO 4  3=1:2:3
 34 SOLUTIONS

(a) 0.05 (b) 0.30

 2 Na 
, SO4 2  (c) 0.15 (d) 0.015
Ans. (d)
26. The osmotic pressures of equimolar solutions of Sol. CuCl2  Cu 2+ +2Cl-
Al2(SO4)3, KCl and sugar will be in the order
(a) KCl < Al2(SO4)3< sugar Tb  i  K b  m
Van’t hoff factors is 3
(b) sugar < KCl < Al2 (SO4)3
(c) sugar > KCl > Al2 (SO4)3 ΔTb =0.52×3×0.01=0.015
30. Which one of the following solutions of sulphuric acid
(d) KCl < sugar < Al2 (SO4)3 will exactly neutralise 25 ml of 0.2 M sodium hydroxide
Ans. (b) solution ?
Sol. As we now that osmotic pressure is given as- (a) 12.5 ml of 0.1 M solution
  iCRT (b) 25 ml of 0.1 M solution
As ‘i’ increases, ‘’ also increases. (c) 25 ml of 0.2 M solution
i  5 for Al2(SO4)3 (d) 50 ml of 0.2 M solution
Ans. (b)
i = 2 for KCl
i = 1 for glucose Sol. H2SO4 + 2NaOH  Na2SO4+2H2O
therefore, osmotic pressure of given solutions will be in number of moles of NaOH = 25  0.2 = 5 mmole
order- 2 moles of NaOH are neutralised by 1 mole of H2SO4
sugar < KCl < Al2 (SO4)3 5 mmoles of NaOH will be neutralised by ½  5 = 2.5
mmoles of H2SO4
27. The freezing point of 1 molal NaCl solution assuming Number of moles in 25 ml of 0.1 M solution = 25  0.1 =
NaCl to be 100% dissociated in water is 2.5 mmoles
(a) –1.860C (b) –3.720C 31. The normality of 10% (weight/volume) acetic acid is
(c) +1.860C (d) +3.720C (a) 1 N (b) 10 N
Ans. (b) (c) 1.7 N (d) 0.83 N
Sol. Tf  i  K f  molality Ans. (c)
10
Tf  Tfo  Tf Sol. Number of moles 
60
ΔTf =1.86×2×1=3.72o C Volume of solution =100 ml =0.1L
Tf  0  3.72 Valence factor of CH 3 COOH =1
o
 3.72 C  N = M  valence factor
28. The molal freezing point constant for water is 1.860C/
mole. Therefore, the freezing point of 0.1M NaCl solution 10
in water is expected to be
(a) –1.860C (b) –0.1860C  60 × 1=1.7 N
0
0.1
(c) –0.372 C (d) +0.3370C 32. 30 ml of solution is neutralised by 15 ml of 0.2 N base.
Ans. (c) The strength of the acid solution is
Sol. Tf  Kf  m  i (a) 0.1 N (b) 0.15 N
(c) 0.3 N (d) 0.4 N
for NaCl  Na   Cl  Ans. (a)
Sol. N1V1  N 2 V2
i 2
N is the normality and V is the volume
Given, m  0.1molal N1V1 (For acid) = N2V2 (for base)
K f  1.86o C / Molal x  30  15  0.2
Tf  1.86  0.1 2 x  0.1N
33. 10 ml of 3N-HCl, 20 ml of N/2 H2SO4 and 30 ml of N/3
Tf  0.372o C
HNO3 are mixed together and volume made to one litre.
Freezing point = 0-0.372oC The normality of the resulting solution is
= -0.372oC
(a) N/2 (b) N/10
29. When 1.345 g of CuCl2 is dissolved in 1 kg of water, the (c) N/20 (d) N/40
elevation in boiling point will be (Kb = 0.52, molar mass Ans. (c)
of CuCl2 = 134.5) Sol. Meq  N  V
Meq is the equivalent molarity N is normality of the
 SOLUTIONS 35

solution, V is the volume of solution. 2

xB 
1. Meq for HCl 3
Meq  3 10  30M ...(1)
Pt  PAo x A  PBo xB
2. Meq For H 2SO 4
2 127
1 Final vapour pressure  173  
Meq   20  10 M ...(2) 3 3
2 =158mm of Hg
3. For HNO3 36. Which of the following statements is correct for a binary
1 solution ?
Meq   30  10 M ...(3) (a) A solution in which heat is evolved exhibits positive
3
deviations from Raoult's law.
For total solution
(b) A solution in which heat is absorbed shows negative
Total Meq  M1  M 2  M3 deviations from Raoult's law.
Total Meq  30  10  10  50 M (c) When one component in solution shows negative
deviation from Raoult's law, the other exhibits
Total Meq  N final  V
positive deviation.
50  N final 1000 (d) When one component in solution shows positive
N deviation from Raoult's law, so does the other.
 Ans. (d)
20
Sol. A binary solution is a type of homogeneous mixture
34. 50 ml of 0.2 N HCl, 50 ml of 0.1 N H2SO4 and 100 ml 0.2 which contains two liquid that are completely miscible
with each other. In case of solution showing positive
N HNO3 are mixed. The normality of resulting solution
deviation absorption of heat takes place.
is
Both component show positive deviation
(a) 0.10 N (b) 0.15 N
simultaneously according to Raoult's law
(c) 0.175 N (d) 0.20 N
37. Which statement about the composition of vapour over
Ans. (c)
an ideal 1 : 1 molar mixture of benzene and toluene is correct?
N1V1  N 2 V2  N3 V3 Assume the temperature is constant at 25ºC.
Sol. Normality 
V1  V2  V3 Vapour pressure data (25ºC) :
Benzene 75 mm Hg
50×0.2 +50×0.1+100×0.2
N final = Toluene 22 mm Hg
200 (a) The vapour will contain higher percentage of
35 benzene
= = 0.175 N
200 (b) The vapour will contain higher percentage of
toluene
35. A solution is prepared containing a 2 : 1 mol ratio of (c) The vapour will contain equal amount of benzene
dibromo ethane (C 2 H4Br 2) and dibromo propane and toluene
(C3H6Br2) what is the total vapour pressure over the (d) Not enough information is given to make a
solution assuming ideal behaviour ? prediction
Vapour pressure (mm Hg) Ans. (a)
C2H4Br2 173 1 1 97
Sol. PT  75   22    48.5
C3H6Br2 127 2 2 2
(a) 300 mm Hg (b) 158 mm Hg 1
(c) 150 mm Hg (d) 142 mm Hg 75× = PT0 ×YC6 H6
2
Ans. (b) 75 22
Sol. A : B  2 :1 YC6 H6 = YC7 H8 =
97 97
1 YC6 H6 > YC7 H8
xA 
3
38. 100 ml of a liquid A was mixed with 25 ml of a liquid B to
 36 SOLUTIONS

give a non-ideal solution of A-B mixture. The volume of

this mixture would be Ans. (b) p  xK H
(a) 75 ml (b) 125 ml 0.96 x x
(c) close to 125 ml (d) just more than 125 ml = 0.0125 =
Sol. 76.8 x + 1000 x + 55.55
Ans. (c)
Sol. Because of non -ideal solutions. 18
 x = 0.69
39. The diagram given below is a vapour pressure- 42. Consider the following statements
composition diagram for a binary solution of A and B. In 1. Isotonic solutions have the same molar
the solution, A–B interactions are concentration at a given temperature.
(a) similar to A–A and B–B interactions 2. The molal elevation constant Kb is characteristic of
(b) greater than A–A and B–B interactions a solvent, and is independent of the solute added.
(c) smaller than A–A and B–B interactions 3. The freezing point of a 0.1 M aqueous KCl solution
(d) unpredictable. is more than that of a 0.1 M aqueous AlCl3 solution.
Which of these statements is correct.
(a) 1 and 2 (b) 2 and 3
(c) 1 and 3 (d) 1, 2 and 3
Ans. (d)
Sol. All three are correct.
Tf  m
Elevation in b.p of a solute is produced when 1 mole of
the solute is dissolved in 1 kg of solvent. It is dependent
on the nature of the solvent and independent of the
nature of solute.
Ans. (c) Greater the concentration of particle, the lower the
Sol. For +ve deviation A-B < A-A and B-B. freezing point will be.
40. Mixture of volatile components A and B has total vapour ‘i’ van’t Hoff factor for KCl is 2
pressure (in torr) :
P = 254 – 119XA KCl  K   Cl
where, XA is mole fraction of A in mixture. Hence ‘i’ for AlCl3 is 4
p0A and pB0 are (in torr) : AlCl3  Al3  3Cl
(a) 254, 119 (b) 119, 254 43. An aqueous solution freezes at –2.550C. What is its
(c) 135, 254 (d) 154, 119
Ans. (c) boiling point ( K b of water  0.52 K / m; K f of water
0 0
Sol. PT = P X A + P X B
A B  1.86 K / m)?
X B =1- X A (a) 107.00C (b) 100.60C
PT = PA0 X A + PB0 1- X A  (c) 100.10C (d) 100.70C
Ans. (d)
 
= PA0 - PB0 X A + PB0 = 254 -119 X A
Sol. Kb =0.52 k/m k f =1.86k/m
PB0 = 254
ΔTf = k f m
PA0 - PB0 = -119 2.55=1.86×m
PA0 =135 M=1.37
41. The millimoles of N2 gas that will dissolve in 1L of water ΔTb =0.52×1.37=0.712
at 298 K. when it is bubbled through water and has a
Tb =100+0.712=100.712o C
partial pressure of 0.96 bar will be
(Given that at 298 K KH = 76.8 k bar) 44. The normal boiling point of toluene is 110.70C, and its
(a) 0.59 (b) 0.69 boiling point elevation constant is 3.32 K kg mol–1. The
(c) 0.79 (d) 0.89 enthalpy of vapourization of toluene is nearly
(a) 17.0 kJ mol–1 (b) 34.0 kJ mol–1
–1
(c) 51.0 kJ mol (d) 68.0 kJ mol–1
Ans. (b)
 SOLUTIONS 37

RTb 2 RTb 2 10 10 10
Sol. Kb = LVap =
1000LVap 1000 K b 60 =π > 180 = π > 342 = π
2 1 3
0.25 0.25 0.25
R  M1  Tb2
Kb   π 2 > π1 > π3
1000   vap H 49. Which of the following pairs of solutions is isotonic ?
 Vap H =34.0 kJ/mol (a) 6% urea and 6% glucose (w/v)
(b) 18% urea and 18% glucose (w/v)
45. During depression of freezing point in a solution the (c) 6% urea and 18% fructose (w/v)
following are in equilibrium (d) 34.2% sucrose and 60% glucose (w/v)
(a) liquid solution, solid solvent Ans. (c)
(b) liquid solvent, solid solute Sol. Isotonic solution has same no. of moles of solute
(c) liquid solute, solid solute 6 18
(d) liquid solute, solid solvent = C urea , C fru ctose =
60 180
Ans. (a)
Sol. At the freezing point, the liquid and solid phases of a 50. Two aqueous solutions S1 and S2 are separated by a
substance are in equilibrium with each other. Thus, at semi-permeable membrane. S2 has lower vapour pressure
the freezing point, the liquid solvent and solid solvent than S1. Then
are in equilibrium.
(a) More solvent will flow from S1 to S2
Thus during depression of freezing point in a solution
liquid solvent and solid solvent are in equilibrium. (b) More solvent will flow from S2 to S1
46. On freezing an aqueous solution of sugar, the solid that (c) Solvent from S1 and S2 will flow at equal rates
starts separating out is (d) No flow will take place.
(a) sugar (b) ice Ans. (a)
(c) solution with the same composition Sol. Water will flow from S1 to S2 because S1 has more vapour
(d) solution with a different composition. pressure than S2, S1 has less concentration of solute
Ans. (b) 51. If a solute undergoes dimerization and trimerization, the
Sol. No Solute is dissolved in the ice that separates out minimum values of the van't Hoff factors are
because only Solvent molecules Solidity at the freezing (a) 0.50 and 1.50 (b) 1.50 and 1.33
point. (c) 0.50 and 0.33 (d) 0.25 and 0.67
47. Given that Tf is the depression in freezing point of the Ans. (c)
solvent in a solution of a non volatile solute of molality 1 1
Sol. and
 T f  2 3
1, the quantity lim   is equal to 52. Solutions A, B, C and D are respectively 0.1 M glucose,
m 1
 m 
0.05 M NaCl, 0.05 M BaCl2 and 0.1 M AlCl3. Which of
(a) Lf (latent heat of fusion) the following pairs is isotonic ?
(b) Kb (ebullioscopic constant) (a) A and B (b) B and C
(c) Kf (cryoscopic constant) (c) A and D (d) A and C
Ans. (a)
(d) Hfus (enthalpy of fusion)
Sol. 0.1 1 for glucose
Ans. (c)
0.05  2 for NaCl
Sol.  ΔTf =K f m
0.05  3 for BaCl2
ΔTf
lim = kf 0.01 4 for AlCl3
m 1 m
53. Among 0.1 M solutions of urea, Na3PO4 and Al2 (SO4)3,
48. 10 g of glucose (1), 10 g of urea (2) and 10 g of sucrose which is incorrect ?
(3) are dissolved in 250 mL of water at 300 K ( = osmotic (a) the vapour pressure and freezing point are the
pressure of solution). The relationship between the lowest for urea
osmotic pressure of the solutions is (b) the vapour pressure and freezing point are the
(a) 1 > 2 > 3 (b) 3 > 1 > 2 highest for urea
(c) the boiling point is the highest for Al2(SO4)3
(c) 2 > 1 > 3 (d) 2 > 3 > 1
(d) the depression in freezing point is the highest for
Ans. (c)
Sol.    CRT
 38 SOLUTIONS

Al2(SO4)3 (a) – 0.45 (b) – 0.90

Ans. (a) (c) – 0.31 (d) – 0.53
Sol. Reason is due to Van’t Hoff’s factors. Ans. (a)
Number of ions furnished by Al2(SO4)3 will be maximum Sol.   20%  0.2
so Tb , Tf , vapour pressure will be maximum for it. i 1 i 1
  0.2 
urea will have minimum Tf . n 1 2 1
54. Which of the following graphs represent the behaviour i  1.2
of ideal binary liquid mixture ?
(a) Plot of 1/PTotal against yA is linear T f  iK f m
(b) Plot of 1/PTotal against yB is non-linear
T f  1.2  1.86  0.2  0.45; T f  T fo  T f
(c) Plot of PTotal against yA is linear
(d) Plot of PTotal against yB is linear  0.45  0  T f
Ans. (a)
T f  0.45C
PA0 X A = PTotal yA
Sol. 57. 0.004 M Na2SO4 is isotonic with 0.01 M glucose. The

For a ideal binary liquid the value is fixed. degree of dissociation of Na2SO4 is
1 (a) 75% (b) 50%
 against y A is linear (c) 25% (d) 85%
PTotal
Ans. (a)
According to Dalton's law of partial pressures, the total Sol. Given the solution is isotonic so the osmotic pressure
pressures PT will be the sum of the partial pressure of all will be equal
components of the solution.
Na 2SO4  glu cos e
PT  PAo 1  y B   PBo y B
total vapour pressures of the solution varies linearly m1RTi1  m 2 RTi 2
with mole fraction. 0.004i1  0.010 1
1 1 i1  2.5
55. The plot of y against x is linear with slope and
A A Na 2SO4  2Na   SO42 
intercept respectively : 1  2 
0 0 0 0 0 0
PA P P A B PA P P B A 2.5  1  (3  1)
(a) P and P 0
0 (b) P and P 0
0
B B B B   0.75
  75%
PB0 PA0  PB0 PB0 PB0  PA0
(c) P 0 and (d) P 0 and Objection Question II
A PA0 A PB0
[One or more than one correct option]
Ans. (c) 58. The solution showing positive deviation
Sol. PA0 X A = PT YA (a) have V (mixing) = + ve
(b) have H (mixing) = – ve
(c) form minimum boiling azeotropes.
PA0 PT (d) have lower vapour pressure of each component in
=
YA X A the solution than their pure vapour pressure.
Ans. (a,c)
PA0
=
 
PA0 - PB0 X A P 0 1
+ B0 Sol. Positive deviation has ΔV = + ve ΔH = +ve
YA PA0 X A PA X A
Minimum boiling azeotrops.
PB0 PA0 - PB0  59. Which pair (s) of liquids on mixing are expected to show
 Slope is 0 and intercept is no net volume change and no heat effect
PA PA0
(a) acetone and ethanol
56. 0.2 molal acid HX is 20% ionised in solution. Kf = 1.86 K
–1 (b) chlorobenzene and bromobenzene
Kg mol . The freezing point of the solution is : (c) chloroform and benzene
(d) n-butyl chloride and n-butyl bromide.
Ans. (b,d)
Sol. Option (b) and option (d) forms ideal solution and option
 SOLUTIONS
(c) and (a) forms non-ideal solution.
60. Which of the following is/are correct statements (s) about
the Raoult’s law applied to a solution of non-volatile
solute ?
(a) Vapour pressure of solution is proportional to mole
fraction of solute
(b) V.P. of solution is proportional to the mole fraction
of solvent
(c) Relative lowering of V.P. = mole fraction of solute
(d) Relative lowering of vapour pressure is proportional
to the mole fraction of solute.
Ans. (b, d)
Sol. For solution containing non-volatile solutes, the
Raoult’s law can be stated as, At a given temperature,
the vapour pressure of a solution containing non-volatile
solute is directly proportional to the mole fraction of the
solvent.
Po  P
x
Po
61. In binary liquid mixture of components, A and B, the
former has greater tendency to escape into the vapour
state than demanded by Raoult’s law. Indicate the correct
statement(s)
(a) Component A shows positive deviation and the
component B negative deviation
(b) Both components show positive deviations
(c) Component A shows negative deviation and the
component B positive deviation
(d) The component B has also greater tendency to
escape into the vapour state than demanded by
Raoult’s law
Ans. (b,d)
Sol. Both show + ve deviation.
62. Colligative properties of a solution are
(a) independent of the nature of solute
(b) inversely proportional to molecular mass of solute
(c) Proportional to concentration of solute
(d) independent of the amount of solvent.
Ans. (a,b,c,d)
Sol. The properties of the solution which depend only on
the number of solute particles but not on the nature of
the solute are colligative properties.
For a particular mass ratio of solute and solvent, all
colligative properties should be inversely proportional
to solute molar mass, colligative property is independent
of amount of solvent and nature of solute.
63. In the depression in freezing point experiment, it is
observed that
(a) the vapour pressure of the solution is less than that
of pure solvent.
(b) the vapour pressure of the solution is more than
that of pure solvent
(c) only solute molecules solidify at the freezing point
39
(d) only solvent molecules solidify at the freezing point.
Ans. (a,d)
Sol. At freezing point, solvent molecules solidify whereas
solute molecules do not and since the solute particles
do not evaporate the vapour pressure of the solution is
lower than that of pure solvent.
64. A binary liquids mixture of two liquid A and B showing
the departure from the ideal behaviour :
(a) behaves as an ideal solution of B into A when XB0
(b) behaves as an ideal solution of A into B when XA0
(c) HSol’n is always positive
(d) TSSol’n is always positive
Ans. (a,b,d)
Sol. According to Raoult’s law, the partial vapour pressure
of two component A and B of a solution are given as
PA  PAo x A and PB  PBo x B
Therefore, the vapour pressure of the components are
linear functions of their mole fractions where xA = 1 i..e.,
the liquid is pure A
PA  PAo 1  PAo
But when xB = 0 i.e., the liquid is pure B
PA  PAo  0  0
It means that when the liquid is pure (xA=1) its vapours
pressre is equal to PAo but as component B is added to
component A (xA decreases), the vapour pressure
decreases till it becomes zero (xA = 0). The same goes
with component B.
 When two pure substance mix there is always an
increase in the entropy.
 Hsol is greater than zero if the solution has positive
deviation from Raoult’s law because it is endothermic
dissolution where heat is absorbed but if the solution
has negative deviation from Raoult’s law, Hsol is less
than zero because it would be exothermic dissolution.
65. Composition of an azeotrope
(a) is independent of external pressure because it is a
compound
(b) alters on changing the external pressure
(c) remains unchanged during distillation at a constant
external pressure
(d) fluctuates even at constant pressure
Ans. (b,c)
Sol. The exact composition of the azeotrope changes if the
boiling point is altered by a change in the external
pressure. An azeotrope is a mixture of two or more liquid
whose proportions cannot be changed by simple
distillation.
when an azeotrope is boiled, the vapour has the same
 40 SOLUTIONS

proportion of constituents as the unboiled mixture. = 33756 34 J/mol  34KJ/mol

66. Study the figure given aside and pick out the correct 68. A non-volatile organic compound X was used to make-
option(s) of the following : up two solution. Solution A contains 5.0 g of X in 100 g
of water and solution B contains 2.0 g of X in 100 g of
benzene. Solution A has vapour pressure of 754.5 mm of
Hg at normal boiling point of water and solution B has
the same vapour pressure at the normal boiling point of
benzene. Assuming X undergo partial dimerization in
benzene, determine percentage of X dimerized in benzene
solution.
Ans. (0085)
Sol. Given

Po  760
P  754.5
(a) A white precipitate of AgCl is formed on AgNO3 side P n 2

(b) A white precipitate of AgCl is formed on BaCl2 side P o n1
(c) No precipitate is formed on either side 760  754.5 5
(d) Meniscus of BaCl2 solution rises and that of AgNO3 
760 m  5.55
solution falls in due course of time m  124.48
Ans. (c,d)
Sol. Only solvent molecule pass through spm For B
Numeric Value Type Questions P in 2
67. When 1.0 g of urea is dissolved in 200 g of an unknown 
o n1
solvent X, the X freezing point is lowered by 0.25ºC. P
When 1.5g of an unknown, non-electrolytic solute Y is 760  754.5 i  0.016

dissolved in 125 g of same solvent X, freezing point is 760 1.282
lowered by 0.2 ºC and vapour pressure is lowered by i  0.576
1%. If freezing point of X, is 12ºC, determine molar For dimerisation, n  2
enthalpy of fusion of X in kJ.
i 1
Ans. (0034) 
Sol. Tf = kf × m 1
1
n
1 1000 0.576  1
0.25  k f   kf  3 
60  200 1
When further 1.5 gm of unknown solute added then 1
2
Tf = kf × m   0.8548
1.5 1000   85%
.2  3   x  180 gm / mol
x 125gm
69. A mixture of NaCl and sucrose of combined mass 10.2 g
Since V.P also decreases by 1% So according to relative is dissolved in enough water to make up a 250 mL
lowering of V.P. equation for same solute. solution. The osmotic pressure of the solution is 7.32
P n atm at 23ºC. Calculate the mass percentage of NaCl in
 x2  .01  2 the mixture.
P0 n1
Ans. (15.7%)
1.5 g  x Sol. V  nRT
0.1 
180 g mol 1  125 gm
x = 150 g/mol [Molecular mass of solvent]
R  M solvent  T f2
We know k f 
1000  H Fus

8.314Ik 1mol 1 150gm mol 1  285k  285k

H 
100  3
 SOLUTIONS 41

benzene show abnormal molecular mass

let(a) g of glu cos e Reason (R) : Abnormal molecular mass is obtained when
(b)g of NaCl the substance in the solution undergoes dissociation
a  b  10g ...(i) or association.
(a) A (b) B
 a b 
V     RT (c) C (d) D
180 58.5  Ans. (a)
 a b  Sol. Concept
7.32  0.25     0.0821 296 ...(ii)
180 58.5  74. Assertion (A) : If more and more non-volatile solute is
added to a solvent, the freezing point of the solution
Solving equation (ii) keeps on reducing.
and equating (i) and (ii) Reason (R) : Presence of large amount of the solid solute
NaCl , b = 1.57 does not allow the solution to freeze.
Mass % = 15.7 % (a) A (b) B
Assertion Reason (c) C (d) D
(A) If both assertion and reason are correct and reason Ans. (b)
is the correct explanation of assertion. Sol. If both Assertion & Reason are true but the reason is
(B) If both assertion and reason are true but reason is not the correct explanation of the assertion.
not the correct explanation of assertion. 75. Assertion (A) : The boiling point of 0.1 M urea solution
(C) If assertion is true but reason is false. is less than that of 0.1 M KCl solution.
(D) If assertion is false but reason is true. Reason (R) : Elevation of boiling point is directly
70. Assertion (A) : The sum of mole fractions of all proportional to the number of species present in the
components of a solution is unity. solution.
Reason : Mole fraction is independent of temperature. (a) A (b) B
(a) A (b) B (c) C (d) D
(c) C (d) D Ans. (a)
Ans. (b) Sol. Elevation of boiling point is directly proportional to the
Sol. Both are true but reason is not correct explanation for number of species present in the solution.
it.
KCl is a strong electrolyte while urea is a non electrolyte.
71. Assertion (A) : Hmix and Vmix are zero for the ideal so more ions are present in KCl solution.
solution. Van’t Hoff factor for urea = 1
Reason : The interactions between the particle of the i for KCl = 2
components of a solution are almost identical as between Match the Following
particles in the liquids. Each question has two columns. Four options are given
(a) A (b) B representing matching of elements from Column-I and
(c) C (d) D Column- II. Only one of these four options corresponds to a
Ans. (a) correct matching.For each question, choose the option
Sol. If no change in interactions. ΔH and ΔV will not corresponding to the correct matching.
change and form an ideal solution. 76. Mn = Normal molecular mass of solute
72. Assertion (A) : The vapour pressure of a liquid Mo = Observed molecular mass of solute from colligative
decreases if some non-volatile solute is dissolved in it. property measurement
Reason (R) : The relative lowering of vapour pressure Match the following :
of a solution containing a non-volatile solute is equal to COLUMN - I COLUMN - II
the mole fraction of the solute in the solution. (A) Mo < Mn (P) 0.1 M CH3COOH is benzene
(a) A (b) B
(B) Mo  Mn/3 (Q) 0.1 M urea in water
(c) C (d) D
Ans. (b) (C) Mo > Mn (R) 0.05 M barium chloride in water
Sol. The vapour pressure of a liquid decreases if some non- (D) Mo = Mn (S) 0.1 M CH3COOH in water
volatile solute is dissolved in it because on adding a Ans. (A–R,S; B–R; C–P; D–Q)
non-volatile solute, the solute particles occupy a certain Sol.
surface area of liquid (solvent) resulting in lowering of
vapour pressure. Normal molecular mass
Van ' t hoff factor 'i ' 
73. Assertion (A) : NaCl in water and organic acids in observed (or abnormal) molecular mass
 42 SOLUTIONS

A Protein has been isolated as sodium salt with their

Mn
i molecular form Na 2 P (this notation means xNa  ions
Mo
0.1 M CH3COOH in benzene undergo association are associated with a negatively charged protein P x ).
Hence van’t Hoff factor i < 1. A solution of this salt was prepared by dissolving x y
(MO > Mn) of this sodium salt of protein in 10g of water and
0.1 M urea in water neither associates nor dissociates, ebullioscopic analysis revealed that solution boils at
Hence i = 1
(Mo = Mn) temperature 6.78×10-3 o C higher than the normal
0.05 M BaCl2 undergo dissociation boiling point of pure water. K b of water of
2 
BaCl 2  Ba  2Cl
0.52k kg mol1 . Also elemental analysis revealed that
i= 3
the salt contain 1% sodium metal by weight.

 Mn  78. Deduce molecular formula of protein.

 Mo  3  (a) NaP (b) Na2P
 
0.1 M CH3COOH in water undergo dissociation (c) Na4P (d) Na5P
Hence i > 1 Ans. (d)
(Mo < Mn) 0.25
Sol. 6.78×10-3 = (x+1)× ×0.52×10
77. Hf = Molar heat of fusion of ice ; Lf = Latent heat of M
–1
fusion of ice (g ) 6.78×10-3  x 1 
= + 
Hv = Molar heat of vaporisation of water ; Lv = Latent 13 M M
–1
heat of vaporisation of water (g ) Na x P  xNa + + P- (x+1) = i
Match the following appropriately 6.78×10-3  1 1
COLUMN - I COLUMN - II  = + 
13  2300 M 
18  373  373  R M =11500 x=5
(A) Molal depression (P)
1000H v Na 5 P
constant of water
373  373  R 79. Determine molecular weight of sodium salt of protein.
(B) Molal elevation (Q) (a) 2300 (b) 4600
1000 L v
(c) 9200 (d) 11500
constant of water Ans. (d)
18  273  273  R 23×x
(C) Tf of solution (R) Sol. 1 o o Na = ×100 =1 o o
1000 H f M
containing 9.0 g of x 1
= M=11500
glucose in 50g of water m 2300
273  273  R 80. Determine molecular weight of acidic form of protein :
(D) Tb of solution (S) 1000 L f (a) 11390 (b) 2278
containing 3.0g of (c) 9112 (d) 4556
urea in 50 g of water Ans. (a)
Ans. (A–R,S; B–P,Q; C–R,S; D–P,Q) Sol. 11390
R×Tb2 ΔH vap
Sol. kb = L vap =
1000 Lvap MB
R×Tf2 ΔH f
Kf = Lf =
1000 Lf MB
Paragraph Type Questions
Use the following passage, solve Q. 78 to Q. 80
Passage