[ 20 ] LIQUID SOLUTION

EXERCISE-1
(FOR JEE MAIN)
(SINGLE CORRECT ANSWER TYPE)
HENRY LAW, OSMOTIC PRESSURE
1. Henery’s law constant for oxygen and nitrogen dissolved in water at 298K are 2 10 4 atm and 5 104 atm
respectively. A sample of water of a temperature just above 273K was equilibrated with air ( 20% oxygen and
80% nitrogen) at 1 atm. The disoolved gas was seperated from a sample of this water and dried. What is the
compossition by mole of this gas.
(A) 38.46%O2 , 61.54% N2 (B) 28%O2 , 72% N2

(C) 28.46%O2 , 71.54%N2 (D) 18%O2, 52% N2

2. Solution A contains 6 g of urea (NH2 CONH2) per litre and solution B contains 18 g glucose (C6H12O6) per
litre. At a temperature TK, the osmotic pressure of
(A) solution A is more than that of solution B (B) solution A is less than that of solution B
(C) both solution is equal (D) both the solutions is 1 atm

3. FeCl3 on reaction with K 4 Fe  CN6  in aq. solution gives blue colour. these are separated by a semiper-
meable membrane PQ as shown. Due to osmosis there is

P
0.1M 0.01M
K4Fe(CN) 6 FeCl3

Side X Side Y

Q
(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

4. A solution of glucose  C6H12O6  is isotonic with of 4g urea (NH2CONH2) per litre of solution. Th concentra-
tion of glucose is :
(A) 4 g /  (B) 8 g/  (C) 12 g /  (D) 14 g / 
5. If ‘A’ contains 2% NaCl and is separated by a semipermeable membrane from ‘B’ which contains 10% NaCl,
which event will occur ?
(A) NaCl will flow from ‘A’ to ‘B’ (B) NaCl will flow from ‘B’ to ‘A’
(C) Water will from ‘A’ to ‘B’ (D) Water will flow from ‘B’ to ‘A’

6. Insulin  C2H10 O5 n is dissolved in a suitable solvent and the osmotic pressure  of the solution of various
concentration (in kg/m3) is measured at 20°C. The slope of a plot of  against c is found to be 8.314  10 3
(SI units) The molecular weight of the insulin (in kg/mol) is :

(A) 4.8  105 (B) 9  105 (C) 293  103 (D) 8.314  105

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LIQUID SOLUTION [ 21 ]
RELATIVE LOWERING OF VAPOUR PRESSURE
7. A sample of 20.0 g of a compound (molecular weight 120) which is a non-electrolyte is dissolved in 10.0
grams of ethanol (C2H5OH). If the vapour pressure of pure ethanol at the temperature used is 0.250 atm,
what is the vapor pressure of ethanol above the solution?
(A) 0.250 atm (B) 0.83 atm (C) 0.125 atm (D) 0.14 atm
8. Which of the following statements is true?
(A) the boiling point of liquid is the temperature at which the vapour pressure becomes equal to 260 mm
(B) passage of solute molecules towards solution side through semipermeable membrane is osmosis
(C) The boiling point of a solution is lower than the solvent.
(D) The relative lowering vapour pressure of a solution is equal to the mole fraction of the non volatile solute
present in the solution
9. The statement given below concerning properties of solutions describes a colligative effect
(A) boiling point of pure water decreases by the addition of ethanol
(B) vapour pressure of pure water decreases by the addition of nitric acid
(C) vapour pressure of pure benzene decreases by the addition of naphthalene
(D) boiling point of pure benzene increases by the addition of toluene
10. The vapour pressure of benzene at 80°C is lowered by 10 mm when 2.0 g of a non-volatile substance is
dissolved in 78 g of benzene. The vapour pressure of pure benzene at 80°C is 750 mm. The molar mass of the
non-volatile substance is
(A) 148 (B) 1050 (C) 1500 (D) 1550
11. The vapour pressure of a solvent is 20 torr whereas that of its dilute solution is 17 torr. The mole fraction of the
solvent is
(A) 0.6 (B) 0.4 (C) 0.85 (D) 0.7
12. At 120°C, the vapour pressure of pure chlorobenzene (C6H5Cl) is 0.736 atm. What is the vapour pressure of
a solution of 12.8 g of naphthalene (C10H8) in 112.5 g of chlorobenzene? (Assume that naphthalene is not
volatile)
(A) 0.736 atm (B) 0.091 atm (C) 0.669 atm (D) 1.00 atm
13. Vapour pressure of pure water is 40 mm . If a non-volatile solute is added to it , vapour pressure falls by
4 mm . Hence, molality of solution is :
(A) 6.173 molal (B) 3.0864 molal (C) 1.543 molal (D) 0.772 molal

VANT HOFF FACTOR

14. Which salt may show the same value of vant Hoff factor (i) as that of K4[Fe(CN)6] in very dilute solution state:
(A) Al2(SO4)3 (B) NaCl (C) Al(NO3)3 (D) Na2SO4
15. Barium ions, CN and Co2 form an ionic complex. If that complex is supposed to be 75% ionised in water
with vant Hoff factor ‘i’ equal to four, then the coordination number of Co2 in the complex can be :
(A) Six (B) Five (C) Four (D) Six and Four both

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[ 22 ] LIQUID SOLUTION

16. If pK a   log ka  4, and K a  Cx2 then van’t Hoff factor for weak monobasic acid when C = 0.01 M is
(where x = degree of dissociation) :
(A) 1.01 (B) 1.02 (C) 1.10 (D) 1.20

ELEVATION IN BOILING POINT AND DEPRESSION IN FREEZING POINT

17. When 0.6 g of urea (mol. wt 60) is dissolved in 100 g of water, The water will boil at (Kbfor water = 0.52
km-1) and normal boiling point of water = 100°C
(A) 372.48 K (B) 373.52 K (C) 373.052 K (D) 273.52 K
18. The phase diagrams for the pure solvent (solid lines) and the solution (non-volatile solute, dashed line) are
recorded below : The quantity indicated by L in the figure is (m = molality) :

(A)  p (B)  Tf (C) Kbm (D) Kfm

19. An aqueous solution of glucose boils at 100.01°C. The molal elevation constant for water is 0.5 K mol–1 Kg.
The number of molecules of glucose in the solution containing 100 g of water is

(A) 6.023  1023 (B) 6.023  1022 (C) 12.046  1020 (D) 12.046  1023
20. Equimolal solutions of A and B show depression in freezing point in the ratio 2:1. A remains in its normal
state in solution. B will be ————————— state
(A) Normal (B) Dissociated (C) Associated (D) Hydrolysis
21. 0.48 g of a non electrolyte substance is dissolved in 10.6 g of C6H6. The freezing point of benzene is lowered
by 1.8°C. What will be the mol. wt. of the substance (Kf for benzene = 5)
(A) 250.2 (B) 90.8 (C) 125.79 (D) 102.5
22. Given a solution of C6H12 O6 and a solution of NaCl, in which equal weights of C6H12O6 and NaCl are dissolved
in equal volume of water,
(A) the two solutions will have same depression of freezing point
(B) the two solutions will have same elevation of boiling point
(C) the Nacl solution will have larger depression of freezing point than the C6H12O6 solution
(D) the C6H12O6 solution will have larger depression of freezing point than the NaCl solution
23. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to
(A) ionisation of benzoic acid (B) dimerization of benzoic acid
(C) trimerization of benzoic acid (D) solvation of benzoic acid

1
24. What weight of NaCl is added to one 1 kg of water so that  Tf/Kf = ?
500
(A) 5.85 g (B) 0.585 g (C) 0.0585 g (D) 0.0855 g

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LIQUID SOLUTION [ 23 ]
25. Which of the following has been arranged in order of decreasing freezing point ?

(A) 0.05M KNO3  0.04MCaCl2  0.140Msugar  0.075MCuSO4

(B) 0.04M BaCl2  0.140Msucrose  0.075MCuSO4  0.05MKNO3

(C) 0.075M CuSO4  0.140Msucrose  0.04MBaCl2  0.05MKNO3

(D) 0.075M CuSO4  0.05MNaNO3  0.140Msucrose  0.04MBaCl2

26. An aqueous solution boils at 100.51°C. The freezing point of the solution would be (Kb for water = 0.51°C/m),
(Kf for water = 1.86°C/m) [No association or dissociation]

(A) 0°C (B) – 1.86°C (C) – 1.82°C (D) + 1.82°C

IDEAL AND NON-IDEAL SOLUTION

27. For A and B to form an ideal solution which of the following conditions should be satisfied?

(A)  H(mixing) = 0 (B)  V(mixing) = 0

(C)  S(mixing) > 0 (D) All the three conditions mentioned above
28. The mole fraction of toluene in vapour phase which is in equilibrium with a solution of benzene and toluene
having a mole fraction of toluene 0.500 is (vapour pressure of pure benzene and pure toluene are 119 torr and
37.0 torr respectively at the same temperature).
(A) 0.5 (B) 0.763 (C) 0.237 (D) 1
29. The vapour pressure of hexane (C6H14) and heptane (C7H16) at 50°C are 408 Torr and 141 Torr, respectively.
The composition of the vapour above a binary solution composition of the vapour above a binary solution
containing a mole fraction of 0.300 hexane is (Y6 = mol fraction of hexane and Y7 = mol fraction of heptane).
(A) Y6 = 0.8, Y7 = 0.2 (B) Y6 = 0.554, Y7 = 0.446
(C) Y6 = 0.300, Y7 = 0.700 (D) Y6 = 0.871, Y7 = 0.129
30. Benzene (C6H6, 78 g/mol) and tolune (C7H8, 92 g/mol) form an ideal solution. At 60°C the vapour pressure of
pure benzene and pure toluene are 0.507 atm and 0.184 atm, respectively. Calculate the mole fraction of
benzene in a solution of these two chemicals that has a vapor pressure of 0.350 atm at 60°C
(A) 0.514 (B) 0.690 (C) 0.486 (D) 0.190
31. At 25°C the vapor pressure of benzene, C6H6 (78g/mole), is 93.2 Torr and the of toluene, C7H8 (92 g/mol), is
28.2 Torr. A solution of 1.0 mole of C6H6 and 1.0 mol of C7H8 is prepared. Calculate the mole fraction of C6H6
in the vapor above this solution (assume the solution is ideal).
(A) 0.607 (B) 0.768 (C) 0.232 (D) 0.393
32. Which of the following plots does not represent the behaviour of an ideal binary liquid solution ?
(A) plot of pA versus xA (mole fraction of a liquid phase) is linear
(B) plot of pB versus xB is linear
(C) plot of ptotal versus xA (or xB) is linear
(D) plot of ptotal versus xA is non – linear

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[ 24 ] LIQUID SOLUTION
33. For an ideal solution with pA > pB, which of the following is true ?
(A) (xA) liquid = (xA) vapour.
(B) (xA) liquid > (xA) vapour
(C) (xA) liquid < (xA) vapour
(D) (xA) liquid and (xA) vapour do not bear any relationship with each other
34. The most likely of the following mixtures to be an ideal solution is:
(A) NaCl – H2O (B) C2H5OH – C6H6 (C) C6H6(l) – H2O (D) C6H5OH – H2O
35. Mixture of volatile components A and B has total vapour pressure (in Torr) :
p = 254 – 119 xA
where xA is mole fraction of A in mixture. Hence, PA0 and PB0 are (in Torr) :
(A) 254, 119 (B) 119, 254 (C) 135, 254 (D) 154, 119

PA
36. For an ideal binary solution with 1 which relation between XA (mole fraction of A in liquid phase) and
PB

YA (mole fraction of A in vapour phase) is correct, XB and YB are mole fraction of B in liquid and vapour
phase respectively :
(A) XA  YA (B) XA  YA

X A YA
(C) X  Y (D) XA , YA , XB and YB cannot be correlated
B B

37. Which of the following is not correct for an ideal solution ?

(A) Rault’s law is obeyed for entire concentration range and temperatures
(B) Hmix  0

(C) Vmix  0

(D) Smix  0
38. Which of the following is less than zero for ideal solutions ?
(A) Hmix (B) Vmix (C) Gmix (D) Smix

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LIQUID SOLUTION [ 25 ]
EXERCISE-2
(FOR JEE MAIN)
(PREVIOUS YEARS AIEEE & IIT-JEE QUESTIONS)
(SINGLE CORRECT ANSWER TYPE)
1. For a dilute solution, Raoult’s law states that [IIT JEE - 1985]
(A) the lowering of vapour pressure is equal to the mole fraction of solute
(B) the relative lowering of vapour pressure is equal to the mole fraction of nonvolatile solute
(C) the relative lowering of vapour pressure is proportional to the amount of solute in solution
(D) the vapour pressure of the solution is equal to the mole fraction of solvent
2. When mercuric iodic is added to the aqueous solution of potassium iodic [IIT JEE - 1987]
(A) freezing point is raised (B) freezing point is lowered
(C) freezing point does not change (D) boiling point does not change
3. Which of the following 0.1 M aqueous solutions will have the lowest freezing point ? [IIT JEE - 1989]
(A) Potassium sulphate (B) Sodium chloride
(C) Urea (D) Glucose
4. The freezing point of equimolal aqueous solutions will be highest for : [IIT JEE - 1990]
(A) C6H5NH3Cl (aniline hydrocloride) (B) Ca(NO3)2
(C) La(NO3)3 (D) C6H12O6 (glucose)
5. 0.2 molal acid HX is 20% ionised in solution Kf = 1.86 K molality–1. The freezing point of the solution is :
[IIT JEE - 1995]
(A) – 0.45 (B) – 0.90 (C) – 0.31 (D) – 0.53
6. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to : [IIT JEE - 1996]
(A) ionization of benzoic acid (B) dimerization of benzoic acid
(C) trimerization of benzoic acid (D) Solvation of benzoic acid
7. In the depression of freezing point experiment, it is found that [IIT JEE - 1999]
(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
8. During depression of freezing point in a solution, the following are in equilibrium [IIT JEE - 2003]
(A) liquid solvent-solid solvent (B) liquid solvent-solid solute
(C) liquid solute-solid solute (D) liquid solute-solid solvent
9. 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 [IIT JEE - 2004]
(A) 25% (B) 50% (C) 75% (D) 85%

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[ 26 ] LIQUID SOLUTION
10. 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] [IIT JEE - 2005]
(A) 0.05 (B) 0.1 (C) 0.156 (D) 0.21

11.  1

When 20g of naphthoic acid  C11H8O2  is dissolved in 50 g of benzene k f  1.72K mol , a freezing point
depression of 2 K is observed. The van’t Hoff factor (i) is [IIT JEE - 2007]

(A) 0.5 (B) 1 (C) 2 (D) 3

12. The Henry’s law constant for the solubility of N2 gas in water at 298 K is 1.0  105 atm. The mole fraction
of N2 in air is 0.8. The number of moles of N2 from air dissolved in 10 moles of water of 298 K and 5 atm
pressure is [IIT JEE - 2009]

(A) 4.0  104 (B) 4.0  105 (C) 5.0  104 (D) 4.0  106
13. The freezing point (inºC) of solution containing 0.1 g of K3[Fe(CN)6] (mol. wt. 329) in 100 g of water (Kf = 1.86
K kg mol–1) is [IIT JEE - 2011]

(A) 2.3  102 (B) 5.7  102 (C) 5.7  10 3 (D) 1.2  102
14. For a dilute solution containing 2.5 g of a non-volatile non-electrolyte solute in 100 g of water, the elevation in
boiling point at 1 atm pressure is 2ºC. Assuming concentration of solute is much lower than the concentra-
tion of solvent, the vapour pressure (mm of Hg) of the solution is (take Kb = 0.76 K kg mol–1).
[IIT JEE - 2012]
(A) 724 (B) 740 (C) 736 (D) 718
15. The vapour pressure of aceotne at 20oC is 185 torr. When 1.2 g of a non-volatile subsatnce was dissolved in
100 g fo acetone at 20oC, its vapour pressure was 183 torr. The molar mass (g mol—1) of the substance is :
(A) 64 (B) 128 (C) 488 (D) 32

(PREVIOUS YEARS AIEEE QUESTIONS)

16. Freezing point of an aqueous solution is (–0.186)ºC. Elevation of boiling point of the same solution is Kb =
0.512ºC, Kf = 1.86ºC, find the increase in boiling point. [AIEEE- 2002]
(A) 0.186 ºC (B) 0.0512 ºC (C) 0.092 ºC (D) 0.2372 ºC
17. In mixture A and B components show -ve deviation as [AIEEE- 2002]

(A) Vmi x  0

(B) Hmi x  0
(C) A – B interaction is weaker than A – A and B – B interaction
(D) A – B interaction is stronger than A – A and B – B interaction
18. A pressure cooker reduces cooking time for food because ; [AIEEE- 2003]
(A) heat is more evenly distributed in he cooking space
(B) boiling point of water involved in cooking is increased
(C) the higher pressure inside the cooker crushes the food material
(D) cooking involves chemical changes helped by arise in temperature

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LIQUID SOLUTION [ 27 ]
19. In a 0.2 molal aqueous solution of a weak acid HX , the degree of ionisation is 0.3.Taking K f for water as
1.85, the freezing point of the solution will be nearest to : [AIEEE- 2003]
(A) –0.4800 C (B) –0.3600 C (C) –0.2600 C (D) +0.4800 C
20. If liquids A and B form an ideal solution, then : [AIEEE- 2003]
(A) enthalpy of mixing is zero
(B) entropy of mixing is zero
(C) free energy of mixing is zero
(D) free energy as well as the entropy of mixing are each zero
21. Which one of the following aqueous solutions will exhibit highest boiling point ? [AIEEE- 2004]
(A) 0.01 M Na2SO4 (B) 0.01 M KNO3 (C) 0.015 M urea (D) 0.015 M glucose
22. For which of the following parameters the structural isomers C2H5OH and CH3OCH3 would be expected to
have the same values ? (Assume ideal behaviour) [AIEEE- 2004]
(A) Heat vaporisation
(B) Vapour pressure at the same temperature
(C) Boiling points
(D) Gaseous densities at the same temperature and pressure
23. Which one of the following statements is false ? [AIEEE- 2004]
(A) Raoult’s law states that the vapour pressure of a component over a solution is proportional to its mole
fraction
(B) The osmotic pressure (p) of a p = MRT, where M is the molarity of the solution
(C) The correct order of osmotic pressure for 0.01 M aqueous solution of each compound is
BaCl2 > KCl > CH3COOH > Sucrose
(D) Two sucrose solutions of same molarity prepared in different solvents will have the same freezing point
depression
24. Which of the following liquid pairs shows a positive deviation from Raoult’s law ? [AIEEE- 2004]
(A) Water - nitric acid (B) Benzene - methanol
(C) Water - hydrochloric acid (D) Acetone - chloroform
25. Equimolar solutions in the same solvent have [AIEEE- 2005]
(A) Same boiling point but different freezing point (B) Same freezing point but different boiling point
(C) Same boiling and same freezing points (D) Different boiling and different freezing points
26. Benzene and toluene form nearly ideal solution. A 20ºC, the vapour pressure of benzene is 75 torr and that of
toluene is 22 torr. The partial vapour pressure of benzene at 20ºC for a solution containing 78 g of benzene
and 46 g of toluene in torr is [AIEEE- 2005]
(A) 53.5 (B) 37.5 (C) 25 (D) 50
27. Among the following mixtures, dipole-dipole as the major interaction, is present in [AIEEE- 2006]
(A) KCl and water (B) Benzene and carbon tetrachloride
(C) Benzene and ethanol (D) Acetonitrile and acetone
28. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The vapour pressure of water for this aqueous solution
at 100ºC. [AIEEE- 2006]
(A) 76.00 Torr (B) 752.40 Torr (C) 759.00 Torr (D) 7.60 Torr

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[ 28 ] LIQUID SOLUTION
29. A mixture of ethyl alcohol and propyl alcohol has a vapour pressure of 290 mm at 300 K. The vapour pressure
of propyl alcohol is 200 mm. If the mole fraction of ethyl alcohol is 0.6, its vapour pressure (in mm) at the
same temperature will be [AIEEE- 2007]
(A) 700 (B) 360 (C) 350 (D) 300
30. Equal masses of methane and oxygen are mixed in an empthy container at 25ºC. The fraction of the total
pressure exerted by oxygen is [AIEEE- 2007]

1 273
(A) 1/2 (B) 2/3 (C)  (D) 1/3
3 298
31. A 5.25% solution of a substance is isotonic with a 1.5% solution of urea (molar mas = 60 g mol–1) in the same
solvent. If the densities of both the solution are assumed to be equal to 1.0 g cm–3, molar mass of the
substance will be [AIEEE- 2007]
(A) 210.0 g mol–1 (B) 90.0 g mol–1 (C) 115.0 g mol–1 (D) 105.0 g mol–1.
32. At 80ºC, the vapour pressure of pure liquid ‘A’ is 520 mm Hg and that of pure liquid ‘B’ is 1000 mm Hg. If a
mixture solution of ‘A’ and ‘B’ boils at 80ºC and 1 atm pressure, the amount of ‘A” in the mixture is (1 atm =
760 mm Hg) [AIEEE- 2008]
(A) 52 mol present (B) 34 mol present (C) 48 mol present (D) 50 mol present
33. The vapour pressure of water at 20ºC is 17.5 mm Hg. If 18g of glucose (C6H12O6) is added to 178.2 g of water
at 20ºC, the vapour pressure of the resulting solution will be [AIEEE- 2008]
(A) 17.325 mm Hg (B) 15.750 mm Hg (C) 16.500 mm Hg (D) 17.500 mm Hg
34. A binary liquid solution is prepared by mixing n-heptane and ethanol. Which one of the following statements
is correct regarding the behaviour of the solution? [AIEEE- 2009]
(A) The solution is non-ideal, showing - ve deviation from Raoult’s Law.
(B) The solution is non-ideal, showing +ve deviation from Raoult’s Law
(C) n-haptane shows +ve deviation while ethanol shows - ve deviation from Raoult’s Law.
(D) The solution formed is an ideal solution
35. Two liquids X and Y form an ideal solution. At 300 K, vapour pressure of the solution containing 1 mole of X
and 3 mol of Y is 550 mmHg. At the same temperature, if 1 mole of Y is further added to this solution, vapour
pressure of the solution increases by 10 mmHg. Vapour pressure (in mmHg) of X and Y in their pure states
will be, respectively ; [AIEEE- 2009]
(A) 300 and 400 (B) 400 and 600 (C) 500 and 600 (D) 200 and 300
36. If sodium sulphate is considered to be completely dissociated into cations and anions in aqueous solution,
the change in freezing point of water ( Tf ) , when 0.01 mol of sodium sulphate is dissolved in 1 kg of water,,

is (K f  1.86 K kg mol1) [AIEEE- 2010]

(A) 0.372 K (B) 0.0558 K (C) 0.0744 K (D) 0.0186 K

37. On mixing, heptane and octane form an ideal solution. At 373 K, the vapour pressure of the two liquid
components (hepatne and octane) are 105 kPa and 45 kPa respectively. Vapour pressure of the solution
obtained by mixing 25.0 g of heptane and 35 g of octane will be (molar mass of hepatane = 100 g mol–1 and
of octane = 114 g mol–1) [AIEEE- 2010]
(A) 72.0 kPa (B) 36.1 kPa (C) 96.2 kPa (D) 144.5 kPa

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LIQUID SOLUTION [ 29 ]
EXERCISE-3
(FOR JEE ADVANCED)
(SINGLE CORRECT ANSWER TYPE)
1. Find the mole fraction of O2 in a saturated solution of oxytgen in water at 25C , when partial pressure of

O2 above the water is 0.21 atm. Given that Henry’s constant for O2 in water at 25C is 2.3 105 atm1 .

(A) 4.8 106 (B) 2.4 105 (C) 1.2 103 (D) 9.6 106

2. The partial pressure of ethane over a saturated solution containing 6.56 102 gm of ethane is 1 bar. If the

solution contains 5 10 2 g gas of ethane. what will be the partial pressure of the gas.

(A) 0.762 bar (B) 0.962 bar (C) 1.32 bar (D) 1.5 bar

3. In the following aqueous solutions

(i) 1 m sucrose (ii) 1 m potassium ferricyanide and

(iii) 1 m potassium sulphate

Maximum value of vapour pressure of solution is that of :

(A) (i) (B) (ii) (C) (iii) (D) equal

RT P0
4. Thermodynamic relation between osmotic pressure and vapour pressure of a solution is  ln , where
V P
‘V’ is the molar volume of solvent. Calculate the osmotic pressure of an aqueous solution of glucose
M.W. 180  at 27C that contains 0.0005 mole glucose per gram of solution. The density of water = 1g/ml

and ln1.01  9.9 103 .

(A) 13.53 atm (B) 10 atm (C) 12.3 atm (D) 14.53 atm

W W
5. A 10% area solution is isotonic with a 20% solution of a non-volatile solute, at the same temperature.
V V
Calculate the molecular weight of the solute.

(A) 240 (B) 120 (C) 360 (D) 480

6. Vapour density of PCl5  g  dissociating into PCl3  g  and Cl2  g  is 100. Hence, van’t Hoff factor for the
case:



PCl5  g  
 PCl3  g  Cl2  g  is

(A) 1.85 (B) 3.70 (C) 1.085 (D) 1.0425

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[ 30 ] LIQUID SOLUTION

7. Tritium ‘T’ (an isotope of H) combined with fluorine to from weak acid TF, which ionises to give T  and F .
Trittium is radioactive and is a  -emitte. A freshly prepared aqueous solution of TF has PT (eqwivalent of
PH) of 1.5 and freezes at 0.372C . If 600 ml of freshly prepared solution were allowed to stand for 24.8
year what will be ionisation constant of TF and  particle emitted. Assume TF as non volatile. Given k f for
water = 1.86 k  kg / mol and t 1 for tritium = 12.4 year & Antilog 0.5 = 3.18 = 10
2

(A) 7.3 103 , 4.55 1022 (b) 8 104 , 4 1022

(c) 104 ,1 (d) 103 , 1022

8. 25 mL of an aqueous solution of KCl was found to requires 20 mL of 1M AgNO3 solution when titrated
using a K 2CrO4 as indicator. Depression in freezing point of KCl solution with 100% ionization will be
[ K f  2.0 mol1 kg and molarity = molality]
(A) 20/45 (B) 16/5 (C) 40/45 (D) 160/45
9. x mole of KCl and y mole of BaCl2 are both dissolved in 1 kgof water. Given that x  y  0.1 and K f for
water is 1.85 K/molal, what is the observed range of Tf , if the ratio of x to y is varied ?
(A) 0.37° to 0.55° (B) 0.185° to 0.93° (C) 0.56° to 0.93° (D) 0.37° to 0.93°
10. What is the mole ratio of benzene (PB°=150 torr) and toluene (PT°=50 torr) in vapour phase if the given
soltuion has a vapour pressure of 120 torr ?
(A) 7:1 (B) 7;3 (C) 8:1 (D) 7:8
11. At 323 K, the vapour pressure in millimeters of mercury of a methanol-ethanol solution is represented by
pA
the equation p  120 X A  140 , whre XA is the mole fraction of methanol. Then the value of xlim is
A 1 XA

(A) 250 mm (B) 140 mm (C) 260 mm (D) 20 mm

12. Which represents correct difference ?

Vapour Solution
Vapour
(S)solvent (S)soluble
I. II. (H)solution= (H)solvent
III. B.P
Solution

Solvent Solvent
Solvent

(A) I, II, III (B) I,III (C) II, III (D) I, II

13. The vapour pressures of benzene, toluene and a xylene are 75 Torr, 22 Torr and 10 Torr at 20°C. Which of
the folloiwng is not a possible value of the vapor pressure of an equimolar binary/ternary solution of these
at 20°C ? Assume all form ideal solution with each other.

1
(A) 48 (B) 16
2

2 1
(C) 35 (D) 53
2 2

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LIQUID SOLUTION [ 31 ]
14. An ideal mixture of liquids A and B with 2 moles of A and 2 moles of B has a total vapour pressure of 1 atm
at a certain temperature, Another mixture with 1 mole of A and 3 moles of B has a vapour pressure greater
than 1 atm. but if 4 moles of C are added to the second mixture, the vapour pressure comes down to 1
atm. Vapour pressure of C, Px0 = 0.8 atm. Calculate the vapour pressures of pure A and pure B.

(A) PA 0  1.4 atm, PB0  0.7 atm (B) PA 0  1.2atm, PB0  0.6 atm

(C) PA 0  1.4 atm, PB0  0.6 atm (D) PA 0  0.6atm, PB0  1.4 atm

(MULTIPLE CORRECT ANSWER TYPE)

15. Osmotic pressure in dilute solution is
(A) inversely proportional to the moles of non-volatile solution
(B) directly proportional to temperature
(C) directly proportional to the molarity of solution
(D) independent of temperature and moles of solute dissolved
16. Which one of the following pairs of solution can we expect to be isotonic at the same temperature?
(A) 0.1 M-urea and 0.1 M-NaCl (B) 0.1 M-urea and 0.1 M  MgCl2

(C) 0.1 M  Na2SO 4 and 0.1 M  MgCl2 (D) 0.1 M  Na2SO 4 and 0.1 M  Ca(NO3 )2
17. Select correct statement(s) regarding a solution of non-volatile solid solute in a liquid solvent
(A) Heats of vaporisation for a pure solvent and for a solution are similar because similar intermolecular
forces between solvent molecules must be overcome in both cases.
(B) Entropy change between solution and vapour is similar to the entropy change between pure solvent
and vapour.
(C) Boiling point of the solution is larger than that of the pure solvent.
(D) Freezing point of the solution is larger than that of pure solvent.
18. The vapour pressure of a dilute solution of a solute is not influenced by the
(A) temperature of the solution (B) melting point of the solute
(C) mole fraction of the solute (D) degree of dissociation of solute
19. Consider 0.1 M solutions of two solutes X and Y. The solute X behaves as a univalent electrolyte
while the solute Y dimerises in solution. W hich of the following Statement are correct regarding
these solutions?
(A) The boiling point of the solution X will be higher than that of Y.
(B) The osmotic pressure of the solution Y will be lower than that of X.
(C) The freezing point of the solution X will be lower than that of Y.
(D) The relative lowering of vapour pressure of both the solutions will be the same.
20. In the depression of freezing point experiment , it is found that the :
(A) vapour pressure of the solution is less than that of pure solvent
(B) vapour pressure of the solution is more than that of pure solvent
(C) only solute molecules solidify at the freezing point
(D) only solvent molecules solidify at the freezing point

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[ 32 ] LIQUID SOLUTION
21. Acetone and carbon disulphide form binary liquid solution showing positive deviation from Raoult’s
law. The normal boiling point of pure acetone is less than that of pure carbon disulphide. Select the
incorrect statement(s) among the following:
(A) Boiling point of mixture is always less than the boiling point of acetone.
(B) Boiling point of the azeotropic mixture is always less than the boiling point of pure carbon
disulphide.
(C) When a small amount of carbon disulphide is added to an excess of acetone, boiling point of
solution increases.
(D) A mixture of acetone and carbon disulphide can be completely separated by simple fractional
distillation.

(ASSERTION-REASON TYPE)
Following questions contains two statements : Statement I (Assertion) and Statement II (Reason). Each of
these questions also has four alternative choices, only one of which is the correct answer. You have to
select one of the codes (a), (b), (c), (d) given below :
(A) Statement I is true; Statement II is true; Statement II is a correct explanation for Statement I.
(B) Statement I is true; Statement II is true; Statement II is not a correct explanation for Statement I.
(C) Statement I is true; Statement II is false.
(D) Statement I is false; Statement II is true.
22. Statement I : The difference in the boiling points of equimolar solution of HCl and HF decreases as their
molarity is decreased.
Statement II : The extent of dissociation decreases steadily with increasing dilution.
23. Statement – I : The freezing of water is an endothermic process.
Statement – II : Heat must be removed from the water to make it freeze.
24. Statement – I : Addition of a non-volatile solute to a volatile solvent increases the boiling point.
Statement – II : Addition of non-volatile solute to a volatile solvent results decrease in the vapour pressure.
25. Statement I : When an ideal binary solution of liquids A and B is distilled, the boiling point of the distillate
becomes lower than of the parental liquid solution.
Statement II : When an ideal binary of liquids A and B is distilled, the distillate contains relatively larger
amount of the more volatile liquid.
26. Statement I : Hmix and Vmix in an ideal solution are zero.
Statement II : A – B interactions in ideal solution are same as between A – B and B – B.

(PARAGRAPH TYPE)
Paragraph-1

The composition of vapour ove a binary ideal solution is determined by the composition of the liquid. X A and YA
are the mole formation of ‘A’ in the liquid and vapour respectively.

27. what is the value of X A for which  YA  XA  has minimum.

PA0 PA0  PB0  PB0 PA0

(A) (B) 0.5 (C) (D) .
PA0  PB0 PA0  PB0  PB0

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LIQUID SOLUTION [ 33 ]
28. What is the value of the pressure of this composition?

PA02 PB0
(A) PA0  PB0 (B) (C) (D) PA0 PB0
PB0 PA0

29. What is the value for YA at this pressure?

PA0  PB0  PB0 PA0  PA0  PB0 PA0

(A) (B) 0.5 (C) (D)
PA0  PB0  PA0  PB0 PA0  PB0 PA0  PB0

Paragraph-2
A system of greater disorder of molecules is more probable. The disorder of molecules is reflected by the
entropy of the system. A liquid vaporises to form a more disordered gas. When a solute is present, there is
additional contribution to the entropy of the liquid due to increased randomness. As the entropy of solution
is higher than that of pure liquid, there is weaker tendency to form the gas. Thus, a solute (non volatile)
lowers the vapour pressure of a liquid, and hence a higher boiling point of the solution.
Similarly, the greater randomness of the solution opposes the tendency to freeze. In consequence, a lower
the temperature must be reached for achieving the equilibrium between the solid (frozen solvent) and the
solution. Elevation of B.Pt. (Tb) and depression of F.Pt. (Tf ) of a solution are the colligative properties
which depend only on the concentration of particles of the solute, not their identity. For dilute solutions, Tb
and Tf are proportional to the molality of the solute in the solution.

2
RTbº M
Tb = Kbm Kb = Ebullioscopic constant =
1000 Hvap

2
RTfº M
And Tf = Kf m Kf = Cryoscopic constant = (M = molecular mass of the solvent)
1000 Hfus

H vap
The values of Kb and Kf do depend on the properties of the solvent. For liquids, is almost constant.
Tbº
[Troutan’s Rule, this constant for most of the unassociated liquids (not having any strong bonding like
Hydrogen bonding in the liquid state) is equal to 90 J/mol.]
For solutes undergoing change of molecular state is solution (ionization or association), the observed T
values differ from the calculated ones using the above relations. In such situations, the relationships are
modified as Tb = i Kb m ; Tf = i Kf m
where i = Van't-Hoff factor, greater than unity for ionization and smaller than unity for association of the
solute molecules.
30. Depression of freezing point of which of the following solutions does represent the cryoscopic constant of
water?
(A) 6% by mass of urea is aqueous solution
(B) 100g of aqueous solution containing 18 g of glucose
(C) 59 g of aqueous solution containing 9 g of glucose
(D) 1 M KCl solution in water.

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[ 34 ] LIQUID SOLUTION
31. Dissolution of a non-volatile solute into a liquid leads to the -
(A) decrease of entropy
(B) increase in tendency of the liquid to freeze
(C) increases in tendency to pass into the vapour phase.
(D) decrease in tendency of the liquid to freeze
32. To aqueous solution of NaI, increasing amounts of solid Hg2 is added. The vapor pressure of the solution
(A) decreases to a constant value
(B) increases to a constant value
(C) increases first and then decreases
(D) remains constant because Hg2 is sparingly soluble in water.
33. A liquid possessing which of the following characteristics will be most suitable for determining the molecular
mass of a compound by cryoscopic measurements?
(A) That having low freezing point and small enthalpy of freezing
(B) That having high freezing point and small enthalpy of freezing
(C) That having high freezing point and small enthalpy of vaporisation
(D) That having large surface tension
34. A mixture of two immiscible liquids at a constant pressure of 1 atm boils at a temperature
(A) equal to the normal boiling point of more volatile liquid.
(B) equal to the mean of the normal boiling points of the two liquids.
(C) greater than the normal boiling point of either of the liquid.
(D) smaller than the normal boiling point of either of the liquid.
PARAGRAPH-III
Properties, whose values depend only on the concentration of solute particles in solution and not on the
identity of the solute are called colligative properties. There may be change in number of moles of solute due
to ionisation or association hence these properties are also affected. Number of moles of the product is
related to degree of ionisation or association by vant Hoff factor ‘i’

 1  
given by i = [ 1 + (n – 1)] for dissociation & i = 1   n  1  for association
   

where n is the number of products (ions or molecules) obtained per mole of the reactant.
A dilute solution contains ‘t’ moles of solute X in 1 Kg of solvent with molal elevation constant Kb . The solute
dimerises in the solution according to the following equation. The degree of association is  .

2X X2
35. The vant Hoff factor will be [ if we start with one mole of X ]
(A) i = 1 – 2 (B) i = 1 – /2 (C) i = 1 + /2 (D) i = 1 + 

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LIQUID SOLUTION [ 35 ]
36. The colligative properties observed will be
(A) Pobs > Pactual (B) Pobs = Pactual
Tb(obs) > Tb(actual) Tb(obs) = Tb(actual)
Tf(obs) > Tf(actual) Tf(obs) = Tf(actual)

(C) Tb(obs) < Tb(actual) (D) Pobs > =Pactual

Tf(obs) < Tf(actual) Tb(obs) = Tb(actual)
Pobs < Pactual Tf obs < Tf actual
37. The equilibrium constant for the process can be expressed as

t
Kb
 T K K t – Tb 
(A) K  b (B) K  b b
1–
Kbt [2Tb – Kbt]2
Tf

2  Kbt – Tb  / Tb Tbobs

(C) K  (D) K 
 2(K t – T )2  Tfobs
2t 1– b b 
 Tb 

(MATRIX MATCH TYPE)

38. Match the solution in Column-I with their nature in Column-II:
Column-I Column-II
(A) n-hexane + n heptane (p) Can be perfectly separated by distillation
(B) Acetone + chloroform (q) Maximum boiling azeotrope
(C) Acetone + aniline (r) Cannot be perfectly separated by distillation
(D) Ethanol + water (s) Nearly ideal
39. Match the solutions in Column-I with their osmotic properties in Column-II:
Column-I Column-II
(A) S1 : 0.1 M glucose, (p) S1 and S2 are isotonic
S2 : 0.1 M urea
(B) S1 : 0.1 M NaCl, (q) No migration of solvent across the membrane

S2 : 0.1 M Na2SO4
(C) S1 : 0.1 M KCl, (r) S1 is hypertonic to S2
S2 : 0.1 M KCl

(D) S1 : 0.1 M CuSO4 , (s) S1 is hypotonic to S2

S2 : 0.1 M sucrose
[Note : Assume that the electrolytes are completely ionised.]

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[ 36 ] LIQUID SOLUTION
40. Match the solution in Column-I with their colligative properties in Column-II:
Column-I Column-II

(A) 0.1 M Ca3 (PO4 )2 (p) Solution with highest boiling point

(B) 0.1 M NaCl (q) Solution with van’t Hoff factor greater than 1
(C) 0.1 M glucose (r) Solution with lowest osmotic pressure

(D) 0.1 M CaCl2 (s) Solution with lowest freezing point

[Note : Assume that the electrolytes are completely ionised.]

41. Match the solutes in Column-I with the van’t Hoff factors in Column-II:
Column-I Column-II

(A) K 4 [Fe(CN)6 ] (p) 1 + 2

(B) Al2 (SO4 )3 (q) Greater than 1

O
(C) NH2 C NH2 (r) (1 + 4  )

(D) CaCl2 (s) 1

 = Degree of ionization.
42. Match the solution in Column-I with their nature in Column-II:
Column-I Column-II
(a) Benzene + toluene (p) Non-ideal solution
(b) Ethanol + water (q) Ideal solution

(c) Benzene + chloroform (r) Hmix  0

(d) Carbon tetrachloride (s) Hmixing  0

+ chloroform

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LIQUID SOLUTION [ 37 ]
EXERCISE-4
(PREVIOUS YEARS IIT-JEE QUESTIONS)
(PARAGRAPH TYPE)
Paragraph-I
Properties such as boiling point, freezing point and vapour pressure of a pure solvent change when solute
molecules are added to get homogeneous solution. These are called colligative properties. Applications of
colligative properties are very useful in day-to-day life. One of its examples is the use of ethylene glycol and
water mixture as anti-freezing liquid in the radiator of automobiles.
A solution M is prepared by mixing ethanol and water. The mole fraction of ethanol in the mixture is 0.9.
Given, Freezing point depression constant of water

kfwater  1.86K kgmol1

Freezing point elevation constant of ethanol

kethanol
f   2.0K kgmol1
Boiling point elevation constant of water

kbwater   0.52K kgmol1

Boiling point elevation constant of ethanol

kbethanol  1.2K kgmol1

Standard freezing point of water = 273 K
Standard freezing point of ethanol = 155.7 K
Standard boiling point of water = 373 K
Standard boiling point of pure ethanol = 351.5 K
Vapour pressure of pure water = 32.8 mm Hg
Vapour pressure of pure ethanol = 40 mm Hg
Molecular weight of water = 18 g mol-1
Molecular weight of ethanol = 46 g mol-1
In answering the following questions, consider the solutions to be ideal dilute solutions and solutes to be
non-volatile and non-dissociative. [IIT JEE - 2008]
1. The freezing point of the solution M is
(A) 268.7 K (B) 268.5 K (C) 234.2 K (D) 150.9 K
2. The vapour pressure of the solution M is
(A) 39.3 mm Hg (B) 36.0 mm Hg (C) 29.5 mm Hg (D) 28.8 mm Hg
3. Water is added to the solution M such that the mole fraction of water in the solution becomes 0.9. The boiling
point of this solution is
(A) 380.4 K (B) 376.2 K (C) 375.5 K (D) 354.7 K

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[ 38 ] LIQUID SOLUTION
(FILL IN THE BLANKS)
7. Given that Tf is the depression in freezing point of the solvent in a solution of a non-volatile solute of
molality, m, the quantity lim ( Tf / m) is equal to .......... [IIT JEE - 1994]
m 0

(MULTIPLE CORRECT ANSWER TYPE)

8. Benzene and naphthalene form an ideal solution at room temperature. For this process the true statement(s)
is (are) [IIT JEE - 2013]

(A) G is Positive (B) Ssystem is positive

(C) Ssurrounding  0 (D) H  0

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LIQUID SOLUTION [ 39 ]
EXERCISE-5
(QUESTIONS BASED ON KVPY & OLYMPIADS)
1. The vapour pressure of two liquids are 15000 and 30000 in a unit. Calculate mole fraction of A and B in
vapour hase, when equimolar soltion of liquids is made.
2. At 30°C, the vapoure pressure of pure ether is 646 mm and of pure acetone is 283 mm. Calculate the mole
fraction of each component in vapour state for the solution of two having mole fraction of ether 0.50. Assume
ideal behaviour.

3. Vapour pressure of C6H6 and C7H8 are 119 mm of Hg and 37 mm of Hg respectively. Calculate molar

composition of C6H6 and C7H8 in a mixture having V.P. of 80 mm of Hg. Also calculate vapour phase
composition over the mixture.
4. Benzene and toluene form an ideal solution. The vapour pressure of benzene and toluene are respectively
75 mm and 22 mm at 20°C. If the mole fraction of benzene and toluene in vapour phase are 0.63 and 0.37
respectively, calculate the vapour pressure of mixture.
5. Solution of two volatile liquids A and B obey Raoult’s law. At a certain temperature, it is found that when the
total vapour pressure above solution is 400 mm of Hg, the mole fraction of A in vapour phases are 0.45 and
in liquid phase 0.65. What are vapour pressures of two pure liquids at the same temperature ?
6. V. P. of pure A p°A= 100 mmHg
V.P. of pure B p°B= 150 mmHg
Calculate the total vapour pressure, approximately, on condensation for Distillate of vapours of a solution
containing 2 moles A and 3 moles B
7. Two liquids A and B have P° A:P°B = 1 : 3 at a certain temperature. If the mole fraction ratio of
xA : xB = 1 : 3, the mole fraction of A in vapour in equilibrium with the solution at a given temperature is :

8. Vapour pressure of benzene and toluene are 90 mm and 40 mm of Hg respectively. Calculate xb  10 when
yb  xb is minimum where xb = m.f. of benzene in liquid phase, yb = m.f. of benzene in vapour phase
9. The vapour pressures of two pure liquids A & B that form an ideal solution are 300 torr and 800 torr,
respectively, at temperature T. A mixture of the vapours of A and B for which the mole fraction of A is 0.25 is
slowly compressed at tempratrue T. Calculate :
(A) the composition of the first drop of the condensate
(B) the total pressure when this drop is formed
(C) the composition of the solution whose normal boiling point is T
(D) the pressure when only the last bubble of vapour remains
(E) composition of the last bubble.
10. 2.8 g of cadmium iodide (Cdl2) in 20 g of water boiled at 0.20 K higher temperature than the boiling point of
pure water. Calculate the molar mass of Cdl2 and comment on result.
Kb for H2O = 0.52 K molality–1.

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[ 40 ] LIQUID SOLUTION
EXERCISE-6
(IIT SUBJECTIVE QUESTIONS OF PREVIOUS YEARS)
1. The vapour pressure of pure benzene is 639.70 mm of Hg and the vapour pressure of solution of a solute in
benzene at the same temperature is 631.9 mm of Hg. Calculate the molality of the solution. [IIT JEE-1981]

2. Two liquids A and B form ideal solution. At 300 K, the vapour pressure of a solution containing 1 mole of A and
3 moles of B is 550 mm of Hg. At the same temperature, if one more mole of B is added to this solution, the
vapour pressure of the solution increases by 10 mm of Hg. Determine the vapour pressure of A and B in their
pure states. [IIT JEE-1982]

3.  
An organic compound C xH2y O y was burnt with twice the amount of oxygen needed for complete combustion

to CO2 and H2O . The hot gases when cooled to 0ºC and 1 atm pressure, measured 2.24 L. The water
collected during cooling weight 0.9 g. The vapour pressure of pure water at 20ºC is 17.5 mm Hg and is
lowered by 0.104 mm when 50 g of the organic compound are dissolved in 1000 g of water. Give the molecular
formula of the organic compound. [IIT JEE-1983]

4. The vapour pressure of ethanol and methanol are 44.5 and 88.7 mm Hg respectively. An ideal solution is
formed at the same temperature by the mixing 60 g of ethanol with 40 g of methanol. Calculate the total
vapour pressure of the solution and the mole fraction of methanol in the vapour. [IIT JEE-1986]

5. The vapour pressure of a dilute aqueous solution of glucose  C6H12O6  is 750 mm of mercury at 373 K.
Calculate (i) molality and (ii) mole fraction of the solute. [IIT JEE-1989]

6. The vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non-volatile, non-electrolyte
solid weighing 2.175 g is added to 39.0 g of benzene. The vapour pressure of the solution is 600 mm Hg.
What is the molecular weight of the solid substance? [IIT JEE-1990]

7. The degree of dissociation of Ca(NO3 )2 in a dilute aqueous solution, containing 7.0 g of the salt per 100 g
of water at 100ºC is 70%. If the vapour-pressure of water at 100ºC is 760mm, calculate the vapour pressure
of the solution. [IIT JEE-1991]

8. Addition of 0.643 g of a compound to 50 mL of benzene (density : 0.879 g/mL) lowers the freezing point from
5.51ºC to 5.03ºC. If kf for benzene is 5.12, calculate the molecular weight of the compound.[IIT JEE-1992]

9. What weight of the non-volatile solute urea  NH2  CO  NH2  needs to be dissolve in 100 g of water, in
order to decrease the vapour pressure of water by 25%? What will be the molality of the solution?

[IIT JEE-1993]

10. The molar volume of liquid benzene (density = 0.877 g/mL) increases by a factor of 2750 as it vapourises at
20ºC and that of liquid toluene (density = 0.867 g mL-1) increases by a factor of 7720 at 20ºC. A solution of
benzene and toluene at 20ºC has a vapour pressure of 45.0 torr. Find the mole fraction of benzene in the
vapour above the solution. [IIT JEE-1996]

11. A solution of a non-volatile solute in water freezes at -0.30ºC. The vapour pressure of pure water at 298 K is
23.51 mm Hg and kf for water is 1.86 K Kg mol-1. Calculate the vapour pressure of this solution at 298 K.

[IIT JEE-1998]

DIVISION OF MENTORS EDUSERV CORPOTATE OFFICE : Parus Lok Complex, Boring Road Crossing, Patna - 1
LIQUID SOLUTION [ 41 ]
12. Nitrobenzene is formed as the major product along with a minor product in the reaction of benzene with a hot
mixture of nitric acid and sulphuric acid. The minor product consists of carbon : 42.86%, hydrogen : 2.40%,
nitrogen : 16.67% and oxygen : 38.07%,

(i) Calculate the empirical formula of the minor product.

(ii) When 5.5 g of the minor product is dissolved in 45 g of benzene, the boiling point of the solution is 1.84ºC
higher than that of pure benzene. Calculate the molar mass of the minor product then determine its molecular
and structural formula. (Molal boiling point elevation constant of benzene is 2.53K kg mol-1).[IIT JEE-1999]
13. 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.
[IIT JEE-2000]
14. Consider the three solvents of identical molar masses. Match their boiling point with their kb values
Solvents Boiling point kb values [IIT JEE-2003]
X 100ºC 0.92
Y 27ºC 0.63
Z 283ºC 0.53

15. 1.22 g C6H5COOH is added into two solvents and data of Tb and kb are given as : [IIT JEE-2014]

(i) In 100 g CH3COCH3 Tb  0.17 , kb = 1.7 K kg/mol

(ii) In 100 g benzene, Tb  0.13 and kb  2.6K kg / mol

Find out the molecular weight of C6H5COOH in both the cases and interpret the result.

16. 75.2 g of C6H5OH (phenol) is dissolved in a 1 kg solvent of kf = 14. If the depression in freezing point is 7
K, then find the percentage of phenol that dimerises. [IIT JEE-2006]

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[ 42 ] LIQUID SOLUTION

ANSWER KEYS
DAILY PRACTICE PROBLEM-1
1. (A) 2. (A) 3. (A) 4. (C)
5. (D) 6. (A) 7. (B) 8. (A)

DAILY PRACTICE PROBLEM-2

1. (D) 2. (C) 3. (D) 4. (B)
5. (C) 6. (C) 7. (B) 8. (i) (A) (ii) (D)
9. (B) 10. (A) 11. (A) 12. (C)

DAILY PRACTICE PROBLEM-3

1. (C) 2. (D) 3. (A) 4. (B)
5. (B) 6. (C) 7. (C) 8. (C)

9. (A) 10. (B)

EXERCISE-1
(FOR JEE MAIN)
(SINGLE CORRECT ANSWER TYPE)
1. (A) 2. (C) 3. (D) 4. (C) 5. (C) 6. (C) 7. (D) 8. (D) 9. (C)
10. (A) 11. (C) 12. (C) 13. (A) 14. (A) 15. (B) 16. (C) 17. (C) 18. (C)
19. (C) 20. (C) 21. (C) 22. (C) 23. (B) 24. (C) 25. (A) 26. (A) 27. (D)
28. (C) 29. (B) 30. (A) 31. (B) 32. (D) 33. (D) 34. (A) 35. (C) 36. (C)
37. (D) 38. (C)

EXERCISE-2
(FOR JEE MAIN)
(SINGLE CORRECT ANSWER TYPE)
1. (B) 2. (A) 3. (A) 4. (D) 5. (A) 6. (B) 7. (C) 8. (A) 9. (C)
10. (C) 11. (A) 12. (A) 13. (A) 14. (A) 15. (A) 16. (B) 17. (D) 18. (B)
19. (A) 20. (A) 21. (A) 22. (D) 23. (D) 24. (B) 25. (C) 26. (D) 27. (D)
28. (B) 29. (C) 30. (D) 31. (A) 32. (D) 33. (A) 34. (B) 35. (B) 36. (B)
37. (A)

DIVISION OF MENTORS EDUSERV CORPOTATE OFFICE : Parus Lok Complex, Boring Road Crossing, Patna - 1
LIQUID SOLUTION [ 43 ]
EXERCISE-3
(FOR JEE ADVANCED)
(SINGLE CORRECT ANSWER TYPE)
1. (A) 2. (A) 3. (A) 4. (A) 5. (B) 6. (D) 7. (A) 8. (B) 9. (A)
10. (B) 11. (C) 12. (A) 13. (D) 14. (D)

(MULTIPLE CORRECT ANSWER TYPE)

15. (B, C) 16. (C, D) 17. (A, C) 18. (B) 19. (A, B) 20. (A, D)

21. (A, C, D)

(ASSERTION-REASON TYPE)
22. ( C) 23. (D) 24. (A) 25. (A) 26. (A)

(PARAGRAPH TYPE)
27. (C) 28. (D) 29. (A) 30. (D) 31. (D) 32. (B) 33. (B) 34. (D) 35. (B)
36. (C) 37. (B)

(MATRIX MATCH TYPE)

38. (a–p, s); (b–q, r); (c–q, r); (d–r) 39. (a–p, q); (b–s); (c–p, q); (d–r)

40. (a–p, q, s); (b–q); (c–r); (d–q) 41. (a–q, r); (b–q, r); (c–s); (d–p, q)

42. (a–q, s); (b–p, r) (c–p); (d–p,r)

EXERCISE-4
(JEE ADVANCED)
(PREVIOUS YEARS IIT-JEE QUESTIONS)
(PARAGRAPH TYPE)
1. (D) 2. (B) 3. (B)

(FILL IN THE BLANKS)

7. (kf)

(MULTIPLE CORRECT ANSWER TYPE)

8. (B, C, D)

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[ 44 ] LIQUID SOLUTION

EXERCISE-5
(QUESTIONS BASED ON KVPY & OLYMPIADS)
1 2
1. ,
3 3

2. 0.695, 0.305

3. Liquid phase = 52.44%, 47.56 % vapour phase = 78% 22%

4. 39.68 mm 5. 276.9 mm, 628.57 mm 6. 135 7. 0.1 8. 4

9. (A) XA = 0.47, XB = 0.53 (B) 565 torr (C) XA  0.08 , XB  0.92 (D) 675 torr (E) XA = 0.11, XB = 0.89

10. 364

EXERCISE-6
(IIT SUBJECTIVE QUESTIONS OF PREVIOUS YEARS)
1. According to Raoult’s law :

p  p0 x1

 631.9 = 639.7 x1

 x1 = 0.9878 ( x1 = mole fraction of solvent)

 x2 = 0.0122 ( x 2 = mole fraction of solute)

0.0122
 Molality =  1000  0.158
0.9878  78
2. When 1.0 mole of A is mixed with 3 moles of B.

550  0.25p0A  0.75pB

0 ....(i)

When 1.0 mole of A is mixed with 4 moles of B.

560  0.20p0A  0.80pB

0 ....(ii)

Now, solving (i) and (ii) : pºA = 400 mm

º = 600 mm
pB

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LIQUID SOLUTION [ 45 ]
3. From lowering of vapour pressure information :

0.104 n2
 x2 
17.5 n1  n2

n1
  1  168.27
n2

n1
 n  167.27
2

1000 M
   167.27
18 50

 M = 150g/mol
Also, the combustion reaction is :

C xH2y O y  xO 2  xCO2  yH2O

 18 y g of H2O is produced from 1.0 mole of compound.

0.9 1
 0.9 g of H2O will be produced from  mol
18y 20y

x
 At the end, moles of O2 left = 20y

x
moles of CO2 formed =
20y

2x 2.24
 Total moles of gases at STP = 
20y 22.4

 x=y
 Molar mass; 150 = 12x + 2x + 16x = 30x

150
 x 5
30

 Formula = C5H10O5

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[ 46 ] LIQUID SOLUTION

60
4. Moles of ethanol =  1.3
46

40
Moles of methanol =  1.25
32

1.3
 Mole fraction of ethanol =  0.51
1.3  1.25

 Vapour pressure of solution = pethanol  pmethanol

= 0.51  44.5  0.49  88.7 = 66.16 mm

Mole fraction of methanol in vapour phase

pmethanol 43.463
= =  0.657
Total vapour pressure 66.16

5. At 373 K (b.p.) of H2O , Vapour pressure = 760 mm

VP of solution at 373 K = 750 mm

 p  p0 x1
or 750 = 760x1

75
 x1   mole fractionof H2O
76

75 1
 x2  1    mole fraction of solute
76 76

n2 1 n1
Now :    75
n1  n2 76 n2

n2 1000
 Molality =  1000 =  0.74molal
n1M1 75  18

6. According to Raoult’s law :

p  p0 x1

 n1  n2 64 1 39 1
 600 = 640  n  n    1  n2    0.033
 1 2 n1 60 15 78 15

2.175
  0.033
M

 M = 65.25

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LIQUID SOLUTION [ 47 ]
7. 
 2 
Ca(NO3 )2  Ca  2NO3

i  1  2 where,   0.7
 i  1  2  0.7  2.4

 100 
n1  18 
   0.982
 Mole fraction of solvent = =
n1  in2  100  7
 18   2.4  164
 

 p  p0 x1 = 760  0.982(VPof H2Oat100º C  760mmof Hg) = 746.32 mm

8.  Tf  5.51  5.03  0.48

0.643 1000
  Tf  0.48  k f  m  0.48  5.12  
M 50  0.879
 M = 156 g/mol
9. Vapour pressure of solution = 0.75  VP of water
 75  100x1, x1 = mole fraction of solvent
3 1
 x1  and x 2  1  x1 
4 4
x2 n2 1 n1 100
    n2    1.85
x1 n1 3 3 18  3
 Weight of urea = 1.85  60  111g

n2 1000 1 1000
Molality = n  M  3  18  18.5
1 1

78
10. Volume of 1.0 mole liquid benzene = mL  88.94mL
0.877
88.94  2750
 Molar volume of benzene vapour at 20ºC = L  244.58L
1000
0.082  293
 VP of pure benzene at 20ºC =  760mm = 74.65 mm
244.58

92 7720
Similarly; molar volume of toluene vapour =  L  819.2L
0.867 1000

0.082  293
 VP of pure toluene =  760mm  22.3mm
819.2
Now, let mole fraction of benzene in the liquid phase = x
 74.65x + 22.3 (1 – x) = 45  x = 0.43
 Mole fraction of benzene in vapour phase

Partialvapour pressure of benzene 74.65  0.43

= =  0.72
Total vapour pressure 45

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[ 48 ] LIQUID SOLUTION

0.3
11.  Tf  k f  m 2  m2   0.1613
1.86

n2 1000 n1 n2  n1
Also, m2  n  M  0.1613  n2  0.1613  18  2.9  103  n  1  n  2.9  103  1
1 1 n1 1000 2 1

n1 1
 n  n  x1   0.997  p  p x  23.51 0.997  23.44mm
0 1
1 2 1  2.9  103

12. 0.229
13. (i) Empirical formula determination
Elements C H N O
Weight % 42.86 2.4 16.67 38.07
Moles 3.57 2.4 1.19 2.38
Simplest ratio 3 2 1 2

 Empirical formula = C3H2NO2

5.5 1000
(ii) Tb  1.84  2.53    M = 168
M 45

 Empirical formula weight (84) is half of molar mass, molecular formula is – C6H4N2O4 – a dinitro benzene :
NO2

(C6H4N2O4) NO2
14. Higher the volume of kb of a solvent suggest that there is larger polarity of solvent molecules, which in turn
implies higher boiling point due to dipole-dipole interaction.
Therefore, the correct order of kb values of the three given solvents is :
Solvents Boiling point kb
X 100ºC 0.63
Y 27ºC 0.53
Z 283ºC 0.92
15. (i) Tb  kb  m2

1.22 1000
 0.17 1.7    M = 122
M 100

1.22 1000
(ii) 0.13  2.6    M = 244
M 100
The above molar masses suggests that benzoic acid is monomeric in acetone while dimeric in benzene.
16.   0.75

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