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S. Santhanam
WS24.C12.06 Solutions-II

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1. Liquids A & B form an ideal solution for all compositions of A & B at 25 C . Two such
solutions with molefractions 0.25 and 0.5 of A (in the liquid phase) have Ptotal 0.3 and 0.4 bar
respectively. Calculate (i) PA ,PB (ii) yA (in the vapour phase), y B for the first solution and for
the second solution

2. Liquids A & B form an ideal solution over the entire range of composition. At T Kelvin
equimolar binary solutions of A & B have vapour pressure 45torr. At the same T, a new
solution of A & B have molefractions A , B has vapour pressure 22.5 torr. A / B in the new
solution is ______ if PA  20 torr

3. Vapour pressure of pure benzene at 25C is 639.7 mm and that of a non-volatile solute in
benzene at the same T is 631.9 mm. Calculate the freezing point of the solution, bpt of the
solution and the osmotic pressure of the solution in atm at 25C . k b  2.626K / molal ,
k f  4.98K / molal for C6 H6 . [bp of pure benzene 80.09C, fp : 5.4C ]

4. An aq. solution of glucose freezes at  0.2C. Calculate the vapour pressure of this solution at
25C if the vapour pressure of H2O at 25C is 23.506 mm.
What is the bp of this solution and osmotic pressure at 25C [ k b  0.52 K kg mol1 and
k f  1.86 K kg mol1 for H2O as solvent]

5. 0.01m aq. Pt  NH 3 4 Cl2 freezes at  0.0558C . Deduce the structure of this complex
(assume 100% dissociation)

6. Examine for a normal liquid k b  104 M1Tb is true or not. (M: molecular mass of pure solvent,
Tb : bp of pure solvent)

7. Estimate the freezing point of 150CC of water sweetened with 7.5g sucrose

8. What is the vapour pressure of sea water at 20C if that of pure water at 20C is 2.338 kPa and
the solute is essentially 0.05 M NaCl.  m M 

9. The osmotic pressure of an aq. solution of urea is 120kPa at 300K. The fpt of the same solution
______ K
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WS24.C12.06 S. Santhanam

10. 1g of a mono basic acid in 100 g water lowers the fpt by 0.168 degrees. 0.2g of the same acid
M
required 15.1ml of NaOH for complete neutralisation. Calculate the % dissociation of the
10
weak acid and its ionization constant

11. Assuming 100% dissociation of solutes what would be the freezing point of an aq. solution that
is 0.1m in NaCl and 0.1m in CaCl2 . what is its bp?

12. The freezing point of 0.02 molefraction of acetic acid in benzene is 4.4 C. The fpt of pure
benzene: 5.4 C , Hfusion 2400 cals/mol. Calculate the equilibrium constant for the dimerisation
reaction 2A A2 if the solute undergoes dimerisation in C6 H6

13. 0.122 kg of C6 H5COOH in 1kg C6 H6 boils at 354.5K bpt of pure benzene 353 K
H vap = 394.57J/g for the solvent. Calculate the % dimerisation of the solute in C6 H6

14. 1.47g of an organic solute, X (normal) in 50g C6 H6 boils at 80.6 C at a pressure of 1atm. bpt of
pure benzene 80.09 C, H vap  32 kJ / mol . Calculate the molecular mass of the solute X.

15. 3.24g Hg  NO3  2 dissolved in 1kg of water and the fpt of the solution to  0.0558C (Mwt 324.6)
while 10.84 g HgCl2 in 1kg of water freezes at  0.0744C Mwt 271.5. k f =1.86 K / molal. Deduce
the molecular state of each solute

16. The % dissociation of a solute in a solution of 7g of Ca  NO3  2 in 100g water is 70 at 100 C .

What is the vapour pressure of this solution

17. 0.2g acetic and in 20g C6 H6 lowers the fpt by 0.45C. % dimerisation is _____ k f =5.12K / molal.

18. 0.01m K 3  Fe  CN 3  aq freezes at  0.062C. % dissociation _____

19. At 1atm an aq solution of urea freezes at 1.5C . Calculate the osmotic pressure in atm, at 27C
k f = 1.85K/molal and density of the solution 1g/cc, assume  m M

20. Liquids A & B form an ideal solution ( PA 75 torr PB 22 torr) A  0.33 . What is yA in
equilibrium with this solution?
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WS24.C12.06 S. Santhanam
Homework Problems

21. Two elements A & B form compounds AB2 , AB4 . When dissolved in 20g benzene 1g AB2
lowers the fpt by 2.3C and 1g AB4 when dissolved separately in 20g C6 H6 lowers the fpt by
1.3 degrees, kf  5.1K / molal . What are the atomic masses of A and B?

22. An aqueous solution of maltose freezes at  0.21C. Calculate (i) the normal bp of this solution
k f  1.86, k b = 0.51 (ii) molality of an aq. solution of KNO3 having the same vapour pressure.
(assume 100% dissociation)

23. The molefraction of urea in 900g water is 0.05. Density of the solution 1.2g/CC. The osmotic
pressure of this solution at 27C is _____ Pascal

24. Account for the following

Po  P
a) Isomolal solutions of glucose, urea, sucrose have the same value for (i) (ii) Tb
Po
(iii) Tf (iv)  but isomolal solutions of NaCl, BaCl2 , K 4  Fe  CN  6  , Al2  SO 4 3 do not.
Arrange the above aq soluns in the order of (i) all colligative properties (ii) bp (iii) fpt
(iv) Po  P

b) The fpt of an aq KI solution is  1.86 C while the fpt of a solution got an adding HgI2 (sold)
to it is 1.41 C , HgI2  s  2KI  aq  K2  HgI4  aq.

25. P-T curves for two solvents X and Y and isomolal solutions of NaCl in these solvents are given
below (100% dissociation of NaCl in both solvents). On addition of equal no. of moles of a non-
volatile solute S in equal amounts (in kg) in these solvents  Tb X   3Tb Y . Also ‘S’ undergoes
dimerisation in these solvents % dimerisation of ‘S’ in solvent Y is 70, % dimerisation in
solvent X ______

(diagram is not to scale)

1 2 3 4
760
mm

1. solvent X
2. NaCl solun in X 360 362 367 368
3. solvent Y T (Kelvin)
4. NaCl solun in Y
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26. 2% solution of a non-volatile solute (X) in toluene has VP 752.4 mm

(normal bp of toluene 110.25C ) (i) Mwt of X _____ (ii) H vap / g of toluene _____

27. 0.1236g o-chloro benzoic acid in 100g water freezes at  0.0147C while 3.265g of the same
solute in 60g benzene freezes at 4.59 C . The fpt of pure benzene is 5.48C .
 k f  water /  k f C H
1
 The ratio of the apparent molecular mass of solute in water to benzene
6 6 2.75
is ________

28. The bp of three liquids P, Q, R are T1 , T2 and T3 Kelvin respectively with T2  T1  T3 All
three have nearly same latent heat of vaporisation per gram. The trend in their k b values
would be  k1 , k 2 , k 3  _____

29. At 343K a solution (ideal) of 1mol A +2mol B is 0.5 atm. At the same temperature 3moles of ‘A’
is added to it and the VP of the solution is 0.7 atm. If some vapour in equilibrium with the first
solution is fully condensed what will be the composition of that condensed liquid. What will be
the nature of the graph for this ideal solun (i) Pt (y-axis) vs  A (liquid phase)
1
(ii) Pt vs yA (vapour) (iii) vs yA (underlined one on Y-axis in each)
Pt

30. k b used in an actual expt for a solvent depends on the barometric pressure. True/ false.

31. Pure water freezes at 273K at 1bar. Addn. of 34.5 g  non-volatile solute, Mwt 46 to 500g
water changes the fpt of the solution. k f of water: 2 K kg mol1. Draw VP-T diagram for the
changes in fpt. Represent the fpt of the solution & that of the solvent in the same diagram.

32. 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 difference in the boiling points 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.)