CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

PART - B : COLLIGATIVE PROPERTIES

Table : 1 Example of ideal solution

Benzene + toluene, Chlorobenzene + bromo – Benzene

n-hexane + nheptane,
CCl4 + SiCl4, C2H5Br + C2H5I
n-butyl chloride + n butyl bromide

Table : 2 Example of Non ideal solution -

Positive deviation from Raoult’s law Negative Deviation from Raoult’s law

1. (CH3)2CO + CS2 1. (CH3)2CO + C6H5NH2

2. (CH3)2CO + C2H5OH 2. (CH3)2 CO + CHCl3
3. CH3CHO + CS2 3. CHCl3 + C6H6
4. C6H6 + (CH3)2CO 4. CHCl3 + CH3COOH
5. CCl4 + C6H6 5. CH3OH + CH3COOH
6. CCl4 + C6H5CH3 6. CHCl3 + (C2H5)2O
7. CCl4 + CHCl3 7. CH3COOH + C5H5N
8. CCl4 + CH3OH 8. H2O + HCl
9. C6H6 + C2H5OH 9. H2O + HNO3
10. CH3OH + H2O
11. C2H5OH + H2O

Table : 3. ¼Molal elevation constants of some solvents½

Solvent B.Pt. (°C) Molal elevation constant (Kb) (K kg mol–1)

Water 100.0 0.52

Acetone 56.0 1.70
Chloroform 61.2 3.67
Carbon tetrachloride 76.8 5.02
Benzene 80.0 2.70
Ethyl alcohol 78.4 1.15

Table : 4. ¼Molal depression constant of some solvents½

Solvent E.P.(°C) Molal depression constant (Kf) (K kg mol–1)

Water 0.0 1.86

Ehtyl alcohol – 114.6 1.99
Chloroform – 63.5 4.70
Carbon tetrachloride – 22.8 29.80
Benzene 5.5 5.12
Camphor 179.0 39.70

15
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

SOLVED EXAMPLES - B
Ex.1 At 300 K, the vapour pressure of an ideal solution Ex.3 What will be the temperature at which a solution
containing one mole of A and 3 moles of B is 550 containing 6 g of glucose per 1000 g water will
mm of Hg. At the same temperature, if one mole boil, if molal elevation constant for water is 0.52 /
of B is added to this solution, the vapour pressure 1000 g.
of solution increases by 10mm of Hg. Calculate (A) 1000.173ºC (B) 100.0173ºC
the vapour pressure of A and B in their pure state. (C) 100.173ºC (D) None (Ans. B)
(A) 400 mm, 600 mm (B) 600 mm, 400 mm Sol. w = 6g, W = 1000 g, Mol. wt. of glucose = 180
(C) 200 mm, 300 mm (D) 300 mm, 200 mm
1000  K b  w
(Ans. A) T b =
m W
Sol. Initially, PM = PºA . XA + PºB . XB
1000  0.52  6
1   3  =
550 = PºA   + PºB   180 1000
 1 3   1 3 
or PºA + 3PºB = 2200 = 0.0173ºC
When 1 mole of B is further added to it Hence boiling point of solution = b.p. of water +
PM = PºA . XA + PºB . XB Tb = 100 + 0.0173 = 100.0173ºC.

1   1 
560 = PºA   + PºB   Ex.4 Calculate the molal elevation constant of water
 1 4   1 4  evaporates at 100ºC with the absorption of 536
or PºA + 4PºB = 2800
calories per gm (R = 2 cals).
By (i) and (ii)
(A) 0.519ºC (B) 0.0519ºC
PºA = 400 mm ;
(C) 1.519ºC (D) 2.519ºC (Ans. A)
PºB = 600 mm
Sol. Molal elevation constant of the solvent.
Ex.2 The vapour pressure of pure liquid ‘A’ at 310ºC is
RT 2 b 2  373  373
120 torr. The vapour pressure of this liquid in Kb = = = 0.519ºC
 v  1000 536 1000
solution with liquid B is 72 torr. Calculate the mole
fraction of ‘A’ in solution if the mixture obeys
Ex.5 The vapour pressure of CCl4 (density = 1.58 g
Raoult’s law. cm–3) at 30ºC is 143 mm. A 0.5 g of a non-volatile
(A) 0.06 (B) 0.9 solute of molecular weight 65 is dissolved in 100
ml of CCl4. Calculate the vapour pressure of the
(C) 0.3 (D) 0.6 (Ans. D)
solution-
(A) 141.93 mm (B) 14.193 mm
Sol. Given is vapour pressure of pure component ‘A’, (C) 1.4193 mm (D) None (Ans. A)
PºA = 120 torr Sol. Here w = 0.5 g, W = 100 × 1.58 = 158 g
Partial vapour pressure of ‘A’, PA = 72 torr (since d = W / V), m = 65,
Suppose, its mole fraction in solution is xA, then p º– p wM
M of CCl4 = 154. =
according to Raoult’s law pº mW
PA = PºA . xA 143 – p 0.5 154
or =
72 = 120 × xA 143 65 158
or p = 141.93 mm
72
or xA = = 0.6
120

16
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Ex.6The freezing point of a solution containing 0.2g of

acetic acid in 20.0 g benzene is lowered by 0.45ºC. 0.2 4.0
So, 160 = x p 0A + x 150
Calculate the degree of association of acetic acid 4.2 4.2
in benzene. Assume acetic acid dimerizes in
benzene. Kf for benzene = 5.12 K mol–1 kg. 17.15  4.2
(A) 49.5 % (B) 94.5% p0 A =
0. 2
(C) 85.5% (D) 58.5% (Ans. B)
Sol. Given, w = 0.2 g, W = 20 g, = 360.15 mm  360 mm
T = 0.45ºC
Ex.8 Twenty grams of a substance were dissolved in
1000  K  w 500 ml. of water and the osmotic pressure of the
T =
mW solution was found to be 600 mm of mercury at
1000  5.12  0.2 150 C. Determine the molecular weight of the
or 0.45 = substance -
20  m
 m(observed) = 113.78 (A) 1120 (B) 1198
Now for 2CH3COOH (CH3COOH)2 (C) 1200 (D) None of these
Before association 1 0 (Ans. B)
After association 1–              /2 Sol. Here it is given that
Where  is degree of association w = 20 gm ; V = 500 ml .
m normal 500
 = 1 –  +  /2 = = 0.5 litre
m observed 1000
60 600
or =1–+/2  = 600 mm = atm ;
113.78 760
or  = 0.945 T = 15 + 273 = 2880 A
or 94.5 % m=?
According to Van’t Hoff equation ,
Ex.7 An aqueous solution containing 28% by mass of  V = nST
a liquid A(mol. mass = 140) has a vapour pressure w
 V = ST
of 160 mm at 370 C. Find the vapour pressure of m
the pure liquid A. (The vapour pressure of water w ST 20  0.0821 288  760
at 370C is 150 mm). m= =
V 600  0.5
(A) 360 mm (B) 150 mm = 1198
(C) 160 mm (D) None (Ans. A)
Sol. For two miscible liquids, Ex.9 Blood plasma has the following composition
(milli-equivalents per litre). Calculate its osmotic
Ptotal = mol. fraction A x p 0A mol. fraction pressure at 370C.
B x p0 B Na + = 138 , Ca 2+ = 5.2, K + = 4.5,
Mg 2+ = 2.0 , Cl¯ = 105, HCO 3 ¯ = 25,
28 PO43– = 2.2 , SO42--- = 0.5 ,
No. of moles of A= = 0.2 Proteins = 16, Others = 1.0
140
(A) 7.47 atm (B) 7.30 atm
Liquid B is water. Its mass is (100 - 28)= (C) 7.29 atm (D) 7.40 atm
i.e. 72 (Ans. A)
Sol. Since for calculating osmotic pressure we require
72 millimoles/litre therefore
No. of moles of B = = 4.0 5.2
18
Na+ = 138 Ca2+ = = 2.6 , K+ = 4.5, Mg 2+
2
Total number of moles = 0.2 + 4.0 = 4.2
2.0
Given Ptotal = 160 mm = = 1.0 , Cl¯ = 105 ,
2
p0B = 150 mm
17
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

But we know
22
HCO3¯ = 24,PO43 – = = 0.73, i = 1 + (n – 1)
3
2.95 = 1 + (3 – 1)  = 1 + 2
0.5
SO4 2– = = 0.25 , Proteins = 16 ,  = 0.975
2
others = 1.0 Van’t Haff factor (i) = 2.95
Degree of dissociation = 0.975
294.18
Total = 294.18 millimoles/litre = Percentage degree of dissociation = 97.5
1000
= 0.294 moles/litre
Now since  = CST Ex.12 Pure benzene boiled at 80°C. The boiling point of a
= 0.294 x 0.0821 x .310 = 7.47 atm
solution containing 1 g of substance dissolved in
Ex.10 0.15g of a substance dissolved in 15g of solvent 83.4 g of benzene is 80.175°C. If latent heat of va-
boiled at a temperature higher by 0.2160C than porization of benzene is 90 cal per g, calculate the
that of the pure solvent. Calculate the molecular molecular weight of solute .
weight of the substance. Molal elevation constant Sol. Boiling point of C6H6 = 80 + 273 = 353 k
for the solvent is 2.160C. Latent heat (1v) = 90 cal/g
(A) 216 (B) 100 T = 80.175 – 80 = 0.175, w = 1 g, W = 83.4 g
(C) 178 (D) None of these RT 2
(Ans. B)  Kb =
10001v
Sol. Here it is given that
2  353  353 –1
w = 0.15 g, Tb = = 0.2160 C or kb = = 2.769 K mol kg
1000  90
W = 15g Kb = 2.160C
m=? k b  1000  w
Now T =
Substituting values in the expression , m W

1000  K b  w
m= 2.769  1000  1
Tb  W 0.175 =
m  83.4
1000  2.16  0.15
m= = 100  m = 189.79
0.216 15

Ex.11 The freezing point of 0.2 molal K 2 SO 4 is Ex.13 At 27°C, 36 g of glucose per litre has an O.P. of 4.92
– 1.1ºC. Calculate Van’t Haff factor and atm. If the osmotic pressure of solution is 1.5 atm at
percentage degree of dissociation of K2SO4. Kf the same temperature, what should be its concen-
for water is 1.86º tration ?
(A) 97.5 (B) 90.75 Sol. Given that, 1 = 4.92 atm, 2 = 1.5 atm
(C) 105.5 (D) 85.75 (Ans. A) 36  w 
Sol. Tf = freezing point of water – freezing point of C1 =  C   C2 = ?
180  1  mV 
solution = 0º C – (–1.1º C) = 1.1º
1V1 = n1S1T1 and 2V2 = n2ST2
We know that, At same temperature
Tf = i × Kf × m 1 n1 V2 C1 4.92 36
1.1 = i × 1.86 × 0.2    or 
2 n 2 V1 C2 1.5 180  C 2
1.1 C2 = 0.061 mol/litre
 i= = 2.95
1.86  0.2

18
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Ex.14 How many g of glucose must be present in 0.5 litre  

of a solution for its osmotic pressure to be same as  10 
that of solution of 9.2 g glucose per litre ?  6 
20 =   10  P0
Sol. For isotonic solutions, C1 = C2 m 
 
w1 w2
or   10m  0
m1V1 m2 V2 20 =   P .........(1)
 6  10m 
w1 9.2
or  If 1 mol water is further added moles of solvent
180  0.5 180  1 N = 10 + 1 = 11 mol
 w1 = 4.60 g
& V.P. of solution becomes
Ex.15 Two liquids A and B form an ideal solution at tem- PS = 20 + 0.02 = 20.02 torr
perature T. When the total vapour pressure above N 0
the solution is 400 torr, the mol fraction of A in the PS = P
nN
vapour phase is 0.4 and in the liquid phase 0.75.
What are the vapour pressure of pure A and pure B  
 11 
at temperature T ?  6 P 0
20.02 =   11 
Sol. Mole fraction of A in vapour phase YA = 0.4 & in m 
liquid phase XA = 0.75  
Ptotal = 400 torr
Let V.P. of pure A and B are PA0 & PB0.  11m  0
 XAPA0 = YA Ptotal 20.02 =   P .........(2)
 6  11m 
YA PTotal 0.4  400 160 divide eqn. (2) by (1)
PA0 = = =
xA 0.75 0.75 20.02 11(6  10m)
PA0 = 213.33 torr =
20 10(6  11m)
m = 54 gm
Ptotal = XAPA0 + (1 – XA)PB0
Put this value of m in equation. (1) or (2)
 160  P0 = 22.22 torr
400 = 0.75   + (1 – 0.75)PB0
 0.75  Ex.17 Phenol associates in benzene to a certain extent to
PB0 = 960 torr form dimmer. A solution containing 20 ×10–3 kg of
phenol in 1.0 kg of benzene has its freezing point
Ex.16 Vapour pressure of solution containing 6g of a non- decreased by 0.69 K. Calculate the fraction of the
phenol that has dimerised. (K f of benzene is
volatile solute in 180 g water is 20.0 torr. If
5.12ºKmol–1). [Roorkee 1998]
1 mol water is further added vapour pressure in- Sol. Given
creases by 0.02 torr. Calculate vapour pressure of w = 20 × 10–3 kg. = 20 gm
water and molecular weight of non-volatile solute W = 1 kg = 103 gm
temperature remaining constant Observed
Sol. Let moelcualr wt. of solute = m  w  1000 
and V.P. of water (solvent) = P0 Tf =i  Kf 
 m W 
Psolution = 20 torr
6  20  1000  5.12 
0.69 = i  
moles of solute n =
m  94  10 3 
180 (i – 1)
moles of solvent N = = 10 
18 i=1–+ or  =  1 – 1

 N  0 n n 
 PS =  P  = 0.733 or 73.3
 nN

19
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Ex.18 Calculate the freezing point of an aqueous solution Ex. 21 0.1 formal solution of NaCl is found to be isotonic
of a non-electrolyte having an osmotic pressure of with 1.10% solution urea. Calculate the apparent
0.2 atmosphere at 300 K. [Roorkee 1993] degree of ionization of NaCl.
Sol.  = CST Sol. 0.1 formal = 0.1 M solu. of NaCl
 2 1.1% solution of urea means 
C= = mol lit–1 100 ml solu. contains 1.1 gm urea
ST 0.0821  300
In dilute solution, the density fo water can be taken NaCl = urea
as 1.0 gm cm–3. i(0.4 × ST) =
Hence molality  molarity 1.1  1000
 ST
 Tf = (molality × Kf ) 60  100
i = 1.83
2
= × 1.86 (i – 1)
0.0821 300
=
 Tf = 0.151 K ( n – 1)
 (Tf)solution = (Tf)solvent –  Tf
= (273 – 0.151) 1 .83 – 1
 = 0.83  = 83%
(Tf)solution = 272.749 K or – 0.151°C 2 –1

Ex.19 x g of a non-electrolytic compound (molar mass

= 200) is dissolved in 1.0 litre of 0.05 M NaCl
solution. The osmotic pressure of this solution is
found to be 4.92 atm at 27ºC. Calculate the value ‘x’.
Assume complete dissociation of NaCl and ideal
behaviour of this solution. [Roorkee 1998]
Sol. (i) For NaCl : 1 = i (CST)
1 = 2 × 0.05 × 0.0821 × 300
1 = 2.463 atm
(ii) for unknown compound :
2 = CST
x
2 = × 0.0821 × 300
200  1
2 = 0.1231 x atm
Total osmotic pressure  = 1 + 2
4.92 = 2.463 + 0.1231x
x = 19.959 gm

Ex.20 To 500 cm3 of water, 3.0 × 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 re-
spectively.
[IIT
–3
2000]
Sol. Mass of solute = 3 × 10 Kg = 3gm
Mass of solvent = 500 × 0.997 = 498.5 gm
 = 23% = 0.23
i = 1 –  + n
= 1 – 0.23 + 2 × 0.23
i = 1.23
Tf = i (molality × kf)

3  1000 
= 1.23 ×   × 1.86
 60  498 .5 
Tf = 0.229

20
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 1
Q. 1 The boiling point of C6H6 , CH3OH , C6H5 NH2 Q. 7 1 mole of heptane (V.P. = 92 mm of Hg) was mixed
and C6H5NO2 are 800 C , 650C , 1840C and with 4 moles of octane (V.P. = 31 mm of Hg). The
2120C respectively. Which will show highest vapour pressure of resulting ideal solution is -
vapour pressure at room temperature- (1) 46.2 mm of Hg (2) 40.0 mm of Hg
(3) 43.2 mm of Hg (4) 38.4 mm of Hg
(1) C6H6 (2) CH3OH
(3) C6H5NH2 (4) C6H5NO2 Q. 8 One mole of non volatile solute is dissolved in
two moles of water. The vapour pressure of the
Q. 2 The relative lowering of vaour pressure is equal solution relative to that of water is -
to the mole fraction of the nonvolatile solute, 2 1
This statement was given by - (1) (2)
(1) Raoult (2) Henry 3 3
(3) Joule (4) Dalton 1 3
(3) (4)
Q. 3 If Raoult’s law is obeyed, the vapour pressure of the 2 2
solvent in a solution is directly proportinal to -
(1) Mole fraction of the solvent Q. 9 The vapour pressure of a dilute aqueous solution
(2) Moe fraction of the solute
of Glucose is 750 mm of mercury at 373 K. The
(3) Mole fraction of the solvent and solute
(4) The volume of the solution mole fraction of solute is -
1 1
Q. 4 Which one of the following is the incorrect form (1) (2)
10 7.6
of Raoult’s law
Ps N P0 1 1
N (3) (4)
(1) 0
 (2) 0 =1+ 35 76
P nN p – Ps n

P 0 – Ps n Ps N Q. 10 The vapour pressure of water at room temperature

(3) = (4) 
Ps nN P – Ps n is 23.8 mm of Hg. The vapour pressure of an
aqueous solution of sucrose with mole fraction
Q. 5 The vapour pressure of a solution having solid 0.1 is equal to -
as solute and liquid as solvent is - (1) 23.9 mm Hg (2) 24.2 mm Hg
(1) Directly proportional to mole fraction of (3) 21.42 mm Hg (4) 31.44 mm Hg
the solvent
(2) Inversely proportional to mole fraction of Q. 11 At 88 °C benzene has a vapour pressure of 900
the solvent torr and toluene has a vapour pressure of 360
(3) Directly proportional to mole fraction of
torr. What is the mole fraction of benzene in the
the solute
(4) Inversely proportional to mole fraction of mixture with toluene that wil boil at 88 °C at 1
the solute atm. pressure, benzene - toluence form an ideal
solution -
Q. 6 If P0 and PS are the vapour pressure of solvent (1) 0.416 (2) 0.588
and its solution respectively. N1 and N2 are the (3) 0.688 (4) 0.740
mole fraction of solvent and solute respectively
then - Q. 12 Among the following, that does not form an ideal
P0 solution is -
(1) PS = (1) C6H6 and C6H5CH3
N2
(2) P0 – PS = P0N2 (2) C2H5Cl and C6 H5OH
(3) PS = P0N2 (3) C6H5Cl and C6H5Br
(4) C2H5Br and C2H5 I
( P0 – PS ) N1
(4) =
PS (N1  N2 )

21
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q. 13 Which condition is not satisfied by an ideal Q. 21 Molal depresion of freezing point of water is
solution 1.86° per 1000g of water. 0.02 mole of urea
(1) H mixing = 0 dissolved in 100g of water will produce a
(2) V mixing = 0 lowering of temperature of -
(3) S mixing = 0 (1) 0.186°C (2) 0.372°C
(4) Obeyance of Raoult’s law (3) 1.86°C (4) 3.72°C

Q. 14 Colligative properties of the solution depend Q. 22 What would be the freezing point of aqueous
upon - solution containing 17 g of C2 H5OH in 1000g of
(1) Nature of the solution water Kf = 1.86 K molality–1
(2) Nature of the solvent (1) – 0.69°C (2) – 0.34°C
(3) Number of solute particles (3) 0.0°C (4) 0.34°C
(4) Number of moles of solvent
Q. 23 A solution of 1.25 g of a non-electrolyte in 20 g
Q. 15 Which is not a colligative property ? of water freezes at 271.94 K. If Kf = 1.86 K
(1) Osmotic pressure molality–1 then the molecular wt. of the solute is -
(2) Lowering in vapour pressure (1) 207.8 g/mol (2) 179.79 g/mol
(3) Depression in freezing point (3) 209.6 g/mol (4) 109.6 g/mol
(4) Refractive index
Q. 16 The lowering of vapour pressure of a solvent by Q. 24 Elevation in boiling point was 0.52 °C when 6 g
addition of a non-volatile solute to it is directly of a compound x was dissolved in 100 g of water.
proportinal to - Molecular weight of x is : (K = 5.2 mol–1 100 g
(1) The strength of the solution H2O)
(2) The nature of the solute in the solution (1) 120 (2) 60 (3) 100 (4) 342
(3) The atmospheric pressure
Q. 25 Pure benzene freezes at 5.45 °C at a certain place
(4) All
but a 0.374 m solution of tetrachloroethane in
benzene freezes at 3.55 °C. The Kf for benzene is -
Q. 17 The molal elevation constant is the ratio of the (1) 5.08 K Kg mol–1 (2) 508 K Kg mol–1
elevation in B.P. to - (3) 0.508 K Kg mol–1 (4) 50.8 °C Kg mol–1
(1) Molarity
(2) Molality Q. 26 An aqueous solution containing 1g of urea boils
(3) Mole fraction of solute at 100.25 °C. The aqueous solution containing
(4) Mole fraction of solvent 3g of glucose in the same volume will boil at -
(1) 100.75 °C (2) 100.5 °C
Q. 18 The molal cryoscopic constant for water is - (3) 100 °C (4) 100.25 °C
(1) 1.86 K molality–1
Q. 27 An queous solution freezes at -
(2) 5.26 K molality–1
0.186 °C (Kf 1.86° ; Kb = 0.512°). What is the
(3) 55.5 K molality–1 elevation in boiling point ?
(4) 0.52 K molality–1 (1) 0.186 (2) 0.512
0.512
Q. 19 The freezing point of a 0.05 molal solution of a (3) (4) 0.0512
non electrolyte in water is - 1.86
(Kf = 1.86 K molality–1 ) Q. 28 The osmotic pressur of a dilute solution is
(1) – 1.86 °C (2) – 0.93°C directly proportional to the -
(3) – 0.093°C (4) 0.093°C (1) Diffusion rate of the solute
(2) Ionic concentration
Q. 20 The molal freezing point constant of water is 1.86 (3) Boiling point
K molality–1. If 342 g of cane sugar (C12H22O11 ) (4) Flow of solvent from a concentrated
solution
are dissolved in 1000g of water, the solution will
freeze at -
(1) –1.86 °C (2) 1.86 °C
(3) –3.92 °C (4) 2.42 °C

22
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q. 29 Which can pass through semipermeable Q. 36 If 0.1 M solution of glucose and 0.1 M urea
membrane ? solution are placed on two sides of a
(1) Molecules of solvent semipermeable membrane to equal heights. then
(2) Molecules of solute it will be correct to say that -
(3) Simple ion (1) There will be not movement across the
(4) Complex ion membrane
Q. 30 In osmosis phenomenon - (2) Glucose will flow towards urea solution
(1) Solvent molecules move from higher (3) Urea will flow towards glucose solution
concentration to lower concentration (4) Water will flow from urea solution towards
(2) Solvent molecules move from lower glucose solution
concentration to higher concentration
(3) Solvent molecules move from higher Q. 37 The plant cell will shrink when placed in -
concentrationh to lower concentration (1) Water
(4) Solute molecules move from lower (2) A hypotonic solution
concentration to higher concetration (3) A hypertonic solution
(4) An isotonic solution
Q. 31 At constant temperature the osmotic pressure of
a solution is - Q. 38 The best colligative property used for the
(1) Directly proportional to the concentration determination of molecular masses of polymers
(2) Inversely proportional to the concentration is -
(3) Directly proportional to the square of (1) Relative lowering in vapour pressure
concentration (2) Osmotic pressure
(4) Directly proportinal to the square root of (3) Elevation in boiling point
concentration (4) Depression in freezing point
Q. 32 Which inorganic precipitate acts as
semipermeable membrane ? Q. 39 The osmotic pressure of a solution increases if -
(1) Calcium sulphate (1) Temperature is lowered
(2) Barium oxalate (2) Volume is increases
(3) Nickel phosphate (3) Number of solute molecules is increases
(4) Copper ferrocyanide (4) None

Q. 33 The correct expression for the determination of Q. 40 Osmotic pressure of a solution (density is 1g/ml)
molecular mass of the solute by osmotic pressure containing 3 g of glucose (molecular weight =
measurement is - 180) in 60 g of water at 15°C is -
(1) 0.34 atm (2) 0.65 atm
WPV WRT (3) 6.25 atm (4) 5.57 atm
(1) m = (2) m =
RT PV
Q. 41 Osmotic pressure of a sugar solution at 24°C is
RT PRT 2.5 atmosphere. The concentration of the solution
(3) m = (4) m =
WPV WV in mole per litre is -
(1) 10.25 (2) 1.025
Q. 34 Osmotic pressure of aqueous solution is (3) 1025 (4) 0.1025
determined by -
(1) Haeber’s method Q. 42 A solution containing 8.6 g urea in one litre was
found to be isotonic with 0.5% (wt./vol) solution
(2) Solvay method
of an organic, non volatile solute. The molecular
(3) Berkeley and Hartley’s method weight of latter is -
(4) Ostwalds method (1) 348.9 (2) 34.89
(3) 3489 (4) 861.2
Q. 35 The osmotic pressure of solution increases if -
(1) Temperature is decreases Q. 43 A solution containing 500 g of a protein per litre
(2) Concentration is decreases is isotonic with a solution containing 3.42 g of
(3) Number of solute particle is increases sucrose per litre. The molecular mass of protein
(4) Volume is increased is -
(1) 5 (2) 146
(3) 34200 (4) 50000

23
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q. 44 Which method cannot be used to find out the Q. 53 The value of observed and calculated molecular
molecular weight of non-volatile solute - weight of silver nitrate are 92.64 and 170
(1) Victor Meyer’s method respectively. The degree of dissociaion of silver
(2) Osmotic pressure method nitrate is -
(3) Cryoscopic method (1) 60% (2) 83.5%
(3) 46.7 % (4) 60.23%
(4) Ebullioscopic method
Q. 54 A 0.004M solution of Na2 SO4 is isotonic with a
Q. 45 Camphor is used as solvent to determine the 0.010M solution of glucose at the 25°C
molecular weight of nonvolatile solute by Rast temperature The apparent degree of dissociation
method because for camphor - of Na2SO4 is -
(1) Molal depresion constant is high (1) 25% (2) 50%
(2) Melting point is high (3) 75% (4) 85%
(3) Being cheap
(4) All Q. 55 Which of the following solutions at the same
temperature wil be isotonic -
Q. 46 Van’t Hoff factor is - (1) 3.42 g of cane sugar in one litre water
and 0.18 g of glucose in one litre water
(1) Less than one in case of dissociation
(2) 3.42 g of cane sugar in one litre water
(2) More than one in case of association and 0.18 g of glucose in 0.1 litre water
(3) Always less than one (3) 3.42 g of cane sugar in one litre water
(4) Less than one in case of association and 0.585g of NaCl in one litre water
(4) 3.42 g of cane sugar in one litre water
Q. 47 The Vant Hoff factor (i) for a dilute solution of and 1.17 g of NaCl in one litre water
K3[Fe(CN)6] is - Q. 56 Which salt shows maximum osmotic pressure in
(1) 10 (2) 4 (3) 5 (4) 0.25 its 1 M solution -
(1) AgNO3 (2) Na2SO4
Q. 48 The experimental molecular weight of an (3) (NH4)3PO4 (4) MgCl2
electrolyte will always be less than its calculated
value because the value of vant Hoff factor, ‘i’
is - Q. 57 Which solution will exert highest osmotic
(1) Less than 1 (2) Greater than 1 pressure ?
(3) One (4) Zero (1) 1 M glucose solutino
(2) 1M urea solution
Q. 49 The Vant Hoff factor (i) for a dilute aqueous (3) 1M Alum solution
solution of Glucose is -
(4) 1M NaCl solution
(1) Zero (2) 1.0 (3) 1.5 (4) 2.0

Q. 50 The ratio of the value of any colligative property Q. 58 Which is the correct relation between osmotic
for KCl solution to that for sugar solution is pressure of 0.1M NaCl solution and 0.1M Na2SO4
nearly.................time - solution ?
(1) 1 (2) 0.5 (3) 2 (4) 2.5 (1) The osmotic pressure of Na2SO4 is less
than NaCl solution
Q. 51 The lowering of vapour pressure of 0.1 M (2) The osmotic pressure Na2SO4 is more
aqueous solution of NaCl, CuSO4 and K2 SO4 than NaCl solution
are - (3) Both have same osmotic pressure
(1) All equal (4) None of the above
(2) In the ratio of 1 : 1 : 1.5
(3) In the ratio of 3 : 2 : 1
(4) In the ratio of 1.5 : 1 : 2.5 Q. 59 Which one of the following solutions will have
highest osmotic pressure ? (Assume that all the
Q. 52 The molal elevation constant of water is 0.51. salts are equally dissociated) -
The boiling point of 0.1 molal aqueous NaCl (1) 0.1M Al2(SO4)3
solution is nearly - (2) 0.1M BaCl2
(1) 100.05 °C(2) 100.1 °C (3) 0.1M Na2SO4
(3) 100.2 °C (4) 101.0 °C (4) The solution obtained by mixing equal
volumes of (2) and (3)

24
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q. 60 The follwoing solutions have equal Q. 68 Which of the following solutions will have
concentration. Which one will show minimum highest boiling point ?
osmotic pressure ? (1) 1% Glucose in water
(1) BaCl2 (2) AgNO3 (2) 1% Sucrose in water
(3) Na2SO4 (4) (NH4)3PO4 (3) 1% NaCl in water
(4) 1% Urea in water
Q. 61 The osmotic pressure of equimolor solutions of
BaCl2 ,NaCl, and glucose will be in the order - Q. 69 The freezing point of equimolal aqueous solution
(1) Glucose > NaCl > BaCl2 will be highest for -
(2) BaCl2 > NaCl > Glucose (1) C6H5NH3Cl (2) Ca(NO3)2
(3) NaCl > BaCl2 > Glucose (3) La(NO3)3 (4) C6H12O6(Glucose)
(4) NaCl > Glucose > BaCl2
Q. 70 Which one has the highest boiling point -
Q. 62 Which one of the following pairs of solutions (1) 0.1 N Na2SO4 (2) 0.1N MgSO4
will be expected to be isotonic under the same (3) 0.1M Al2(SO4)3 (4) 0.1M BaSO4
temperature -
(1) 0.1M urea and 0.1M NaCl Q. 71 Which of the following plots does not represent
(2) 0.1M urea and 0.2M MgCl2 the behaviour of an ideal binary liquid solution -
(3) 0.1M NaCl and 0.1M Na2SO4 (1) Plot of PA versus XA (mole fraction of A
(4) 0.1M Ca(NO3)2 and 0.1M Na2SO4 in liquid phase) is linear
(2) Plot of PB versus XB is linear
Q. 63 Two solution of KNO3 and CH3 COOH are (3) Plot of Ptotal versus XA (or XB) is linear
prepared separately. Molarity of both is 0.1 M (4) Plot of Ptotal versus XA is non linear
and osmotic pressures are P1 and P2 respectively.
The correct relationship between the osmotic Q. 72 Arrange the following aqueous solutions in the
pressures is - order of their increasing boiling points -
(1) P2 > P1 (2) P1 = P2 (i) 10–4 M NaCl (ii) 10–4M Urea
–3
(iii) 10 M MgCl2 (iv) 10–2 M NaCl
P1 P2
(3) P1 > P2 (4)  (1) (i) < (ii) < (iv) < (iii)
P1  P2 P1  P2 (2) (ii) < (i) = (iii) < (iv)
(3) (ii) < (i) < (iii) < (iv)
Q. 64 Which of the following 0.1 M aqueous solution (4) (iv) < (iii) < (i) = (ii)
will have the lowest freezing point -
(1) Potassium Sulphate Q. 73 A mixture of liquid showing positive deviaion in
(2) Sodium Chloride Raoult’s law is -
(3) Urea (1) (CH3)2 CO + C2H5OH
(4) Glucose (2) (CH3)2CO + CHCl3
Q. 65 Which has the minimum freezing point - (3) (C2H5)2O + CHCl3
(1) 1 molal NaCl solution (4) (CH3)2 CO + C6H5NH2
(2) 1 molal KCl solution
(3) 1 molal CaCl2 solution Q. 74 The van’t Hoff factor for 0.1 M Ba(NO3)2 solution
(4) 1 molal urea soultion is 2.74. The degree of dissociation is -
(1) 91.3% (2) 87%
Q. 66 Which has maximum freezing point - (3) 100% (4) 74%
(1) 1 molar of NaCl solution
(2) 1 molar of KCl solution Q. 75 Osmosis of A into solution B will not take place
(3) 1 molar of CaCl2 solution if -
(4) 1 molar of urea solution (1) A is hypertonic
Q.67 The following aqueous solution in the correct (2) A is hypotonic
order of decreasing freezing point is - (3) A is isotonic
(1) 0.2M BaCl2, 0.2M KCl, 0.1M Na2SO4
(4) Either 1 or 3 may correct
(2) 0.2M KCl, 0.1M Na2SO4, 0.2M BaCl2
(3) 0.1M Na2SO4, 0.2M KCl, 0.2M BaCl2
(4) 0.1M Na2SO4, 0.2M BaCl2, 0.2M KCl

25
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q. 76 Among 0.1M solution of urea, Na 3 PO4 and Q. 82 When equimolar aqueous solutions of glucose,
Al2(SO4)3 - sodium chloride and barium nitrate are compared
(A) The vapour pressure and freezing point the vapour pressure of the solutions will be in
are the lowest for urea the following order -
(B) The vapour pressure and freezing point (1) Glucose > NaCl > Ba(NO3)2
are the highest for urea (2) Glucose = NaCl = Ba(NO3)2
(C) The elevation in boiling point is the (3) Ba(NO3 )2 > NaCl > Glucose
highest for Al2(SO4)3 (4) NaCl > Ba(NO3)2 > Glucose
(D) The depression in freezing point is the
highest for Al2(SO4)3 Q. 83 The substance when dissolved in water would
(1) Only a (2) b & c both decrease the vapour pressure of water to the
(3) b, c and d (4) a, b, c and d greatest extent is -
(1) 0.1 M KCl (2) 0.1 M urea
Q. 77 Glucose is added to 1 litre water to such an (3) 0.1 M BaCl2 (4) 0.1 M NaCl
T1 1
extent that becomes equal to , the wt. Q. 84 The vapour pressure of a pure liquid solvent (X)
Kf 1000
is decreased to 0.60 atm. from 0.80 atm on
of glucose added is - additional of a non volatile substance (Y). The
(1) 180 g (2) 18 g mole fraction of (Y) in the solution is -
(3) 1.8 g (4) 0.18 g (1) 0.20 (2) 0.25 (3) 0.5 (4) 0.75

Q. 78 The vapour pressure of a solution of 5gm of non Q. 85 For a solution of two liquids A and B, it was
electrolyte in 100gm of water at particular proved that P = XA (PA0 – PB0 ) + PB0. The
temperature is 2985 Nm–2. The vapour pressure solution is -
of pure water at that temperature is 3000Nm2 . (1) Ideal (2) Non ideal
The molecualr weight of the solute is -
(3) Semiideal (4) None of the above
(1) 180 (2) 90 (3) 270 (4) 200
Q. 86 The molar mass of NaCl determined by the
Q. 79 How many grams of a non volatile solute having osmotic pressure method will be -
a molecular weight of 90 are to be dissolved in (1) Higher than the theoreticlal value
97.5 g water in order to decrease the vapour (2) Lower than the theoretical value
pressure of water by 2.5 percent - (3) The same as the theoretical value
(1) 25 (2) 18 (3) 12.5 (4) 9 (4) None of these

Q. 80 Colligative properties depend on the - Q. 87 Mole fraction of A vapours above solution in

(1) Relative no. of solute molecules in soln. mixture of A and B (XA = 0.4) will be -
and the nature of the solvent (PA° = 100mm, PB° = 200mm)
(2) Relative no. of solute molecules in solvent (1) 0.4 (2) 0.8
and the nature of solute (3) 0.25 (4) None
(3) Relative no. of solute molecules and the Q. 88 The vapour pressure of pure benzene and toluene
nature of solute and solvent are 160 and 60 torr respectively. The mole fraction
(4) Relative no. of solute molecules, of toluene is vapour phase in contact with
irrespective of the nature of solvent and equimolar solution of benzene and toluene is -
solute (1) 0.50 (2) 0.6
Q. 81 The vapour pressure of two pure liquids (A) and (3) 0.27 (4) 0.73
(B) are 100 and 80 torr respectively. The total
pressure of the solution obtained by mixing 2 Q. 89 Solutions which distil without change in
mol of (A) and 3 mol of (B) would be - composition or temperature are called -
(1) 20 torr (2) 36 torr (1) Amorphous (2) Azeotropic mixture
(3) 88 torr (4) 180 torr (3) super saturated (4) ideal

26
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES
Q. 90 Azeotropic mixture are - Q. 93 An azeotropic solution of two liquids has boiling
(1) Mixture of two solids point lower than either of them when it -
(2) Those which boil at different temperatures (1) Shows a negative deviation from Raoult’s
(3) Those which can be fractionally distilled law
(4) Constant boiling mixtures (2) Shows no deviation from Raoult’s law
Q. 91 An azeotropic mixture of two liquids boil at a (3) Shows positive deviation from Raoult’s law
lower temperature than either of them when (4) Is saturated
(1) It is saturated
(2) It does not deviate from Raoult’s law Q. 94 Dry air was passes successively through a
(3) It shows negative deviation from Raoult’s solution of 5g of a solute in 180 g of water and
law then through pure water. The loss in weight of
(4) It show positive deviation from Raoult’s solution was 2.50g and that of pure solvent 0.04g.
law The molecular weight of the solute is -
(1) 31.25 (2) 3.125
Q. 92 The azeotropic mixture of water (B.P 100°C) and (3) 312.5 (4) None
HCl (B.P. 85°C) boils at 108.5°C. When this mixture
is distilled, it is possible to obtain -
(1) Pure HCl
(2) Pure water
(3) Pure water as well as HCl
(4) Neither HCl nor H2O in their pure states

27
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 2
Q.1 Select correct statement - Q.8 The vapour pressure of a pure liquid ‘A’ is 70
(1) b.p. of 1 molal NaCl solution is twice that of torr at 27°C. It forms an ideal solution with
1 molal sucrose solution another liquid B. The mole fraction of B is 0.2
(2) b.p. elevation of 1 molal glucose solution is and total vapour pressure of the solution is 84
half of the 1 molal KCl solution torr at 27°C. The vapour rpessure of pure liquid
(3) b.p. is a colligative property B at 27°C is -
(4) All of the above (1) 14 (2) 56 (3) 140 (4) 70
Q.2 At a given temperature, total vapour pressure in Q.9 The vapour pressure of pure A is 10 torr and at
Torr of a mixture of volatile components A and B the same temperature when 1g of B is dissolved
is given by in 20 gm of A, its vapour pressure is reduced to
P = 120 – 75 XB 9.0 torr. If the molecular mass of A is 200 amu,
hence, vapour pressure of pure A and B then the molecular mass of B is -
respectively (in Torr) are - (1) 100 amu (2) 90 amu
(1) 120, 75 (2) 120, 195 (3) 75 amu (4) 120 amu
(3) 120, 45 (4) 75, 45
Q.10 The value of Kb for water is 1.86, calculated from
Q.3 Decimolar solution of potassium ferricyanide, Glucose solution. The value of Kb for water
K3[Fe(CN)6] has osmotic pressure of 3.94 atm at calculated for NaCl solution will be -
27ºC. Hence percent ionisation of the solute is - (1) = 1.86 (2) < 1.86
(1) 10% (2) 20% (3) 30% (4) 40% (3) > 1.86 (4) Zero

Q.11 As a result of osmosis the volume of the

Q.4 A complex containing K+, Pt (IV) and Cl– is 100% concentrated solution -
ionised giving i = 3. Thus, complex is - (1) Gradually decreases
(1) K2 [PtCl4 ] (2) K2[PtCl6] (2) Gradually increases
(3) K3[PtCl5] (4) K[PtCl3] (3) Suddenly increases
(4) None
Q.5 If pKa = – log Ka = 4, and Ka = C2 then van't
Hoff factor for weak monobasic acid when Q.12 If a thin slice of sugar beet is placed in
C = 0.01 M is - concentrated solution of NaCl then -
(1) 0.01 (2) 1.02 (3) 1.10 (4) 1.20 (1) Sugar beet will lose water from its cells
(2) Sugar beet will absorb water from solution
Q.6 In which case van't Hoff factor is maximum ?
(3) Sugar beet will neither absorb nor lose
(1) KCl, 50% ionised
water
(2) K2SO4 40% ionised
(4) Sugar beet will dissolve in solution
(3) FeCl3 , 30% ionised
(4) SnCl4, 20% ionised
Q.13 If mole fraction of the solvent in solution
Q.7 The hard shell of an egg is dissolved in acetic decreases then -
acid and then egg was subsequently placed in (1) Vapour pressure of solution increases
saturated solution of NaCl
(2) B. P. decreases
(1) The egg will shrink
(2) The egg will become harder (3) Osmotic pressure increases
(3) The egg will swell (4) All are correct
(4) No change in the size of egg
28
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.14 A solution containing 4g of a non volatile organic Q.21 Solute A is ternary electrolyte and solute B is
solute per 100 ml was found to have an osmotic non-electrolyte. If 0.1 M solution of solute B
pressure equal to 500 cm of mercury at 27°C. The produces an osmotic pressure of 2P, then 0.05M
molecular weight of solute is - solution of A at the same temperature will
(1) 14.97 (2) 149.7 (3) 1697 (4) 1.497 produce an osmotic pressure equal to -
(1) P (2) 1.5 P (3) 2 P (4) 3 P
Q.15 if a 6.84% (wt./ vol.) solution of cane-sugar
(mol. wt. 342) is isotonic with 1.52% (wt./vol.) Q.22 The values of observed and calculated molecular
solution of thiocarbamide, then the molecular weight of calcium nitrate are respectively 65.6
weight of thiocarbamide is - and 164. The degree of dissociation of calcium
(1) 152 (2) 76 (3) 60 (4) 180 nitrate will be -
(1) 25% (2) 50 %
Q.16 The osmotic pressure of blood is 7.65 atm. at 310 (3) 75% (4) 60 %
K. an aqueous solution of Glucose that will be
isotonic with blood is ......wt/vol. - Q.23 A 5.8% (wt./vol.) NaCl solution will exert an
(1) 5.41% (2) 54.1% (3) 3.5% (4) 4.53% osmotic pressure closest to which one of the
following -
Q.17 Equimolal solutions of A and B show depression (1) 5.8% (wt./vol) sucrose solution
in freezing point in the ratio of (2) 5.8% (wt./vol) glucose solution
2 : 1. A remains in normal state in solution. B will (3) 2 M sucrose solution
be in.......state in solution - (4) 1 M glucose solution
(1) Normal (2) Associated
(3) Hydrolysed (4) Dissociated Q.24 The correct relationship between the boiling
points of very dilute solutions of AlCl3 (t1 ) and
Q. 18 The substance A when dissolved in solvent B CaCl2 (t2 ), having the same molar concentration
shows the molecular mass corresponding to A3 . is -
The vant Hoff’s factor will be - (1) t1 = t 2 (2) t1 > t 2
1 (3) t2 > t 1 (4) t2  t 1
(1) 1 (2) 2 (3) 3 (4)
3 Q.25 Which aqueous solution has minimum freezing
point -
Q.19 The freezing point of 1 molal NaCl solution (1) 0.01 M NaCl (2) 0.005 M C2H5OH
assuming NaCl to be 100% dissociated inwater is (3) 0.005 M MgI2 (4) 0.005 M MgSO4
(Kf = 1.86 K Molality–1 )
(1) – 1.86 °C (2) –3.72 °C
Q.26 Which solution will have least vapour pressure -
(3) +1.86 °C (4) +3.72 °C
(1) 0.1 M BaCl2 (2) 0.1 M urea
(3) 0.1 M Na2SO4 (4) 0.1 M Na3PO4
Q.20 The molal elevation constant of water = 0.52 K
molality–1. The boiling point of 1.0 molal aqueous
Q.27 The freezing point of 1% aqueous solution of
KCl solution (assuming complete dissociation of
calcium nitrate will be -
KCl), should be -
(1) 0°C (2) Above 0°C
(1) 100.52°C (2) 101.04°C
(3) 1°C (4) Below 0°C
(3) 99.48°C (4) 98.96°C

29
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.28 When mercuric Iodide is added to the aqueous Q.34 The vapour pressure of ethanol and methanol
solution of potassium iodide ? are 42.0 mm and 88.5 mm Hg respectively. An
(1) The boiling point does not change ideal solution is formed at the same temperature
(2) Freezing point is raised by mixing 46.0 g of ethanol with 16.0 g of
(3) The freezing point is lowered methanol. The mole fraction of methanol in the
(4) Freezing point does not change vapour is -
(1) 0.467 (2) 0.502 (3) 0.513 (4) 0.556
Q.29 The molecular weight of benzoic acid in benzene
as determined by depression in freezing point Q.35 An ideal solution was obtained by mixing
method corresponds to - methanol and ethanol. If the partial vapour
(1) Ioniation of benzoic acid pressure of methanol and ethanol are 2.619 K Pa
(2) Dimerization of benzoic acid and 4.556 K Pa respectively, the composition of
vapour (in terms of mole fraction) will be -
(3) Trimerization of benzoic acid (1) 0.635 MeOH, 0.365 EtOH
(4) Solvation of benzoic acid (2) 0.365 MeOH, 0.635 EtOH
(3) 0.574 MeOH, 0.326 EtOH
Q.30 The vapour pressure of a solvent decreases by (4) 0.173 MeOH, 0.827 EtOH
10 mm. of Hg when a non volatile solute was
added to the solvent. The mole fraction of the Q.36 Insulin (C2 H10O5)n is dissolved in a suitable
solvent and the osmotic pressure () of solutions
solute in the solution is 0.2. What should be the
of various concentrations (g/cm3 ) C is measured
mole fraction of the solvent if the decrease in at 20 °C. The slope of a plot of  against C is
vapour pressure is to be 20 mm. of Hg - found to be 4.65 × 10–3. The molecular weight of
(1) 0.2 (2) 0.4 (3) 0.6 (4) 0.8 the insulin is -
(1) 4.8 × 105 (2) 9 × 105
(3) 3 × 10 5 (4) 5.16 × 106
Q.31 The relationship between the values of osmotic
pressure of solutions obtained by dissolving 6.00 Q.37 The boiling point of an aqueous solution of a
gL–1 of CH3COOH (1) and 7.45 gL–1 of KCl non volatile solute is 100.15°C. What is the
(2) is - freezing point of an aqueous solution obtained
(1) 1 > 2 (2) 1 < 2 by diluting the above solution with an equal
volume of water ? The values of Kb adn Kf for
(3) 1 = 2 (4) None of these water are 0.512 and 1.86 K molality–1
(1) –0.544 °C (2) –0.512 °C
Q.32 What is the freezing point of a solution (3) –0.272 °C (4) –1.86°C
containing 8.1 gm. of HBr is 100 gm. water Q.38 In ideal solution of non volatile solute B in
assuming the acid to be 90% ionised. solvent A in 2 : 5 molar ratio has vapour pressrue
(Kf for water = 1.86 K molality–1 ) 250 mm. If another solution in ratio 3 : 4 prepared
(1) 0.85°C (2) –3.53°C then vapour pressure above this solution
(3) 0°C (4) – 0.35°C (1) 200 mm (2) 250 mm
(3) 350 mm (4) 400 mm
Q.33 A 0.2 molal aqueous solution of a weak acid
(HX) is 20% ionised. The freezing point of this Q.39 Two liquids having vapour pressures P10 and
P20 in pure state in the ratio of 2 : 1 are mixed
solution is (Given : Kf = 1.86°C/m for water)
(1) – 0.31°C (2) – 0.45°C in the molar ratio of 1 : 2. The ratio of their moles
in the vapour state would be -
(3) – 0.53°C (4) – 0.90°C
(1) 1 : 1 (2) 1 2
(3) 2 : 1 (4) 3 : 2

30
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 3A
Q.1 Which of the following solutions would have Q.8 The vapour pressure of an ideal solution having
the highest osmotic pressure - [AIPMT-91] 0.2 Mole non-volatile solute & 0.8 mole solvent,
M M is 60 mm. The vapour pressure of pure solvent
(1) NaCl (2) Urea
10 10 at this temperature will be - [AIPMT-96]
(1) 120 mm (2) 150 mm
M M
(3) BaCl2 (4) Glucose (3) 60 mm (4) 75 mm
10 10
Q.9 Vapour pressure of CCl4 at 25°C is 143 mm Hg.
Q.2 Which of the following solution has the highest
0.5 gm of a non-volatile solute (mol. wt. 65) is
boiling point - [AIPMT-91]
dissolved in 100 ml of CCl4 . Find the vapour
(1) 0.1 M glucose (2) 0.1 M BaCl2
(3) 0.1 M NaCl (4) 0.1 M Urea pressure of the solution. (Density of CCl 4
1.58 gm/cm3) [AIPMT-96]
Q.3 Which of the following is a colligative property - (1) 141.93 mm (2) 94.39 mm
[AIPMT-92] (3) 199.34 mm (4) 143.9 mm
(1) Viscosity (2) Surface tension
(3) Optical rotation (4) Osmotic pressure Q.10 The vapour pressure decreases by 10 mm of Hg
when solute’s mole fraction in a solution is 0.2.
Q.4 The compound whose 0.1 M solution has
If the vapour pressure decreases is 20 mm of Hg
maximum osmotic pressure at 25°C will be -
then the mole fraction of solute will be -
[AIPMT-94]
(1) CaCl2 (2) KCl [AIPMT-98]
(3) Glucose (4) Urea (1) 0.2 (2) 0.4 (3) 0.6 (4) 0.8

Q.5 Which of the following salt has the same value Q.11 5% solution of sucrose is isotonic with 1%
of Vont Hoff’s factor as that of K3[Fe(CN)6 ] solution of a compound ‘A’ then the molecular
[AIPMT-94] weight of compound ‘A’ is - [AIPMT-98]
(1) Al2(SO4)3 (2) NaCl (1) 32.4 (2) 68.4
(3) Al(NO3)3 (4) Na2SO4 (3) 121.6 (4) 34.2
Q.12 The vapour pressrue of benzene at a certain
Q.6 According to raoult’s law the relative lowering of temperature is 640 mm of Hg. A non-volatile and
vapour pressure for a solution is equal to - electrolytic solid weighting 2.175 g is added to
[AIPMT-95] 39.08 g of benzene. If the vapour pressure of the
(1) Moles of solute solution is 600 mm of Hg. What is the molecular
weight of the solid substance ? [AIPMT-99]
(2) Mole fraction of solvent
(1) 79.82 (2) 65.25
(3) Moles of solvents (3) 59.60 (4) 49.50
(4) Mole fraction of solute
Q.13 From the colligative properties of solution which
one is the best method for the determination of
Q.7 The relationship between osmotic pressure at mol. wt. of proteins & polymers - [AIPMT-2001]
273 K when 10 g glucose (P1) 10 g urea (P2) and (1) Osmotic pressure
10 g sucrose (P3) are dissolved in 250 ml of water
(2) Lowering in freezing point
is - [AIPMT-96]
(3) Lowering in V.P.
(1) P1 > P2 > P3 (2) P3 > P1 > P2
(4) Elevation in B.Pt.
(3) P2 > P1 > P3 (4) P3 > P2 > P1

31
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.14 Pure water can be obtain from sea water by - Q.18 Which one of the statements given below
[AIPMT-2001] concerning properties of solutions, describes a
(1) Centrifugation (2) Plasmolysis colligative effect - [AIIMS-2003]
(3) Reverse osmosis (4) Sedimentation (1) boiling point of pure water decreses by the
addition of ethanol
Q.15 A solution contains non volatile solute of
(2) vapour pressure of pure water decreases by
molecular mass M2 . Which of the following can
the addition of nitric acid
be used to calculate the molecular mass of solute
(3) vapour pressure of pure benzene decreases
in terms of osmotic pressure - [AIPMT-2002]
by the addition of naphthalene
 m2   m 2  RT (4) boiling point of pure benzene increases by
(1) M2 =   VRT
T (2) M2 =  
the addition of toluene
    V  

 m2   m2   Q.19 The average osmotic pressure of human blood is

(3) M2 =   RT
T (4) M2 =   7.8 bar at 37°C. What is the concentration of an
 V   V  RT
aqueous NaCl solution that could be used in the
Note : m 2  mass of solute
blood stream - [AIIMS-2004]
V  Volume of solution (1) 0.16 mol/L (2) 0.32 mol/L
          Osmotic pressure
(3) 0.60 mol/L (4) 0.45 mol/L

Q.16 A solution containing components A and B

Q.20 Camphor is often used in molecular mass
follows Raoult’s law [AIPMT-2002] determination because - [AIPMT-2004]
(1) A – B attraction force is greater than
(1) It has a very high cryosopic constant
A – A and B – B (2) It is volatile
(2) A – B attraction force is less than A – A and
(3) It is solvent for organic substances
B–B (4) It is readily available
(3) A – B attraction force remains same as A – A
and B – B Q.21 The vapour pressure of two liquids ‘P’ and ‘Q’
(4) Volume of solution is different from sum of
are 80 and 60 torr, respectively. The total vapour
volume of solute and solvent pressure of solution obtained by mixing 3 mole of
P and 2 mol of Q would be - [AIPMT-2005]
Q.17 Formation of a solution from two components (1) 68 torr (2) 140 torr
can be considered as - [AIPMT-2003]
(3) 72 torr (4) 20 torr
(i) Pure solvent  separated solvent molecules, H1
(ii) Pure solute  separated solute molecules, H2
Q.22 A solution of urea (mol. mass 56 g mol–1 ) boils
(iii) Separated solvent and solute molecules   at 100.18°C at the atomospheric pressure. If Kf
solution, H3
and Kb for water are 1.86 and 0.512K kg mol–1
Solution so formed will be ideal if - respectively, the above solution will freeze at -
(1) Hsoln = H1 + H2 + H3
[AIPMT-2005]
(2) Hsoln = H1 + H2 – H3 (1) –6.54°C (2) –0.654°C
(3) Hsoln = H1 – H2 – H3
(3) 6.54°C (4) 0.654°C
(4) Hsoln = H3 – H1 – H2

32
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.23 A solution has a 1 : 4 mole ratio of pentane to Q.28 A 5% solution (by mass) of cane sugar in water
hexane. The vapour pressures of the pure has freezing point of 271 K and freezing point of
hydrocarbonds at 20°C are 440 mmHg for pentane pure water is 273.15K. The freezing point of a 5%
and 120 mmHg for hexane. The mole fraction of solution (by mass) of glucose in water is -
pentane in the vapour phase would be - [AIIMS-2006]
[AIPMT-2005] (1) 271 K (2) 273.15 K
(1) 0.200 (2) 0.478 (3) 269.07 K (4) 277.23 K
(3) 0.549 (4) 0.786
Q.29 A mixture of ethyl alcohol and propyl alcohol
Q.24 A solution containing 10g per dm 3 of urea has a vapour pressure of 290 mm at 300 K. the
(molecular mass = 60g mol–1) is isotonic with a vapour pressure of propyl alcohol is 200 mm. If
5% solution of a nonvolatile solute. The the mole fraction of ehtyl alcohol is 0.6, its vapour
molecular mass of this nonvolatile solute is - pressure (in mm) at the same temperature will be
[AIPMT-2006] [AIEEE-2007]
(1) 250g mol –1 (2) 300g mol–1 (1) 300 (2) 700
(3) 350g mol–1 (4) 200g mol–1 (3) 360 (4) 350
Q.25 1.00g of a non-electrolyte solute (molar mass 250g
mol–1 ) w was dissolved in 51.2g of benzene. If Q.30 0.5 molal aqueous solution of a weak acid (HX)
the freezing point depression constant, Kf of is 20% ionised. If Kf for water is 1.86 K kg mol–
1, the lowering in freezing point of the solution
benzene is 5.12 K kg mol–1, the freezing point of
benzene will be lowered by - [AIPMT-2006] is - [AIPMT-2007]
(1) 0.4 K (2) 0.3 K (1) –0.56 K (2) –1.12 K
(3) 0.5 K (4) 0.2 K (3) 0.56 K (4) 1.12 K

Q.26 A solution of acetone in ethanol -

Q.31 A 0.0020 M aqueous solution of an ionic compound
[AIPMT-2006]
Co(NH3)5(NO2)Cl freezes at – 0.00732ºC. Number of
(1) shows a positive deviation from Raoult’s law
moles of ions which 1 mole of ionic compound pro-
(2) behaves like a near ideal solution
duces on being dissolved in water will be : (kf = –
(3) Obey Raoult’s law
1.86ºC/m) - [AIPMT-2009]
(4) shows a negative deviation from Raoult’s law
(1) 1 (2) 2 (3) 3 (4) 4
Q.27 During osmosis, flow of water through a
semipermeable membrane is - [AIPMT-2006] Q.32 An aqueous solution is 1.00 molal in KI. Which
change will cause the vapour pressure of the solu-
(1) from both sides of semipermeable membrane tion to increase? [AIPMT-2010]
with equal flow rates (1) addition of NaCl
(2) from both sides of semipermeable membrane (2) addition of Na2SO4
(3) addition of 1.00 molal KI
with unequal flow rates (4) addition of water
(3) from solution having lower concentration Q.33 A solution of sucrose (molar mass = 342 g mol–1)
only has been prepared by dissolving 68.5 g of sucrose
(4) from solution having higher concentration in 1000 g of water. The freezing point of the solution
obtained will be : (Kf for water = 1.86 K kg mol–1)
only
[AIPMT-2010]
(1) –0.372°C (2) –0.520°C
(3) + 0.372°C (4) – 0.570°C

33
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.34 The freezing point depression constant for water is

–1.86ºCm–1. If 5.00 g Na2SO4 is dissolved in 45.0g
H2O, the freezing point is changed by –3.82ºC. Cal-
culate the Van’t Hoff factor for Na2SO4
(1) 0.381 (2) 2.05 [AIPMT-2011]
(3) 2.63 (4) 3.11
Q.35 The Van’t Hoff factor i for a compound which
undergoes dissociation in one solvent and asso-
ciation in other solvent is respectively :
[AIPMT-2011]
(1) greater than one and greater than one
(2) less than one and greater than one
(3) less than one and less than one
(4) greater than one and less than one

Q.36 A 0.1 molal aqueous solution of a weak acid is 30%

ionized. If Kf for water is 1.86°C/m, the freezing point
of the solution will be - [AIPMT MAINS-2011]
(1) –0.24°C (2) –0.18°C
(3) –0.54°C (4) –0.36°C

Q.37 200 mL of an aqueous solution of a protein con-

tains its 1.26 g. The Osmotic pressure of this solu-
tion at 300 K is found to be 2.57 × 10–3 bar. The molar
mass of protein will be (R = 0.083 L bar mol–1 K–1):
[AIPMT MAINS-2011]
–1
(1) 61038 g mol (2) 51022 g mol–1
(3) 122044 g mol–1 (4) 31011 g mol–1

34
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 3B
Q.1 In a mixture of A and B, components show Q.6 Two liquids X and Y form an ideal solution At 300
negative deviation when – [AIEEE-2002] K, vapour pressure of the solution containing 1 mol
(1) A – B interaction is stronger than A – A and B – of X and 3 mol of Y is 550 mmHg. At the same tem-
B interaction perature, if 1 mol of Y is further added to this solu-
(2) A – B interaction is weaker than A – A and B – B tion, vapour pressure of the solution increases by
interaction 10 mmHg. Vapour pressure (in mmHg) of X and Y in
(3) Vmix > 0, Smix > 0 their pure states will be, respectively -
(4) Vmix = 0, Smix > 0 [AIEEE 2009]
(1) 300 and 400 (2) 400 and 600
Q.2 Benzene and toluene form nearly ideal solutions. (3) 500 and 600 (4) 200 and 300
At 20ºC, the vapour pressure of benzene is 75
torr and that of toluene is 22 torr. The partial Q.7 Aqueous solutions of 0.004 M Na2 SO4 and 0.01
vapour pressure of benzene at 20ºC for a solution M Glucose are isotonic. The degree of
containing 78 g of benzene and 46 g of toluene dissociation of Na2SO4 is - [IIT-2004]
in torr is – [AIEEE-2005] (1) 25% (2) 60% (3) 75% (4) 85%
(1) 25 (2) 50 (3) 53.5 (4) 37.5
Q.8 Which of the following does not show positive
Q.3 Equimolal solutions in the same solvent have – deviation from Raoult’s law ? [MP-PMT-2000]
[AIEEE-2005] (1) Benzene - Chloroform
(1) Same freezing point but different boiling point (2) Benzene-Acetone
(2) Same boling point but different freezing point (3) Benzene-Ethanol
(3) Different boiling and different freezing point (4) Benzene-carbontetrachloride
(4) Same boiling and same freezing points
Q.9 The vapour pressure of a solvent A is 0.80 atm.
When a nonvolatile substance B is added to this
Q.4 The vapour pressure of water at 20º C is 17.5 mm
solvent its vapour pressure drops to 0.6 atm.
Hg. If 18g of glucose (C6H12O6) is added to 178.2 What is mole fraction of B in solution ?
g of water at 20° C, the vapour pressure of the [MP-PMT-2000]
resulting solution will be - [AIEEE 2008] (1) 0.25 (2) 0.50 (3) 0.75 (4) 0.90
(1) 15.750 mm Hg (2) 16.500 mm Hg
(3) 17.325 mm Hg (4) 17.675 mm Hg Q.10 The vapour pressure of a pure liquid ‘A’ is 0.80
atm. When a non-volatile solute ‘B’ is dissolved
in ‘A’, it vapour pressure becomes 0.60 atm. The
Q.5 A binary liquid solution is prepared by mixing n- mole fraction of ‘B’ in the solution -
heptane and ethanol. Which one of the following [MP-PMT-2001]
statements is correct regarding the behaviour of (1) 0.125 (2) 0.25 (3) 0.50 (4) 0.75
the solution ? [AIEEE 2009] Q.11 Which of the following does not show negative
(1) The solution is non-ideal, showing +ve deviation deviation from Raoult’s law ? [MP-PMT-2001]
form Raoult’s Law (1) Acetone – Chloroform
(2) Acetone – Benzene
(2) The solution is non-ideal, showing –ve deviation (3) Chloroform – Ether
from Raoult’s Law (4) Chloroform – Benzene
(3) n-heptane shows +ve deviation while ethanol Q.12 A solution of 1 molal concentration of a solute
shows – ve deviation from Raoult’s Law will have maximum boiling point elevation when
(4) The solution formed is an ideal solution the solvent is - [MP-PMT-2000]
(1) Ethyl alcohol (2) Acetone
(3) Benzene (4) Chloroform

35
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES
Q.13 A 0.001 molal solution of [Pt(NH3)4Cl4] in water Q.18 Ethylene glycol is used as an antifreeze in a cold
has a freezing point depression of 0.0054°C.1 Kf climate. Mass of ethylene glycol which should
for water is 1.80, the correct formulaion for the be added to 4 kg of water to prevent it from
above molecule is - [Kerla PMT-2003] freezing at –6º C will be : (Kf for water = 1.86 K
(1) [Pt(NH3)4Cl3]Cl (2) [Pt(NH3)4Cl2]Cl2 kg mol–1, and molar mass of ethylene glycol = 62
(3) Pt(NH3)4Cl]Cl3 (4) [Pt(NH3)4Cl4] g mol–1) [AIEEE-2011]
(5) None of the above (1) 804.32 g (2) 204.30 g
(3) 400.00 g (4) 304.60 g
Q.14 In a 0.2 molal aqueous solution of a weak acid
HX the degree of ionization is 0.3. Taking kf for Q.19 The degree of dissociation () of a weak
water as 1.85, the freezing point of the solution electrolyte, AxBy is related to van’t Hoff factor (i)
will be nearest to - [AIEEE-2003] by the expression : [AIEEE-2011]
(1) – 0.480°C (2) – 0.360°C i 1 i 1
(3) – 0.260°C (4) + 0.480°C (1)   (2)  
( x  y  1) x  y 1
Q.15 If liquids A and B form an ideal solution -
[AIEEE-2003] x  y 1 x  y 1
(1) the enthalpy of mixing is zero (3)   (4)  
(2) the entropy of mixing is zero i 1 i 1
(3) the free energy of mixing is zero Q.20 The molality of a urea solution in which 0.0100g of
(4) the free energy as well as the entropy of urea, [(NH2)2CO] is added to 0.3000 dm3 of water at
mixing are each zero STP is - [AIEEE-2011]
Q.16 18 g of glucose (C6H12O6) is added to 178.2g of (1) 5.55 × 10–4 m (2) 33.3 m
water. The vapour pressure of water for this (3) 3.33 × 10–2 m (4) 0.555 m
aqueous solution at 100°C is - [AIEEE-2006]
(1) 759.00 torr (2) 7.60 torr Q.21 A 5% solution of can sugar (molar mass 342) is iso-
(3) 76.00 torr (4) 752.40 torr tonic with 1% of a solution of an unknown solute.
Q.17 A 5.25% solution of a substance is isotonic with The molar mass of unknown solute in g/mol is -
a 1.5% solution of urea (molar mass = 60g mol– (1) 171.2 (2) 68.4 [AIEEE-2011]
1) in the same solvent. If the densities of both
(3) 34.2 (4) 136.2
the solutions are assumed to be equal to 1.0
gcm–3, molar mass of the substance will be -
[AIEEE-2007]
(1) 115.0 g mol–1 (2) 105.0 g mol–1
(3) 210.0 g mol–1 (4) 90.0 g mol–1

36
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 4
(ASSERTION & REASON TYPE)

The following questions 1 to 27 consists of two Q.6 Assertion : Vant Hoff factor for electrolytes is
statements each, printed as Assertion and Reason. always geater than unity.
While answering these questions you are to choose Reason : The no. of particles increases in solution
any one of the following four responses. due to electrolytic dissociation.
(A) If both Assertion and Reason are true and the (1) A (2) B (3) C (4) D
Reason is correct explanation of the Asser-
tion. Q.7 Assertion : Blood cells are isotonic with 0.16 M
(B) If both Assertion and Reason are true but the NaCl solution.
Reason is not correct explanation of the As- Reason : Cell wall of blood cells acts as semi-
sertion. permeable membrane.
(C) If Assertion is true but the Reason is false. (1) A (2) B (3) C (4) D
(D) If Assertion & Reason are false.
Q.8 Assertion : Isotonic solution don’t show net
Q.1 Assertion : Addition of a non-volatile solute phenomenon of osmosis.
causes a depression in vapour pressure. Reason : Isotonic solution have equal osmotic
Reason : Vapour pressure of a solution is directly pressure at constant temp.
(1) A (2) B (3) C (4) D
proportional to mole fraction of solvent.
(1) A (2) B (3) C (4) D
Q.9 Assertion : When Benzoic acid is dissolved in
benzene its Vant Hoff factor is less than one.
Q.2 Assertion : 0.02 m solutions of urea and sucrose Reason : In benzene, benzoic acid has tendency
will freeze at same temperature. to form dimer.
Reason : Freezing point of a solution is inversely (1) A (2) B (3) C (4) D
proportional to the concentration of solution.
(1) A (2) B (3) C (4) D Q.10 Assertion : The sum of the mole fraction of all
the components are unity.
Q.3 Assertion : Benzene-toluene mixture forms ideal Reason : Mole fraction is a temperature dependent
solution at low concentrations. mode of concentraction.
Reason : Components with structural similarity (1) A (2) B (3) C (4) D
forms ideal solution in general.
Q.11 Assertion : In positive deviation of non-ideal
(1) A (2) B (3) C (4) D
solution attraction between solute solvent is less
than the attraction between solute-solute &
Q.4 Assertion : Dissolution of sulphuric acid in water solvent-solvent.
gives a solution which shows negative deviation. Reason : In negative deviation of non-ideal
Reason : The solutions which have same vapour solution attraction between solute-solvent is more
pressure at a given temperature are called isotonic than the attraction between solute-solute &
solutions. solvent-solvent.
(1) A (2) B (3) C (4) D (1) A (2) B (3) C (4) D

Q.5 Assertion : Greater the molal depression constant Q.12 Assertion : Non-ideal solutions form azeotropic
mixture.
of the solvent used less is the freezing point of
Reason : Boiling point of azeotropic mixture is
the solution.
only higher than boiling points of both the
Reason : Depression in freezing point depends components.
upon the nature of the solvent. (1) A (2) B (3) C (4) D
(1) A (2) B (3) C (4) D

37
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Q.13 Assertion : Van’t Hoff factor for benzoic acid in Q.22 Assertion : The osmotic pressure of
benzene is one. 1M K4 [Fe(CN)6] is equal to 1M Al2(SO4)3.
Reason : Benzoic acid behaves as a weaker Reason : Both gives 5 ions.
electrolyte in benzene (1) A (2) B (3) C (4) D
(1) A (2) B (3) C (4) D
Q.23 Assertion : A mixture of C2H5OH & water shows
Q.14 Assertion : Ideal solutions are one which obeys +ve deviation.
raoult’s law at all temp. & concentration. Reason : The vapour pressure of water is more
Reason : Very dilute solution can be treated as
than C2H5OH.
ideal solution.
(1) A (2) B (3) C (4) D
(1) A (2) B (3) C (4) D

Q.15 Assertion : Van’t Hoff factor is always more or

equal to one.
Reason : Van’t Hoff factor is the ratio of
experimental C.P. to observed C.P.
(1) A (2) B (3) C (4) D
Q.16 Assertion : Azeotropic mixture can’t be separated
by fractional distillation.
Reason : Azeotropic mixtures are contant boiling
mixtures.
(1) A (2) B (3) C (4) D

Q.17 Assertion : Cooking time is reduced in pressure

cookers.
Reason : Boiling point inside the pressure cooker
is raised.
(1) A (2) B (3) C (4) D

Q.18 Assertion : Hmix. & Vmix. for the preparation of

ideal solution is zero.
Reason : A-B interaction in ideal solution are
same as betwen A-A & B-B in the two liquids
before mixing.
(1) A (2) B (3) C (4) D
Q.19 Assertion : 0.1 M solution of NaCl have low
freezing point than 0.1M urea solution.
Reason : Van’t Hoff factor for NaCl is more than
urea.
(1) A (2) B (3) C (4) D

Q.20 Assertion : The boiling point of 1 M NaCl is

double than 1 M sugar soluion.
Reason : Boiling point is the colligative property.
(1) A (2) B (3) C (4) D

Q.21 Assertion : The van’t Hoff factor for the 90%

dissociation of NaCl is 1.9.
Reason : The freezing point of water decreases
after the addition of NaCl.
(1) A (2) B (3) C (4) D

38
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 5 (NCERT QUESTIONS)

Ex.1 An aqueous solution of 2 percent non-volatile sol- Ex.4 A solution containing 30 g of a non-volatile solute
ute exerts a pressure of 1.004 bar at the boiling point exactly in 90 g water has a vapour pressure of 2.8
of the solvent. What is the molecular mass of the
kPa at 298K. Further 18 g of water is then added to
solute ?
Sol. Given PS = 1.004 bar, P° = 1.013 bar solution, the new vapour pressure becomes 2.9 kPa
(at boiling point P = 1.013 bar) at 298 K. Calculate : (i) Molecular mass of the sol-
Note :- 2% solution should be reported in terms of ute, (ii) vapour pressure of water at 298 K.
w/W and not simply 2%
w = 2 gm and W = 100 – 2 = 98 gm P – PS w  M
Sol. 
PS m W
P – PS w  M
From Raoult’s law : 
PS m W
P – 2.8 30  18 6
For I case : = = .....(1)
1.013 – 1.004 2  18 2.8 m  90 m

1.004 m  98
P – 2.9 30  18 5
For II case :   .......(2)
m = 41 g mol–1. 2.9 m  108 m
By (1) and (2) p° = 3.53 kPa
Ex.2 The vapour pressure of water is 12.3 kPa at 300 K.
Calculate vapour pressure of 1 molal solution of a m = 23 g mol–1
solute in it. Note : - Answers will be 3.4 kPa and 34 g mol–1 if
Sol. 1 molal = 1000gm solvent contains 1 mole of solute,
P – PS n
1000  is used which is only valid for dilute
moles of solvent = P N
18
solution.
 n=1
N Ex.5 A 5% solution (by mass) of cane sugar in water has
 PS = P°
nN freezing point of 271 K. Calculate the freezing point
 PS = 12.08 kPa of a 5% glucose in water if freezing point of pure
water is 273.15 K.
Ex.3 Calculate the mass of a non-volatile solute (molecu-
lar mass 40) which should be dissolved in 114 g 1000  K  w
Sol. T = ; Assuming 5% weight per--
octane to reduce its vapour pressure to 80%. m W

P – PS n wM cent, we have
Sol.   w = 5g, W = 100 – 5 = 95 g;
PS N mW
Tf = 273.15 – 271 = 2.15, m = 342 (for sugar)
(Given m = 40, W = 114 g, Moctane = 114)
1000  K  5
100 – 80 w  114  2.15 = .......(1)
 342  95
80 40  114
w = 10 g 1000  K  5
For glucose Tf = .......(2)
P – PS n 180  95
Note : By =
P N By equation (1) and (2); Tf = 4.085
(only for dilute solutions, the answer comes 8g) Freezing point = 273.15 – 4.09 = 269.06 K

39
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

Ex.6 Two elements A and B form compounds having Ex.7 At 300 K, 36 g of glucose present per litre in its
solution has an osmotic pressure of 4.98 bar. If the
molecular formula AB2 and AB4. When dissolved in
osmotic pressure of solution is 1.52 bar at the same
20 g C6H6, 1g of AB2 lowers the freezing point by 2.3 temperatures, what would be its concentration ?
K, whereas 1.0 g of AB4 lowers it by 1.3 K. The molal
depression constant for benzene is 5.1 K kg mol–1. Sol. Given :
Calculate atomic mass of A and B. O.P. =4.98 bar, w = 36g, V = 1 litre (case 1)
O.P. = 1.52 bar, (case 2)
Sol. For AB2 : molecular mass = a + 2 b
(a and b are atomic mass of A and B) w
For I : V =  S T
For AB4 : molecular mass = a + 4b m
1000  K  w 36
By : Tf =  4.98 × 1 =  S  T .......(1)
m W 180
1000  5.1 1  w 
For AB2 : 2.3 =
( a  2 b)  20 For II: 1.52 = C × S × T  C   ....(2)
 mV 
a + 2b = 110.87 ........(1) By equation (1) and (2);
1000  5.1  1 C = 0.061 molar
For AB4 : 1.3 = Ex.8 The partial pressure of ethane over a saturated so-
(a  4b)  20
lution containing 6.56 × 10–2 g of ethane is 1 bar. If
a + 4b = 196. 15 ........(2) the solution contains 5.00 × 10–2 g of ethane, then
By equation (1) and (2) what shall be the partial pressure of the gas.
a = 25.59; b = 42.64 Sol. xP (Solubility  Partial pressure)
6.56 × 10–2  1 (P = 1 bar)
5.00 × 10–2  P

1  5 . 00  10 –2
 P= = 0.762 bar
6 . 56  10 – 2

40
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 6
Ex.1 Why does the used of pressure cooker reduce cook- Ex.7 CaCO3 shell is removed from the two eggs by
ing time ? treatement with dil. HCl. One of the egg is , then,
Sol. At higher pressure over the liquid (due to weight of placed in pure water while the other in saturated
the pressure cooker lid) the liquid boils at higher solution of NaCl. What will be observed and why ?
temperature and cooking occurs faster. Sol. The egg placed in water will increase in size due to
osmosis of pure water into the egg, while the other
Ex.2 When dried fruits and vegetables are placed in wa- egg placed in NaCl solution, will shrink due to os-
ter, they slowly swell up. Why ? What is the effect mosis of water out of the egg.
of temperature on this process ?
Sol. Fruits and vegetables absorb water due to endo- Ex.8 Aerated water bottles are kept under water during
osmosis. The endo-osmosis incerases with increase summer. Why ?
in temperature. Sol. Aerated water bottles contain CO2 dissolved in
water at high pressure. In summer, the solubility of
Ex.3 Why does water boil at lower temperature in Simla gas in was decreases due to increase in tempera-
than in Dehli ? ture and high pressure may be developed inside
Sol. Atmospheric pressure (lower at Simla) decreases bottle which may cause the explosion. To avoid it,
with altitude. aerated water bottles are placed in water during
summer.
Ex.4 Molecular mass of benzoic acid when determined
by colligative properties in benzene yields abnor- Ex.9 What role does the molecular interaction play in
mally higher values ? solution of alcohol and water ?
Sol. benzoic acid gets dimerized in benzene to show Sol. In alcohol-water solution interaction between alco-
double molecular weight. hol and water molecules shows inter molecular H-
bonding but this is weaker than H2O -H2O and alco-
Ex.5 Why does cook cries less on cutting onion if cooled hol-alcohol H-bonding or mixing of these two de-
in fridge rather than cutting onion at room tempera- crease the interaction between alcohol-H2O. This
ture ? results in more escaping tendency of molecule in
Sol. Onion kept in fridge has low vapour pressure of its vapour phase or positive deviation from Raoult’s
contents at low temperature. law is obeyed.

Ex.6 Semipermeable membrane of Cu2[Fe(CN6)] is not

used for studying osmosis in non-aqueous solu-
tions.
Sol. Cu2[Fe(CN)6] is soluble in non-aqueous solutions.

41
 CHAPTER : SOLUTION AND COLLIGATIVE PROPERTIES

EXERCISE # 1
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 2 1 1 3 1 2 3 1 4 3 4 2 3 3 4 1 2 1 3 1
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 2 1 4 2 1 4 4 2 1 2 1 4 2 3 3 1 3 2 3 3
Q.No. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. 4 2 4 1 1 4 2 2 2 3 2 2 2 3 2 3 3 2 1 2
Q.No. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
Ans. 2 4 3 1 3 4 3 3 4 3 4 3 1 2 4 3 4 1 3 1
Q.No. 81 82 83 84 85 86 87 88 89 90 91 92 93 94
Ans. 3 1 3 2 1 2 3 3 2 4 4 4 3 1

EXERCISE # 2
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 2 3 2 2 3 3 1 3 2 1 2 1 3 2 2 1 2 4 2 2
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
Ans. 4 3 3 2 1 4 4 2 2 3 2 2 2 3 2 4 3 1 1
EXERCISE # 3A
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 2 4 1 3 4 3 4 1 2 2 2 1 3 2 3 1 3 1 1
Q.No. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37
Ans. 3 2 2 2 1 1 2 3 4 4 2 4 1 3 4 1 1

EXERCISE # 3B
Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Ans. 1 2 4 3 1 2 3 1 1 2 2 4 2 1 1 4 3 1 1
Q.No. 20 21
Ans. 1 2

EXERCISE # 4

Q.No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 1 2 1 3 1 1 2 1 1 3 2 3 4 2 4 1 1 1 1 4
Q.No. 21 22 23
Ans. 2 1 3

42