Solution: STR Ycl Asses

SOLUTION
IIT-JEE SYLLABUS
Law of partial pressures : Vapour pressure ; Raoult’s Law ; Molecular weight determination from
lowering of vapour pressure, elevation of boiling and depression of freezing point.
CHAPTER CONTENTS :
 Introduction  Colligative properties
s
 Basic definitions  Relative lowering of vapour pressure
sse
 Types of solutions  Elevation in boiling point
 Methods of expressing the strength of  Depression in freezing point
la
solution  Osmotic pressure
 Vapour Pressure of solution  van’t Hoff factor and abnormal molecular mass
yC
 Factor affecting vapour pressure  Association of slute
 Raoult’s law  Dissociation of solute
 Ideal and non-ideal solutions
 Composition of vapour
 Azeotropic mixture
str
mi
1. MIND MAP
he
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1. Out of the concentration terms, the 2. Vapour pressure of a liquid at a given 3. According to Raout’s law,
ones in which volume of solutionis temperature is the pressure exerted by Psolution = Xsolvent Pºsolvent. If both
involved changes with temperature. It the vapours of a liquid when the solute & solvent are volatile, then
is assumed that evaporation of a liquid vapours are in equilibrium with liquid.
R
does not appreciably alter the On adding a non-volatile solute, the PT = X A = PA + X BPB
composition of a solution. vapour pressure of the solution
SI
becomes less than that of the pure

solvent.
O
PT
8. van’t Hoff factor (i) is 4. The ideal solution of a non-volatile solute is a

highly dilute solution. For a volatile solute, it is
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Value of experimental colligative property

 LIQUID a solution in which solute-solute forces are equal
Value of theoretical colligative property to solvent-solvent forces which in turn are equal
SOLUTION
SU
For solutes that dissociates i > 1 and for those to solute forces.
that associate i < 1.
7. Depression of freezing point is given 6. Elevation of boiling point is given by 5. Relative lowering of vapour pressure
by Tf = Kf mobs Tb = Kb mobs
Pº P
is given by  X solute .
Pº
CHEMISTRY SOLUTION
LIQUID SOLUTION
Solution: A homogeneous mixture of two or more substances. (Solute + solvent = solution)
Saturated Solution : A solution that is in equilibrium with pure solid solute. No more solute can be dissolved in it.
1. METHOD OF EXPRESSING THE CONCENTRATION OF SOLUTION
The concentration of a solution can be expressed in a number of ways. The important methods are:
(i) Mass percentage or per cent by mass:
Mass of solute
%(w/w) Mass percentage of solute = × 100
Mass of solution
Mass of solute
=
s
Mass of solute + Mass of solvent
sse
Mass of solute

Volume of solution  Density of solution
la
(ii) Percent mass by volume:
yC
× 100 ; %   
Mass of solute v VA
%(w/v)   100
Volume of soltuion  v  Volume of solution
(iii) Parts per million (ppm) :
ppm =
Mass of solute
× 106
str
mi
Mass of solution
(iv) Mole fraction:
he
Let n moles of solute (A) and N moles of solvent (B) be presnet in a solution.
n N
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Mole fraction of solute = = XA , Mole fraction of solvent = = XB

Nn Nn
In binary solution, XA + XB = 1
Mole fraction is independent of temperature of the solution.
R
(v) Molality
SI
No. of moles of solute

Molality (m) =
weight (in kg) of solvent
O
Let wA grams of the solute of molecular mass mA be present in wB grams of the solvent, then
PT
wA
Molality (m) = × 1000
mA  wB
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(vi) Relation between mole fraction and Molality :
 1 
SU
nA
n A  1000     1000
X A  1000 w A  100  M B  n A  1000 n A  n B A  solute
m   
XB  mB MA  w B  1  nB  MB nB B  solvent
wB     MB
 MB  nA  nB
Note: (i) Molality is the most convenient method to express the concentration because it involves the mass of
liquids rather than their volumes. It is also independent of the variation in temperature.
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CHEMISTRY SOLUTION
(vii) Molarity (Molar concentration)

No. of moles of solute
Molarity (M) =
Volume (in litre) of solution
wA
Molarity of the solution = × 1000
mA  V
(viii) Relation between molarity and % solute by mass :
Let d = density of solution in g/mL and let it contains × % (w/w) solute by mass.
Number of moles of solute in 1 litre
mass of solute in gram x  d  10
s
= =
sse
grams molecular mass of solute Msolute
x  d  10 (M) × Molecular weight of the solute

M %
la
mA 10  d
(ix) Molarity of dilution:
yC
Before dilution After dilution
M1 V 1 = M2 V 2
(x) Molarity of mixing:
M1V1 + M2V2 + M3V3 = MR(V1 + V2 + V3)
MR = resultant molarity
str
mi
(xi) Relationship between molality and molarity :
he
molarity molality (M) implies (M) moles in 1 lit solution

Molality (m) = =
d  molarity  msolute mass of the solution  mass of the solute
-C
(xii) Concentration or strength of a solution (S) :

The numbers of grams of solute dissolved in one litre solution is known as its strength in grams per litre.
– Strength in grams per litre
R
weight of solutein grams  1000

S=
SI
volumeof solution in mL
S = Molarity of solution  molecular weight of solute.
O
S = Normality of solution  equivalent weight of solute.

(xiii) Normality (N) : The number of equivalents or gram equivalents of solute dissolved in one litre of the solution is known as
PT
normality (N) of the solution.
Number of gram equivalents of solute

Normality(N) 
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volumeof solution in litre

SU
weight of solute in gram

=
equivalent weight  volume of solution (litre)
strength of solution in gram / litre

=
Equivalent weight of solute
Equivalent weight of a substance is that weight which reacts with or displaces one gram of hydrogen, 8 grams of oxygen
or 35.5 grams of chlorine.
BLACK BOARD CLASSES - By Sudipto Sir  Ph : 86978 74159/9073541305 (Office), M : 98309 82734, Website : www.sudiptosirchemistryclass.in 3
CHEMISTRY SOLUTION
(xiv) Relation between molarity and normality :-

S = Molarity × molecular weight of solute
and S = Normality × equivalent weight of solute.
So we can write
Molarity × Molecular weight of solute = Normality × equivalent weight of solute.
molarity  molecular weight of solute
Normality 
equivalent weight of solute
molarity  molecular weight of solute

(molecular weight of solute/valency factor)
Normality = molarity × valency factor
s
N=M×n;N > M
sse
Illustration 1. The density of a solution containng 13% by mass of sulphric acid is 1.09 g/mL. Calculate the
molarity of the solution.
Solution: In solving such numericals, the following formula can be applied:
la
% strength of soln.  density of soln.  10
yC
Molarity =
Mol. mass
13  1.09  10
M= = 1.445 M
98
str
Illustration 2. The density of a 3 M sodium thiosulphate solution (Na 2S2O3) is 1.25 g/mL. Calculate (i) the
percentage by mass of sodium thiosulphate, (ii) the mole fraction of sodium thiosulphate and
mi
(iii) molalities of Na+ and S2O32– ions.
he
x  d  10 x  1.25  10
Solution: M=  3=
mA 158
-C
 x = 37.92
474
(ii) No. of moles of Na2S2O3 = =3
158
R
776
SI
Mass of water = (1250 – 474) = 776 g , No. of moles of water = = 43.1

18
3 3
O
Mole fraction of Na2S2O3 = = = 0.065

43.1  3 46.1
PT
(iii) No. of moles of Na+ ions

= 2 × No. of moles of Na2S2O3 = 2 × 3 = 6
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No. of moles of Na  ions

Molality of Na+ ion =
Mass of water in kg
SU
6
= × 1000 = 7.73 m
776
No. of moles of S2O32– ions = No. of moles of Na2S2O3
3
Molality of S2O32– ions = × 1000 = 3.86 m
776
CHEMISTRY SOLUTION
Illustration 3. Density of a 16% (by mass) solution of H2SO4 is 1.1094 g/mL. Calculate molality, molarity and
normality of solution
Solution: Given that, w = 16 g, mass of solution = 100 g
Mass of solution 100

 Volue of solution   = 90.139 mL
Density of solvent 1.1094
Mass of solvent = Mass of solution – Mass of solute = 100 – 16 = 84 g
Molecular mass of solute (M) = 98 (H2SO4)
w  1000 16  1000
Now, m    1.94
M  W 98  84
s
sse
w  1000 16  1000
M   1.81
M  VmL 98  90.139
la
w  1000 16  1000
Normality (N)    3.88
yC
E  V(in mL) 49  84
Illustration 4. How many gram of sodium carbonate should be dissolved in water in order to prepare 500 mL
solution of 0.01 M concentration ?
Solution: milli-moles of Na2CO3 

w
 1000 str
mi
m
w Na 2CO3  1000
 0.01  500  w Na 2CO3  0.56 g
he
106
Illustration 5. 20.6 g NaBr dissolved in 500 mL solution. What is the molarity of resulting solution ?
-C
w
Solution: m-mole of NaBr =  1000  M  VmL
m
R
20.6
 1000  M  500  M  0.4
SI
103
Illustration 6. 2.8 g nitrogen is dissolved in 500 mL solution. Calculate the molar concentration of nitrogen in the
O
solution.
w 1000 2.8 1000

PT
Solution: M     0.2
m VmL 28 500
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Illustration 7. Density of 2.03 M aqueous solution of acetic acid is 1.017 g/mL. Molecular mass of of acetic acid
is 60. Calculate the molality of solution.
Solution: Given that molarity (M) = 2.03 i.e., 2.03 moles (or 2.03 × 60 = 121.8 g) acid is dissolved in 1000 mL
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solution.
Because density of solution is 1.017 g mL–1, so mass of 1000 mL solution = VmL × d = 1000 × 1.017
= 1017 g
 Mass of water = mass of solution – mass of acid = 1017 – 121.8 = 895.2 g
moles of solute 2.03  1000

Now, molality   1000   2.27
mass of solvent (in g) 895.2
CHEMISTRY SOLUTION
Illustration 8. 500 mL of a solution contains 1/10th of equivalent mass of HCl. Calculate the normality of solution.
w 1000 1 1000
Solution: N     0.2
E VmL 10 500
Illustration 9. 5.8 g acetone is dissolved in 450 g water. Calculate mole fractions of acetone and water in the
solution.
Mass of acetone (w) 5.8
Solution: n acetone    0.1
Mol of mass of acetone (m) 58
Mass (w) 450

and n water    25
Mol. of mass of water (m) 18
s
sse
n acetone 0.1
X acetone    3.98  103
n acetone  n water 25  0.1
la
25
and X water   9.96  101
25.1
yC
Illustration 10. Calcualte molality of the solution obtained by dissolving 117.7 g NaCl in 500 g water.
w 1000 11.7  1000
Molality     0.4 m
Solution:
2. Vapour Pressure
M  Wg 58.5  500
str
mi
Thermostat Vapours
P
The pressure exerted by the vapour (molecules in the vapour
phase) over the surface of the liquid at the equilibrium at
he
given temperature is called the vapour pressure of the liquid. Liquid

Factors affecting vapour pressure
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(i) Temperature : Manometer

Vapour pressure  Temperature Physical equilibrium between
liquid vapours
H  T2  T1 
R
P
log 2   
P1 2.30  R  T1T2 
SI
(ii) Nature of liquid:

1
O
Vapour pressure of liquid 

The strength of intermolecular forces
acting between molecules
PT
For example, ethyl alcohol has higher vapour pressure because of the weak intermolecular forces acting between
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its molecules than water which has stronger intermolecular forces acting between water molecules of volatile
liquid has lower boiling point than a non-volatile liquid.
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3. Vapour Pressure of a Solution

Vapour Pressure of a Solution Containing Non Volatile Solute - Raoult’s Law
Vapour pressure – At a constant temperature, the pressure exerted by the vapours of a liquid on its surface when
they (liquid and its vapours) are in equilibrium, is know as vapour pressure.
Raoult's law :- According to this law, the partial pressure of any volatile constituents of a solution at a constant
temperature is equal to the vapour pressure of pure constituents multiplied by the mole fraction of that constituent
in the solution.
CHEMISTRY SOLUTION
(i) For liquid – liquid solution :- Let a mixture (solution) be prepared by mixing nA moles of liquid A and nB
moles of li quid B. Let PA' and PB' be the partial pressures of two constituents A and B in solution and PA0 and
PB0 the vapour pressures in pure state respectivity.
Thus, according Raoult's law
nA
PA  PA0 ..................................(1)
nA  nB
Partial pressure of A = mole fraction of A × PA0 = XAPA0
nB
and PB  PB0 ..................................(2)
nA  nB
s
sse
Partial pressure of B = mole fraction of B × PB0 = XAPB0
If total pressure be PS, then
la
nA nB
PS = PA' + PB'  PA 0  PB0
nA  nB nA  nB
yC
= XAPA0 + XB PB0 ................................(3)
PS = XAPA0 + (1 – XA)PB0 [ XA + XB = 1]
PS = XAPA0 – XA PB0 + PB0
PS = XA [PA0 – PB0] + PB0 str
................................(4)
mi
Equation 1, 2 and 3 are the straight line equation so we can draw it as follows.
he
Vapour pressure 
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' + P B' PA 0
PS = PA
0
PB 0 PA
= XA
R
P A'
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P '
B =X
B P 0
B
O
XA=0 and XB=1 Mole fraction  XA=1 and XB=0

PT
Example : 1 mole heptane (V.P. = 92 mm of Hg) is mixed with 4 mol. Octane (V.P. = 31 mm of Hg), form an ideal
solution. Find out the vapour pressure of solution.
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Solution : total mole = 1 + 4 = 5

Mole fraction of heptane = XA = 1 /5
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Mole fraction of octane = XB = 4 / 5
1 4
PS = XAPA0 + XBPB0 =  92   31 = 43.2 mm of Hg.
5 5
Example : At 880C benzene has a vapour pressure of 900 torr and toluene has a vapour pressure of 360 torr. What
is the mole fraction of benzene in the mixture with toluene that will be boil at 88ºC at 1 atm pressure,
benzene – toluene form an ideal solution.
CHEMISTRY SOLUTION
Solution : PS = 760 torr, because solution boils at 88ºC
Now PS = PC6H6 X C6H6  Ptoluene X toluene

0 0
760 = 900 × mole fraction of C6H6 + 360 × [1 – mole fraction of C6H6]

760 = 900 a + 360 – 360 a
a = 0.74 where 'a' is mole fraction C6H6.
(ii) Solid – liquid solution –
A = non volatile solids
B = volatile liquid
s
According to Raoult's law : Pm = XAPA0 + XBPB0
sse
for A, PA0 = 0
 Pm = XBPB0 ...................................(5)
la
Let PB = 0 P0 = Vapour pressure of pure state of solvant.
yC
here XB is mole fraction of solvant
nB
PS  P0 ...................................(6)
nA  nB
PS 
nB str
mi
nA  nB
i.e. vapour pressure of solution  mole fraction of solvant
he
 PS = XBPB0
 PS = (1 – XA) PB0
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 PS = PB0 – XA PB0
PB0  PS
 X A or P  PS  X A
0
R
..........(7)
PB0 P0
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P0  PS nA
or  ..........(8)
O
P 0 nA  nB
PT
P0 nA  nB P0 n P0 n
or  or 0  1  B or 0 1  B
P 0  PS nA P  PS nA P  PS nA
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PS nB P0  PS n A
or  or  ..........(9)
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P0  PS nA PS nB
P0  PS w A .m B
or 
PS m A .w B
wM
or ..........(10)
mW
CHEMISTRY SOLUTION
Example : The vapour pressure of benzene at 90ºC is 1020 torr. A solution of 5 g of a solute in 58.5 g benzene has
vapour pressure 990 torr. The molecular weight of the solute is?
P0  PS w  M 1020  990 5  78
  
m  58.5 
Solution : m = 220
PS mW 990
Example : How much urea should be dissolved in 100 g of water in order to reduce its vapour by 25% ? Also,
calculate the molality of resulting solutions.
Solution : Given that, Pº = 100, PS = 75, w = ?, m = 60, W = 100 g, M = 18
Pº PS n w / m
(a)  
Pº N W/M
s
100  75 w  18
sse
   w  83.33 g (incorrect answer)
100 60  100
la
Pº  PS
(b)  m
yC
Pº w W

m M
w
100  75

100
 60
w 100

60 18
 w  111.11 g (correct answer)
str
mi
Pº PS w M
(c)  
he
PS m W
100  75 w 18
    w  111.11 g (correct answer)
-C
75 60 100
w  1000 111.11 1000
Molality of solution    18.51 mol / kg
m W 60  1000
R
Example : At 310 K, the vapour pressure of an ideal solution containing 2 moles of A and 3 moles of B is 550 mm
of Hg. At the same temperature, if one mole of B is added to this solution, the vapour pressure of
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solution increases by 10 mm of Hg. Calculate the V.P. of A and B their pure state.
According to Raoult’s law PM  PA  X A  PB  X B

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Solution :
Given that PM = 550 mm, and nA and nB are 2 and 3 moles respectively
PT
 2    3 
550  PA     PB   
 23  23
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or, 2PA  3PB  2750 (intially) ................... (1)

SU
Now or adding 1 mole of B, and using Raoult’s law again

 2    4 
560  PA     PB    ( PM = 560 mm, nA = 2 mole, nB = 4 mole)
24 24
or, 2PA  4PB  3360 ................... (1)
Solving equations (1) and (2) ; PA = 460 mm ; PB = 610 mm
CHEMISTRY SOLUTION
Example : At 25ºC vapour pressure of pure benzene is 639.7 mm in which a solute is dissolved in benzene at the
same temperature, vapour pressure of resulting solution is 631.9 mm. Find out molality of solution.
Pº PS w  M w  M  1000
Solution :  
PS m  W m  W  1000
w  1000 Pº PS 1000

 Molality (m)    (Mbenzene = 78)
m W PS M
639.7  631.9 1000

   0.15 mol/kg (solvent)
631.9 78
s
Example : Vapour pressure of an aqueous solution of glucose at 373 K is 750 mm Hg. Calculate the molality of
sse
solution and mole fraction of glucose.
Pº PS w  M w  M  1000
Solution : Using the relation,  
la
PS m  W m  W  1000
yC
Pº = 760 mm (V.P. of pure water at 373 K), M H 2O  18
Pº  PS 1000 760  750 1000

 Molality (m)      0.7407 mol/kg (solvent)
PS M H 2O 750 18
 moles of glucose = 0.7407, moles of water 

str 1000
 55.6
mi
18
he
0.7407
 Mole fraction of glucose   0.013
0.7407  55.6
-C
Example : At a given temperature, vapour pressure of pure benzene is 200 mm Hg. At the same temperature, a
solution contains 2 g of a non-volatile solute in 78 g of benzene and vapour pressure of solution is
195 mm Hg. Calculate the molecular mass of solute.
Pº PS w  M
R
Solution : 
PS m W
SI
Pº = 200 mm, PS = 195 mm, w = 2g, M = 78, W = 78 g

200  195 2  78
O
   m  78
195 m  78
PT
Example : An aqueous solution of glucose is prepared at 303 K by dissolving 10 g glucose in 90 g water. If vapour
pressure of water is 32.8 mm Hg, what is the vapour pressure of solutions ?
DI
Pº PS w  M
Solution : 
PS m W
SU
32.8  PS 10  18
 
PS 180  90
 PS = 32.44 mm Hg.
Illustration 11: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour pressure of an aqueous
solution at 37°C containing 20 g of glucose dissolved in 500 gm of water. Also calculate vapour
pressure lowering.
CHEMISTRY SOLUTION
500 20
Solution : n H2O   27.78 mol , n(glucose)   0.11 mol
18 180
n H2O 27.78 27.78

X H2O     0.996
n H2O  n (glu cos e) 27.78  0.11 27.89
According to Raoult’s law,
Vapour pressure of solution PH2O  PHo 2O X H 2O  47.1 0.996  46.9 torr
Lowring of vapour pressure PHo 2O – PH2O  47.1 – 46.9  0.2 torr
s
sse
Illustration 12. The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure of a solution of urea in
ethyl alcohol is 51.3 torr. What is the molality of the solution?
la
Solution : Given: PAo = 59.2 torr, pA = 51.3 torr
yC
7.9
By RLVP  Xsolute = = .1334
59.2
XB 1000 XB 1000
 (molality) m =  
X A Msolvent
=
str
1  X B  Msolvent
( XA + XB = 1)
mi
0.1334 1000
m=  = 3.346 molal
0.8666 46
he
Illustration 13. Calculate relative lowering of vapour pressure of 0.161 molal aqueous solution.
-C
X B  1000 X B  1000
Solution : we know Molality =  0.161 =
1  X B   msolvent 1  X B   18
XA = 0.00289  RLVP = XA = 0.00289
R
Illustration 14. An aqueous solution containing 28% by mass of a liquid A (mol. mass = 140) has a vapour pressure of
SI
160 mm at 37ºC. Find the vapour pressure of the pure liquid A. (The vapour pressure of water at 37ºC
is 150 mm.)
O
Solution : For two miscible liquids,

28
PT
Ptotal = PA  PB  PAo X A  PBo X B nA = = 0.2,

140
72
DI
Liquid B is water. Its mass is (100–28), i.e. 72. nB = = 4.0

18
Total number of moles = 0.2 + 4.0 = 4.2
SU
Given Ptotal = 160 mm, PB0 = 150 mm

0.2 0 4.0
So 160 =  PA   5.0
4.2 4.2
17.15  4.2
p0A   360.15mm
0.2
CHEMISTRY SOLUTION
4. DETERMINATION OF COMPOSTION IN VAPOURE PHASE

Dalton’s Law v/s Raoult’s Law :
The composition of the vapour in equilibrium with the solution can be calculated applying Daltons’ law of partial
pressures. Let the mole fractions of vapours A and B be YA and YB respectively. Let pA and pB be the partial
pressure of vaours A and B respectively and total pressure P.
A B A B A B A B A B A vapours (Dalton's law)

yA = more fraction of A in vapour phase
yB = more fraction of B in vapour phase
(YA + YB = 1)
s
sse
A B A B A B A B A B A solution (Raoult's law)
XA = more fraction of A in liquid phase
la
XB = more fraction of B in liquid phase
Solution of (A & B)
yC
(XA + XB = 1)
oX + P oX
From Raoult's law P = PA A B B
o X and P = P o X
PA= PA A B
From Dalton's law,
B B
str
mi
Partial pressure = Mole fraction × Total pressure
he
For A PA = yA × P
PAo X A
-C
oX = y × P
PA A A yA = .....(1)
P
Above formula is used for calculation of mole fraction of A in vapour phase
R
For B, PB = yB × P
SI
o
PBo XB = yB × P yB = PB XB .....(2)
P
O
Above formula is used for calculation of mole fraction of B in vapour phase

PT
P  yA P  yB
From (1) , XA = From (2) XB =
PAo PBo
DI
P  yA P  yB
on addingXA + XB = + =1
PAo
SU
PBo
1 yA yB
 = o + o .....(3)
P PA PB
Above formula is used to calculate total vapour pressure when mole fractions are given in vapoure phase
CHEMISTRY SOLUTION
Avoid confusion
oX + P oX  This formula is used to calculate total pressure when mole fraction are given in liquid phase
P = PA A B B
1 y y
 Ao  Bo This formula is used to calculate total pressure when mole fraction are given in vapour
P PA PB
phase
Note : Thus, in case of ideal solution the vapour phase is phase is richer with more volatile component i.e., the one
having relatively greater vapour pressure.
Illustration: 15. The vapour pressures of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal
solution is formed at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate
s
the total vapour pressure of the solution and the mole fracion of methanol in the vapour.
sse
60 40
Solution: No. of moles of C2H5OH = = 1.304, No. of moles of CH3OH = = 1.25
46 32
la
1.304
yC
‘XA’ of ethyl alcohol = = 0.5107
1.304  1.25
1.25
‘XB’ of methyl alcohol =
1.304  1.25
= 0.4893
str
Partial pressure of ethyl alcohol = XA.PA0 = 0.5107 × 44.5 = 22.73 mm Hg
mi
Partial pressure of methyl alcohol = XB.PB0 = 0.4893 × 88.7 = 43.40 mm Hg
he
Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg

-C
Partial pressure of CH3OH

Mole fraction of methyl alcohol in the vapour =
Total vapour pressure
R
43.40
= = 0.6563
SI
66.13
Effects of Pressure on solubility of gases in liquids
O
The effect of pressure on the solubility of a given gas in a particular liquid at constant temperature can be obtained
by carefully observing the process in reverse direction viz. the gas as a solute which vapourizes to establish a
PT
vapour pressure above the solution.

Henry’s Law :
DI
It states that at constant temperature the solubility of a gas in a liquid is directly proportional to the pressure of the
gas above it.
SU
When several gases are dissolved simultaneously in a solvent, the solubility of each gas from a mixture of gases is
directly proportional to the partial pressure of the gas mixture. The proportionality constant will however be
different for each gas.
The strict applicability of Henry’s law is limited to the lower pressure and at high pressures the law becomes less
exact.
Generally, higher the temperature and lower the pressure, the more closely is the law obeyed. This law is not valid
when the gas reacts with the solvent, or when the dissolved gas ionizes.
CHEMISTRY SOLUTION
Daily Practice Problem Sheet - 1

Q.1 An aqueous solution containing liquid A (M. wt. = 128) 64% by weight has a V. P. of 145 mm. If the vapour
pressure of water is 155 mm then vapour pressure of A at the same temperature will be -
(A) 205 mm (B) 105 mm (C) 185 mm (D) 52.5 mm
Q.2 The vapour pressure of pure ethylene bromide and propylene bromide are 170 and 127 mm of Hg at a temperature.
Find out :
(i) The vapour pressure of ethylene bromide & propyline bromide in a 60% by weight solution of ethylene
bromide in propylene bromide at same temperature, is -
(A) 52.4 mm, 24.31 mm (C) 52.4 mm, 48.63 mm
(C) 104.9 mm, 48.63 mm (D) 104.9 mm, 24.31 mm
s
(ii) Total vapour pressure of solution, is -
sse
(A) 153.53 mm (B) 76.71 mm (C) 101.03 mm (D) 129.21 mm
Q.3 Two liquids A and B form ideal solution at 300 K. The vapour pressure of a solution containing one mole of A and
la
four mole of B is 560 mm of Hg. At the same temperature if one mole of B is taken out from the solution, the
vapour pressure of solution decreases by 10 mm of Hg. Vapour pressures of A and B in pure state will be-
yC
(A) 330, 550 (B) 200, 300 (C) 400, 600 (D) 800, 1200
Q.4 The vapour pressure of two volatile liquid mixture is PT = (5.3 – 2XB) in cm of Hg ; where XB is mole fraction of
B in mixture. What are vapour pressure of pure liquids A and B ?
(A) 3.3 and 2.1 cm of Hg
(C) 5.3 and 2.3 cm of Hg str
(B) 2.3 and 3.3 cm of Hg
(D) 5.3 and 3.3 cm of Hg
mi
Q.5 A mixture contains 1 mole volatile liquid A (PºA = 100 mg Hg) and 3 moles volatile liquid B(PºB = 80 mm). If solution
be haves ideally, total vapour pressure of the solution is approximately -
(A) 80 mmHg (B) 85 mmHg (C) 90 mmHg (D) 92 mmHg
he
Q.6 At 40ºC the vapour pressure in torr of methanol and ethanol solution is P = 119 x + 135 where x is the mole
fraction of methanol, hence,
-C
(A) vapour pressure of pure methanol is 119 torr

(B) vapour pressure of pure ethanol is 135 torr
(C) vapour pressure of equimolar mixture of each is 127 torr
R
(D) mixture is completely immiscible

SI
Q.7 Vapour pressure of pure A is 70 mm of Hg at 25ºC it forms an ideal solution with B in which mole fraction of A is
0.8. If vapour pressure of solution is 84 mm of Hg at 25ºC, the vapour pressure of pure B at 25ºC is -
(A) 1 atm (B) 14 mm of Hg (C) 140 mm of Hg (D) 56 cm of Hg
O
Q.8 Vapour pressure (in torr) of an ideal solution of two liquids A and B is given by : P = 52 XA + 114
PT
where XA is the mole fraction of A in the mixture. The vapour pressure (in torr) of equimolar mixture of the two
liquids will be -
(A) 166 (B) 83 (C) 140 (D) 280
DI
Q.9 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 phase is 0.45 and in liquid phase
SU
0.65 then the vapour pressures of two pure liquids at the same temperature will be -
(A) 138.4 mm, 628.57 mm (B) 276.9 mm, 628.57 mm
(C) 276.9 mm, 314.28 mm (D) 138.4 mm, 314.28 mm
Q.10 The vapour pressure of benzene and toluene at 20ºC are 75 mm of Hg and 22 mm of Hg respectively.
23.4 g of benzene and 64.4g of toluene are mixed. If two forms ideal solution, the mole fraction of benzene in
vapour phase when vapours are in equilibrium with liquid mixture, is -
(A) 0.59, 0.41 (B) 0.25, 0.75 (C) 0.5, 0.5 (D) 0.35, 0.65
CHEMISTRY SOLUTION
Q.11 The vapour pressure of two liquids are 15000 and 30000 in a unit. When equimolar solution of liquids is made.
Then the mole fraction of A and B in vapour phase will be -
2 1 1 2 1 1 1 3
(A) , (B) , (C) , (D) ,
3 3 3 3 2 2 4 4
Q.12 At 30ºC, the vapour pressure of pure ether is 646 mm and of pure acetone is 283 mm. Find out the mole fraction
of each component in vapour state for the solution of two having mole fraction of ether 0.50. Assume ideal
behaviour.
(A) 0.20, 0.80 (B) 0.799, 0.201 (C) 0.695, 0.305 (D) 0.535, 0.465
Q.13 Benzene and toluene form an ideal solution. The vapour pressure of benzene and toluene are respectively
75 mm and 22 mm at 20ºC. If the mole fraction of benzene and toluene in vapour phase are 0.63 and 0.37
respectively, then :
s
sse
(i) The vapour pressure of mixture is -
(A) 39.68 mm (B) 79.32 mm (C) 58.56 mm (D) 29.24 mm
(ii) Mole fraction of benzene & toluene in liquid phase is -
la
(A) 0.2, 0.8 (B) 0.63, 0.37 (C) 0.54, 0.46 (D) 0.33, 0.67
yC
Q.14 At 90ºC, the vapour pressure of toluene is 400 mm and that of xylene is 150 mm. The composition of liquid
mixture that will boil at 90ºC when the pressure of mixture is 0.5 atm, is -
(A) 0.8, 0.2 (B) 0.75 , 0.25 (C) 0.92 , 0.08 (D) 0.66 , 0.34
Q.15 V. P. of pure A pºA = 100 mmHg
V. P. of pure B pºB = 150 mmHg
str
Distillate of vapours of a solution containing 2 moles A and 3 moles B will have total vapour pressure, approximately,
mi
on condensation
(A) 135 mm (B) 130 mm (C) 140 mm (D) 145 mm
he
Q.16 1 mole benzene (Pº = 42 mm) and 2 moles toluene (Pº = 36 mm) will have
(A) total vapour pressure 38 mm
-C
(B) mole fraction of vapours of benzene above liquid mixture is 7/19

(C) ideal behaviour
(D) all of the above
R
Q.17 At a given temperature, the vapour pressure of pure A and B is 108 and 36 torr respectively. What will be the mole
fraction of B in the vapour phase which is in equilibrium with a solution containing equimole fraction of A and B,
SI
under ideal behaviour conditions ?

(A) 0.25 (B) 0.33 (C) 0.50 (D) 0.60
O
Q.18 A solution of benzene (pº = 120 torr) and toluene (pº = 80 torr) has 2.0 mol of each component. At equilibrium the
mol fraction of toluene in vapour phase is -
PT
(A) 0.50 (B) 0.25 (C) 0.60 (D) 0.40

Q.19 Liquids A and B form an ideal solution and the former has stronger intermolecular forces. If XA and XA are the
DI
mole fractions of A in the solution and vapour in equilibrium, then -

X 'A X 'A X 'A
SU
(A) =1 (B) >1 (C) <1 (D) X'A + X A = 1

XA XA XA
Q.20 Mole fraction of a liquid A in an ideal mixture with another liquid b is XA. If XA is the mole fraction of component
A in the vapour in equilibrium, the total pressure of the liquid mixture is -
(PºA = vapour pressure of pure A ; PºB = vapour pressure of pure B )
X 'A Pº A X A Pº B X 'A Pº B X A
(A) Pº A (B) X 'A (C) XA (D) X 'A
XA
CHEMISTRY SOLUTION
Q.21 Two liquids A and B have Pº A : Pº 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-
(A) 0.1 (B) 0.2 (C) 0.5 (D) 1.0
Q.22 At a certain temperature pure liquid A and liquid B have vapour pressures 10 torr and 37 torr respectively. For a
certain ideal solution of A and B, the vapour in equilibrium with the liquid has the components A and B in the
partial pressure ratio PA : PB = 1 : 7 . What is the mole fraction of A in the solution ?
(A) 0.346 (B) 0.654 (C) 0.5 (D) none of these
Q.23 Mole fraction of the toluene in the vapour phase which is in equilibrium with a solution of benzene
(pº = 120) and toluene (pº = 80 ) having 2.0 moles of each, is –
(A) 0.50 (B) 0.25 (C) 0.60 (D) 0.40
Q.24 The vapour pressure of pure liquid A at 300 K is 575 torr and that of pure liquid B is 390 torr. These two
s
compounds form ideal liquid and gaseous mixtures. The mole fraction of A in the vapour phase is 0.35. Then :
sse
(i) The total pressure of the mixture is
(A) 526 torr (B) 965 torr (C) 440 torr (D) 715 torr
la
(ii) composition of the liquid mixture is -
(A) A = 27%, B = 73% (B) A = 57 %, B = 43 %
yC
(C) A = 33% . B = 67% (D) A = 30%, B = 70%
Q.25 64 gm of methanol & 46 gm of ethanol forms in an ideal solution at 350 K. If the vapour pressure of methanol and
ethanol at 350 K are 8.1 × 104 and 4.5 × 104 N m-2 respectively, then mole fraction of methanol in vapour phase
is -
(A) 0.62 (B) 0.22 (C) 0.80 str (D) 0.78
Q.26 Two liquids A and B forms an ideal solution at temperature T. When the total vapour pressure above the solution
mi
is 400 torr, the mole fraction of A in the vapour phase is 0.40 and in the liquid phase 0.75. The vapour pressure of
pure A and B respectively are -
he
(A) 165.54 torr , 772.00 torr (B) 240.24 torr , 840.00 torr
(C) 213.33 torr, 960.00 torr (D) 312.15 torr , 865.00 torr
-C
Q.27 Vapour pressure of a mixture of benzene and toluene is given by P = 179 xB + 92 where xB is mole fraction of
benzene. Determine :
(i) vapour pressure of the solution obtained by mixing 936 gm of benzene and 736 gm of toluene
(A) 199.4 mm (B) 271 mm (C) 280 mm (D 289 mm
R
(ii) If vapours are removed and condensed into liquid then what will be the ratio of mole fractionof benzene and
SI
toluene in first condensate -

(A) 2.8 (B) 1.5 (C) 3.5 (D) 4.5
O
(iii) This condensed liquid again brought to the same temperature then what will be the mole fraction of benzene
in vapour phase -
PT
(A) 0.07 (B) 0.93 (C) 0.65 (D) 0.45

Q.28 Benzene and toluene from nearly ideal solutions. If at 27ºC the vapour pressures of pure toluene and pure benzene
are 32.06 mm and 103.01 mm respectively, the vapour pressure of a solution containing 0.60 mole fraction of
DI
toluene, is -
(A) 60.44 mm (B) 30.22 mm (C) 120.12 mm (D) 76.52 mm
SU
Q.29 An aqueous solution containing 28% by mass of a liquid A (mol. mass = 140) has a vapour pressure of
160 mm at 37ºC. The vapour pressure of water at 37ºC is 150 mm, then the pressure of pure liquid A, is -
(A) 180.22 mm (B) 300.32 mm (C) 360.15 mm (D) 276.55 mm
Q.30 The vapour pressure of ethyl alcohol and methyl alcohol are 45 mm and 90 mm. An ideal solution is formed at the
same temperature by mixing 60 g of C2H5OH with 40 g of CH3OH. Total vapour pressure of the solution is
approximately -
(A) 70 mm (B) 35 mm (C) 105 mm (D) 140 mm
CHEMISTRY SOLUTION
5. TYPE OF SOLUTIONS
(i) Ideal Solution
An ideal solution may be defined as the one which obeys Raoult’s law over all concentration ranges at a given
temperature. The total vapour pressure of an ideal solution containing liquids A and B is given by the following
equation.
P  PA  PB  PAo X A  PBo X B
In an ideal solution of two components A and B, all attractive forces between A and B molecules or between A and
A molecules or between B and B molecules (A–B, A–A and B–B) must be identical so that the escaping tendency
of an A or B molecule is independent of whether it is surrounded by A molecules, B, molecules or varying proportions
of A and B molecules. The escaping tendency of pure liquid A in solution remains the same. Similarly the escaping
s
tendency of B remains the same. Liquids form ideal solution only when they have nearly same molecular size and
sse
related constitution so that they have similar molecular environment in the pure state as well as in solution. A
perfect ideal solution is rare but many liquids form nearly ideal solution. Liquid heptane and hexane form an ideal
solution because the interaction between a hexane molecule and another hexane molecule is the same as the
la
interaction between two heptane molecules other examples of ideal solutions are :
yC
benzene + toluene, chlorobenzene + bromobenzene;
ethyl bromde + ethyl iodide; n-butyl chloride + n-butyl bromide
ethyl alcohol + methyl alcohol
1. str
Conditions for Forming Ideal Solution : Two liquids on mixing form an ideal solution only when
both have similar structures and polarity so that they have similar molecular environment.
mi
2. both have similar molecular sizes.
3. both have identical intermolecular forces.
he
Characteristics Of Ideal Solution :

Mixing of two substances results in an ideal solution only when:
-C
1. They obey Raoult’s Law
2. H mixing  0  that is no heat is absorbed or released during dissolution

R
3. Vmixing  0  that is the total volume of the solution is equal to the sum of the volume of the pure liquids mixed
SI
to form the solution.

Graphical Representation of Vapour Pressure of Ideal Solutions :
O
Figure shows the relationship between partial vapour pressure and mole fraction of an ideal solution at constant
temperature.
PT
o
P XB PAo
o
P XA+ B
III. P= A
DI
Vapour pressure
PBo o XA
=P
A
SU
I. P
A
II.
P
B =Po
B XB
0 XA 1
1 XB 0
Note : Components of ideal solution can be saperated in pure form by fractional distillation
CHEMISTRY SOLUTION
(ii) Non-Ideal Solutions

Solutions which do not obey Raoult’s law over all concentration ranges at constant temperature are called non-
ideal solutions.
Characteristic of nonideal solution
o
(i) PA  PAo X A + PB  PB X B , P  PA
o X + P oX
A B B
(ii) Vmix  0 ,
(iii) Hmix  0
Types of Non-Ideal Solutions
1. Non ideal solutions showing +ve deviation
s
2. Non ideal solutions showing –ve deviation.
sse
1. Non ideal solutions showing +ve deviation
Condition for forming non-ideal solution showing +ve deviation from Raoult’s law.
la
Tow liquids A and B on mixing form this type of solution when
yC
1. A—B attractive force should be weaker than A—A and B—B attractive forces.
2. ‘A’ and ‘B’ have different shape, size and charater.
3. ‘A’ and ‘B’ escape easily showing higher vapour pressure than the expected value.
Characteristic of non-ideal solution showing +ve deviation
1. Do not obey Raoult’s law str
mi
2. Hmix > 0. (endothermic dissolution heat is absorbed.)
3. V mix > 0. (Volume is increased after dissolution)
he
4. pA > pA0 XA; pB > pBoXB ,  pA + pB > poAXA + pBoXB

Example :
-C
acetone + ethanol acetone + CS2 water + methanol;

water + ethanol ; CCl4 + toluene ; CCl4 + CHCl3 ;
acetone + benzene ; CCl4 + CH3OH ; cyclohexane + ethanol
R
Graphical representation of vapour of non-ideal solution showing +ve deviation

SI
V.P.= max.
B.P. = min.
P>
P +
O
A P
Vapour pressure
B
PT
P
A >
P o
B
DI
X
B
SU
XA = 0 Mole fraction XA = 1
XB = 1 XB = 0
2. Non ideal solutions showing –ve deviation.
Condition for forming non-ideal solution showing +ve deviation from Raoult’s law.
Two liquids A and B on mixing form this type of solution when
1. A—B attractive force should be greater than A—A and B—B attractive forces.
2. ‘A’ and ‘B’ have different shape, size and character
CHEMISTRY SOLUTION
3. Escaping tendency of both components ‘A’ and ‘B’ is lowered showing lower vapour pressure than expected
ideally.
Characteristic of non-ideal solution showing +ve deviation
1. Do not obey Raoult’s law.
2. Hmix < 0. (Exothermic dissolution; heat is evolved.)
3. Vmix < 0. (Volume is decreased during dissoluton)
4. pA < PA0 XA; pB < pB0XB,  pA + pB < poAXA + pBoXB
Example
acetone + aniline; CH3OH + CH3COOH;
chlorofrom + diethyl ether, acetic acid + pyridine;
s
sse
chloroform + benzene H2O + HNO3;
water + HCl
la
Cl
CH 3
acetone + chloroform; Cl C H OC
yC
CH 3
Cl
Graphical representation of vapour of non-ideal solution showing +ve deviation
V.P.= min.
B.P. = max.
str
Vapour pressure
mi
P
P A+ B
P<
o XA
< PA
he
P
A
P A
>P
B o
X
B
-C
XA = 0 Mole fraction XA = 1
XB = 1 XB = 0
(iii) Azeotropes
R
The non-ideal solution showing large deviations from Raoult’s law can not be purified by distillation. A solution at
SI
certain composition which continues to boil at constant temperature without change in the composition of the
solution and its vapour is called an AZEOTROPE or constant boiling mixture. Azeotropes are of two types:
O
1. Azeotropes with Max. vapour pressure and Min. BP : When liquid in a solution do not have great chemical
affinity for each other (+ve deviation from ideality) their higher escape tendencies increase the vapour pressure
PT
much more than expected on the basis of Raoult’s law. In many cases, the deviations are so extreme as to lead to
a maximum in the curve. The point of maximum vapour pressure means that the bp at this composition will be
minimum and constant.
DI
Example of Minimum Boiling Azeotrope

Components Boiling point (K)
SU
A B Mass% of B A B Azeoterope
H 2O C2 H 5OH 95.57 373 351.3 351.10
H 2O C3 H 7 OH 71.69 373 370.0 350.72
CHCl3 C2 H 5OH 67.00 334 351.3 332.30
CHEMISTRY SOLUTION
2. Azeotropes with Min. vapour pressure and Max. bp : When liquids in solution form chemical bonds (–ve
deviation from ideality), their escape tendencies and hence the vapour pressure decreases than expected on the
basis of Raoult’s law. In many cases, the maximum in the temperature composition curve is obtained. The point of
minimum vapour pressure in the curve means that the bp of this composition will be max. and constant.
6. Colligative Propertygative Properties
The property of a solution which depends upon the fraction of solute particles and solvent particles and not upon
the chemical nature of solute is called a colligative property. Greater the no. of particles of solute in solution,
greater is the extent to which colligative property is affected.
Type of colligative properties
(i) Lowering of vapour pressure (ii) Elevation of Boiling point
s
(iii) Depression of Freezing point (iv) Osmotic Pressure
sse
Factors that Affect the Colligative Property: The no. of solute particles in solution. To be more accurate, the colligative
property depends upon the fraction of solute and solvent particles in solution.
(1) Nature of the solvent
la
(2) Independent of the nature of the solute
yC
(3) Extent of association and dissociation of solute particles in solution.
(i) Lowering of Vapour Pressure: Vapour pressure lowering of a solution has already been explained under Raoult’
Law. It was derived that the relative lowering of vapour pressure is given by the equation
PAo – PA
PAo
 XB 
nB
nA  nB str
mi
(ii) Elevation of Boiling Point: The boiling point of a liquid is the temperature at which its vapour pressure becomes
equal to the atmospheric pressure. When the atmospheric pressure is 1 atm, boiling point is called the normal
he
boiling point.
-C
1 atm
en
t
vapour pressure
olv
R
s
re
Pu ion
lut
SI
So
O
Tb0 Tb
PT
Temperture
Plot of variation of vapour pressure elevation of boiling point
DI
The vapour pressure of a liquid decreases when a non-volatile solute is dissolved in it. The decreased vapour-
pressure means that the solution would have to be heated to a higher temperature so that its vapour pressure
becomes equal to the atmospheric pressure. In other words, the boiling point of the solution Tb is higher than the
SU
boiling point of the pure solvent Tb0. The difference Tsb – Tb0 is called the boiling point elevation and denoted by
Tb.
Tb = Tb – Tb0 ......(1)
It is found that the elevation of boiling point is directly proportional to the number of moles of the solute in a given
amount of the solvent (m).
T  P T  m  Tb = Kb.m ......(2)
CHEMISTRY SOLUTION
where m is the molality of the solution and Kb is a constant for a given solvent known as boiling-point elevation
constant or molal boiling point elevation constant or ebullioscopic constant of solution.
Molal Elevation Constant or Ebullioscopic Constant: When molality of the solution is 1m, (1 mole of the solute is
dissolved in 1 kg of the solvent) the above equation reduces to
Tb  K b  1m  K b
This indicates that molal elevation constant of a liquid (Kb) is equal to elevation of boiling point when molality of
the solution is 1 m. the unit of Kb is Km–1. K (mol/kg)–1 = K kg mol–1.
Determination of Kb of solvent :
RTb2
Kb  .......(3)
s
1000L v
sse
where R is molar gas constant, Tb is the boiling point of the solvent on Kelvin scale and Lv the latent heat of
vaporization of solvent in calories per gram.
2  (373) 2
la
For water K b   0.515 K-kg/mol
1000  540
yC
Illustration 16. Estimate the boiling point of a solution of 25.0g of urea NH2CONH2 plus 25.0g of thiourea NH2CSNH2
in 500g of chloroform, CHCl3. The boiling point of pure chloroform is 61.2°C, Kb of chloroform = 3.63
Km–1.
Solution : Moles of urea =

Mass of urea

25.0g
Molecular mass of urea 60g / mol str
 0.42mol
mi
25.0
Moles of thiourea =  0.33mol  Total moles of solute = 0.42 + 0.33 = 075
he
76 g/mol
Moles of solute 0.75mol

Molality, m = Mass of solvent in kg  (500g /1000g)kg  1.50m
-C
Tb = Tb – Tb0 = Kbm = 3.63 × 1.50 = 5.44K = 5.445°C

Tb = 5.445°C + Tb0 = 5.445°C + 61.2°C = 66.645°C
R
Example : At 310 K, the vapour pressure of an ideal solution containing 2 moles of A and 3 moles fo B is 550 mm
SI
of Hg. At the same temperature, if one mole of B is added to this solution, the vapour pressure of
solution increases by 10 mm of Hg. Calculate the V.P. of A and B in their pure state.
O
Solution : According to Raoult’s law PM  PA  X A  PB  X B

Given that PM = 550 mm, and nA and nB are 2 and 3 moles respectively
PT
 2    3 
550  PA     PB   
 23  23
DI
or, 2PAo  3PBo  2750 (initially) ......... (1)

SU
Now or adding 1 mole of B, and using Raoult’s law again
 2    4  ( P = 560 mm, n = 2 mole, n = 4 mole) ......... (2)

560  PA     PB    M A B
24 24
or, 2PA  4PB  3360
Solving equations (1) and (2) ; PA = 460 mm ; PB = 610 mm.
CHEMISTRY SOLUTION
Example : At 25ºC, vapour pressure of pure benzene is 639.7 mm in which a solute is dissolved in benzene at the
same temperature, vapour pressure of resulting solution is 631.9 mm. Find out molality of soultion.
Pº PS w  M w  M  1000
Solution :  
PS m  W m  W  1000
w  1000 Pº PS 1000

 Molality (m)    (Mbenzene = 78)
m W PS M
639.7  631.9 1000

  = 0.15 mol / kg (solvent)
631.9 78
s
Example : Vapour pressures of ethanol and methanol are 44.5 mm Hg and 88.7 mm Hg respectively. At the same
sse
temperature, 60 gram of ethanol is mixed with 40 gram of methanol forming an ideal solution. Calculate
total vapour pressure of the solution and mole fraction of methanol in solution vapour.
Solution : Since, both are component of solution are liquids, thus,
la
wA wB
yC
mA mB
PM  PA  PB
wA wB wA wB
 
mA mB mA mB

Given that, PA(alcohol) 
 44.5 mm , PA(methanol) str
 88.37 mm , wA = 60 g, wB = 40 g
mi
Mol. mass of methanol = 32.
he
60 40
PM  44.5  46  88.7  32  66.13 m
-C
60 40 60 40
 
46 32 46 32

 OH  PCH
Now, PCH  XCH3OH ......... (i) (From Raoult’s law)
3OH
R
 OH  PM  X CH OH ......... (ii) (From Dalton’s law of partial pressure)

SI
or, PCH 3 3
X CH3OH and X CH3OH are mole fractions of CH OH in solution and vapour phase respectively..
3
O
40
PT
 88.7  32  66.13 × mole fraction of CH3OH is in vapour phase.

60 40

DI
40 32
Mole fraction of CH3OH in vapour phase = 0.6563.
SU
Example : Vapour pressure of an aqueous solution of glucose at 373 K is 750 mm Hg. Calculate the molality of
solution and mole fraction of glucose.
Pº PS w  M w  M  1000
Solution : Using the relation,  
PS m  W m  W  1000
Pº = 760 mm (V.P. of pure water at 373 K), M H 2O  18
CHEMISTRY SOLUTION
Pº  PS 1000 760  750 1000

 Molality (m)     = 0.7407 mol/ kg (solvent)
PS M H 2O 750 18
1000
moles of glucose = 0.7407, moles of water   55.6
18
0.7407
 Mole fraction of glucose   0.013
0.7407  55.6
Example : At a given temperature, vapour pressure of pure benzene is 200 mm Hg. At the same temperture, a
solution contains 2 g of a non-volatile solute in 78 g of benzene and vapour pressure of solution is 195
s
mm Hg. Calculate the molecular mass of solute.
sse
Pº PS w  M
Solution : 
PS m W
la
Pº = 200 mm, PS = 195 mm, w = 2 g, M = 78, W = 78 g
200  195 2  78
yC
   m  78
195 m  78
Example : An aqueous of glucose is prepared at 303 K by dissolving 10 g glucose in 90 g water. If vapour pressure
Pº PS w  M

str
of water is 32.8 mm Hg, what is the vapour pressure of solution ?
mi
Solution : PS m W
32.8  PS 10  18
he
 
PS 180  90
-C
 PS = 32.44 mm Hg.
Example : On dissolving 6.0 gram glucose in 50 g water, 0.34ºC elevation is boiling point was recorded. Calculate
molal elevation constant of water.
R
1000Kb  w
Solution : Tb 
m W
SI
Given, Tb = 0.34ºC, w = 6 g, W = 50 g, m = 180

1000  K b  6
O
 0.34 
50  180
PT
 K b  0.51 molality–1
Example : When 10.8 g glucose is dissolved in 240 g water, its boiling point elevates by 0.13ºC. Calculate molar
DI
elevation constant of water.

1000K b  w
SU
m W
Given, Tb = 0.13ºC = 0.13 K, w = 10.8 g, W = 240 g, m = 180
1000  Kb  10.8
 0.13 
180  240
 K b  5.2 K/mol/100g solvent
CHEMISTRY SOLUTION
Example : An aqueous solution of glucose boils at 100.01ºC. Molal elevation constant of water is 0.5 K molality–1.
How many molecules of glucose are present in 100 g water ?
1000Kb  w 1000  n
Solution : Since, Tb  
m W W
Given, Tb = 100.01 – 100 = 0.01 K, W = 100 g, Kb = 0.5 K molality–1
1000  0.5  n
 0.041   n  2  103 mole
1000
Number of molecules in 2 × 10–3 mole of glucose = 2 × 10–3 × 6.023 × 1023 = 1.2 × 1021 molecules
s
Example : A solution of 2.5 g non-volatile solute in 100 g benzene boils at a higher temperature of 0.42ºC than
sse
boiling point of pure benzene. Calculate molecular mass of the solute. Molal elevation constant of
benzene is 2.67.
la
1000K b  w
m W
yC
Given Tb = 0.42ºC, w = 2.5 g, W = 100 g, Kb = 2.67 molality
1000  2.67  2.5

0.42   m  158.93
Example :
100  m
str
When 2.56 g of an element is dissolved in 100 gram of carbon disulphide, boiling point is elevated by
mi
0.24ºC. Find out atomicity of the element. Boiling point of CS2 is 45ºC and its heat of vaporization is 84
calorie/g. (Atomic mass of the element = 31.98)
he
1000K b  w
Solution : Since, Tb  .......... (i)
m W
-C
RT 2
Kb  .......... (ii)
1000  l
R
Given that, boiling point of CS2 = 273 + 46 = 319 K, l = 84 cal/g

SI
2  319  319
From equation (ii), K b   2.42 K molality–1
1000  84
O
w = 256 g, W = 100 g, Tb = 0.24 K, Kb = 2.42 K molality–1

PT
1000  2.42  2.56

From equation (i), 0.24   m  258.13
100  m
DI
Since, atomic mass = 31.98

SU
and molecular mass = 258.13
258.13
 Atomicity (n)  8
31.98
Example : Pure benzene boiled at 80ºC. The boiling point of a solution containing 1 g of substance dissolved in
83.4 g of benzene is 80.175ºC. If latent heat of vaporization of benzene is 90 cal per g, calculate the
molecular mass of solute.
CHEMISTRY SOLUTION
Solution : Boiling point of C6H6 = 80 + 273 = 353 K ; Latent heat (lv) = 90 cal/g
Tb = 80.175 – 80 = 0.175 K, w = 1 g, W = 83.4 g
RT 2
Kb  (l is latent heat of vaporization / g in the unit of R)
1000 lv v
2  353  353
K b   2.769 mol–1 kg
1000  90
Kb  1000  w
Tb 
m W
s
2.769  1000  1
Using the data given 0.175   m  189.72
sse
m  83.4
(iii) Depression in Freezing Point: The freezing point of a liquid is the temperature at which it begins to freeze and
la
the crystallized solid and liquid are in equilibrium. At freezing point, the vapour pressure of the solid is equal to the
vapour pressure of the liquid. When a dilute solution is cooled to freezing point, it is assumed that crystals of pure
yC
solvent always separate out first.
Solid solvent nt
lve
so
str so
lut
ion
vapour pressure
mi
he
T T0
Temperature f f
-C
Plot of variation of vapour pressure of a solution

with temperature and depression in freezing point.
The vapour pressure of a liquid decreases when a non-volatile solute is dissolved in it. Therefore, a solid-
liquid equilibrium exists only at a temperature lower than the freezing point of the pure solvent. In other words, for
R
a solid to have the same vapour pressure as that of the solution, the freezing point should lower down. If Tf0 is the
freezing point of the pure solvent and Tf that of the solution, the difference Tf0 – Tf is called the freezing point
SI
depression and denoted by Ts
Ts = Tf0 – Tf  TS  P  m

O
.......(1)
It is found that the depression in freezing point is directly proportional to the number of moles of the solute in a
PT
solute given amount of the solvent.

Tf = Kfm .......(2)
DI
where m is the molality of the solution and Kf is a constant for a given solvent known as molal depression constant
or cryoscopic constant.
SU
Molal Depression Constant or Cryoscopic Constant: When molality of the solution is 1m,
(1 mole of the solute is dissolved in 1 kg of the solvent) the above equation reduces to
Tf = Kf × 1m = Kf
This indicates that molal depression constant of a liquid (Kf) is equal to depression of freezing point when molality
of the solution is 1 m. the unit of Kf is Km–1. K (mol/kg)–1 = K kg mol–1.
CHEMISTRY SOLUTION
Determination of Kf of solvent
Kf is characteristic of a particular solvent and can be calculated from the thermodynamical relationship.
RTf2
Kf  ......(3)
1000Lf
where Tf is the freezing point of solvent in absolute scale and Lf the latent heat of fusion in calories per gram of
the solvent. For water,
0.002  (273) 2
Kf   1.86 K-kg/mole
80
s
Illustration 17. What is the percent by mass of iodine needed to reduce the freezing point of benzene to 3.5°C? The
sse
freezing point and cryoscopic constant of pure benzene are 5.5°C and 5.12 K/m respectively.
Solution : Tf = Tf0 – Tf = Kf . m
la
5.5°C – 3.5°C = 5.12 × m
yC
2
m  0.39m
molal
5.12
 Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
str
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
 1000g + 99.06g solution contains 99.06g I2
mi
99.06g  100
100g solution contains  9.01%
he
1099.06g
Example : On dissolving 13.6 g of a substance in 20 g water, freezing point is depressed by 3.7ºC. Calculate the
-C
molecular mass of solute. Molal depression contstant for water is 1.863 K molality–1.
1000K f  w
Solution : Tf 
mW
R
Given that, w = 13.6, W = 20 g, Tf = 3.7ºC = 3.7 K

SI
K f = 1.863 molality–1
1000  1.863  13.6

O
 3.7   m  342.4
20  m
PT
Example : On dissolving 1.822 g of a organic compound (mol. mass = 155) in 100 g benzene, value of depression
of freezing point is 0.60ºC. Calculate the molal depression constant of benzene.
DI
1000K f  w
Solution : Tf 
m W
SU
Tf = 0.60ºC, w = 1.822 g, W = 100 g, m = 155
1000  Kf  1.822

0.6   K f  5.1 K molality–1.
155  100
Example : When 1.9 g of a substance is dissolved in 128 g water, freezing point of solution is depressed by
–0.35ºC. Calculate molecular mass of the substance. K f of water is 18.6 K mol–1 100 g water.
CHEMISTRY SOLUTION
Solution : Since, molar depression constant, Kf = 18.6
1000K f  w
Tf 
m W
Given that, w = 1.9 g, W = 128 g, Tf = 0 – (–0.35) = 0.35 K
1000  18.6  1.9

0.35   m  78.88
m  128
Example : On dissolving 0.36 g of substance in 25.5 g benzene, freezing point of benzene depresses by 0.42ºC.
Compute the molecular mass of the substance. Molal depression constant of benzene is 5.15 K molality–1.
s
1000K f  w
Tf 
sse
Solution :
mW
Given that, w = 0.36 g, W = 25.5 g, Tf = 0.42ºC = 0.42 K
la
Kf = 5.15 K molality–1
1000  5.15  0.36
yC
0.42   m  173.1
m  25.5
Example : Freezing point of benzene is 5.40ºC. On dissolving a non-volatile solute in benzene, freezing point of
is 5.1 K molality–1.
Since, Tf = Kf × molality
str
benzene is depressed by 0.80ºC. Compute the molality of solution. Molal depression constant of benzene
mi
Solution :
Given, Tf = 0.80 K, Kf =5.1 K molality–1
he
0.80 = 5.1 × molality  Molality = 0.157.

Example : What is osmotic pressure of the aqueous solution of the given solute at 27ºC if depression in freezing
-C
point is 0.93ºC ? Molal depression constant of water is 1.86 K mol–1 kg. Assume molality as molarity.
Solution : Tf = Kf × molality,  = molarity × ST
Tf K f

R
or, ( given that molality = molarity)

 ST
SI
0.93 1.86
    12.315 atm
 0.0821 300
O
Example : Calculate :
PT
(a) Kb for water if its latent heat vaporisation is 540 cal/g.

(b) Kf for water if its latent heat of fusion is 80 cal/g.
DI
2   373
2
RT 2
Solution : (a) Kb  
1000 lv 1000  540
SU
( R = 2 cal K–1mol–1, T = 373 K, lv = latent heat of vaporisation)

= 0.515 K mol–1 kg
2   373
2
RT 2
(b) Kf    1.863 K mol kg
1000 lf 1000  80
CHEMISTRY SOLUTION

Q.1 A solution containing 0.52 g of C10H8 in CCl4 produced an elevation in boiling point by 0.402ºC. On the other hand
a solution of 0.62 g of an unknown solute dissolved in same amount of CCl4 produced an elevation by 0.65ºC.
Molecular weight of solute is -
(A) 85.53 (B) 181.51 (C) 94.38 (D) 160.62
Q.2 0.65 g naphthalene (C10H8) was dissolved in 100 g methyl acetate. Elevation of b. pt of methyl acetate solution
was 0.103ºC. If b. pt. of pure methyl acetate is 57ºC, its molar heat of vaporisation will be -
(A) 8.96 kcal mol–1 (B) 7.946 kcal mol–1 (C) 6.24 kcal mol–1 (D) 15.65 kcal mol–1
Q.3 When 174.5 mg of octa atomic sulphur is added to 78 g of bromine, the boiling point of bromine is -
[Given Kb for Br2 is 5.2 K mol–1 kg and b. pt. of Br2 is 332.15 K ]
s
sse
(A) 415.23 K (B) 330 K (C) 220.92 K (D) 332.19 K
Q.4 4.00 g of substance A, dissolved in 100 g H2O depressed the f. pt. of water by 0.1ºC. While 4 g of another
substance B, depressed the f. pt. by 0.2 ºC. What is the relation between molecular weights of the two substance -
la
(A) MA = 4MB (B) MA = MB (C) MA = 0.5MB (D) MA = 2MB
yC
Q.5 An aqueous solution containing 5% by weight of urea and 10% by weight of glucose. Freezing point of solution is
[Kf for H2O is 1.86 K mol–1 kg]
(A) 3.04º C (B) –3.04º C (C) –5.96º C (D) 5.96º C
Q.6
str
The amount of ice that will separate out from a solution containing 25 g of ethylene glycol in 100 g of water and
is cooled to –10ºC, will be - [ Given : Kf for H2O = 1.86 K mol–1 kg ]
mi
(A) 50.0 g (B) 25.0 g (C) 12.5 gm (D) 30.0 gm
Q.7 It has been found that minimum temperature recorded in a hill station is –10ºC. The amount of glycerine to be added
he
to 40 dm3 water used in car radiator, so that it does not freeze, is - [ Hfusion = 6.01 kJ mol–1]
(A) 39.78 kg (B) 22.45 kg (C) 19.89 kg (D) 42.66 kg
-C
Q.8 In winter, the normal temperature in Kullu valley was found to be –11ºC. Is a 28% (by mass) aqueous solution of
ethylene glycol suitable for a car radiator ? Kf for water = 1.86 K kg mol–1.
(A) Yes (B) No (C) can’t predict
R
Q.9 The temperature at which ice will begin to separate from a mixture of 20 mass percent of glycol (C 2H6O2) in
water, is - [ Kf(water) = 1.86 K kg mol–1 ]
SI
(A) 280.5 K (B) 265.5 K (C) 276.5 K (D) 269.5 K

Q.10 The amount of urea to be dissolved in 500 ml of water (Kf = 18.6 K mol-1 100 g solvent) to produce a depression
O
of 0.186ºC in freezing point is -

PT
(A) 0.3 gm (B) 3 gm (C) 6 gm (D) 9 gm

Q.11 The molal boiling point constant of water is 0.53ºC. When 2 mole of glucose are dissolved in 4000 gm of water, the
solution will boil at -
DI
(A) 100.53ºC (B) 101.06ºC (C) 100.265ºC (D) 99.47ºC

Q.12 The boiling point of an aqueous solution of a non-volatile solute is 100.15ºC. What is the freezing point of an
SU
aqueous solution obtained by diluting the above solution with an equal volume of water ?
[ Kb and Kf for water are 0.512 and 1.86 K molality-1 ]
(A) –0.544ºC (B) –0.512ºC (C) –0.272ºC (D) –1.86ºC
Q.13 The freezing point of a solution prepared from 1.25 gm of non-electrolyte and 20 gm of water is 271.9 K. If molar
depression constant is 1.86 K molality-1. Then molar mass of the solute will be -
(A) 105.68 (B) 106.7 (C) 115.3 (D) 93.9
CHEMISTRY SOLUTION
Q.14 Elevation in b. p of a solution of non-electrolyte in CCl4 is 0.60. What is depression in f. p. for the same solution ?
Kf (CCl4) = 30.00 kg mol–1 K ; Kb (CCl4) = 5.02 kg mol–1 K.
(A) 0º (B) 5.39º (C) 3.59º (D) 2.49º
Q.15 A solution of a non-volatile solute in water has a boiling point of 375. 3 K. The vapour pressure of water above this
solution at 338 K is -
[Given p0 (water) = 0.2467 atm at 338 K and Kb for water =0.52 K kg mol-1]
(A) 0.18 atm (B) 0.23 atm (C) 0.34 atm (D) 0.42 atm
Q.16 Elevation in boiling point of an aqueous urea solution is 0.52º. (Kb = 0.52K kg mol-1). Hence mole fraction of urea
in this solution is -
(A) 0.982 (B) 0.0567 (C) 0.943 (D) 0.018
s
Q.17 Density of 1 M solution of a non-electrolyte C6H12O6 is 1.18 g/mL. If Kf (H2O) is 1.86 K mol-1 kg, solution
sse
freezes at -
(A) 1.58ºC (B) –1.86ºC (C) –3.16ºC (D) 1.86ºC
la
Q.18 When a solution containing w g of urea in 1 kg of water is cooled to -.372ºC, 200 g of ice is separated. If Kf for
water is 1.86 K kg mol-1, w is -
yC
(A) 4.8 g (B) 12.0 g (C) 9.6 g (D) 6.0 g
Q.19 Relative decrease in V. P. of an aqueous glucose dilute solution is found to be 0.018. Hence, elevation in boiling
point is : (it is given 1 molal aq. urea solution boils at 100.54ºC at 1 atm. pressure)
(A) 0.018º (B) 0.18º (C) 0.54º
str (D) 0.03º
Q.20 Glucose is added to 1 litre water to such an extent that Tf/Kf becomes equal to 1/1000, the weight of glucose
added is
mi
(A) 180 gm (B) 18 gm (C) 1.8 gm (D) 0.18 gm
he
(iv) Osmosis:
Spontaneous flow of solvent molecules through a semipermeable membrane from a pure solvent to the solution (or
from a dilute solution to a concentrated solution) is termed as osmosis.
-C
Osmotic Semi
pressure permiable
membrane
Piston
R
SI
Pure liquid
Solution
O
Solvent
PT
Osmotic Pressure (): The hydrostatic pressure built up on the solution which just stops osmosis. Alternatively,
DI
it may be defined as the pressure which must be applied to the concentrated solution in order to stop osmosis.
For dilute solutions  = CRT = hg (hydrostatic pressure)
SU
Where C is the total molar concentration of all the free species present in the solution, h is the height developed by
the column of the concentrated solution and  is the density of the solution in the column. On the basis of osmotic
pressure, the solutions can be classified in three classes.
(a) Hypertonic solution:When two solutions are being compared, then the solution with higher osmotic pressure is
termed as hypertonic.
(b) Hypotonic solution:When two solutions are being compared, then the solution with lower osmotic pressure is
termed as hypertonic.
CHEMISTRY SOLUTION
(c) Isotonic solutions: Two solutions having same osmotic pressures at same temperature. (This implies C1 = C2).
Note:-Osmotic pressures can be determined quite accurately, hence it is used in the determination molecular
weights of large proteins and similar substances.
Reverse Osmosis: If a pressure greater than the osmotic pressure is applied on the concentrated solution, the
solvent starts to flow from concentrated solution to dilute solution (or pure solvent). This is reverse osmosis. One
of its chief uses is desalination of sea water to get pure drinking water.
Illustration 18. Calculate osmotic pressure of 5% solution of cane sugar (sucrose) at 15ºC.
Solution : m = mol. mass of sucrose (C12H22O11) = 342
w = 5g, V = – 100 mL = 0.1 litre
S = 0.082, T = (15 + 273) = 288 K
s
w 5 1
sse
Applying the equation PV = ST, P = × = 0.082 × 288 = 3.453]
m 342 0.1
Illustration 19. Consider a vertical tube of corss-sectional area of 1cm2. The bottom of the tube is closed with a
semipermeable membrane and 1 g glucose is placed in the tube. The closed end of the tube is immersed
la
in pure water. What will be the height of the liquid level in the tube at equilibrium? The density of
solution may be taken as 1g/cm2. What is the osmotic pressure at equilibrium at 25ºC? Assume negligible
yC
depth of immersion of tube.
Solution: Let height in tube = h cm
V = (h × 1) cm3  Cross-sectional area = 1cm2
V = nRT
 h 1 
str
mi
1
×   = × 0.0821 × 298
 1000  180
he
134.92
= atm
h
-C
=h×d×g
134.92 h 1 9.8
= × 1 atm = 101.325 KPa
h 100 101.325
R
h = 375 cm = 3.75 m
 = h × d × g = 3.75 ×1 × 9.8
SI
= 36.7 KPa
[Ans. 3.75 m; 36.7 KPa]
llustration 20. A 5% soltuion of cane sugar is isotonic with 0.877% soltuion of urea. Calculate the molecular mass of
O
urea if molecular mass of cansugar is 342.

PT
Solution : Let the molecular mass of urea be m2

w1 5
Molarity of sugar = =
m1  V1 342  0.1
DI
w2 0.877
Molarity of urea = =
m 2  V2 m 2  0.1
SU
For isotonic solutions,

w1 w2 5 0.877
=  =
m1  V1 m 2  V2 342  0.1 m 2  0.1
0.877  342
m2 = = 59.987
5
CHEMISTRY SOLUTION
Example : At 27ºC, 36 g of glucose per litre has an O.P. of 4.92 atm. If the osmitc pressure of solution is 1.5 atm
at the same temperature, what should be its concentration ?
Solution : V = nST
Using the given data 1 = 4.92 atm, 2 = 1.5 atm
36  w 
C1   C   C =?
180  1  mV  2
1V1 = n1ST1
2V2 = n2ST2
1 n1 V2 C1
  
s
(If T1 = T2)
2 V1 n 2 C2
sse
4.92 36
   C2  0.061 mol/L
1.5 180  C2
la
Example : Calculate the osmotic pressure at 17ºC of an aqueous solution containing 1.75 g of sucrose per 150 mL
yC
solution.
w
Solution : According to van’t Hoff equation of solution V  nST  ST
Using the date, w = 1.75 g ; m = 342, V 

150str
L , T = 290 K
m
mi
1000
150 1.75
    0.0821 290    0.812 atm
he
1000 342
Example : Calculate O.P. of a solution obtained by mixing 100 mL of 3.4% solution (mass/vol.) of urea (m. mass
-C
60) and 100 mL of 1.6% solution (mass/vol.) of cane-sugar (m. mass 342) at 20ºC.
3.4 1.6
Solution : Total moles in solution  (urea)  (cane-sugar)
60 342
R
Total volume of solution = 200 mL (100 mL each)

SI
 3.4 1.6 
V     ST
 60 342 
O
200  3.4 1.6 

     0.0821 293  7.38 atm
PT
100  60 342 
Example : At 300 K, two solutions of glucose in water of concentration 0.01 M and 0.001j M separated by
DI
semipermeable membrane with respect to water. On which solution, the pressure must be applied to
prevent osmosis ? Calculate magnitude of this applied pressure.
SU
n1
Solution : For 0.01 M solution,  0.01 , T = 300 K
V1
1V1 = n1S1T1
1 = 0.01 × 0.0821 × 300 = 0.2463 atm
CHEMISTRY SOLUTION
n2
For 0.001 M solution,  0.001 , T = 300 K
V2
2V2 = n2ST2
2 = 0.001 × 0.0821 × 300 = 0.02463 atm
Q.1 A solution containing 4 gm of a non-volatile organic solute per 100 ml was found to have an osmotic pressure
equal to 500 cm of mercury at 27ºC. The molecular weight of solute is -
(A) 14.97 (B) 29.44 (C) 149.7 (D) 137.2
Q.2 The osmotic pressure of decimolar solution of glucose at 30ºC is -
s
sse
Q.3 A solution containing 8.6 gm urea in one litre was found to be isotonic with a 5% (wt/vol) solution of an organic
volatile solute. The molecular weight of solute is -
la
(A) 348.9 (B) 34.89 (C) 861.2 (D) 86.12
Q.4 The osmotic pressure of a solution containing 100 ml of 3.4% solution (w/v) of urea (m. wt. 60) and 50 ml of 1.6%
yC
solution (w/v) of cane-sugar (m. wt 342) at 27ºC is -
Q.5 Two solutions each in 100 mL having 4 g glucose and 10 g sucrose respectively. How much urea should be added
to one of them in order to make them isotonic ?
(A) 0.4218 g urea in glucose solution str
(B) 0.77 g urea in glucose solution
mi
(C) 0.72 g urea in sucrose solution (D) 0.421 g urea in sucrose solution
Q.6 5 g of a polymer of molecular weight 50kg mol is dissolved in 1 dm3 solution. If the density of this solution is
–1
0.96 kg dm–3 at 300 K, the height of solution that will represent this pressure is -
he
(A) 28.13 mm (B) 20.85 mm (C) 26.52 mm (D) 24.94 mm

-C
Q.7 100 mL aqueous solution of glucose with osmotic pressure 1.2 atm at 25ºC is mixed with 300 mL aqueous solution
of urea at 2.4 atm at 25ºC. Osmotic pressure of the mixture is -
Q.8 10 g of solute A and 20 g of solute B are present in 500 mL of solution. The solution has the same osmotic pressure
R
as 6.67 g of A and 30 g of B present in same volume of solution at same temperature. The ratio of molar masses of
SI
solute A and B will be -

(A) 0.25 (B) 0.66 (C) 0.33 (D) 0.75
Q.9 At 10ºC, the osmotic pressure of urea solution is 500 mm. The solution is diluted and the temperature is raised to
O
25ºC, when the osmotic pressure is found to be 105.3 mm. Find out the extent of dilution
PT
(A) 5 (B) 2.5 (C) 1.25 (D) 6.5

Q.10 The relation ship between osmotic pressure at 273 K, when 10 gm glucose (P1), 10 gm urea (P2) and 10 gm
sucrose (P3) are dissolved in 250 ml of water is
DI
(A) P1 > P2 > P3 (B) P3 > P1 > P2 (C) P2 > P1 > P3 (D) P2 > P3 > P1
Q.11 What osmotic pressure would the 1.25 molal sucrose solution exhibit at 25ºC ? The density of this solution is 1.34
SU
g/mL.
Q.12 The osmotic pressure of blood is 8.21 atm at 37ºC. How much glucose is used per lit for an intravenous injection
that is to isotonic with blood ?
(A) 180 gm (B) 342 gm (C) 58.06 gm (D) 55.55 gm
CHEMISTRY SOLUTION
Q.13 Osmotic pressure of insulin solution at 298 K is found to be 0.0072 atm. Hence, height of water column due to this
pressure is [given d (Hg) = 13.6 g/mL] –
(A) 0.760 mm (B) 70.28 mm (C) 74 mm (D) 760 mm
Q.14 At certain temperature, the osmotic pressure of an aqueous solution of urea was found to be 405 mm. How many
times the solution should be diluted in order to exhibit the osmotic pressure of 81 mm at the same temperature ?
(A) 2 times (B) 4 times (C) 8 times (D) 5 times
Q.15 If depression in freezing point is 0.93ºC then the osmotic pressure of aqueous solution of the given non-electrolyte
at 27ºC is -
[Given : Kf for water = 1.86 K kg mol-1 & molality is equal to molarity]
s
7. ABNORMAL MOLECULAR MASSESMolecular Masses
sse
Vapour pressure lowering, boiling point elevation, freezing point depression and osmotic pressure are colligative
properties which depend upon the fraction of solute and solvent particles in solution and not upon the chemical
nature of the solute. If solute molecules dissociates in solution, there are more particles in solution and therefore,
la
lowering of vapour pressure shows an increased effect.
yC
NaCl(s) Na +(aq) + Cl –(aq)
If the solute molecules associates in solution, there are less particles in solution, and therefore lowering of vapour
pressure shows a decreased effect.
nAB (AB) n
2C 6H5COOH (C6H 5COOH) 2 str
mi
The molecular mass of a solute is inversely proportional to its molality. If colligative molality is 2 m, the
calculated molecular mass is one-half of the actual molecular mass of the solute. If colligative molality is 3 m, the
he
calculated molecular mass is one third of the actual molecular mass of the solute. The molecular mass of benzoic
acid is 122 g/mol. But the molecular mass of benzoic acid dissolved in benzene is found to be 244 g/mol by using
a colligative property. Benzoic acid associates to form a dimer and therefore its colligative molality is one-half of
-C
the molality of benzoic acid. As molecular mass of a solute is inversely proportional to molality, the molecular
mass of benzoic acid determined using a colligative property is double the actual molecular mass of benzoic acid.
We can summarize the results as:
1. The extent of dissociation and colligative property. A solute dissociates completely or partially in solution
R
makes available more particles than would otherwise be present in solution and therefore, a colligative property
SI
shows an increased effect. For example, molecular masses obtained of strong acids, bases and salts are much
less than their normal values. As an example, one particle of potassium chloride on dissociation in water gives two
particles, K+ and Cl– and therefore, the molecular mass obtained by a colligative property is half of its normal
O
molecular mass.
K  Cl(s)
  
PT
 nH 2 O 
 K (aq)  Cl(aq)
1 mol 1mol 1 mol
2. The extent of association and colligative property: A solute that associates in solution provides less particles
DI
that would otherwise be present in solution and therefore, the colligative property shows the decreased effect. For
example, benzoic acid in benzene is found to have molecular mass which is justtwice its normalmolecular mass.
SU
It is found that compounds which are capable of forming hydrogen bonds, e.g., phenols, carboxylic aids, alcohols:
because of association show decreased effect of colligative property.
O H O
H5C 6 C 6H5
O H O
A dimer of benzoic acid
CHEMISTRY SOLUTION
8. Van’t Hoff, factor

In 1886, Van’t Hoff, Jacobus Henricus (Dutch chemist, 1859,-1911) introduced a factor ‘i’ known as Van’t Hoff
factor to express the extent to association or dissociation of a solute in solution. It can be calculated as:
number of solute particles actually present in solution
i=
number of solute particles dissolved
Observed colligative property observed molality normal molecular weight of solute
= = =
normal colligative property normal molality observed molecular weight of solute
The Van’t Hoff factor for a solute can be calculated by the following modified equations:
PA0  PA
s
(i) = i XB (ii) Tf = iKfm (iii) Tb = iKbm (iv)  = iCRT
sse
PA0
where C is molarity of the solution.
Note: For non-electrolytes; i = 1
la
For electrolytes; i > 1 ( If solute particles undergo Dissociation in the solution)
yC
i < 1 ( If solute particles undergo Association in the solution)
Application of Van’t Hoff Factor:
i) Calculation of Degree of Dissociation of solute particles:
No. of moles dissolved 1 mol

An
0
nA
str
mi
No. of moles after dissociation 1– n
Total number of moles present in solution = (1 – ) + n
he
Moles of solute actually present in solution

Van’t Hoff factor, i 
Moles of solute dissolved
-C
(1  )  n i 1
=  1  (n  1) or  
1 n 1
R
ii) Calculation of Degree of Association of solute particles: Let n moles of the solute, A, associate to form
(A)n. If  is the degree of association.
SI
nA An
No. of moles dissolved 1 mol 0
O
No. of moles after dissociation 1– /n

Total number of moles present in solution = (1 – ) + /n
PT
  1  i 1 n
i  1   1    Hence    (i  1) 
DI
  n  1 1 n
1
n
SU
Number of particles after association i  1       1 i

i ,   or  
Number of particles beforeassociation n 1
1  
n
Illustration 21. A solution is prepared by dissolving 26.3g of CdSO4 in 1000g water. The depression in freezing point of
solution was found to be 0.284K. Calculate the Van’t Hoff factor. The cryoscopic constant of water is
1.86K kg solvent mol–1- solute.
CHEMISTRY SOLUTION
Solution : Molecular mass CdSO4 = 112.4 +32 + 4 × 16 = 208.4 g/mol

Mass CdSO 4
Molality CdSO4 =
Molecular mass CdSO 4  Mass solvent in kg
26.3g
= = 0.216m
 1000 
(208.4g / mol)   kg 
 1000 
Tf 0.284K
Tf = iKfm or i  
K f m 1.86K / m  0.126m = 1.21
s
sse
Illustration 22. Three particles of a solute, A, associate in benzene to form species A3. Calculate the freezing point of
0.25 molal solution. The degree of association of solute A is found to be 0.80. the freezing point of
benzene and its cryoscopic constant are 5.5°C and 5.12 Km–1 respectively.
la
Solution: 3A  A3
No. of moles dissolved 3 0
yC
No. of moles after dissociation m(1–) m/3
Total moles present after dissociation
    2   3  2  0.8 
= m(1   )  m
3
 m 1      m 1 
 3  3  str
 = 0.25m 
 3  = 0.177m

mi
Tf = Kfm or Tf0 – Tf = 5.12 Km–1 × 0.117 m = 0.6
Tf = Tf0 – 0.6°C = 5.5°C – 0.6°C = 4.9°C
he
Illustration 23. A 5% solution of anhydrous CaCl2 at 00C developed 15 atm. Osmotic pressure. What is the degree of
dissociation of CaCl2.
-C
100  111
Solution : 5 g. of CaCl2 are present in 100 mL, so 111 g (MW of CaCl2) will be present in  2.22 litre
5  1000
0.082  273 22.47
R
Now V = ST {  n = 1} or     10.09 atm

2.22 2.22
SI
observed colligative property 15

We know that Van't Hoff factor i  =
Normalcolligative property 10.09
O
15
1
i 1
PT
10.09 4.91
and   or    0.2433 or 24.33%
n 1 3 1 10.09  2
Example : A 0.001 molal solution of a complex represented at Pt(NH3)4Cl4 in water had freezing point depression
DI
of 0.0054ºC. Given Kf for H2O = 1.86 K molality–1. Assuming 100% ionisation of the complex, write
the ionisation nature and formula of complex.
SU
Solution : Let n Cl-atoms are attached as ligand, then formula of complex and its ionisation is
+
[Pt(NH3)4Cln]Cl4 – n  [Pt(NH3)4Cln](4 – n) + (4 – n)Cl–
1 0 0
0 1 4–n
Thus number of particles after dissociation = 4 – n + 1 = 5 – n
So, van’t Hoff factor (i) = 5 – n
CHEMISTRY SOLUTION
Now, Tf  K f × molality × van’t Hoff factor (i)

0.0054 = 1.86 × 0.001 × (5 – n) n = 2.1  2 (integer value)
Thus complex and its ionisation is : [Pt(NH3)4Cl2]Cl2  [Pt(NH3)4Cl2]2+ + 2Cl–
Example : One mole of (C6H5)3C dissolved in 1000 g of 100% sulphuric acid lower the reezing point of sulphuric
acid twice as one mole of CH3OH shows in 1000 g of 100% sulphuric acid. Comment on it assuming
that CH3OH is neither dissociated nor associated in sulphuric acid.
CH3OH w
Solution : For the solution , given that T1 = Tb ; W = 100 g, n  1 
H 2SO4 m
1000  K f  w 1000  K f  1
Tb    Kf
s
Wm 1000
sse
 C6 H5 3 COH
For the solution
H 2SO 4
la
T2 = 2 × Tb ; W = 1000 g, n = 1
 w = 260 g
yC
1000  K f  260
2Tb   m  130  Tb  K f 
1000  m
 m C H COH  130 , thus it is dissociated in H SO
6 5
(C6H5)3COH  (C6H5)3C+ + OH–

2 4
str
mi
at t = 0 1 0 0
at eqm. (1 – ) 
he
m th
But = 1 –  +  +  = 1 +  (van’t Hoff factor)
-C
m exp
260
 = 1 +  = 1 i.e., 100% dissociation.
130
R
w
Example : Caltulate the osmotic pressure of 20%   ahnydrous Ca(NO3)2 solution at 0ºC assuming 100%
SI
V
ionisation.
Solution : Ca(NO3)2 dissociates as follows
O
Ca(NO3)2 Ca2+ + 2NO3

PT
at t = 0 1 0 0
After dissociation (1 – )  2
DI
Given that, w = 20g, V = 100 mL, T = 273 K, m = 164
 S  T  20  1000  0.0821 273  27.33 atm

w
SU
N 
mV 164  100
exp.
But, = TOtal number of moles of in solution
N
= 1 + 2 = 1 + 2 = 3 (  = 1)
pexp. = 27.33 × 3 = 82.0 atm
CHEMISTRY SOLUTION
Example : The vapour pressure of a solution containing 2 g of NaCl in 100 g wate, which dissociated in one Na+
and one Cl– ion in water, is 751 mm, at 100ºC. Calculate the degree of ionisation of NaCl.
Solution : According to Raoult’s law
Pº PS w  M
 
PS m W
760  751 2  18
  mexp.  30.04
751 m  100
For the dissociation of NaCl
NaCl  Na+ + Cl–
s
sse
at t = 0 1
After dissociation 1 – 
la
mN
 1   (i.e. total moles in solution)
m exp.
yC
58.5
 1    = 0.9474 or 94.74%
30.04
Example :
str
Predict the correct order of osmotic pressure of the following solution :
A. 0.1 N urea ; B. 0.1 N NaCl ; C. 0.1 N Na2SO4 ; D. 0.1 N Na3PO4
mi
0.1
Solution : M (urea) = 0.1 M ; M (NaCl)   0.1 M
1
he
0.1 0.1
M  Na 2SO4    0.05 M ; M  Na 3PO4    0.033 M
-C
2 3
 Factor ‘f’  M × (1 –  + x + y)
 M × [1 + (x + y)] [at 100% ionisation]
R
Thus factor ‘f’ of urea = 0.1 × 1 = 0.1

for NaCl = 0.1 × 2 = 0.2
SI
for NaSO4 = 0.05 × 3 = 0.15

for Na3PO4 = 0.033 × 4 = 0.132
O
 C.P. order : 0.1 N NaCl > 0.1 N Na2SO4 > 0.1 N Na3PO4 > 0.1 N urea.
PT
Example : At 27ºC, 1.25 L of a solution containing 7.6 g KBr shows an osmotic pressure of 1.804 atm. Wha is the
value of osmotic coefficient (g) ?
DI
n 7.6 1000
Solution : th  ST    0.0821 300
V 119 1250
SU
th = 1.258 atm

But exp. = 1.804 atm
exp. 1.804
i    1.434
 th 1.258
i 1.434
Now osmotic coefficient (g)    0.717 ( n = 2)
n 2
CHEMISTRY SOLUTION

Q.1 A pentimolal solution of potassium chloride freezes at -0.68ºC. If Kf for H2O is 1.86, the degree of dissociation of
KCl is -
(A) 75% (B) 83% (C) 65% (D) 92%
Q.2 The depressions in freezing point of 1 M urea, 1 M glucose and 1 M NaCl are in the ratio :
(A) 1 : 2 : 3 (B) 3 : 2 : 2 (C) 1 : 1 : 2 (D) none of these
Q.3 An electrolyte A gives 3 ions and B is a non-electrolyte. If 0.1 M solution of B produces an osmotic pressure P,
then 0.05 M solution of A will produce an osmotic pressure, assuming that the electrolyte is completely ionised.
(A) 1.5 P (B) P (C) 0.5 P (D) 0.75 P
Q.4 Which is the correct relation between osmotic pressure of 0.1 M NaCl solution and 0.1 M Na2SO4 solution ?
s
(A) the osmotic pressure of Na2SO4 is less than NaCl solution
sse
(B) the osmotic pressure of Na2SO4 is more than NaCl solution
(C) both have same osmotic pressures
la
(D) none of the above
Q.5 Which one of the following pairs of solutions will be expected to be isotonic under the same temperature?
yC
(A) 0.1 M urea and 0.1 M NaCl (B) 0.1 M urea and 0.2 M MgCl2
(C) 0.1 M NaCl and 0.1 M Na2SO4 (D) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4
Q.6 The van’t Hoff factor of a 0.005 M aqueous solution of KCl is 1.95. The degree of ionisation of KCl is-
Q.7
(A) 0.95 (B) 0.97 (C) 0.94
str (D) 0.96
What is the freezing point of a solution containing 8.1 g HBr in 100 g water, assuming the acid to be 90% ionised. ?
mi
[Kf for water = 1.86 K kg mol-1]
(A) 0.85ºC (B) –-3.53ºC (C) 0ºC (D) –0.35ºC
he
Q.8 –1
The molal freezing point constant for water is 1.86 K kg mol . Therefore, the freezing point of 0.1 M NaCl
solution in water is expected to be :
-C
(A) –1.86ºC (B) –0.186ºC (C) –0.372ºC (D) +372ºC

Q.9 Select correct statement :
(A) b. p. of 1 molal NaCl solution is twice that of 1 molal sucrose solution
R
(B) b. p. elevation of 1 molal glucose solution is half of the 1 molal KCl solution
SI
(C) b.p. is a colligative property

(D) all of the above
Q.10 Two solution of KNO3 and CH3COOH are prepared separately molarity of both in 0.1 M and osmotic pressure
O
are P1 & P2. The correct relationship between the osmotic pressure is -
PT
P1 P2
(A) P2 > P1 (B) P1 > P2 (C) P1 = P2 (D) +
P1  P2 P1  P2
DI
Q.11 A 5.8% wt/vol. NaCl solution will exert an osmotic pressure closest to which one of the following -
(A) 5.8% (wt/vol) sucrose solution (B) 5.8% (wt/vol) glucose solution
SU
(C) 2 molal sucrose solution (D) 1 molal glucose solution

Q.12 How many grams of NaBr must be added to270 gm of water to lower the vapour pressure by
3.125 mm Hg at temperature at which vapour pressure of water is 50 mm Hg. Assume 100% ionisation of NaBr
(A) 51.5 gm (B) 103 gm (C) 75 gm (D) 37.5 gm
Q.13 Sea water is found to contain NaCl & MgCl2. If NaCl is 80% ionised and MgCl2 is 50% ionised then van’t Hoff
factor is -
(A) 1.3 (B) 5.0 (C) 3.3 (D) 3.8
CHEMISTRY SOLUTION
Q.14 The f.p of a 0.08 molal solution of NaHSO4 is –0.372ºC. The dissociation constant for the reaction,
HSO4– H+ + SO42– ; is -[Kf for water = 1.86ºC]
(A) 2 × 10–4 (B) 4 × 10–4 (C) 2 × 10–2 (D) 4 × 10–2
Q.15 If the observed and normal osmotic pressures of a 1% NaCl solution are 5.75 and 3.00 atm, the degree of
dissociation of NaCl is –
(A) 0.9 (B) 1.0 (C) 0.57 (D) 0.3
Q.16 0.01 M solution of KCl and BaCl2 are prepared in water. The freezing point of KCl is found to be –2ºC. What
freezing point would you expect for BaCl2 solution –
(A) –5ºC (B) –4ºC (C) –3ºC (D) –2ºC
Q.17 The elevation in boiling point of a solution of 10 g of a binary electrolyte (molecular mass 100) in 100 of water is
Tb. The value of Kb for water is –
s
sse
Tb Tb
(A) (B) 10 (C) 10TB (D)
2 10
Q.18 Van’t Hoff factors are x, y, z in the case of association, dissociation and no change respectively. Increasing order
la
is -
yC
(A) x < y < z (B) x = y = z (C) y < x < z (D) x < z < y
Q.19 1 mole each of following solutes are taken in 5 moles water,
(i) NaCl (ii) K2SO4 (iii) Na3PO4 (iv) glucose
(B) iv < iii < ii < i

str
Assuming 100% ionisation of the electrolyte, relative decrease in V. P. will be in order
(A) i < ii < iii < iv (C) iv < i < ii < iii (D) equal
Q.20 A 0.002 molar solution of NaCl having degree of dissociation of 90% at 27ºC has osmotic pressure equal to -
mi
(A) 0.94 bar (B) 9.4 bar (C) 0.094 bar (D) 9.4 × 10-4 bar
Q.21 At 20ºC, the vapour pressure of 0.1 M solution of urea is 0.0311 mm less than that of water and the vapour
he
pressure of 0.1 M solution of KCl is 0.0574 mm less than that of water. The apparent degree of dissociation of KCl
at this dilution is -
-C
(A) 92.1% (B) 84.6% (C) 68.4% (D) 54.1%

Q.22 The freezing point of a solution of 20.5 g NH4Br in 100 g of water is –6.2ºC. The freezing point of a solution of
3.42 g cane-sugar in 100 g of water is –0.185ºC. The degree of ionisation of salt is -
R
(A) 80% (B) 30% (C) 60% (D) 40%

Q.23 A 1.2% solution (wt./ volume) of NaCl is isotonic with 7.2% solution (wt. /volume) of glucose. Degree of ionisation
SI
and van’t Hoff factor of NaCl is -

(A) = 95%, i = 1.95 (B) = 90%, i = 1.90
O
(C) = 85%, i = 1.85 (D) = 75%, i = 1.75

Q.24 1 g of monobasic acid in 100 g of water lowers the freezing point by 0.168º. If 0.2 g of same acid requires 15.1 mL of
PT
N/10 alkali for complete neutralization, degree of dissociation of acid will be -

[Kf for H2O is 1.86 K mol–1 kg]
DI
(A) 16.8% (B) 22.4% (C) 19.6% (D) 26.2%

Q.25 The molal depression of the freezing point in 1000 g of water is 1.86. What would be the depression of freezing
point of water when :
SU
(i) 120 g of urea is dissolved in 1000 gm of water.

(A) 1.86ºC (B) 8.26ºC (C) 7.87ºC (D) 3.72ºC
(ii) 117 g of sodium chloride is dissolved in 1000 gm of water (Assuming sodium chloride is fully ionised)
(A) 7.44ºC (B) 3.72ºC (C) 11.16ºC (D) 6.18ºC
(iii) 488.74 g of BaCl2.2H2O have been dissolved in 1000 g of water. (Assuming barium chloride is fully ionised)
(A) 7.44ºC (B) 11.16ºC (C) 3.72ºC (D) 5.87ºC
CHEMISTRY SOLUTION
ANSWER KEY

1. (B) 2. (C) 3. (C) 4. (D)
5. (B) 6. (B) 7. (C) 8. (C)
9. (B) 10. (A) 11. (B) 12. (C)
13. (i) (A) (ii) (D) 14. (C) 15. (A) 16. (D)
17. (A) 18. (D) 19. (C) 20. (B)
s
sse
21. (A) 22. (A) 23. (D) 24. (A)
25. (D) 26. (C) 27. (i) (A) (ii) (D) (iii) (B) 28. (A)
la
29. (C) 30. (A)
yC
1. (C) 2. (B) 3. (D) 4. (D)
5. (B) 6. (B) 7. (C) 8. (A)
9. (B) 10. (B) str
11. (C) 12. (A)
mi
13. (A) 14. (C) 15. (B) 16. (D)
17. (B) 18. (C) 19. (C) 20. (D)
he

-C
1. (C) 2. (B) 3. (A) 4. (D)

5. (A) 6. (C) 7. (D) 8. (C)
R
9. (A) 10. (C) 11. (A) 12. (C)

SI
13. (C) 14. (B) 15. (A)

O
1. (B) 2. (C) 3. (A) 4. (B)

PT
5. (D) 6. (A) 7. (B) 8. (C)

9. (B) 10. (D) 11. (C) 12. (A)
DI
13. (C) 14. (D) 15. (A) 16. (C)

SU
17. (A) 18. (D) 19. (C) 20. (C)

21. (B) 22. (C) 23. (A) 24. (C)
25. (i) (D) (ii) (A) (iii) (B)

Solution: STR Ycl Asses

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SOLUTION

becomes less than that of the pure

8. van’t Hoff factor (i) is 4. The ideal solution of a non-volatile solute is a

Value of experimental colligative property

Mole fraction of solute = = XA , Mole fraction of solvent = = XB

No. of moles of solute

(vi) Relation between mole fraction and Molality :

(vii) Molarity (Molar concentration)

x  d  10 (M) × Molecular weight of the solute

molarity molality (M) implies (M) moles in 1 lit solution

(xii) Concentration or strength of a solution (S) :

weight of solutein grams  1000

S = Normality of solution  equivalent weight of solute.

normality (N) of the solution.

Number of gram equivalents of solute

volumeof solution in litre

weight of solute in gram

strength of solution in gram / litre

(xiv) Relation between molarity and normality :-

Mass of water = (1250 – 474) = 776 g , No. of moles of water = = 43.1

Mole fraction of Na2S2O3 = = = 0.065

(iii) No. of moles of Na+ ions

No. of moles of Na  ions

Mass of solution 100

Solution: milli-moles of Na2CO3 

w 1000 2.8 1000

moles of solute 2.03  1000

Mass (w) 450

given temperature is called the vapour pressure of the liquid. Liquid

(i) Temperature : Manometer

(ii) Nature of liquid:

Vapour pressure of liquid 

3. Vapour Pressure of a Solution

XA=0 and XB=1 Mole fraction  XA=1 and XB=0

Solution : total mole = 1 + 4 = 5

Mole fraction of octane = XB = 4 / 5

Solution : PS = 760 torr, because solution boils at 88ºC

Now PS = PC6H6 X C6H6  Ptoluene X toluene

760 = 900 × mole fraction of C6H6 + 360 × [1 – mole fraction of C6H6]

According to Raoult’s law PM  PA  X A  PB  X B

or, 2PA  3PB  2750 (intially) ................... (1)

Now or adding 1 mole of B, and using Raoult’s law again

Solving equations (1) and (2) ; PA = 460 mm ; PB = 610 mm

w  1000 Pº PS 1000

639.7  631.9 1000

Pº  PS 1000 760  750 1000

 moles of glucose = 0.7407, moles of water 

Pº = 200 mm, PS = 195 mm, w = 2g, M = 78, W = 78 g

n H2O 27.78 27.78

Vapour pressure of solution PH2O  PHo 2O X H 2O  47.1 0.996  46.9 torr

Lowring of vapour pressure PHo 2O – PH2O  47.1 – 46.9  0.2 torr

Solution : For two miscible liquids,

Ptotal = PA  PB  PAo X A  PBo X B nA = = 0.2,

Liquid B is water. Its mass is (100–28), i.e. 72. nB = = 4.0

Given Ptotal = 160 mm, PB0 = 150 mm

4. DETERMINATION OF COMPOSTION IN VAPOURE PHASE

A B A B A B A B A B A vapours (Dalton's law)

Above formula is used for calculation of mole fraction of B in vapour phase

Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg

Partial pressure of CH3OH

vapour pressure above the solution.

Daily Practice Problem Sheet - 1

(A) vapour pressure of pure methanol is 119 torr