Hand-Out Chemistry

Chapter 2 : Solution
A solution may be defined as a Homogeneous mixtures of a single phase containing one or more of the chemical species
dispersed on a molecular scale.

SOLUTE AND SOLVENT

(a)

The component whose physical state is same as that of resulting solution is called as Solvent and the other
component whose physical state changes is termed as Solute. e.g. In a homogenous mixture of Na(s) and Hg(l)
resulting in the formation of NaHg(s), Na(s) is considered as solvent and Hg(l) is termed as Solute which is contrary
to the common belief that liquids are solvents.;

(b)

When both components are having the same phase as that of that the resulting solution and the relative amount of
one substance in a solution is much greater than that of the other, the substance present in greater amount is
generally regarded as the solvent.

METHODS OF EXPRESSING CONCENTRATIONS OF SOLUTIONS

The concentration of solutions are generally expressed in the following ways: Solute: designated as b

Solvent:

designated as a
1.

Molarity (M) : No. of moles of solute per litre of solution.

M=

2.

(Wb ) 1000
nb
number of moles of b
=
= (M ) V ; where, V(ml)
Volume of solution in Liter
VL
b
( ml )

Volume of Solution in mililitres.

Molality (m) : No. of moles of solute per kg of solvent.

Number of moles of solute
m = Weight of solvent in Kg = m

3.

nb
= W kg ; m
a

Wb 1000
; Wa = Weight of solvent in gms
M b Wa

Normality (N) : No. of Gram equivalent of solute per litre of solution.

Gm. equivalent =

Weight of solute
Molar mass of solute
;
Equivalent mass of solute ; Equivalent mass =
n factor

N = M nf : Where M is the molarity and nf = n factor

4.

Mole fraction (X) : Ratio of number of moles of one of the components to the total number of moles present in the
solution.
nb
na
Xb = n n n ......... ; Xa = n n n ......... ; Total mole fraction of a solution is Xa + Xb = 1.
a
b
c
a
b
c
Mass of solute (gram)
100 ;A 10% aqueous NaCl solution contains 10 grams
Mass of solution (gram)
of NaCl per 100 grams of solution. Ten grams of NaCl is mixed with 90 grams of water to form 100 grams of solution.

5.

Mass Percentage (w/W %) =

6.

Volume Percentage (v/V %) =

7.

Mass by Volume Percentage (w/V%) =

8.

Parts per Million =

Volume of solute (ml)

100 ;e.g.
Volume of solution (ml)
of ethanol means 10 mL solute present in 100mL of the solution.

10% volume percentage of aqueous solution

Mass of solute (gram)

100
Volume of solution (mL)

Number of parts of the component

106
Total number of parts of all the components of thesolution

Concentration in parts per million can also be expressed as mass to mass, volume to volume and mass to volume.

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Chapter 2 : Solution
Illustration 1:

Calculate the molality and mole fraction of the solute in aqueous solution containing 3.0 g of urea (mol.
mass=60) per 250 g of water.

Solution:

Weight of solute = 3 g ;Mol. mass (Mb)[urea] = 60 g mol1;

m=

Weight of solvent = 250 g

Weight in gm
3
Wb 1000 3 1000
=
= 0.2m; nb= molar mass 60 = 0.05 ;
M b Wa
60 250

Weight in gm 250
0.05
na = molar mass 18 = 13.89; Xb =
=
0.05 13.89
Illustration2.

0.0037

Calculate the molarity and normality of a solution containing 9.8 g of H2SO4 in 250 cm3 of the solution.[Mol.
mass (Mb) [H2SO4] = 98 g mol1 ]

Solution:

(Wb ) 1000 9.81000

M = (M ) V
=
= 0.4 M;Normality = M nf ;
98 250
b
( ml )

Illustration 3.

Find the molarity and molality of a 15% solution of H2SO4 (density =1.020 g cm3).

solution:

Let the solution be 100 g ;

Weight of solute = 15 g ; Weight of solvent = 85 g

Volume of solution taken =

m=

N = 0.4 2 = 0.8 N

100
(Wb ) 1000 151000
ml; M =
=
= 1.56 M;
100
1.020
(M b ) V( ml )
98
1.020

(Wb ) 1000 151000

=
= 1.8 m
9885
(M b ) Wa

Illustration 4.

A solution of ethanol in water is 1.54 molal. How much grams of it are there in 2500 g of the solvent.

Solution:

Molality = 1.54 m; Weight of solvent = 2500 g ; m =

Illustration 5.

What volume of 95 % H2SO4 (density = 1.85 g cm3) and what mass of water must be taken to prepare 100
cm3 of 15% solution of H2SO4 (density = 1.10 g cm3).

Solution:

Given solution: Let there be 100 g of solution, Weight of solute = 95 g; Density = 1.85 g cm3

(Wb ) 1000
Wb 1000
= 1.54
;Wb = 177.1 g
46 2500
(M b ) Wa

Mass
100
Volume of solution = Density =
= 54.04 ml;
1.85

(Wb ) 1000
951000
M = (M ) V
=
= 18 M
98 54.04
b
( ml )

Required solution: Let there be 100 g of solution,

Weight of solute = 15 g;Density = 1.10 g cm3 ;

Volume of solution =

Mass
100
=
= 90.91 ml
Density 1.10

M=

151000
(Wb ) 1000
=
= 1.68 M
9890.91
(M b ) V( ml )

Now if the required solution is to be prepared from the given solution then :
M1n1V1 = M2n2V2 ;18 V1 = 1.68 100
V1 = 9.33 ml [rest of volume is due to water add. = 100 9.33 = 90.67ml ]

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Chapter 2 : Solution
PRACTICE QUESTION
1.

Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of C2H6O2 by mass. (Ans - 0.068).

2.

Calculate the molarity of a solution containing 5 g of NaOH in 450 mL solution. (0.278 mol dm-3)

3.

Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.

4.

Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20% (m/m) aqueous KI is 1.202 g mL-1.

(Ans- 0.556 mol kg-1)

Ans. (a) 1.5 mol kg1 (b) 1.45 M (c) 0.0263

5.

Calculate the molarity of each of the following solutions (a) 30 mL of 0.5 M H 2 SO4 diluted to 500 mL.
(b) 30 g of Co No3 2 .6H 2 O in 4.3 L of solution.

Ans. (a) 0.03 M;(b)0.022 M

Saturated solution: The solution in which no more solute can be dissolved at the same temperature and pressure.
Solubility: The maximum amount of a solute that can be dissolved in a given volume of solution at a constant temperature
and pressure is called its solubility.

FACTORS EFFECTING SOLUBILITY OF A SOLID IN LIQUID

(i)

Temperature : The solubility of a solid in a liquid is significantly affected by temperature changes. This, being
dynamic equilibrium, follow Le Chateliers Principle. In general, if in a nearly saturated solution, the dissolution
process is endothermic ( sol H>0), the solubility should increase with rise in temperature and if it is exothermic
( sol H<0) the solubility should decrease. These trends are also observed experimentally..

(ii)

Pressure: Pressure does not have any significant effect on solubility of solids in liquids. It is so because solids and
liquids are highly incompressible and practically remain unaffected by change in pressure.

HENRYS LAW
The law states that at a constant temperature the solubility of a gas in liquid is directly proportional to the pressure of
the gas. The most commonly used form of the Henrys law state that the partial pressure of the gas in vapour phase (p)
is proportional to the mole fraction of the gas(x) in the solution and is expressed as:
p = KH x ;Here KH is the Henrys law constant.
From equation p = KHx, we can say that higher the value of KH at a given pressure, the lower is the solubility of the gas
in the liquid. KH value for both N2 and O2 increases with an increase of temperature indicating that the solubility of gases
increases with the decrease of temperature. It is due to this reason that aquatic species are more comfortable in cold
waters rather than in warm waters.

LIMITATIONS OF HENRYS LAW

(i)

It is applicable at moderate temperature and pressure and falls when pressure used is too high and temperature
used is too low.

(ii)

The gas should not get dissociated or associated when it is dissolved in the solvent.

(iii)

The solubility of the gas should not be high in the solvent NH3, CO2, HCl in water.

(iv)

The gas should not form a new species after reacting with the solvent when it is dissolved. For example, NH3 does
not follow Henrys law due to this reason.

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Chapter 2 : Solution
APPLICATIONS OF HENRYS LAW
(i)

In aerated soft drinks the carbon dioxide in soft drinks is sealded under high pressure to increase the solubility of
CO2 in it for desired taste.

(ii)

Scuba divers must cope with high concentrations of dissolved gases while breathing air at high pressure underwater.
Increased pressure increases the solubility of atmospheric gases in blood. When the divers come towards surface,
the pressure gradually decreases. This releases the dissolved gases and leads to the formation of bubbles of
nitrogen in the blood. This blocks capillaries and creates a medical condition known as bends, which are painful
and dangerous to life. To avoid bends, as well as the toxic effects of high concentrations of nitrogen in the blood,
the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1%
oxygen).

(iii)

At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low concentrations
of oxygen in the blood and tissues of people living at high altitudes or climbers. Low blood oxygen causes
climbers to become weak and unable to think clearly, symptoms of a condition known as anoxia.

EFFECT OF TEMPERATURE
According to Le Chateliers Principle, solubility should increase with the increase of temperature for endothermic
processes ( sol H > 0) and should decrease with the increase of temperature for exothermic ( sol H< 0) processes. When
dissolved, the gas molecules are present in liquid phase and the process can be considered similar to the condensation
process. Heat is evolved in this process.

Illustration 6.

H2S, toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of H2S in
water at STP is 0.195 m, calculate Henrys law constant.

Solution:

As the condition is given as STP ;

X =

KH =

p = 1 atm and Solubility = 0.195 m

0.195
0.195
0.195
m
=
=
=
= 3.5 103 = KH 3.5 103 ;
1000
0.195 55.5 55.70
100
0
.
195

m
18
Ma
1
103 = 2.86 102
3. 5

Illustration 7.

Henrys law constant for CO2 in water is 1.67 108 Pa at 298 K. Calculate the quantity of CO2 per ml of soda
water when packed under 2.5 atm CO2 pressure at 298K.

Solution:

1 atm = 101325 pa;

X=

1.67 108 pa = 1648.123 atm; KH = 1.648 103 ; P = KH.X ; 2.5= 1.648 103 X ;

2. 5
= 1.5 103 ; X =
1.648103

moles

moles of CO2
1
moles of CO 2 +
18

; 1.5 103 =

moles
;
mol + 0.055

0.055
= 8.3 105 moles ;
665.67

Mass of CO2 = 8.3 105 44 = 3.6 103 g

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Chapter 2 : Solution
PRACTICE QUESTIONS
1.

If

N 2 is bubbled through water at 293 K, how many milli moles of N2 gas would dissolve in 1 litre of water. Assume N2

exerts a partial pressure of 0.987 bar. Given the Henrys law constant for N2 at 293 K is 76.48 kbar.
2.

Ans. 7.17 108

Calculate the concentration of CO2 in a soft drink that is bottled with a partial pressure CO2 of 4 atm over the liquid at
2
25C . The Henrys law constant for CO2 in water at 25C is 3.110 mol/litre atm.

Ans. 129 M

3.

The Henrys law constant for oxygen dissolved in water is 4.34 104 atm at 25C. If the partial pressure of oxygen in air
is 0.2 atm under atmospheric conditions, calculate the concentration of dissolved oxygen in water in equilibrium with air
at 25C.
Ans. Mole fraction of O2 = 4.6 106 & Molar is 2.56 104 M

4.

Calculate the solubility of H2 in water at 25C if its partial pressure above the solution is 1 bar. Given that Henrys constant
for H2 in water at 25C is 71.18 kbar.
Ans. 1.40 105

5.

Henrys law constant for the molarity of methane in benzene at 298 K is 4.27 105 mm Hg. Calculate the solubility of
methane in benzene at 298 K under 760 mm Hg.
Ans. 1.78 103

VAPOUR PRESSURE OF LIQUID SOLUTIONS

It is the Pressure exerted by vapours of the liquid on its liquid surface at equilibrium. Following are the important points
regarding vapour presseure.
1.

More volatile is the substance more will be the vapour pressure.

2.

Lesser is the inter-molecular force of attraction between liquid molecules higher is the vapour pressure (as there is
more volatile nature)

3.

Vapour Pressure of liquid is not considered as surface phenomenon. Although evaporation is a surface phenomenon
and condensation occurs at surface.

4.

Vapour pressure of liquid doesnt depend on size or shape of vessel.

5.

Vapour Pressure of liquid depends on temperature. As the temperature increases the vapour pressure increases.

Let the total vapour pressure at this stage be ptotal and

p1 and p2 be the partial vapour pressures of the two component

1 and 2 respectively. These partial pressures are related to the mole fractions

x1 and x2 of the two components 1 and 2

respectively. The quantitative relationship between them, known as the Raoults law, states:
For a solution of volatile liquids, the partial vapour pressure of each component in the solution is directly proportional
to its mole fraction.
Thus for component 1

p1 x1 and p1 = p10 x1

0
(Where p1 = Saturated vapour pressure.)

Similarly, for component 2

p2 = p 20 x 2

0
(Where p2 Saturated vapour pressure.)

According to Daltons law of partial pressures Ptotal

p1 + p2

0
0
0
0
0
Substituting the values of p1 and p2, we get Ptotal
= p1 + p2 = (1 x2) p1 x2 p2 = p1 ( p2 p1 ) x2
The composition of vapour phase in equilibrium with the solution is determined by the partial pressures of the components.

If

y1 and y2 are the mole fractions of the components 1 and 2 respectively in the vapour phase, then using Daltons law

of partial pressures:

p1 = y1ptotal ; p2= y2ptotal ; In general pi = yiptotal

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Chapter 2 : Solution
RAOULTSS LAW AS A SPECIAL CASE OF HENRYS LAW
If we compare the equations for Raoults Law (pi = yiptotal) and Henrys law (p = KHx), we see that the partial pressure of the
volatile component of gas is directly proportional to its mole fraction in solution. Only the proportionality constant KH
0
differs from p10 . Thus, Raoults law becomes a special case of Henrys law in which KH becomes equal to p1 only if the
solution is ideal and thats why Raoults Law is applicable only to Ideal Solution whereas Henrys law is applicable to Nonideal Solutions as well. A plot between the vapour pressure and the mole fraction of the solvent is linear.

Illustration 8.

Benzene(C6H6)and Toluene(C7H8) form an ideal solution at 313K. The vapour pressures of pure Benzene
and Toluene are 160 mmHg and 60 mmHg respectively. Calculate the partial pressures of Benzene and
Toluene and total pressure over the following solutions:
(i)

Containing equal weights of benzene and toluene.

(ii)

Containing 1 mole of benzene and 4 moles of toluene

(iii)

Containing equal molecules of benzene and toluene.

Solution:

(do it yourselft)

Illustration 9.

The vapour pressure of benzene and toluene at 293 K are 75 mm and 22 mmHg respectively. 23.4 g of
benzene and 64.4 g of toluene are mixed. If the two form an ideal solution, calculate the mole fraction of
benzene in the vapour phase assuming that the vapour are in equilibrium with the liquid mixture at this
temperature.

Solution:

PB = 75 mmHg

PT = 22 mmHg

Weight of Benzene = 23.4 g

Weight of Toluene = 64.4 g

Mol. Mass of Benzene = 78 g mol1

nB =

Mol. Mass of Toluene = 92 g mol1

Weight in gm
23.4
=
= 0.3
Molar mass
78

nT =

nB
0. 3
XB = n n =
= 0.3
0
.
3
0.7
B
T

Weight in gm
64.4
=
= 0.7
Molar mass
92

nT
0.7
XT = n n =
= 0.7
0
.
3
0.7
B
T

PB = PB. XB = 75 0.3 = 22.5 mmHg

PT = PTO. XT = 22 0.7 = 15.4 mmHg

Ptotal = PB + PT = 22.5 + 15.4 = 37.9 mmHg

yB =

PB
22.5
=
= 0.59
37.9
Ptotal

yA =

PA
15.4
=
= 0.41
Ptotal
37.9

IDEAL AND NON-IDEAL SOLUTIONS

Ideal Solutions : The solution which obey Raoults law over the entire range of concentration are known as ideal
solution. The ideal solutions have two other important properties. The heat of mixing of the pure component to form the
solution is zero and the volume of mixing is also zero, i.e., mixH = 0; mixV = 0
Non-ideal Solutions : When a solution does not obey Raoults law over the entire range of concentration then it is called
non-ideal solution. The vapour pressure of such a solution is either higher or lower than that predicted by Raoults law.
If it is higher, the solution exhibits positive deviation and if it is lower, it exhibits negative deviation from Raoults law. If
psolution > psolvent ,the solution shows positive deviation and if psolution < psolvent, the solutions shows negative deviation from
Raoults law.

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In case of positive deviation, solute-solvent (AB) intermolecular forces are weaker than solvent-solvent (AA) and
solute-solute (BB) intermolecular forces. So it is easier for solution (AB) to escape than in pure state. This increases
the vapour pressure and result in positive deviation. For example: Mixtures of ethanol and acetone, carbon disulphide
and acetone, acetone-benzene, methyl alcohol-water, ethyl alcohol-water, carbon tetrachloride-chloroform, carbon
tetrachloride-benzene, carbon tetrachloride-toluene show positive deviation.

(a) Positive Deviation

(b) Negative Deviation

In case of negative deviations from Raoults law, the intermolecular attractive forces, between solvent-solvent (AA) and
solute-solute (BB) are weaker than those between solvent-solute (AB) and lead to negative deviations.
For examples: Mixtures of phenol-aniline, chloroform-diethyl ether, acetone-aniline, HCl-water, HNO3water, acetic acidpyridine, etc.

AZEOTROPES
Some liquid mixtures, having definite composition, boil like pure liquid and are called azeotropic mixtures or azeotropes or
constant boiling mixtures. The components of these mixtures can not be separated by fractional distillation.
(i)

Minimum Boiling Azeotropes: The solutions that show large positive deviation from Raoults law form minimum
boiling azeotrope at a specific composition, e.g. ethanol-water mixture containing a 95.4% ethanol boils at 351.5 K,
chloroform-ethanol mixture with 6.8% ethanol, etc.

(ii)

Maximum Boiling Azeotropes: The solutions that show large negative deviation from Raoults law form maximum
boiling azeotrope at a specific composition, e.g. 68% nitric acid and 32% water by mass, with a boiling point 393.5
K, water-ethanol with 20.3% HCl.

COLLIG ATIVE PROP ERTIES

The properties of dilute solutions which are induced on addition of Non-volatile solute to a volatile solvent are called
Colligative Properties.The properties that depend on the number of solute particles irrespective of their nature are relative
to the total number of particles present in the solution.
(i)

Lowering of vapour pressure

(ii)

Depression in freezing point

(iii)

Elevation in boiling point

(iv)

Osmotic pressure

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Chapter 2 : Solution
RELATIVE LOWERING OF VAPOUR PRESSURE
The vapour pressure of the solvent in solution is less than that of the pure solvent. The relation between vapour pressure
of the solution, mole fraction and vapour pressure of the solvent is p1 = x1p10
p1 = vapour pressure of the solution;

x1 = mole fraction of the solute; p1 0 = vapour pressure of the solvent

p1
n2
p10 p1
p1
=
=
x
=
0
0
2
n1 n2 ; p0 is called relative lowering of vapour pressure and is equal to the mole fraction of the
p1
p1
1
n2
p10 p1
p10 p1
solute.For dilute solutions n2 << n1 hence neglecting n2 in the denominator we have
= n Or
=
p10
p10
1
w2 M 1
M 2 w1 ;

ELEVATION OF BOILING POINT

It is seen that for dilute solutions the elevation of boiling point (Tb) is directly proportional to the molal concentration of
the solute in a solution. Thus, Tb m ; Tb = Kb m
Kb is called Boiling Point Elevation Constant or Molal Elevation Constant. The unit of Kb is K kg mol1.
m=

1000 w2
K b 1000 w2
; Tb =
M 2 w1
M 2 w1

DEPRESSION OF FREEZING POINT

A solution freezes when its vapour pressure equals the vapour pressure of the pure solid solvent. According to Raoults
law, when a non-volatile solid is added to the solvent its vapour pressure decreases and would become equal to that of
solid solvent at lower temperature.Thus, the freezing point of the solvent decreases. Depression of freezing point (Tf) for
dilute solution (ideal solution) is directly proportional to molality m of the solution.
Or

Tf m ; Or Tf K f m ; Tf0 Tf 0 Tf

The proportionality constant Kf, which depends on the nature of the solvent is known as Freezing point depression
constant or Molal depression constant or Cryoscopic constant.The unit of Kf is K kg mol1.
Tf

K f w2 1000
;
M 2 w1

Kf =

R M 1 Tf2
;
1000 fus H

Kb =

R M 1 Tb2
1000 vap H

Here R and M1 are the gas constant and molar mass of the solvent, respectively and Tf and Tb denote the freezing point
and the boiling point of the pure solvent respectively in Kelvin. fus H and vap H are the enthalpies for the fusion and
vapourisation of the solvent, respectively.

OSMOSIS AND OSMOTIC PRESSURE

When a solution is separated from the pure solvent by a semi-permeable membrane, it is observed that the solvent flows
from the region of pure solvent into solution. The passage of solvent from pure solvent or from solution of lower
concentration into solution of higher concentration through a semi-permeable membrane is called osmosis.The osmotic
pressure of the solution at a given temperature may be defined as the excess hydrostatic pressure that builds up when
the solution is separated from the solvent by a semi-permeable membrane. It is denoted by .

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Chapter 2 : Solution
DETERMINATION OF MOLAR MASS FROM OSMOTIC PRESSURE
In order to determine the molar mass of an unknown non-volatile compound, a known mass (say w g) of the compound is
dissolved to prepare a known volume (say V litre) of solution and the osmotic pressure of the solution is determined.
From this, the molecular mass of the compound is calculated as follows:
According to Vant Hoff equation, M =
wRT
V

CONDITIONS FOR GETTING ACCURATE VALUE OF MOLECULAR MASS

(i)

The solute must be non-volatile.

(ii)

The solution must be dilute. The solute should not undergo dissociation or association in the solution.

REVERSE OSMOSIS
If the pressure applied on the solution is greater than the osmotic pressure,
then solvent starts passing from solution into solvent. This is called reverse
osmosis, generally used for purification of sea water or hard water.

Relativ e lowering of
v apour pressure

p1 p 1
p 1

p1
p1

Elev atio n of boiling point

Depression of freezing po int

w 2 M1
M 2 w1

p1 = vapour pressure of
pure compound

p1 = vapour pressure of
so lution
p
p11== p
p11 p1 ==
red uction in v apour
pressur e of so lvent

T b = elevation of boiling
point
K b = Molal elevation constant
or ebullioscopic constant or
boiling point elevation
constant
The value of K b depends on
th e nature of the solvent
Kb

RM 1Tb2
1000 vapH

vapH = Enthalpy of
vapourisation

T f = d epr ession of freezing

point
K f = Molal depression
constant or cryoscopic
constant or f reezing point
depr ession constant
The value of K f depends on
the nature of the solvent
Kf

RM 1Tf2
1000 fus H

fus H = Enthalp y of f usion

w 1 = weight of solvent, M 1 = mo lar mass o f solvent, w 2 = weight of solute, M 2 = molar

mass of solute, R = Gas co nstant

ABNORMAL MOLAR MASSES

Abnormal molar masses are observed when the solution is non-ideal, i.e. solution is not dilute.

When the solution undergoes Dissociation/association in the solution.

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Chapter 2 : Solution
Vant Hoff factor i, which accounts for the extent of association or dissociation, is the ratio of the experimental value of
the colligative property to the calculated value of the colligative property.
i=

Normal molar mass

Observed colligative property
N o . o f m o le s o f p a rticle s a fte r a sso c ia tio n / d iss o ciatio n
=
=
N o . o f m o le s o f p a rtic le s b efo re ass o ciatio n / d isso c ia tio n
Abnormal molar mass Calculated colligative property

PRACTICE PROBLEM
1.

An aqueous solution freezes at 0.186C (Kf = 1.86; Kb = 0.512). What is the elevation in boiling point?Ans. 0.051C

2.

Calculate the amount of NaCl that must be added to one kilogram of water so that the freezing point is depressed by 3 K.
(Given Kf for water = 1.86 K/m).
Ans. 94.35 g

3.

Ethylene glycol (molar mass = 62 g mol1) is a common automobile antifreeze. Calculate the freezing point of a solution
containing 12.4 g of this substance in 100 g of water. Would it be advisable to keep this substance in the car radiator
during summer? Given: Kf for water =1.86 K kg/mol, Kb for water =0.512 K kg/mol.
Ans. 3.72C

4.

Boiling point of water at 750mm Hg is 96.63C. How much sucrose is to be added to 500 g of water such that it boils at
100C? (Molal elevation constant for water is 0.52 K kg mol1.)
Ans. 23.44 mm Hg

5.

A solution of a non-volatile solute in water freezes at 0.30C. The vapour pressure of pure water at 298 K is 23.51 mm Hg
and Kf for water is 1.86 degree/molal. Calculate the vapour pressure of this solution at 298 K.
Ans.1.108 kg

SOLVED EXAMPLES
1.

Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.

Sol.

30% of benzene in carbon tetrachloride by mass means that

Mass of benzene in the solution = 30g

Mass of solution = 100g ;Mass of carbon tetrachloride = 10030 g =70 g ;Molar mass of benzene (C6H6) = 78 g mol-1
Molar mass of CCl4 =12 + 4 35.5 = 154 g mol-1; No of moles of benzene

No. of moles of CCI 4=

7 0 g
1 5 4 m

m o l

0 .4 5 5

30
7 8 g m o l

0 .3 8 5

Mole fraction of benzene = 0.458

2.

H2S, toxic gas with rotten egg like smell, is used for qualitative analysis. If the solubility of H2S in water at STP is
0.195 m, calculate Henrys law constant.

Sol.

Solubulity of H2S gas = 0.195 m i.e. 0.195 mole in 1 kg of the solvent (water)
1 kg of the solvent (water) = 1000g =

1000
18g mol-1

= 55.55 moles

Mole fraction of H2S gas in the solution x

Pressure at STP = 0.987 bar ;

0.195
0.195

0.0035
0.195 55.55 55.745

Applying Henrys law, PH2 S = KH xH2 S or KH

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10

pH 2 S
xH 2 S

0.987 bar
282 bar.
0.0035

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Hand-Out Chemistry
Chapter 2 : Solution
3.

Henrys law constant for CO2 in water is 1.67 108 Pa at 298 K. Calculate the quantity of CO2in 500 mL
of soda water when packed under 2.5 atm CO2 pressure at 298 K.

Sol.

KH =1.67 108 Pa, pCO2 = 2.5 atm =2.5 101325 Pa ; Applying Henry s law, pCO2 K H xCO2

xCO2

pCO2
KH

2.5101325 Pa
1.67 10 Pa
8

1.517 103 , i.e.,

nCO2
nH 2 O nCO2

For 500 mL of soda water, water present 500mL 500 g

nCO2
nH 2 O

500
27.78 mole ;
18

1.517 103

i.e., nH2 O 27.78 mole

CO2
1.517 103 or nCO2 42.14103 mole 42.14 42.14 103 44 g 1.854 g.
27.78

4.

The vapour pressures of pure liquids A and B are 450 and 700 mm Hg at 350 K respectively. Find out the
composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.

Sol.

0
0
0
0
0
pA x A p A0 ; pB xB pB 0 (1 xA ) pB 0 ; P Total = p A pB x A p A (1 x A ) pB pB ( p A pB ) x A

Substituting the given values, we get

600 700 (450 700) x A or 250 x A 100 or x A

Thus, composition the liquid mixture will be

100
0.40
250

x A (mole fraction of A) =0.45, xB (mole fraction of B)= 1 0.40 = 0.60

p A x p A0 0.40 450mm 180mm, pB xB pB 0 0.60 700mm 420mm Mole fraction of A in the

vapour phase =

pA
180

0.30 ; Mole fraction of B in the vapour phase = 1 0.30 = 0.70.

p A pB 180 420

5.

Boilling point of water at 750 mm Hg is 96.63C.How much sucrose is to be added to 500 g of water such that it boils at
100C ? Molal elevation constant for water is 0.52 K kg mol1 .

Sol.

Elevation in boiling point required ( Tb ) = 100 96.630=3.370Applying the formula, M2 =

6.

Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolved 1.0 g of polymer of molar mass
185,000 in 450 mL of water at 37C.

Sol. CRT
7.

1000 K b w2
Ans- 1108.2
w2 Tb

1
1

mol
8.314 103 Pa L K 1mol 1 310K 30.96 Pa.
RT ;
185,
000
0.45L
V

The partial pressure of ethane over a saturated solution containing 6.56 102 g of ethane is 1 bar.
If the solution contains 5.00 102 g of ethane, then what shall be the partial pressure of the gas ?

Sol.

Applying the relationship m = KH p ; In the first case, 6.56 102 g = KH 1 bar or KH = 6.56 102 g bar1
In the second case,5.00 10 g = (6.56 10 g bar ) p or p
1

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5.0010 2 g
6.5610 2 g bar 1

0.762bar.

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Chapter 2 : Solution
8.

An aqueous solution of 2% non - volatile solute exerts a pressure of 1.004 bar at the normal boiling
point of the solvent, What is the molecular mass of the solute ?

Sol.

Vapour pressure of pure water at the boiling point (p0) = 1 atm = 1.013 bar ; Vapour pressure of solution (ps) = 1.004 bar
p ps
n2
n
w / M2
w
M
1.013 1.004 2 g 18g mol 1

2 2
2 1

or M2 = 41.35 g mol1
p
n1 n2
n1
w1 / M1
M 2 w1
1.013bar
M2
98g

9.

Heptane and octane form ideal solution . At 373 K, the vapour pressures of the two liquid components are 105.2 kPa and
46.8 kPa respectively . What will be the vapour pressure of a mixture of 26.0 g of heptane and 35.0 g of octane ?

Sol.

x (octane) = 1 0.456 = 0.544

10.

The vapour pressure of water is 12.3 k Pa at 300 K. Calculate the vapour pressure of 1 molal

Sol.
11.

solution of a solute in it .

p ps
12.3 ps
1
0.0177 ; Now , p x2 , i.e., 12.3 0.0177 or ps = 12.08 k Pa.
1 55.5
Calculate the mass of a non - volatile solute (molar mass 40 g mol1) which should be dissolved in 114 g octane to reduce
its vapour pressure to 80%. Ans- 73.43 kPa.

Mol fraction of solute

12.

A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing point of a 5%
glucose in water if freezing point of pure water is 273.15 K. Ans 269.06 K

13.

Two elements A and B form compounds having molecular formula AB2 and AB4. When dissolved in 20 g of benzene (C6H6),
1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g of AB4 lowers it by 1.3 K. The molal depression constant for
benzene is 5.1 K kg mol1. Calculate atomic masses of A and B.

Sol.

M2

1000 K f w2

; M AB 2

1000 5.11
10005.11
110.87 g mol1 , M AB4
196.15 g mol1
20 2.3
201.3

w1 f
Suppose atomic masses of A and B are a and b respectively. Then Molar mass of AB2 = a + 2 b = 110 .87 g mol1
Molar mass of AB4 = a + 4 b = 196.15 g mol1; Thus, Atomic mass of A = 25.59 u,

14.

atomic mass of B = 42.64 u

Based on solute-solvent interactions, arrange the following in order of increasing solubility in noctane and explain.
Cyclohexane, KCI, CH3OH,CH3CN

Sol.

(i)

Cyclohexane and n-octane both are non-polar. Hence,they mix completely in all propotions.

(ii)

KCI is an ionic compound while n-octane is non-polar.Hence, KCI will not dissolve at all in n-octane (iii) CH3OH
and CH3CN both are polar but CH3CN is less polar than CH3OH.As the solvent is non-polar, CH3CN will dissolve
more than CH3OH in n-octane. Thus,the order of solubility will be KCI < CH3OH<CH3CN < Cyclohexane.

15.

If the solubility product of CuS is 6 1016, calculate the maximum molarity of CuS in aqueous solution.

Sol.

Maximum molarity of CuS in aqueous solution = Solubility of CuS in mol L1. If S is the solubility of CuS in mol L1 ,
2
2
16
2
2
2
2.45108 mol L1.
then CuS Cu S , K sp Cu S S S S , S 610
s
s

16.

The depression in freezing point of water observed for the same amount of acetic acid trichloroacetic acid and trifluoroacetic
acid increases in the order given above. Explain briefly.

Sol.

The depression in freezing points are in the order :

acetic acid

<

trichloroacetic acid

<

trifluoroacetic acid

Fluorine, being most electronegative, has the highest electron withdrawing inductive effect. Consequently, Trifluoroacetic
acid is the strongest acid while acetic acid is the weakest acid. Hence, trifluoroacetic acid ionizes to the largest extent while
acetic acid ionizes to the minimum extent to give ions in their sloutions in water. Greater the ions produced, greater is the
depression in freezing point. Hence, the depression in freezing point is maximum for the fluroacetic acid amd minimum for
acetic acid.
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Hand-Out Chemistry
Chapter 2 : Solution
17.

Calculate the depression in the freezing point of water when 10 g of CH3CH2CHClCOOH is added to 250 g of water.
= 1.4 103 , Kf = 1.86 K kg mole1.

Sol.

Molality of the solution m

Ka

8.1610 2 mole
1000 g 0.3264
250 g

If is the degree of dissociation of CH3CH2CHClCOOH, then

CH3CH2CHClCOOH CH3CH2CHClCOO + H+
Initial conc.

C mol L1

At eqm.

C (1 )

Ka

C.C
C 2 or
C (1 )

Ka
1.410 3

0.065
C
0.3264

CH3CH2CHClCOO
CH3CH2CHClCOOH
Initial moles
Moles at eqm.

H+

1
1

1
1 1 .065 1.065 ;
1

Total = 1 +

T f i K f m 1.0651.860.3264 0.65.

18.

19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point observed is 1.0C. Calculate the
vant Hoff factor and dissociation constant of fluoroacetic acid. Kf for water is 1.86 K kg mol1 .

19.

Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of water at 293 K when 25 g of
glucose is dissolved in 450 g of water. Ans- 17.44 mm.

20.

Henrys law constant for the molarity of methane in benezene at 298 K is 4.27 105 mm Hg . Calculate the solubility of
methane in benzene at 298 K under 760 mm Hg. Ans- 1.78 103 .

21.

100 g of liquid A (molar mass 140 g mol1) was dissolved in 1000 g of liquid B (molar mass180 g mol1)
The vapour pressure of pure liquid B was found to be 500 torr. Calculate the vapour pressure of pure liqued A and its
vapour pressure in the solution if the total vapour pressure of the solution is 475 torr. Ans- 32 torr.

22.

Benzene and toluene form ideal solution over the entire range of composition. The vapour pressures of pure benzene and
toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole fraction of benzene in the vapour phase
if 80 g of benzene is mixed with 100 g of toluene. Ans- 0.60

23.

The air is a mixture of a number of gases. The major components are oxygen and nitrgen with approximate proportion of
20% is to 79% by volume at 298 K The water is in equilibrium with air at a pressure of 10 atm. At 298 K, if the Henrys law
constants for oxygen and nitrogen are 3.30 107 mm and 6.51 107 mm respectively, calculate the composition of these
gases in water.

Sol.

Total pressure of air in equilibrium with water = 10 atm ;

As air contains 20% oxygen and 79 nitrogen by volume,

20
Partial pressure of oxygen ( Po2 ) 10 atm = 2 atn = 2 760 mm = 1520 mm
100

Partial pressure of nitrogen

79
10 atm = 7.9 atm = 7.9 760 mm = 6004 mm
pN2 100

pO2 K H xO2 or xO2

pO2
KH

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1520mm
3.3010 mm
7

4.61105 ; xN 2

13
13

pN2
KH

6004mm
6.5110 mm
7

9.22105.

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Chapter 2 : Solution
24.
25.
Sol.

Determine the amount of CaCl2 (i 2.47) dissolved in 2.5 litre of water such that its osmotic pressure is 0.75 atm at
27 C. Ans- 3.42 g.
Determine the osmotic pressure of a solution prepared by dissolved 25 mg of K2SO4 in 2 litre of water at 25C, assuming
that it is completely dissociated.
As K2SO4 dissociates completely as K2SO4 2K+ + SO24 ;
n

= i CRT = i V

RT i

i.e., ions produced = 3,

i = 3

w 1
0.025g
1
RT 3
0.0821 L atm K1 mol 1 298 K = 5.27 103 atm
1
M V
2L
174g mol

PREVIOUS YEAR QUESTIONS

2012
1.

(a)

(b)

Define the following terms:

(i)
Mole fraction;
(ii)
Ideal solution.
15.0 g of an unknown molecular material is dissolved in 450 g of water. The resulting solution freezes at 0.34C.
What is the molar mass of the material? (Kf for water = 1.86 K kg mol1)
OR

(a)

(b)

Explain the following:

(i)

Henrys law about dissolution of a gas in a liquid.

(ii)

Boiling point elevation constant for a solvent.

A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in 500 g of water. This solution
has a boiling point of 100.42C. What mass if glycerol was dissolved to make this solution? (Kb for water = 0.512 K
kg mol1)

1.
2.

1.
2.

1.
2.

1.
2.

2011
(i) Raoults law in its general from in reference to solutions. (ii) Henrys law about partial pressure of a gas in a mixture.
What mass of NaCl must be dissolved in 65.0 g of water to lower the freezing point of water by 7.50C ? The freezing point
depression constant (Kf) for water is 1.86 C/m. Assume Vant Hoff factor for NaCl is 1.87. (Molar mass of NaCl = 58.5 g)
2010
Define the terms, osmosis and osmotic pressure. What is the advantage of using osmotic pressure as compared to other
colligative properties for the determination of molar masses of solutes in solutions?
Describe the role of the following : (i) NaCN in the extraction of silver from a silver ore
(ii) Iodine in the refining of titanium (iii) Cryolite in the metallurgy of aluminium.
2009
Differentiate between molality and molarity of a solution. What is the effect of change in temperature of a solution on its
molality and molarity.
100 mg of a protein is dissolved in just enough water to make 10.0 mL of solution. If this solution has an osmotic pressure
of 13.3 mm Hg at 25 C, what is the molar mass of the protein.
(R = 0.0821 L atm mol1 K1 and 760 mm Hg = 1 atm.)
Ans. 13980
2008
State Henrys law correlating the pressure of a gas and its solubility in a solvent and mention two applications of the law.
(2 marks)
Calculate the temperature at which a solution 54 g of glucose, (C6H12O6), in 250 g of water will freeze.
(Kf for water = 1.86 K mol-1kg).
(2 marks)
Hint: T f

K f w2 1000

Ans: 102.23C.

M 2 w1

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