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SOLUTIONS

GUPTA CLASSES
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SOLUTIONS
SOLUTIONS: Homogeneous mixture of two or more components.

Binary solution: Consisting of only two components.

Solute & Solvent: If two components are in different physical states. The component which is in the same physical state as
that of solution is solvent & other is solute. e.g. solution of sugar in water is a liquid. Solution & water are in same physical
state, so water is solvent and sugar is solute.
If two components are in same physical state, the component in larger quantities is solvent and one in smaller quantities is
solute.

TYPES OF SOLUTIONS
1. Gas (solute) in gas (solvent): Air i.e. O
2
in N
2
.
2. Liquid (solute) in gas (solvent): Chloroform mixed with N
2
gas.
3. Solid (solute) in gas (solvent): Camphor in N
2
gas.
4. Gas (solute) in liquid (solvent): CO
2
dissolved in water.
5. Liquid (solute) in liquid (solvent): Ethanol in water.
6. Solid (solute) in liquid (solvent): Sugar in water.
7. Gas (solute) in solid (solvent): H
2
in Pd.
8. Liquid (solute) in solid (solvent): Hg/Na
9. Solid (solute) in solid (solvent): Alloys

Methods of expressing concentration of a solution
1. Mass percentage (w/w):
Mass% =
of a component
100
mass of solution
Mass
Total

2. Mass-Volume percentage (w/v)
Mass-Volume% = 100
ml in solution of Volume
component a of Mass

3. Volume percentage
Volume% = 100
solution of volume Total
component of Volume

4. Parts per million (ppm) =
6
10
solution of parts of number Total
solute of parts of Number

5. Normality of solution (N)
N =
litres in Volume
solute of mass equivalent gm of Number


EQUIVALENT MASS OF A SOLUTE
(i) Eq. mass of acid =
acid of Basicity
. M . M

(ii) Eq. mass of base =
base of Acidity
. M . M

(iii) Eq. mass of oxidizing or reducing agent =
moluecule 1 by lost or gained electrons of . No
. M . M

(iv) Eq. mass of simple salt =
anions or cations all over charge Total
. M . M

6. Molarity of a solution (M)
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M =
litres in solution of Volume
solute of moles of . No

7. Molality of a solution (m)
m =
Kg in solvent of ass M
solute of moles of . No

8. Mole fraction of a component =
2 1
1
n n
n
+

n
1
= Number of moles of one component
n
2
= Number of moles of 2
nd
component

SOME IMPORTANT RELATIONSHIPS
1. N = x M : x =
mass . Eq
. M . M

2. Normality equation: N
1
V
1
= N
2
V
2

3. Molarity equation : M
1
V
1
= M
2
V
2

x
1
M
1
V
1
= x
2
M
2
V
2

4. Number of gm equivalents of solute = N volume in litres
5. Number of mgm equivalents of solute = N volume in ml
6. Number of gm moles of solute = M volume in litres
7. Number of mgm mole of solute = M volume in ml
8. Relation between molarity (M) and molality (m) of a solution
m =
1000 / M M d
M
2

, m = molality
M = molarity
d = density of solution
M
2
= M.M. of solute
9. Relation between molality (m) and mole fraction (x
2
)
m =
1 1
2
M x
x 1000
x
1
= mole fraction of solvent
x
2
= mole fraction of solute
M
1
= M.M. of solvent
10. Relation between molarity (M) and mole fraction of solute (x
2
)
M =
2 2 1 1
2
M x M x
x d 1000
+



ASSIGNMENT
1. Calculate the mole fraction of ethylene glycol (C
2
H
6
O
2
) in a solution containing 20% of ethylene glycol by mass.
[0.067]
2. Calculate molarity of a solution containing 5gm of NaOH in 450 ml solution [0.28 M]
3. Calculate molality of 2.5 gm of ethanoic acid (CH
3
COOH) in 75 gm of benzene [0.55 m]
4. Calculate the mass % of benzene and carbon tetrachloride if 22 gm of benzene is dissolved in 122 gm of carbon
tetrachloride. [benzene =15.28%, CCl
4
=84.72%]
5. Calculate the mole fraction of benzene in solution containing 30% by mass of CCl
4
.[0.82]
6. Calculate the mass of urea (NH
2
CONH
2
) required in making 2.5 kg of 0.25 m aqueous solution[36.95 g]
7. Calculate
(a) molality, [1.50]
(b) molarity [1.448]
(c) mole fraction [0.026]
of KI if the density of 20% (w/w) aqueous KI is 1.202 gm/ml. [c mol
8. Concentrated HNO
3
used in the lab is 68% by mass in aqueous solution. What is the molarity of the acid if
density of solution is 1.504 gm/ml. [16.23 M]
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9. A solution of glucose in water is labeled as 10% (w/w). What would be the molality, molarity and mole fraction if
the density of solution is 1.2 gm/ml [M=0.667,m 0.617 mole fraction= 0.011 ]
10. How many ml of 0.1 M HCl are required to react completely with 1 gm mixture of Na
2
CO
3
and NaHCO
3
containing equimolar amounts of both. [157.5ml]
11. A solution is obtained by mixing 300 gm of 25% solution and 400 gm of 40% solution by mass. Calculate the
mass % of the resulting solution. [33.57%]
12. An antifreeze solution is prepared from 222.6 gm of ethylene glycol (C
2
H
6
O
2
) and 200 gm of water. Calculate
molality of solution. If the density of the solution is 1.072 gm/ml, then what shall be molarity of solution?
[m=17.95 N 9.1]
13. A sample of drinking water was found to be severely contaminated with chloroform supposed to be a carcinogen.
The level of contamination was 15 ppm (by mass)
(i) Express this in % by mass [% by mass=1.5x10
-3
, m = 1.255x 10
-4
]
(ii) Determine the molality of solution in water
14. A 6.90 M solution of KOH in water contains 30% by mass. Calculate density of KOH solution. [1.288g/ml]
15. Define the term molarity and molality of a solution. How does a change in temperature effects the molarity &
molality of the solution.

SOLUBILITY: Maximum amount of solute that can be dissolved in the given amount of solvent to give a saturated solution
at a given temperature. Solubility depends upon nature of solute, nature of solvent, temperature & pressure.
Solubility of a solid in a liquid: Principle of solubility is like dissolves like i.e. a solute dissolves in a solvent if inter-
molecular interactions are similar in the two. Polar solutes dissolve in polar solvents, e.g. Sodium chloride & barium chloride
are polar, so soluble in polar solvents like water. Sugar, glucose and alcohol dissolve in water due to hydrogen bonding.
Naphthalene and anthracene are non-polar, so soluble in non-polar solvents like benzene.
Effect of temperature on solubility: This follows Le-Chatelier principle. If the dissolution of a solid in a liquid is
exothermic then increase in temperature will decrease the solubility. If the dissolution is endothermic then increase in
temperature will increase the solubility.
Effect of pressure: There is no significant effect of change in pressure on the solubility of a solid in a liquid.

Solubility of a gas in a liquid
Factors effecting solubility of a gas in a liquid
1. Pressure:
Henrys Law: At a given temperature the solubility of a gas in a liquid is directly proportional to the pressure of the gas.
Mole fraction of the gas in a solution is directly proportional to partial pressure of the gas over the solution.
X (g) p (g)
= K
H
p (g) In this equation unit of K
H
in bar
1
or atm
1
.
Or
p (g) X (g)
= K
H
X (g) In this equation units of K
H
in bar or atm.
X (g) = Mole fraction of gas in solution
p (g) = Partial pressure of gas over solution
K
H
= Henrys constant
If value of K
H
is in bar or atm higher is the value of K
H
lower will be solubility of gas and with increase in temperature value
of K
H
will increase.
Applications of Henrys law
(i) To increase the solubility of CO
2
in soft drinks the bottles are sealed under high pressure.
(ii) For respiration of deep sea divers air is diluted with helium in place of air.
(iii) Anoxia is created at high altitudes as partial pressure of oxygen is less, this leads to low concentration of
oxygen in blood and tissues.

2. Effect of temperature
With increase in temperature the solubility of a gas in a liquid decreases.

ASSIGNMENT
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Contact: 9953168795, 9268789880

1. If N
2
gas is bubbled through water at 293 K, how many milimoles of N
2
gas would dissolve in 1 litre of water.
Assume that N
2
exerts a partial pressure of 0.987 bar. Given that Henrys law constant for N
2
gas at 293 K is 76.48
kbar. [0.716 m moles]
2. H
2
S is a toxic gas with rotten egg like smell, is used for qualitative analysis. If the solubility of H
2
S gas in water at
STP is 0.195 m. Calculate the Henrys law constant. [285.71 atm]
3. Henrys law constant for CO
2
in water is 1.67 10
8
Pa. at 298 K. Calculate the quantity CO
2
in 500 ml of soda
water when packed under 2.5 atm, CO
2
pressure at 298 K. [27.78 moles]
4. The partial pressure of ethane over a solution containing 6.56 10
3
gm of ethane is 1 bar. If the solution contains
5.00 10
2
gm of ethane, then what shall be partial pressure of the gas? [7.62 bar]
5. Henrys law constant for the molarity of methane in benzene at 298 K is 4.27 10
5
mm Hg. Calculate the solubility
of methane in benzene at 298 K under 760 mm Hg. [mol fraction of CH
4
=1.78 x 10
-3
]
6. State Henrys law correlating the pressure of a gas and its solubility in a solvent and mention two applications of the
law.
7. At the same temperature hydrogen is more soluble in water than helium. Which of them will have higher value of
K
H
and Y.

Vapour pressure of a liquid
Equilibrium pressure exerted by the vapours of the liquid over the liquid in equilibrium with the liquid.
Raoults law:
At a given temperature the vapour pressure due to a volatile component of a solution is directly proportional to mole fraction
of this component in the solution.
In case of a binary solution of two volatile liquids A and B if partial vapour pressure of A is p
1
and partial vapour pressure of
B is p
2
and vapour pressures of pure liquids A and B are p
1
o
and p
2
o
and respective mole fractions are x
1
and x
2
.
For component A p
1
x
1

= p
1
o
x
1

For component B
p
2
= p
2
o
x
2

so total pressure will be equal to p
1
+ p
2

p
total
= x
1
p
1
o
+ x
2
p
2
o

= (1 x
2
) p
1
o
+ x
2
p
2
o

= p
1
o
+ (p
2
o
p
1
o
) x
2


Raoults law for the solution of a non-volatile solute in a liquid
At a given temperature the vapour pressure of a solution of a non-volatile solute is directly proportional to the mole fraction
of solvent in the solution.
p
1
x
2

p
1
= p
o
x
2
p
1
is vapour pressure of solution,
p
o
is vapour pressure of pure liquid
x
2
is mole fraction of liquid
Let the mole fraction of solute in the solvent is x
1

So mole fraction of solvent x
2
= 1 x
1

So p
1
= p
o
(1 x
1
)
o
1
p
p
= (1 x
1
)
x
1
= 1
o
1
p
p
=
o
1
o
p
p p

i.e. relative lowering of vapour pressure of the solution of a non-volatile solute is equal to mole fraction of solute.

IDEAL SOLUTIONS
The solutions which obey Raoults law at entire range of concentration are known as ideal solutions. When such solutions
are formed there is neither any heat change nor any volume change.

mix
H = 0,
mix
V = 0
mix
S > 0
Ideal solutions are formed when inter molecular attractions between the molecules of two liquids are of the same order.
Examples: (i) Benzene + Toluene
(ii) Cyclohexane + Cycloheptane (iii) Hexane + Heptane
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(iv) C
6
H
5
Cl + C
6
H
5
Br (v) C
2
H
5
Cl + C
2
H
5
Br

ASSIGNMENT
1. Vapour pressure of Chloroform (CHCl
3
) and dichloromethane (CH
2
Cl
2
) at 298 K are 200 mm Hg and 415 mm Hg
respectively. Calculate (i) the vapour pressure of solution prepared by mixing 25.5 gm of CHCl
3
and 40 gm of
CH
2
Cl
2
at 298 K (ii) mole fraction of each component in vapour phase. [3947.9 mm] .[X
CHCl3
= 0.78],
2. Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure 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
vapour phase if 80 gm of benzene is mixed with 100 gm of toluene.[X
benzene
=0.598 X
toluene
= 0.402]
3. 100 gm of liquid A (molar mass 140 gm / mole) was dissolved in 1000 gm of liquid B (molar mass 180 gm / mole)
the vapour pressure of pure liquid B was found to be 500 torr. Calculate the vapour pressure of pure liquid A and its
vapour pressure in the solution if the total vapour pressure of the solution 475 torr. [280.7 mm]

Non-Ideal solutions
The solutions which do not obey Raoults law over the entire range of concentration are known as non-ideal solutions. In this
solutions new intermolecular interactions (A vs B) are different from old intermolecular forces of interactions (A vs A and B
vs B). So escaping tendency of molecules is different from expected so vapour pressure of the solution is different from
expected.

mix
H 0,
mix
V 0

Non-Ideal solution with positive deviation
In these solutions new intermolecular forces of interaction (A vs B) are lower than old intermolecular forces of interaction (A
vs A and B vs B). So escaping tendency of molecules is more than expected and vapour pressure is more than expected.
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In this solutions
mix
H = +ve,
mix
V = +ve
The partial vapour pressure of both components is more than expected as per Raoults law.
The solution of composition corresponding to maxima of the curve forms a constant boiling mixture. i.e. solution of this
composition boils at a constant temperature & distils over without change in composition as if it is a pure liquid. Such a
mixture is known as azeotropic mixture or azeotrope. Since the partial pressures of the two components is more than
expected. So boiling point of the mixture is lower than both the components of the mixture. So such an azeotrope is known as
low boiling azeotrope.
(i) Acetone + Carbon disulphide
(ii) Acetone + Ethyl alcohol
(iii) Acetone + Benzene
(iv) Methyl alcohol + water
(v) Ethyl alcohol + Water
(vi) Carbon tetrachloride + Chloroform
(vii) Carbon telrachloride + Benzene
(viii) Carbon tetrachloride + Toluene

Non-Ideal solution with negative deviation
In this type of solution the new intermolecular interactions (A vs B) are stronger than old intermolecular interactions (A vs A
and B vsB). So escaping tendency of molecules is less than expected. So partial vapour pressures of the two components are
less than expected.

In this solution
mix
H = ve,
mix
V = ve
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The partial vapour pressures of both the components of the mixture are less than expected as from Raoults law. The solution
of composition corresponding to minima of the curve forms a constant boiling mixture, i.e. azeotrope. Since the partial
vapour pressures of both the components is less than expected, so boiling point of the mixture will be more than both the
components. Such a mixture is known as high boiling azeotrope.
(i) Chloroform + benzene
(ii) Chloroform + diethylether
(iii) Acetone + aniline
(iv) HCl + water
(v) HNO3 + water
(vi) Acetic acid + pyridine

COLLIGATIVE PROPERTIES
The properties of dilute solutions of non-volatile solutes which depend upon number of solute particles in the solution and are
independent of the nature of solute are known as colligative properties.
The important colligative properties are
(i) Relative lowering of vapour pressure
(ii) Elevation in boiling point
(iii) Depression in freezing point
(iv) Osmotic pressure
Relative lowering of vapour pressure
According to Raoults law for the solution of a non-volatile solute.
2 1
1
o
s
o
n n
n
p
p p
+
=

, where p
o
= vapour pressure of pure solvent
p
s
= vapour pressure of solution
n
1
= number of mole of solute
n
2
= number of moles of solvent
From this expression it is clear that the relative lowering of vapour pressure depends only on the number of moles of solute
dissolved in a definite number of moles solvent, so it is a colligative property.

Determination of molecular masses of solute from relative lowering of vapour pressure
According to Raoults law for the solution of a non-volatile solute.
2 1
1
o
s
o
n n
n
p
p p
+
=

,
2
2
2
1
1
1
M
w
n ,
M
w
n = =
w
1
= mass of solute
w
2
= mass of solvent
M
1
= M.M. of solute
M
2
= M.M. of solvent
Substituting these values
2 2 1 1
1 1
o
s
o
M / w M / w
M / w
p
p p
+
=


For a very dilute solution n
1
is negligible as compared to n
2
, so n
1
can be neglected in comparision with n
2
. So expression will
be

2
1
o
s
o
n
n
p
p p
=


And
2 2
1 1
o
s
o
M / w
M / w
p
p p
=


In case of both dilute as well as concentrated solution following modified formula is used
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1 2
2 1
s
s
o
M w
M w
p
p p



ASSIGNMENTS
1. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-electrolyte solid
weighing 0.5 gm when added to 39.0 gm of benzene (M.M. 78 gm/mole), vapour pressure of the solution then is
0.845 bar. What is the molecular mass of the solid?
2. Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of water at 293 K, when 25 gm
of glucose is dissolve in 450 gm of water.
3. A solution containing 30 gm of non-volatile solute exactly in 90 gm of water has a vapour pressure of 2.8 KPa at
298 K. Further 18 gm of water is then added to this solution and new vapour pressure becomes 2.9 KPa at 298 K.
Calculate (i) Molar mass of solute (ii) Vapour pressure of water at 298 K.
4. Calculate the mass of a non-volatile solute (M.M = 40 gm/mole) which should be dissolved in 114 gm of octane to
reduce its vapour pressure to 80%.
5. Vapour pressure of water is 12.3 KPa at 300 K. Calculate the vapour pressure of 1 molal solution of a non-volatile
solute in it.
6. 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 molar mass of solute? (vapour pressure of pure water at 100
o
C is 1.013 bar)
7. Two liquids A and B boil at 145
o
C and 190
o
C respectively. Which of them has higher vapour pressure at 80
o
C.
8. Urea forms an ideal solution in water. Determine the vapour pressure of an aqueous solution containing 10% by
mass of urea at 40
o
C. (vapour pressure of water at 40
o
C = 55.3 mm Hg).
9. A solution is made by dissolving 30 gm of non-volatile solute in 90 gm of water. It has a vapour pressure of 2.8 KPa
at 298 K. At 298 K vapour pressure of pure water is 3.64 KPa. Calculate molecular mass of solute.
10. How much urea (M.M = 60gm/mole) should be dissolved in 50 gm of water, so that its vapour pressure at room
temperature is reduced by 25%. Calculate molality of the solution.
11. Expain with a suitable diagram and appropriate example why some non-ideal solutions show negative deviation.
12. What are ideal and non-ideal solutions? Explain with a suitable diagram the behaviour of ideal solutions.

Elevation in boiling point
The boiling point of a liquid is the temperature at which vapour pressure of the liquid becomes equal to atmospheric
pressure.
By addition of a non-volatile solute to a solvent the mole fraction of solvent becomes less than 1 in the solution and as
the vapour pressure of a solution is directly proportional to mole fraction of the solvent. So vapour pressure of a solvent
decreases on addition of non-volatile solute to it. i.e. vapour pressure of the solution of a non-volatile solute is always
less than vapour pressure of pure solvent. This may be explained by taking of plot between vapour pressures of solvent
& solutions & temperature.

At point E (T
o
b) vapour pressure of solvent is equal to atmospheric pressure
So T
o
b is the boiling point of solvent. At point F (Tb) the vapour pressure of solution becomes equal to atmospheric
pressure. So Tb is the boiling point of solution as Tb is greater than T
o
b, i.e. boiling point of solution of non-volatile
solute is higher than boiling point of pure solvent. The difference is known as elevation in boiling point.
Tb = Tb T
o
b
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Tb m
Or Tb = Kb m [ Kb = molal elevation constant or Ebullioscopic constant]
Molal elevation constant is equal to elevation in boiling point shown by 1 molal solution.
As m =
2 1
1
2
1 1
w M
w 1000
1000 / w
M / w

= w
1
= weight of solute
w
2
= weight of solvent
M
1
= molecular mass of solute
Or Tb =
2 1
1
w M
w 1000
Kb


M
1
=
2
1
w Tb
w 1000
Kb
A


Form the above expression it is clear that elevation in boiling point is directly proportional to molality of the solution, i.e.
depends upon on the concentration of the solute. So it is a colligative property.

K
b
=
v
2
o 2
v
2
o
H 1000
RT M
l 1000
RT
A
=
T
o
= boiling point pure solvent
l
v
= latent heat of vaporization per gram of solvent
H
v
= latent heat of vaporization per mole of the solvent
M
2
= M.M. of solvent
R = Molar gas constant
ASSIGNMENT
1. 18 gm of glucose (C
6
H
12
O
6
) is dissolved in 1 Kg of water. At what temperature will water boil at 1.013 bar? Kb for
water is 0.52 K Kg / mole.
2. The boiling point of benzene is 353.23 K. When 1.80 gm of a non-volatile solute was dissolved in 90 gm of
benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of solute. Kb for benzene is 2.53 K
Kg/mole.
3. A solution containing 8 gm of a compound in 100 gm of diethylether boils at 36.86
o
C, whereas the pure ether boils
at 35.60
o
C. Determine the molecular mass of solute. (For ether Kb = 2.02 K Kg/mole)
4. On dissolving 3.24 gm of sulphur in 40 gm of benzene boiling point of solution was higher than that of benzene by
0.81 K. kb value for benzene is 2.53 K Kg/mole. What is molecular formula of sulphur? (At. Mass of sulphur is 32
gm/mole)
5. A solution containing 12.5 gm of non-electrolytic substance in 175 gm of water gave a boiling point elevation of
0.70 K. Calculate molar mass of the substance. (Kb = 0.52 K Kg/mole)
6. 0.90 gm of a non-electrolyte was dissolved in 87.90 gm of benzene. This raised the boiling point of benzene by
0.25
o
C. If the molecular mass of the non-electrolyte is 103.0 gm/mole. Calculate molal elevation constant for
benzene.

Depression in freezing point
At freezing point the solid phase is in equilibrium with the liquid phase. So freezing point is the temperature at which
vapour pressure of the substance in its liquid phase is equal to its vapour pressure in the liquid phase. On addition of non-
volatile solute, the freezing point of a liquid decreases. This can be shown by plotting curves between vapour pressures
of liquid solvent, solution and solid solvent.
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In this plot at point B i.e. at
o
f
T , the vapour pressure of solvent becomes equal to vapour pressure in solid phase. So
o
f
T
is the freezing point of solvent. At point E i.e. at T
f
, the vapour pressure of solution becomes equal to vapour pressure in
solid phase, so T
f
is the freezing point of solution as T
f
is smaller than
o
f
T i.e. freezing point of solution is always less
than freezing point of solvent. This decrease in freezing point is known as depression in freezing point.

f
T =
o
f
T - T
f
, where T
f
= depression in freezing point

o
f
T = freezing point of solvent
T
f
= freezing point of solution

f
T m
Or,
f
T = K
f
m, K
f
= molal depression constant or Cryoscopic constant
It is the depression in freezing point shown by 1 molal solution.
m =
1000 / w
M / w
2
1 1
w
1
= wt. of solute,
w
2
= wt. of solvent
M
1
= M.M. of solute
So T
f
=
1 2
1 f
M w
1000 w K



Or M
1
=
f 2
1 f
T w
1000 w K
A


From this expression, it is clear that depression in freezing depends only on the molality i.e. concentration of solute, so it is a
colligative property.
K
f
=
H 1000
T M R
fusion
o
f 2
2
A


R = molar gas constant,
M
2
= M.M. of solvent,
T
f
o
=freezing point of pure solvent

fusion
H = enthalpy of fusion of solvent

ASSIGNMENT
1. 45 gm of ethylene glycol (C
2
H
6
O
2
) is mixed with 600 gm of water. Calculate (a) freezing point depression ( b) The
freezing point of solution. (K
f
for water = 1.86 K Kg/mole)
2. 1.00 gm of non-electrolyte solute is dissolved in 50 gm of benzene lowered the freezing point of benzene by 0.40 K.
The freezing point depression constant of benzene is 5.12 K Kg/mole. Find the molar mass of solute.
3. A 5% solution by mass of cane sugar in water has a freezing point 271 K. Calculate the freezing point of 5% glucose
in water if freezing point of pure water is 273.15 K.
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4. Two elements A and B form compounds having molecular formula AB
2
and AB
4
. When dissolved in 20 gm of
benzene 1 gm of AB
2
lowers the freezing point by 2.3 K, whereas 1.0 gm of AB
4
lowers it by 1.3 K. The molar
depression constant for benzene is 5.1 K Kg/mole. Calculate atomic masses of A and B.
5. Calculate the temperature at which a solution containing 54 gm of glucose (C
6
H
12
O
6
) in 250 gm of water will freeze.
(K
f
for water = 1.86 K Kg/mole)
6. A 0.1539 molal aqueous solution of cane sugar (M.M. = 342 gm/mole) has a freezing point of 271 K. While the
freezing point of pure water is 273.15 K, what will be the freezing point of an aqueous solution containing 5 gm of
glucose per 100 gm of solution?
7. Calculate the freezing point of a solution containing 0.52 gm of glucose dissolved in 80.2 gm of water.
8. Show graphically that freezing point of a liquid will be depressed when a non-volatile solute is dissolved in it.
9. The molal freezing point depression constant of benzene is 4.90 K Kg/mole. Selenium exists as a polymer Se
x
.
When 3.26 gm of Selenium is dissolved in 226 gm of benzene. The observed freezing point is 0.112
o
lower than
pure benzene. Determine the molecular formula of Selenium (At. Mass of Se = 78.8 gm/mole)
10. An aqueous solution freezes at 272.4 K, while pure water freezes at 273 K. Determine (i) Molality of solution (ii)
Boiling point of solution (iii) Lowering of vapour pressure at 298 K (K
f
= 1.86 K Kg/mole, K
b
= 0.512 K Kg/mole
and vapour pressure of pure water at 298 K = 23.756 mm Hg)
Osmosis & Osmotic pressure
Osmosis
When a solution is separated from solvent or two solutions of different concentration are separated by a semi permeable
membrane, then solvent molecules flow from solvent to solution or from solution of lower concentration of solute to
solution of higher concentration of solute. This spontaneous flow of the solvent molecules from the solvent to solution or
from a less concentrated solution to a more concentrated solution through a semi permeable membrane is known as
osmosis.

Types of semi permeable membranes
(a) Natural semi permeable membranes: Vegetable and animal membranes found just under the outer skin act as semi
permeable membrane. Most common animal membrane is pigs bladder.
(b) Artificial semi permeable membranes : Parchment paper, cello phane, copper ferrocyanide, silicates of ironc cobalt
and nickel.
Exo-osmosis : When a cell is placed in a solution having higher concentration the cell save, there is flow of solvent from cell
to outside this process involves shrinkage of cell (plasmolysis). It is known as exo-osmosis. This is also known as crenation.
Endo-osmosis: When a cell is placed in less concentrated solution, solvent flows from outside to cell and swelling of cell
takes place. This process is known as endo-osmosis. This may also result in rupture of cell wall, this process is known as
hemolysis.
Torgor : The pressure developed inside the shell due to osmosis is known as torgor.
Osmotic Pressure:
(1) It is the equilibrium hydrostatic pressure developed due to osmosis.
(2) It is the minimum pressure that has to be applied on solution to prevent the flow of the solvent to semi permeable
membrane is called osmotic pressure.
Reverse osmosis: When pressure more than osmotic pressure is applied on the solution then solvent molecules flow from
solution to solvent. This process is known as reverse osmosis. This is used for desalination of water.
C
T
C T
= R C T
C =
V
n

So, =
V
n
RT
As n = w/M
So =
V
RT
M
w

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Or M =
V
wRT
t
, [Vant Hoff equation for dilute solution]
Where M= M.M. of solute
w = wt. of solute
R = molar gas constant
= osmotic pressure
V = volume of solution in L
T = temperature in K

Method used for finding out the osmotic pressure
Barkeley and Hartleys Method
The above expression shows that osmotic pressure depends only on the concentration of solute, so it is a colligative property.
The method use to find out the molecular masses of macro-molecules like proteins is osmotic pressure as
(i) The osmotic pressure is determined at room temperature, so denaturation of proteins is avoided.
(ii) The molecular mass of macro-molecules is so large that in the solution, the molar concentration is very small
and it is only osmotic pressure whose value is measurable.
Isotonic solution: Solutions having same osmotic pressure.
Hypotonic solution: Solution having lower osmotic pressure.
Hypertonic solutions: Solution having higher osmotic pressure.
0.91% solution of NaCl is isotonic with human red blood cell (RBC).

ASSIGNMENT
1. 200 ml of an aqueous solution of a protein contains 1.26 gm of protein. The osmotic pressure of such a solution at
300 K is found to be 2.57 10
3
bar. Calculate the molar mass of protein. (R = 0.083 L bar mole
1
K
1
)
2. Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 gm of polymer of molar
mass 185000 in 450 ml of water at 37
o
C.
3. At 300 K 36 gm of glucose present in 1 L of its solution has an osmotic pressure of 4.98 bars. If the osmotic
pressure of the solution is 1.52 bars at the same temperature, what would be its concentration?
4. Define osmotic pressure. Describe how the molecular mass of a substance; can be determined by a method based on
measurement of osmotic pressure?
5. What are conditions which result in reverse osmosis?
6. A 4% solution of sucrose is isotonic with 3% solution of an unknown organic substance. Calculate molecular mass
of unknown substance.
7. 1 L aqueous solution of sucrose (M.M. = 342 gm/mole) weighing 1015 gm is found to record an osmotic pressure of
4.82 atm at 293 K. What is the molarity of the solution?
8. Calculate the osmotic pressure of a solution obtained by mixing 100 ml of 1.5% solution of urea and 100 ml of
3.42% solution of cane sugar at 20
o
C.

ABNORMAL MOLECULAR MASSES
The colligative properties depend upon actual concentration of solute particles in the solution. In some solutions, the
solute may undergo dissociation or association. So effective concentration of solute particles is not as calculated and the
calculated molecular mass using these properties will be different from the actual molecular mass. So the molecular
masses determinate are known as abnormal molecular masses.
If the solute dissociates in the solution then the effective concentration of solute particles will be more than calculated.
So observed colligative properties will be higher than calculated and observed molecular mass will have lower value
than calculated.
If the solute molecules associate in solution then effective concentration of solute particles will be less than calculated
and colligative properties will be less than calculated and observed molecular masses will be higher than calculated. In
some cases on addition of a solute to a solution, due to complex formation the concentration of solute particles decreases
(instead of increasing).
e.g. when HgI
2
is added to KI solution following complex is formed
2KI + HgI
2
K
2
[HgI
4
]
2KI 2K
+
+ 2I


K
2
[HgI
4
] 2K
+
+ HgI
4
2

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So on addition of HgI
2
to KI solution the effective concentration of solute particle decreases, so magnitude of colligative
properties decreases.
Vant Hoff factor (i)
This factor gives the extent of association or dissociation of solute molecules in the solution.
i =
on dissociati nor n associatio neither is hen there property w e colligativ of value Calculated
property e colligativ of value al Experiment
.
i =
f
f
T of value Normal
T of value Observed
A
A
or i =
b
b
T of value Normal
T of value Observed
A
A

i =
t
t
of value Normal
of value Observed

i =
pressure vapour weringof relativelo of value Normal
pressure vapour of lowering relative of value Observed

i =
M.M. Observed
M.M. Normal

Calculation of the degree of dissociation of solute in a solution
Degree of dissociation is defined as defraction of the total number of molecules that ionizes. Let the degree of dissociation be
.
An nA
1- n
So total number of moles of solute in solution equal to 1 + n = 1 + (n 1)
i =
1
) 1 n ( 1 o +

=
1 n
1 i


Calculation of degree of association of solute molecules in solution
Degree of association is fraction of total number of molecules of solute which have undergone association in the solution. Let
degree of association be . Let n molecules of solute undergo association.
nA An
1- /n
So total number of moles of solute particles in solution = 1 + /n
i =
1
/n - 1 o + o

So =
1 - n
n i) - (1



ASSIGNMENT
1. 2 gm of benzoic acid (C
6
H
5
COOH) dissolved in 25 gm of benzene shows a depression in freezing point equal to
1.62 K. Molal depression constant for benzene is 4.9 K Kg/mole. What is the percentage association of the acid if it
forms a dimmer in the solution?
2. 0.6 ml of acetic acid (CH
3
COOH) having density 1.06 gm/ml is dissolved in 1 L of water. The depression in
freezing point observed was 0.0205
o
C. Calculate the Vant Hoff factor and the dissociation constant of acid.
3. Determine the osmotic pressure of a solution prepared by dissolving 25 mgm of K
2
SO
4
in 2 L of water at 25
o
C
assuming that it is completely dissociated.
4. Determine the amount of CaCl
2
(i = 2.47) dissolved in 2.5 L of water, such that its osmotic pressure is 0.75 atm at
27
o
C.
5. 19.5 gm of CH
2
FCOH is dissolved in 500 gm of water. The depression in the freezing point of water observed is
1.0
o
C. Calculate the Vant Hoff factor and dissociation constant of acid.
6. Calculate the depression in freezing point of water when 10 gm of CH
3
CH
2
CHClCOOH is added to 250 gm of
water. (K
a
= 1.4 10
3
, K
f
= 1.86 K Kg/mole)
7. Of 0.1 m solution of glucose and NaCl respectively which one will have higher boiling point and why?
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8. On dissolving 3.1 gm of BaCl
2
in 250 gm of water, the solution boils at 100.083
o
C. Calculate Vant Hoff factor and
molality of solution. (K
b
= 0.52 K Kg/mole, M.M of BaCl
2
= 208.3 gm/mole)
9. The depression in freezing point of water observed for same molar concentration of acetic acid, trichloro acetic acid
and trifluoro acetic acid increases as stated about. Explain.
10. Why is the freezing point of 0.1 M solution of NaCl nearly twice that of 0.1 M glucose solution?
11. The freezing point of a solution containing 0.3 gm of acetic acid in 30.0 gm of benzene is lowered by 0.45
o
C.
Calculate Vant Hoff factor. (K
f
= 5.13 K Kg/mole)
12. What is meant by Vant Hoff factor? The osmotic pressure of 0.0103 M solution of an electrolytic is found to be
0.70 atm at 27
o
C. Calculate the Vant Hoff factor. R = 0.082 L atm mole
1
K
1
.)

Multiple Choice Questions with one Answer
1. The ratio of the value of any colligative property for KCl solution to that for sugar solution is nearly
(a) 1.0 (b) 0.5 (c) 2.0 (d) 2.5
2. Which of the following solutions will have maximum freezing point ?
(a) 0.01 M urea (b) 0.01 M KCl (c) 0.01 M BaCl
2
(d) 0.01 M NaCl
3. The osmotic pressure observed when benzoic acid is dissolved in benzene is less than expected.This may be due to the
reason that
(a) Benzoic acid is an organic solute
(b) Benzoic acid has higher molar mass than benzene
(c) Benzoic acid gets associated in benzene
(d) Benzoic acid gets dissociated in benzene .
4. The relative lowering of vapour pressure of a solution on the addition of a non- volatile sloute
(a) Is equal to mole fraction of the solute
(b) Is equal to the mole fraction of the solvent
(c) Depends upon the nature of the solute
(d) Depends upon the nature of the solute and solvent.
5. What happens when an egg is kept in a saturated solution of NaCl after removing hard shell of the egg in dilute
hydrochloric acid ?
(a) Egg will shrink (b) Egg will grow
(c) Egg will remain same (d) Egg will first shrink and then grow
6. The normality of 1 M H
3
PO
4
is
(a) 1N (b) 3N (c) 0.33N (d) 0.5 N
7. Osmotic pressure is measured by
(a) Ostwald's method (b) Berkeley and Hartley method
(c) Pfeffer's method (d) Beckmann's method
8. When glycerine is added to a litre of water, which of the following is observed ?
(a) Water evaporates more readily
(b) The viscosity of water decreases
(c) The freezing point of water is lowered
(d) The temperature of water increases
9. What will happen if a thin slice of sugar beet is placed in a concentrated solution of sodium chloride?
(a) Sugar beet will lose water from its cells
(b) Sugar beet will absorb water from solution
(c) Sugar beet will neither absorb nor lose water
(d) Sugar beet will dissolve in solution.
10. A solution contains 16 g of methanol and 90 g of water. The mole fraction of methanol in the solution is
(a) 0.909 (b) 0.826 (c) 0.091 (d) 0.182
11. What volume of 36N and 1N sulphuric acid should be mixed to get 1L of 6N acid solution
(a) 96.7 ml of 36N +903.3 ml of 1N (b) 142.8ml of 36N +857.2ml of 1N
(b) 903.3ml of 36N +96.7ml of 1N (d) 100ml of 36N +900ml of 1N
12. An aqueous solution of urea having 6 g in 500ml has a density of 1.05. If the molar mass of urea is 60 , its molality
will be
(a) 0.193m (b) 0.190m (c) 0.200m (d) 0.10m
13. The weight of (COOH)
2
2H
2
O needed to prepare 500ml of 0.1M solution is
(a) 12.6 g (b) 9.0 g (c) 4.5 g (d) 6.3 g
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14. The vapour pressure of ethanol at 298K is 40mm of mercury. Its mole fraction in a solution with methanol is 0.80. Its
vapour pressure in the solution is
(a) 8 mm Hg (b) 32 mm Hg (c) 48 mm Hg (d) 80 mm Hg
15. The osmotic pressure of a 0.2 m solution of non- electrolyte at 27
0
C (R= 0.082 L K
-1
mol
-1
) is :
(a) 4.92 atm (b) 1 atm (c) 0.2 atm (d) 27 atm
16. Two liquids A and B have vapour pressures 500 and 200 torr respectively at a certain temperature. In an ideal solution of
the two, the mole fraction of A at which two liquids have equal partial pressures is
(a) 0.50 (b) 0.20 (c) 0.286 (d) 0.714
17. Phenol associates in benzene to form the dimers, (C
6
H
5
OH)
2
. The normal mass and the observed molar mass of phenol in
benzene have been found to be 94 and 146.3 respectively.The degree of association of phenol in benzene is :
(a) 72.7% (b) 75% (c) 32.6% (d) 71.5%
18. A litre of public water contains 5 mg of chlorine. The concentration of chlorine in ppm is :
(a) 5 10
-4
(b) 5 (c) 50 (d) 0.5
19. The molality of 1 litre solution of 98% sulphuric acid (w/v)having density 1.88g/ml is
(a) 10.1 (b) 11.1 (c) 5.55 (d) 2.6
20. The Van't Hoff factor for calcium nitrate Ca(NO
3
)
2
is 2.5 .Using the dissociation equilibrium,
Ca(NO
3
)
2
Ca
2+
+ 2NO
3
-
the degree of dissociation is :
(a) 0.25 (b) 0.33 (c) 0.66 (d) 0.75
21. 100 ml of 0.3 N HCl are mixed with 200 ml of 0.6 N H
2
SO
4
. The final normality of the resulting solution will be
(a) 0.1 N (b) 0.2 N (c) 0.3 N (d) 0.5 N
22. How many grams of a dibasic acid (molar mass = 200) should be present in 100 ml of its aqueous solution to give
decinormal strength?
(a) 1 g (b) 2g (c) 10 g (d) 20 g
23. 0.01 M solution each of urea, common salt and Na
2
SO
4
are taken, the ratio of depression of freezing point is
(a) 1 : 1 : 1 (b) 1 : 2 : 1 (c) 1 : 2 : 3 (d) 2 : 2 : 3
24. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method corresponds to
(a) Ionization of benzoic acid (b) Dimerization of benzoic acid
(c) Trimerization of benzoic acid (d) Saturation of benzoic acid
25. 6.3g of hydrated oxalic acid is dissolved to get 500ml solution. Its normality will be:
(a) 0.1N (b) 0.2N (c) 0.25N (d) 0.4N
26. Out of molarity (M), molality(m), mole fraction (x) and normality (N), those depenedent on temperature are:
(a) M. m (b) m. x (c) M, N (d) N, x
27. 100 ml of decinormal HCl is mixed with 400ml of decimolar HCl. The normality of the resultant solution will be:
(a) 0.1 (b) 0.01 (c) 0.05 (d) 0.2
28. The molecular mass of KCl as determined by cryoscopic method is nearly:
(a) 74.5 (b) 149.0 (c) 37.25 (d) None

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