AIEEE-Chemistry 79 Day 6: Solutions

35
days
QUICK CONCEPT KIT
1. Solution: Homogeneous mixture of two or
more non reacting components whose
composition can be varied within certain
limits is known as solution. In binary
solution.
(i) Solute: The component which is
present relatively in smaller
proportion in the solution is called
solute.
(ii) Solvent: The component which is
present in larger proportion in the
solution is called solvent.
2. Types of solutions:
Solute Solvent Example
Gas Gas Air
Gas Liquid Aerated water
Gas Solid Occluded hydrogen on Pt
Liquid Gas Moist air
Liquid Liquid Alcohol in water
Liquid Solid Mercury in zinc amalgam
Solid Gas Iodine vapour in air
Solid Liquid Salt solution
Solid Solid Alloys
3. Factors affecting solubility:
(a) Temperature: If the dissolution is
endothermic the solubility increases
with increase in temperature e.g.
KNO
3
, NaCl.
If the dissolution is exothermic the
solubility decreases with increase in
temperature e.g. Li
2
CO
3
, Na
2
CO
3
.
(b) Nature of solute and solvent.
4. Factors affecting the solubility of a gas
(i) Nature of the gas: Easily liquifiable
gases have more solublity. e.g. CO
2
is
more soluble than O
2
and H
2
.
(ii) Nature of Solvent: Gases capable of
forming ions in aqueous solution are
more soluble in water than in other
solvents. e.g. HCl, NH
3
etc.
(iii) Temperature: Solubility decreases with
rise of temperature at constant pressure.
(iv) Pressure of the gas (Henrys Law).
5. Henrys law: The law states that mole
fraction of gas in the solution is
proportional to the partial pressure of the
gas over the solution.
p = k
H
x
Here k
H
is the Henrys constant. Different
gas have different k
H
values at the same
temperature.
Applications:
(i) To increase the solubility of CO
2
in soft
drinks, the bottle is sealed under high
pressure.
Day
6
SOLUTIONS
Trend Analysis
2002 3 2007 3
2003 3 2008 2
2004 5 2009 2
2005 6 2010 2
2006 2011 *
Day 6: Solutions 80 AIEEE-Chemistry
35
days
(ii) To avoid bends scuba divers use oxygen
diluted by nitrogen and helium.
6. Expression of the concentration of a
solution:
(a) Percentage (%):
By mass: Mass of solute per 100 g of
solution.
By volume: Volume of solute per 100
mL of solution.
(b) Normality (N): Number of gram
equivalents of the solute dissolved per
litre of the solution.
N =
mass of solute 1000
Eq. mass of solute volume (in mL)
(c) Molarity (M): Number of gram moles
of the solute dissolved in one litre of
solution.
M =
0 mass of solute 100
M. mass of solute volume (in mL)
(e) Molality (m): Number of gram moles
of solute dissolved in 1000 g of the
solvent.
m =
mass of solute 1000
M. mass of solute mass of solvent (in g)
(e) Mole fraction: The ratio of the number
of moles of one component to the total
number of moles of solution. For
components A & B.
x
A
=
A B
B A B
A B A B
n n
; x = ; x x =1
n +n n + n
+
(f) ppm (parts per million): It is the mass of
the solute present in million (10
6
) parts
by mass of the solution.
ppm =
6
Mass of solute 10
Mass of solution
Molality (m), mole fraction (x), ppm and
mass fraction do not change with
tempe-rature.
(g) Demal (D): When one mole of solute
is present in one litre of the solution
at 0C, it is known as one Demal.
(h) Formality (F): Number of gram formula
mass present in one litre of solution. It
is generally used for ionic compounds.
7. Vapour pressure: It is defined as the
pressure of the vapour phase in equilibrium
on the surface of liquid at particular
temperature.
(i) Vapour pressure of a liquid increases
with rise in temperature.
(ii) When intermolecular forces are weak,
the liquid is more volatile and has more
vapour pressure.
8. Raoults Law: The partial pressure of a
volatile component of a solution is directly
proportional to its mole fraction in solution
at any temperature.
P
A
x
A
, P
B
x
B
and p
A
= p
o
A
. x
A
, P
B
= P
o
B
x
B
where P
A
= partial pressure of component A,
P
o
A
= vapour pressure of component A in
pure form,
x
A
= mole fraction of component A in
solution.
Remember P
A
= P
t
Y
A
, P
B
= P
t
Y
B
also,
where P
t
= Total pressure and Y
A
& Y
B
are
Mole fraction of component A and B in
vapour phase respectively.
9. Ideal solution: The solution which fulfill
following conditions. (I) Obey Raoults law
at all temperatures and concentrations (II)
H
mix
= 0 (no heat is evolved or absorbed
when components are mixed to form the
solution) (III) V
mix
= 0 (no change in
volume). In ideal solution the A B
intermolecular interactions are the same as
A A and B B intermolecular interactions.
Strictly there is no ideal solution. The
following pairs almost behave as ideal
solutions.
(a) Benzene and toluene
AIEEE-Chemistry 81 Day 6: Solutions
35
days
(b) ethyl bromide and ethyl chloride
(c) n-Heptane and n-hexane
10. Non ideal solutions: Solutions which (I) do
not obey Raoults law (II) H
mix
0 (III)
V
mix
0.
Types of non ideal solutions:
(I) Showing positive deviations: For such
solutions (a) A B intermolecular
interactions are weaker than A A
and B B intermolecular interactions
(b) H
mix
is +ve (c) V
mix
is +ve.
Examples: Acetone + Ethyl alcohol,
Acetone + Benzene, Ethyl alcohol +
Water.
(II) Showing negative deviations: For such
solutions (a) A B intermolecular
interactions are stronger than A A
and B B intermolecular interactions
(b) H
mix
is ve (c) V
mix
is ve.
Examples: Chloroform + Acetone, HCl
+ Water, HNO
3
+ Water.
11. Azeotropic mixture or Constant boiling
mixture: A mixture of two or more
components which like a pure chemical
compound boils and distills over
completely at the same temperature
without change in composition is called an
azeotrope. Non ideal solutions form
azeotropes.
(i) Azeotropic mixture with minimum
boiling point: Formed by liquids
showing positive deviation. An
intermediate composition of liquids
having highest vapour pressure, hence
lowest boiling point gives this
azeotrope. Such azeotropes have boiling
points lower than either of the pure
component, e.g. Rectified spirit (ethanol
95.5% + H
2
O 4.50%) b.pt. 351.5 K.
(ii) Azeotropic mixture with maximum
boiling point: Formed by liquids
showing negative deviation. An
intermediate composition of liquids
having minimum vapour pressure,
hence highest boiling point gives this
azeotrope. Such azeotropes have boiling
points higher than either of the pure
components e.g. Water & HNO
3
(HNO
3
68% + H
2
O 32%) b.pt. 393.5 K.
12. Graphical representation of ideal and non
ideal solutions.
Ideal Solution
Positive Deviation
Negative Deviation
13. Colligative properties: Properties which
depend only upon the number of particles
irrespective of their nature (ions or
molecules) are called colligative properties.
Day 6: Solutions 82 AIEEE-Chemistry
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(I) Relative lowering of vapour pressure:
It is measured by Ostwald Walkers
method (Gas saturation method).
o
s
o
p p
p

= X
solute
where X
solute
is mole fraction of solute.
For dilute solutions
M
B
=
o
B A
A S
W .M P
W P-P
| |
|
\
where W
B
and W
A
are mass of solute
and solvent and M
B
is the molar mass
of solute.
(II) Osmotic pressure: Osmotic pressure is
external pressure applied on solution to
stop osmosis. Osmosis is the spon-
taneous flow of the solvent through a
semi-permeable membrane from pure
solvent to solution or from a dilute
solution to concentrated solution.
Some natural semipermeable
membranes are pigs bladder and red
blood corpuscles.
Cupric ferrocyanide Cu
2
[Fe(CN)
6
] is
artificially prepared semipermeable
membranes. It is not suitable for non
aqueous solution as it gets dissolved.
Osmotic pressure is also defined as the
hydrostatic pressure developed on the
solution which j ust prevents the
osmosis of pure solvent into the solution
through a semipermeable membrane is
called osmotic pressure.
= CRT
M
B
=

W R T
V
Determination of Osmotic pressure:
(a) Pfeffers Method
(a) Berkeley and Hartleys Method
Isotonic Solutions: Solutions having
the same osmotic pressure. 0.91% NaCl
solution is isotonic with human RBCs.
Hypotonic Solution: Solution having
lower osmotic pressure than other solution.
Hypertonic Solution: Solution having
higher osmotic pressure than other
solution.
Reverse Osmosis: When the external
pressure applied on the solution is more
than osmotic pressure, the solvent flows
from the solution to the pure solvent it
is called reverse osmosis. Desalination
of sea water is done by reverse osmosis
to make it potable.
Exo-Osmosis: Outward osmotic flow of
fluid from a cell through semipermeable
membranes e.g. grape in conc. NaCl
solution.
Endo-Osmosis: Inward osmotic flow of
fluid from a cell through semipermeable
membrane e.g. grape in water.
(III) Elevation in boiling point ( T
b
):
Addition of non volatile solute in a
solvent lowers the vapour pressure and
increases the boiling point. Elevation in
boiling point is directly proportional to
the molality of solution.
T
b
m, T
b
= K
b
m =
b B
B A
K W 1000
M W
K
b
= molal elevation constant or
Ebullioscopic constant. It is characteristic
for given solvent. When
m = 1, T
b
= K
b
.
Thus molal elevation constant is
defined as the elevation in boiling point
caused by one molal solution.
Units of K
b
= K kg mol
1
(IV) Depression in freezing point ( T
f
): The
temperature at which the vapour
pressure of the solvent in its liquid and
solid phase becomes the same is known
as freezing point of solvent.
When non volatile solute is dissolved
in a solvent, the freezing point
decreases. Depression in freezing point
(T
f
) is given by
T
f
m, T
f
= K
f
m =
f B
B A
K W 1000
M W
AIEEE-Chemistry 83 Day 6: Solutions
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days
K
f
is molal depression constant or molal
Cryoscopic constant, When m (molality)
= 1 then T
f
= K
f
Hence molal depression constant or
molal Cryoscopic constant is equal to
depression in freezing point caused by
one molal solution.
Units of K
f
= K. kg mol
1
14. Abnormal Molecular Masses and
Colligative Properties: When solutes
undergo association or dissociation in
solution, there is decrease or increase
in number of particles and there are
discrepancies between observed and
calculated values of colligative properties.
Colligative property
1
.
Molecular
mass of solute
Hence higher values are obtained for
molecular masses in case of association.
Acetic acid in benzene associates and its
observed molecular mass is 120.
KCl in water dissociates and its observed
molecular mass is 37.25.
These observed values are corrected by
multiplying by Vant Hoff factor (i) to get
normal molar mass.
15. Vant Hoff Factor (i): Its value is obtained
by any of the following expression
(I)
Normal molecular mass
Observed molecular mass
= i
(II)
Observed valueof colligative property
=
Calculated valueof colligative property
i
(III)
No.of particles after association or dissociation
=
No.of particles beforeassociation or dissociation
i
16. Degree of dissociation ( ):
1
=
m 1
i

Here m = number of particles.

i = Vant Hoff factor i.
17. Degree of association ( ):
1
=
1
1
m

i
IMPORTANT CONCEPTUAL FACTS
1. Normality = n Molarity
where n =
Molecular mass
Equivalent mass
2. When solvent is water, a molar solution (1
M) is more concentrated than a one molal
(1 m) solution.
3. Mole fraction is a dimensionless quantity.
4. Deep sea divers dilute O
2
with He in place
of N
2
because of its least solubility in water.
5. The rupture of a cell due to inflow of solvent
into it is called hemolysis whereas
shrinking of the cell due to outflow of the
solvent is called Crenation or plasmolysis.
6. Osmotic pressure is the best colligative
property to determine the molecular mass
of polymers and proteins because the value
of other colligative property is too small to
be measured with accuracy.
7. Ethylene glycol is commonly added to car
radiators to depress the freezing point of
water. It is known as antifreeze solution.
8. When two solutions of a substance are mixed
then resulting molarity of solution =
1 1 2 2
1 2
M V + M V
V + V
.
9. NaCl or CaCl
2
(anhydrous) are used to clear
snow on roads. It depreses the freezing point
of water and reduces the temperature at
which ice is expected to be formed.
10. Modified expression for colligative
properties
o
A A
solute
o
A
P P
= i X ,
P
T
b
= i k
b
m,
T
f
= i K
f
m, = i CRT
11. For solution of different solutes of the same
percent strength, the magnitude of the
Day 6: Solutions 84 AIEEE-Chemistry
35
days
colligative property is more for that solute
which gives more number of particles
which can be known from the knowledge
of molecular mass and its ionisation
behaviour. For example,
(i) Amongst the 0.1 M solution of urea,
NaCl, BaCl
2
, Na
3
PO
4
and Al
2
(SO
4
)
3
,
the vapour pressure and freezing point
will be the lowest while boiling point
will be highest for Al
2
(SO
4
)
3
.
(ii) Amongst the 0.1 percent solution of
urea, glucose and sucrose, vapour
pressure and freezing point are the lowest
while boiling point is highest for urea.
PREVIOUS YEAR

S AIEEE QUESTIONS
1. Which of the following concentration factor
is affected by change in temperature?
(a) Molarity (b) Molality
(c) Mole fraction (d) Weight fraction
(2002)
2. In a mixture of A and B, components show
negative deviation when
(a) AB interaction is stronger than AA
and BB interaction
(b) AB interaction is weaker than AA
and BB interaction
(c) V
mix
> 0, S
mix
> 0
(d) V
mix
= 0, S
mix
> 0 (2002)
3. For an aqueous solution, freezing point is
0.186C. Elevation of the boiling point of
the same solution is (k
f
= 1.86C mol
1
kg
and k
b
= 0.512C mol
1
kg)
(a) 0.186C (b) 0.0512C
(c) 1.86C (d) 5.12C (2002)
4. In a 0.2 molal aqueous solution of a weak
acid HX, the degree of ionization is 0.3.
Taking K
f
for water is 1.85, the freezing
point of the solution will be nearest to
(a) 0.480C (b) 0.360C
(c) 0.260C (d) +0.480C (2003)
5. 25 mL of a solution of barium hydroxide
on titration with a 0.1 molar solution of
hydrochloric acid gave a titre value of 35
mL. The molarity of barium hydroxide
solution was
(a) 0.07 (b) 0.14
(c) 0.28 (d) 0.35 (2003)
6. If liquids A and B form an ideal solution,
the
(a) enthaply of mixing is zero
(b) entropy of mixing is zero
(c) free energy of mixing is zero
(d) free energy as well as the entropy of
mixing are each zero. (2003)
7. Which one of the following aqueous
solutions will exhibit highest boiling
point?
(a) 0.01 M Na
2
SO
4
(b) 0.01 M KNO
3
(c) 0.015 M urea (d) 0.015 M glucose
(2004)
8. 6.02 10
20
molecules of urea are present
in 100 mL of its solution. The concentration
of urea solution is
(a) 0.001 M (b) 0.01 M
(c) 0.02 M (d) 0.1 M (2004)
9. To neutralize completely 20 mL of 0.1 M
aqueous solution of phosphorous acid
(H
3
PO
3
), the volume of 0.1 M aqueous
KOH solution required is
(a) 10 mL (b) 20 mL
( c) 40 mL (d) 60 mL (2004)
10. Which of the following liquid pairs shows
a positive deviation from Raoults law?
(a) Water-hydrochloric acid
(b) Benzene-methanol
(c) Water-nitric acid
(d) Acetone-chloroform (2004)
11. Which of the following statement is false?
(a) Raoults law states that the vapour
pressure of a component over a solution
is proportional to its mole fraction.
(b) The osmotic pressure () of a solution is
given by the equation = MRT, where
M is the molarity of the solution.
AIEEE-Chemistry 85 Day 6: Solutions
35
days
(c) The correct order of osmotic pressure for
0. 01 M aqueous solution of each
compound is BaCl
2
> KCl > CH
3
COOH
> sucrose.
(d) Two sucrose solutions of same molality
prepared in different solvents will have
the same freezing point depression.
(2004)
12. If is the degree of dissociation of Na
2
SO
4
,
the Vant Hoff factor (i) used for calculating
the molecular mass is
(a) 1 + (b) 1
(c) 1 + 2 (d) 1 2 (2005)
13. Benzene and toluene form nearly ideal
solutions. At 20C, the vapour pressure of
benzene is 75 torr and that of toluene is
22 torr. The partial vapour pressure of
benezene at 20C for a solution containing
78 g of benzene and 46 g of toluene in
torr is
(a) 50 (b) 25
(c) 37.5 (d) 53.5 (2005)
14. Two solutions of a substance (non
electrolyte) are mixed in the following
manner. 480 mL of 1.5 M first solution
+520 mL of 1.2 M second solution. What is
the molarity of the final mixture?
(a) 1.20 M (b) 1.50 M
(c) 1.344 M (d) 2.70 M (2005)
15. Equimolal solutions in the same solvent
have
(a) same boiling point but different freezing
point
(b) same freezing point but different boiling
point
(c) same boiling and same freezing points
(d) different boiling and different freezing
(2005)
16. Density of a 2.05 M solution of acetic acid
is 1.02 g/mL. The molality of the solution
(a) 1.14 mol kg
1
(b) 3.28 mol kg
1
(c) 2.28 mol kg
1
(d) 0.44 mol kg
1
(2005)
17. 18 g of glucose (C
6
H
12
O
6
) is added to 178g
water. The vapour pressure of water for this
aqu. solution at 100C is
(a) 759.00 torr (b) 7.60 torr
(c) 76.00 torr (d) 752.40 torr. (2005)
18. The density (in g mL
1
) of a 3.60 M sulphuric
acid solution that is 29% H
2
SO
4
(molar mass
= 98 g mol
1
) by mass will be
(a) 1.45 (b) 1.64
(c) 1.88 (d) 1.22 (2007)
19. A mixture of ethyl alcohol and propyl
alcohol has a vapour pressure of 290 mm
and 300 K. The vapour pressure of propyl
alcohol is 200 mm. If the mole fraction of
ethyl alcohol is 0.6, its vapour pressure (in
mm) at the same temperature will be
(a) 360 (b) 350
( c) 300 (d) 700 (2007)
20. A 5.25% solution of a substance is isotonic
with a 1.5% solution of urea (molar mass
= 60 g mol
1
) in the same solvent. If the
densities of both the solutions are assumed
to be equal to 1.0 g cm
3
, molar mass of the
substance will be
(a) 210.0 g mol
1
(b) 90.0 g mol
1
(c) 115.0 g mol
1
(d) 105.0 g mol
1
(2007)
21. At 80C, the vapour pressure of pure liquid
A is 520 mmHg and that of pure liquid B
is 1000 mm Hg. If a mixture solution of A
and B boils at 80C and 1 atm pressure,
the amount of A in the mixture is (1 atm =
760 mm Hg)
(a) 52 mole percent (b) 34 mole percent
(c) 48 mole percent (d) 50 mole percent
(2008)
22. The vapour pressure of water at 20C is 17.5
mmHg. If 18 g of glucose (C
6
H
12
O
6
) is
added to 178.2 g of water at 20C, the
vapour pressure of the resulting solution
will be
(a) 17.675 mmHg (b) 15.750 mmHg
(c) 16.500 mmHg (d) 17.325 mmHg
(2008)
Day 6: Solutions 86 AIEEE-Chemistry
35
days
23. Two liquids X and Y form an ideal solution.
At 300 K, vapour pressure of the solution
containing 1 mol of X and 3 mol of Y is 550
mm Hg. At the same temperature, if one
mole of Y is further added to this solution,
vapour pressure of the solution increases
by 10 mmHg, vapour pressure (in mmHg)
of X and Y in their pure states will be
respectively:
(a) 200 and 300 mm (b) 300 and 400 mm
(c) 400 and 600 mm (d) 500 and 600 mm
(2009)
24. A binary liquid solution is prepared by
mixing n-heptane and ethanol. Which one
of the following statement is correct
regarding the behaviour of the solution?
(a) The solution formed is an ideal solution
(b) The solution is non-ideal, showing +ve
deviation from Raoults Law
(c) The solution is non-ideal, showing ve
deviation from Raoults Law
(d) n-heptane shows +ve deviation while
ethanol shows ve deviation from
Raoults Law. (2009)
25. On mixing, heptane and octane form an
ideal solution. At 373 K, the vapour
pressures of the two liquid components
(heptane and octane) are 105 kPa and 45 kPa
respectively. Vapour pressure of the solution
obtained by mixing 25 g of heptane and 35 g
of octane will be (molar mass of heptane 100
g mol
1
and of octane = 114 g mol
1
).
(a) 72.0 kPa (b) 36.1 kPa
(c) 96.2 kPa (d) 144.5 kPa (2010)
26. If sodium sulphate is consider to be
completely dissociated into cations and
anion in aqueous solution then what will
be the change in freezing point of water
( T
f
), when 0.01 mol of sodium sulphate
is dissolved in 1 kg of water. [K
f
= 1.86
Kkg mol
1
]
(a) 0.0372 K (b) 0.0556 K
(c) 0.0744 K (d) 0.0186 K (2010)
HINTS AND SOLUTIONS
1. (a): Molarity get changed by temperature
because it depends upon volume [Volume is
a temperature dependent term].
2. (a): Negative deviation means lower vapour
pressure, thus resultant intermolecular force
should be stronger than individual one.
3. (b): T
b
= mk
b
, T
f
= mk
f
b
f
T
T

=
0.512
=
1.86
b
f
k
k
T
b
=
0.512
0.186
1.86
= 0.0512C
4. (a): HX

H
+
+ X

initial 1 0 0
final 1 0.3 0.3 0.3
Total number of moles after dissociation
= 1 0.3 + 0.3 + 0.3 = 1.3.
(observed)
no. of moles after dissociation
(experimental) no. of moles before dissociation
f
f
K
K
=
or,
(observed)
1.3
1.85 1
=
f
K
or, K
f
(observed) = 1.85 1.3 = 2.405.
T
f
= K
f
molality = 2.405 0.2 = 0.4810.
Freezing point of solution = 0 0.481 =
0.481(c)
5. Ba(OH)
2
+ 2HCl BaCl
2
+ 2H
2
O
1 1
M V
2
=
2 1
M V
2
M
1
=

0.1 35
= 0.07
2 25
AIEEE-Chemistry 87 Day 6: Solutions
35
days
13. (a): According to Raoults law,
0
B B B
P =P X
0
B
P 75 torr. =
B
78/78 1 1
X = = =
(78/78) +(46/92) 1+0.5 1.5
B
1
P =75 =50 torr.
1.5
14. (c): M =
1 1 2 2
1 2
M V + M V
V + V
=
1.5 480 + 1.2 520
1000
= 1.344 M
15. (c): According to Raoults law equimolal
solutions of all the substances in the same
solvent will show equal elevation in boiling
points as well as equal depression in
freezing point.
16. (c): Molality,
2
M
(m) = 1000
1000d-MM
where M = molarity, d = density, M
2
=
molecular mass

2.05 2.05
m = =
10001.022.0560 897
m = 2.28 10
3
mol g
1
= 2.28 mol kg
1
.
17. (d): No of moles of glucose = =
18
0.1
180
No. of moles of water = =
178.2
9.9
180

S
P P
P
= x
solute
=

= =
S
S
760 P 0.1
P 752.4 torr
760 10
18. (d): 3.6 M solution corresponds that 3.6
mole of H
2
SO
4
is dissolved in 1000 mL of
solution.
Mass of 3.6 moles of H
2
SO
4
= 3.6 98g
= 352.8 g
Mass of H
2
SO
4
in 1000 mL of solution
= 352.8 g
Given, 29 g of H
2
SO
4
is present in 100 g of
solution
6. (a): For ideal solution, H
mix
= 0, neither
heat is evolved nor absorbed during
dissolution process.
7. (a): Elevation in boiling point (T
b
) is a
colligative property which depends upon
the number of solute particles,
Greater the number of solute particles in a
solution, higher the extent of elevation in
boiling point.
Na
2
SO
4
2Na
+
+ SO
4
2
8. (b): Moles of urea =
20
3
23
6.02 10
10
6.02 10

moles
Molarity
3
no. of moles of solute 10
1000 0.01 M.
no. of litres of solution 100

= =
9. (c): H
3
PO
3
is a dibasic acid.
N
1
V
1
(acid) = N
2
V
2
(base)
0.1 2 20 = 0.1 1 V
2
V
2
= 40 mL
10. (b): In solution of methanol and benzene,
methanol molecules are held together by
hydrogen bonding as shown below.
On adding benzene, the benzene molecules
comes in between the molecules of
methanol, and causes breaking the
hydrogen bonds. As the result
intermolecular attractions decreases, the
escaping tendency of alcohol and benzene
molecules from the solution increases.
11. (d): Depression in freezing point varies
as T
f
= k
f
m
For different solvents, value of k
f
is also
different. So, for two different solvents the
extent of depression may vary even if same
number of solute particles be dissolved in
them.
12. (c): Na
2
SO
4
2Na
+
+ SO
4
2
initial 1 0 0
final 1 2
Vant Hoff factor (i) =
1 2
1 2 .
1
+ +
= +
Day 6: Solutions 88 AIEEE-Chemistry
35
days
352.8 g of H
2
SO
4
is present in

100
352.8
29

= 1216 g of solution
Now, density =
Mass 1216
Volume 1000
=
= 1.216 g/mL = 1.22 g/mL
19. (b): According to Raoults law,

0 0
A B A A B B
p=p +p =p x +p x
or 290 =
0
A
p (0.6)+200(1-0.6)
or 290 =
0
A
0.6p +0.4200

0
A
p =350 mm.
20. (a): Isotonic solutions have same osmotic
pressure
1 1 2 2
=C RT, =C RT
For isotonic solution,
1
=
2
C
1
= C
2
.
or,
B
5.25/M 1.5/60
=
V V
or,
B
1.5 5.25
60 M
= or M
B
= 210.
21. (d): p
T
= p
A
X
A
+ p
B
X
B
Mixture solution boils at 1 atm = 760 mm =
total pressure.
760 = 520X
A
+ 1000(1 X
A
)
X
A
= 0.5, mol % of A = 50%
22. (d): Moles of glucose =
18
= 0.1
180
Moles of H
2
O =
178.2
= 9.9
18
According to Raoults law
o
S
o
p p
p
= X
solute
17.5
17.5
s
p
=
0.1
10
So, p
s
= 17.325 mmHg
23. (c): [0.25P
x
+ 0.75P
y
= 550 mm] 4
[0.20P
x
+ 0.80P
y
= 560 mm] 5
P
x
+ 3P
y
= 2200
P
x
+ 4P
y
= 2800
P
y
= 600 mm, P
x
= 400 mm
24. (b): On mixing n-heptane and ethanol; strong
interactions are replaced by weak
interaction and hence it less non-ideal
solution with positive deviation.
25. (a): Number of moles of heptane =
25 1
=
100 4
number of moles of octane =
35
114
Total pressure of the solution (applying
Raoults)
P
T
= P
heptane
X
heptane
+ P
octane
X
octane
=
57 70
105 45
127 127
+
=
19 23
105 45 =72 kPa
42 42
+
26. (b): Na
2
SO
4
2Na
+
+ SO
4
2
Vant Hoff factor for Na
2
SO
4
= 3
T
f
= ik
f
m
= 3 1.86 0.01
T
f
= 0.0556 K
PRACTICE EXERCISE
4 MARKS QUESTIONS
1. 12 g of urea is dissolved in 1 litre of water
and 68.4 g of sucrose is dissolved in 1 litre
of water. The lowering of vapour pressure
of first case is
(a) equal to second
(b) greater than second
(c) less than second
(d) double than second
2. At a particular temperature, the vapour
pressure of two liquids A and B are
respectively 120 and 180 mm of mercury. If
AIEEE-Chemistry 89 Day 6: Solutions
35
days
2 moles of A and 3 moles of B are mixed to
form an ideal solution, the vapour pressures
of the solution at the same temperature will
be (in mm of Hg)
(a) 156 (b) 145
(c) 150 (d) 108
3. If the solution boil at a temperature T
1
and
the solvent boil at a temperature T
2
the
elevation of boiling point is given by
(a) T
1
+ T
2
(b) T
1
T
2
(c) T
2
T
1
(d) T
1
+ T
2
4. If the elevation in boiling point of a solution
of 10 gm of solute (mol. wt. = 100) in 100 gm
of water is T
b
, the Ebullioscopic constant
of water is
(a) 10 (b) 10 T
b
(c) T
b
(d)
b
T
10

5. The freezing point of equimolal aqueous

solution will be highest for
(a) C
6
H
5
+
NH
3
Cl

(b) Ca(NO
3
)
2
(c) La(NO
3
)
2
(d) C
6
H
12
O
6
6. If all the following four compounds were
sold at the same price, which would be
cheapest for preparing an antifreeze
solution for a car radiator?
(a) CH
3
OH (b) C
2
H
5
OH
(c) C
2
H
4
(OH)
2
(d) C
3
H
5
(OH)
3
7. The vant Hoff factor for 0.1 M Ba(NO
3
)
2
solution is 2.74. The degree of dissociation is
(a) 91. 3% (b) 87%
(c) 100% (d) 74%
8. The vant Hoff factors i for an electrolyte
which undergoes dissociation and
association in solvents are respectively
(a) greater than 1 and greater than 1
(b) less than 1 and greater than 1
(c) less than 1 and less than 1
(d) greater than 1 and less than 1
9. Consider the following vapour-pressure
composition graph.
SP is equal to
(a) PQ + RS (b) PQ + QR + RS
(c) SR + SQ (d) PQ + QR
10. The vapour pressure of water at 50C is 92.5
torr. What will be the vapour pressure of
solution which consists of 1 mole of non-
volatile solute in 100 g of water at 50C
(a) 906.5 torr (b) 94.2 torr
(c) 91.8 torr (d) 90.8 torr
11. Which of the following solutions will have
the highest boiling point
(a) 0.5 molal BaCl
2
(b) 1.0 molal KBr
(c) 1.8 10
24
glucose molecules per litre
(d) 100 g powdered glucose in one litre water
12. How many grams of sucrose (M. wt. 342)
must be dissolved in 100 g water to
produce a solution with a 105.0C
difference between the freezing point and
the boiling point temperature?
(a) 460 g (b) 342 g
(c) 72 g (d) 34.2 g
13. The total vapour pressure of a solution of
components A and B is 600 torr. The mole
fraction of component A in liquid and
vapour phase are 0.70 and 0.35 respectively.
The vapour pressure of pure A and B are
(a) 300 torr, 130 torr (b) 1300 torr, 300 torr
(c) 300 torr, 1300 torr(d) 300 torr, 300 torr
14. To neutralise completely 40 mL of 0.1 M
aqueous solution of phosphorus acid
(H
3
PO
3
), the value of 0.1 M aqueous KOH
solution required is
Day 6: Solutions 90 AIEEE-Chemistry
35
days
(a) 80 mL (b) 20 mL
(c) 10 mL (d) 60 mL
15. For which of the following parameters the
structural isomers C
2
H
5
OH and CH
3
OCH
3
would be expected to have the same
values? (Assume ideal behaviour)
(a) Boiling points
(b) Vapour pressure at the same
temperature
(c) Heat of vaporization
(d) Gaseous densities at the same
temperature and pressure
16. Which of the following solutions will have
the maximum lowering of vapour pressure
at 300 K
(a) 1 M CaCl
2
(b) 1 M NaCl
(c) 1 M Phenol (d) 1 M sucrose
17. At certain Hill Station pure water boils
at 99.725C, If K
b
for water is 0.513C Kg
mol
1
, the boiling point of 0.69 m solution
of urea will be
(a) 103C (b) 100.079C
(c) 100.359C (d) unpredictable
18. A tooth paste has 0.2 g L
1
fluoride. Its
concentration in ppm will be:
(a) 250 (b) 200
(c) 400 (d) 1000
19. An azeotropic solution of two liquids has
boiling point lower than either of them
when it:
(a) shows negative deviation from Raoults
law
(b) shows no deviation from Raoults law
(c) shows positive deviation from Roults
law
(d) is saturated solution.
20. A compound X undergoes tetramerization
in a given organic solvent. The vant Hoff
factor i is
(a) 4 (b) 0.35
(c)
1
4
(d) 4.25
8 MARKS QUESTIONS
21. Coolant used in car radiator is aqueous
solution of ethylene glycol. In order to
prevent the solution from freezing at
0.3C. How much ethylene glycol must
be added to 5 kg of water ? (K
f
= 1.86 K
kg mol
1
)
(a) 50 kg (b) 55 kg
(c) 45 kg (d) 40 kg
22. The vapour pressure of ethanol and
methanol are 42.0 mm and 88.5 mm Hg
respectively. An ideal solution is formed
at the same temperature by mixing 46.0 g
of ethanol with 16.0 g of methanol. What
is the mole fraction of methanol vapour?
(a) 0. 467 (b) 0. 502
(c) 0. 513 (d) 0. 556
23. What is the degree of dissociation of
sodium chloride, if the molar mass
determined by a cryoscopic method was
found to be 31.80 g mol
1
[Atomic mass
Na = 23, Cl = 35.5]?
(a) 0.58 (b) 0.73
(c) 0.83 (d) 0.92
24. Two elements A and B form compounds of
formula AB
2
and AB
4
. When dissolved in
20.0 g of benzene 1.0 g of AB
2
lowers f. pt.
by 2.3C whereas 1.0 g of AB
4
lowers f.pt.
by 1.3C. The K
f
for benzene is 5.4 K/m.
The atomic masses of A and B are
(a) 25, 42 (b) 42, 25
(c) 52, 48 (d) 48, 52
25. The freezing point of 0.1 M solution of
glucose is 1.86C. If an equal volume of
0.3 M glucose solution is added, the
freezing point of the mixture will be
(a) 7.44C (b) 3.72C
(c) 3.72C (d) 2.79C
COMPREHENSION TYPE
QUESTIONS
Passage-I
The solubility is governed by number of
factors such as nature of solute and solvent,
AIEEE-Chemistry 91 Day 6: Solutions
35
days
temperature, pressure etc. The concentrations of
the solutions can be expressed in different ways
such as normality, molarity, molality, mole
fraction etc. Mole fraction and molality do not
change with the change in temperature.
26. If 5.85 g of NaCl are dissolved in 90 g of
water, the mole fraction of NaCl is
(a) 0.1 (b) 0. 01
(c) 0.2 (d) 0. 0196
27. 2.5 litre of 1 M NaOH solution are mixed
with another 3 litre of 0.5 M NaOH
solution. Then the molarity of the
resulting solution is
(a) 0.80 M (b) 0.1 M
(c) 0.73 M (d) 0.50 M
Passage-II
All colligative properties help in calculating
the observed molar mass of the solute which is
inversely proportional to the colligative property
involved. Out of these, osmotic pressure may
be regarded as the best for the determination of
molecular mass of polymers.
28. 0.1 M NaCl and 0.1 M CH
3
COOH are kept
in separate containers. If their osmotic
pressures are P
1
and P
2
respectively then
what is the correct statement?
(a) P
1
> P
2
(b) P
1
= P
2
(c) P
1
< P
2
(d) P
1
= P
2
= 0 atm.
29. Which among the following will show
maximum Osmotic pressure?
(a) 1 M NaCl (b) 1 M MgCl
2
(c) 1 M (NH
4
)
3
PO
4
(d) 1 M Na
2
SO
4
30. The molecular mass of a solute can not
be calculated by one of the following
(a)
B
B
W RT
M =
V
(b)
0
B A
B
0
S A
p W M
M =
(p P )W
(c)
b B
B
b A
T W 1000
M =
K W
(d)
b B
B
b A
K W 1000
M =
T W
ASSERTION REASON TYPE
QUESTIONS
Directions: This section contains reasoning type
question. Each question has four choices: a, b, c
and d out of which only one is correct. Answer
should be
(a) If statement-I is true, statement-II is true,
statement-II is a correct explanation of
statement-I.
(b) If statement-I is true, statement-II is true,
statement-II is not a correct explanation for
statement-I.
(c) Statement-I is true, statement-II is false.
(d) Statement-I is false, statement II is true.
31. Statement-I: The solubility of HCl in water
does not follow Henrys law.
Statement-II: Henrys law is not applicable
for polar substances.
32. Statement-I: Vant Hoff factor for benzoic
acid in benzene solvent is less than 1.
Statement-II: Benzoic acid get associated in
benzene solvent.
33. Statement-I: Ethyl alcohol and water form
maximum boiling azeotropes.
Statement-II: Attractive forces (AB) in a
solution of C
2
H
5
OH and H
2
O are less than
AA or BB forces.
34. Statement-I: Higher value of k
f
of the solvent
used less will be freezing point of the solution.
Statement-II: T
f
depends upon the nature
of the solvent.
35. Statement-I: If RBC are placed in pure water,
the cells swell.
Statement-II: Endosmosis occurs when RBC
placed in pure water.
Day 6: Solutions 92 AIEEE-Chemistry
35
days
1. Moles of urea =
12
0.2
60
=
Moles of sucrose =
68.4
0.2
342
=
Both are non electrolyte hence lowering of
V.P. will be same.
2. Vapour pressure of solution =
A B
p +p
=
o 0
A A B B
1202 1803
p x +p x = + =156 mm
5 5
3. T
b
= T
1
T
2
4.
b b
b b b
K w1000
T = ; K = =
MW 101000
b b
b b b
T 100100
T = ; K = =T
MW 101000

5. Glucose is non electrolyte hence depression

in freezing point will be minimum, hence
freezing point will be highest.
6.
f
f
K w1000
T = .
Mw
Other things being
equal, the smaller the molecular weight, the
more is the T
f
7. Ba (NO
3
)
2
Ba
2+
+ 2NO
3

1 2
1 2
2.74;
1
+ +
= = = 0.87 = 87% i
8. When an electrolyte dissociates Vant Hoff
factor i is greater than 1 and when it
associates the i is less than 1.
9. The vapour pressure of a solution is sum
of the vapour pressures of components.
SP = SR + SQ
10. Moles of water
1000
55.5;
18
= Mole fraction
of water
A A
55.5
= =0.982p = 0.98292.5; p = 90.8 torr
55.5+1
11. For electrolytes multiply the concentration
by Vant Hoffs factor (i)
0.5 .3 = 1.5 for BaCl
2
; 1.0 2 = 2 for KBr,
24
23
1.8 10
2.98
6.023 10

and for glucose

100
0.55
180
= for powered glucose.
Hence highest b.pt. will be observed in case
of (III)
12. (c): B. pt. = 100 + T
b
= 100 + K
b
m
F. pt. = 0 T
f
= 0 K
f
m
T
b
T
f
= 100 + K
b
m ( K
f
m)
105 = 100 + 0.51 m + 1.86 m
m =
5
2.11
2.37
=
Weight of sucrose to be dissolved in 10 g
water
=
2.11 342 100
72g
1000

=
13. (c): X
A
= 0.70 X
B
= 0.30;
Y
A
= 0.35 X
B
= 0.65;
p
A
= 600 0.35
0
A
6000.35
=p
0.70

0
A
p 300 torr =
ANSWERS
1. (a) 2. (a) 3. (b) 4. (c) 5. (d) 6. (a) 7. (b) 8. (d) 9. (c) 10. (d)
11. (c) 12. (c) 13. (c) 14. (a) 15. (d) 16. (a) 17. (b) 18. (b) 19. (d) 20. (c)
21. (a) 22. (c) 23. (c) 24. (a) 25. (c) 26. (d) 27. (c) 28. (a) 29. (c) 30. (c)
31. (c) 32. (a) 33. (d) 34. (d) 35. (a)
HINTS AND SOLUTIONS
AIEEE-Chemistry 93 Day 6: Solutions
35
days
Vant Hoff factor
1
( ) 1
1
+ +
= = + i
Again Vant Hoff factor (i)

Normal mol. wt 58.5
1.83
Observed Mol. wt 31.8
= = =
Equate both values of i, 1 + = 1.83
= 0.83
24. Let the masses of A and B be a and b. The
mass of B
2
will be (a + 2b)g mol
1
and AB
4
will be (a + 4b) g mol
1
For AB
2
2.3 =
5.111000
(a + 2b)20
...(I)
For AB
4
1.3 =
5.111000
(a + 4b) 20
...(II)
On solving (I) and (II),
a = 25.49 and b = 42.64
25. K
f
=
f
T 1.86
18.6
m 0.1

= =
Form M
1
V
1
+ M
2
V
2
= MV
0.1 V + 0.3 V = M
3
2V
M
3
= 0.2
T
f
= K
f
. m = 18.6 0.2 = 3.72C
26. Moles of NaCl =
5.85 1
58.5 10
=
Mole of H
2
O =
90
5
18
=
x
NaCl
=
0.1
0.0196
5.1
=
27. M
1
V
1
+ M
2
V
2
= M
3
V
3
1 2.5 + 0.5 3 M
3
5.5
(Total solution = 5.5 L)
2.5 + 1.5 = M
3
+ 5.5 M
3
= 0.73 M
28. Molecular mass of NaCl is less, so P
1
> P
2
(
=
(

B
B
W
RT
M
29. (NH
4
)
3
PO
4
show maximum osmotic
pressure due to highest Vant Hoff factor
(i) i.e. 4.
30. Option (c) is not correct.
31. Henrys law is applicable for polar as well
as non polar substances.
p
B
= 600 0.65
0
B
600 0.35
p
0.70

=

0
B
p 1300 torr =
14. N
1
V
1
= N
2
V
2
(H
3
PO
3
is dibasic M = 2N)
40 0.2 = 0.1 V, V = 80 mL
15. The heat of vapourisation, V.P. and b.pt. will
differ due to H-bonding in ethanol.
16. 1M CaCl
2
has maximum lowering due to
highest Vant Hoff factor.
17. T
b
= K
b
m = 0.513 0.69 = 0.3539C
b.pt. of solution = 99.725C + 0.3539C
= 100.079C
18. ppm =
6
0.2 g
10
1000
= 200
19. For azeotropic solution of two liquids, It
most be saturated.
20. (c): Compound on tetramerization gives
1
4
effective molecules, so colligative properties
will becomes
1
4
and i =
1
4
.
21. (a): T
f
= 0.3C
0.3C =
f B
B A
K W 1000
M W
=
1.86 1000
62 5000

B
W
W
B
= 50 g
22. (c): C
2
H
5
OH CH
3
OH
42.0 mm 88.5 mm
46.0 g 16.0 g
1 mole 0.5 mole
Total moles 1 + 0.5 = 1.5
Total pressure P
=
0
A A A
1 88.5 0.5
42 (p =p x )
1.5 1.5

+
p = 28 + 29.5 = 57.5
Mole fraction in vapour phase
p
A
= Y
A
Total pressure
x
A
=
29.3
0.513
57.5
=
23. Let be the give of dissociation then

+
1
NaCl Na +Cl
Day 6: Solutions 94 AIEEE-Chemistry
35
days
32. Benzoic acid get dimerize, so its Vant Hoff
factor is 1/2.
33. Ethyl alcohol and water form minimum
boiling azeotropes.
34. T
f
= k
f
m
T
f
depends upon the nature of solvent (k
f
)
as well as molarity of solution.
35. RBC placed in water get swell up due to
endosmosis.
SELF ASSESSMENT TEST
1. The relationship between osmotic pressure
at 273 K when 10 g glucose (P
1
) 10 g urea
(P
2
), and 20 g sucrose (P
3
) are dissolved in
150 mL of water is:
(a) P
1
> P
2
> P
3
(b) P
3
> P
1
> P
2
(c) P
2
> P
1
> P
3
(d) P
2
> P
3
> P
1
2. A solution of 1.25 g of a non-electrolyte in
20 g of water freezes at 271.94 K. If K
f
is
1.86 K m
1
then the molecular mass of the
solute will be:
(a) 207.8 g mol
1
(b) 209.6 g mol
1
(c) 109.5 g mol
1
(d) 179.79 g mol
1
3. Hydrochloric acid solutions A and B have
concentration. 0.5 N and 0.1 N respectively.
The volume of solutions A and B required to
make 2 litres of 0.2 N hydrochloric acid are:
(a) 0.5 L of A and 1.5 L of B
(b) 1.5 L of A and 0.5 L of B
(c) 1.0 L of A and 1.0 L of B
(d) 0.75 L of A and 1.25 L of B
4. When cyclohexane is added to ethanol, it
reduces the ethanol-cyclohexane inter
molecular forces. Such a liquid pair causes:
(a) positive deviation form Raoults law
(b) negative deviation from Raoults law
(c) no deviation from Raoults law
(d) none of the above
5. The osmotic pressure of equimolecular
solution of glucose, sodium chloride and
barium chloride will be in the order:
(a) Glucose > BaCl
2
> NaCl
(b) NaCl > BaCl
2
> Glucose
(c) Glucose > NaCl > BaCl
2
(d) BaCl
2
> NaCl > Glucose
6. To 5.85 g NaCl is added one kg of water to
prepare a solution. What is the strength of
NaCl in this solution? (Mol. mass of NaCl =
58.5 mol
1)
(a) 0.1 normal (b) 0.1 molal
(c) 0.1 molar (d) 0.1 formal
7. Which one of the following solution of
H
2
SO
4
will completely neutralize 25 mL of
0.2 M NaOH:
(a) 12.5 mL of 0.1 M solution
(b) 25 mL of 0.1 M solution
(c) 25 mL of 0.2 M solution
(d) 50 mL of 0.2 M solution
8. Vapour pressure of CCl
4
at 25C is 143 mm
Hg. 0.5 gm of a non-volatile solute (mol.
weight = 65) is dissolved in 100 mL CCl
4
.
Find the vapour pressure of the solution.
(Density of CCl
4
= 1.58 g/cm
3
)
(a) 149.93 mm (b) 94.39 mm
(c) 199.34 mm (d) 143.99 mm
9. In which of the following pairs of solution
the values of Vant Hoff factor will be the
same.
(a) 0.05 M K
4
[Fe(CN)
6
] and 0.1 M FeSO
4
(b) 0.1 M K
4
[Fe(CN)
6
] and 0.05 Mohr salt
(c) 0.2 M NaCl and 0.1 M BaCl
2
(d) 0.05 M Mohr salt and 0.2 M KMNO
4
10. A 0.004 M solution of Na
2
SO
4
is isotonic
with 0.010 M solution of glucose at the same
temperature. The apparent percentage
dissociation of Na
2
SO
4
is
(a) 25% (b) 50%
(c) 75% (d) 85%
ANSWERS
1. (c) 2. (c) 3. (a) 4. (a) 5. (d) 6. (b) 7. (b) 8. (a) 9. (b) 10. (c)