Liquid Solutions [1]

1. Introduction:

1.1 Solution: A homogeneous mixture of two or more components is called solution.

In a solution, component in excess is generally called solvent and component in limited

amount is called solute.

A solution consisting of two components only is called binary solution. The relative ratio of
solute and solvent in a solution can be expressed in different concentration terms as you
have studied in class 11th.
Example:
mass of solute
1. Mass percentage(w / w)  100
mass of solution
volume of solute
2. Volume percentage(v / v)  100
volume of solution
mass of solute (g)
3. Mass by volume percentage(w / v)  100
volume of solution (mL)
moles of solute
4. Molarity 
volume of solution(L)
moles of solute
5. Molality 
mass of solvent( kg)
moles of solute
6. Mole fraction of solute 
moles of solute  moles of solvent
parts of solute
7. Parts per million(ppm)  106
parts of solution
Illustration: Calculate the molarity of NaOH in the solution prepared by dissolving its 4 g in
enough water to form 250 mL of the solution.

No. of moles of solute Mass of NaOH/Molar mass of NaOH

Solution: Since molarity (M)  
Volume of solution in litres 0.250 L
4g /40g 0.1mol
= = = 0.4mol L-1 = 0.4M
0.250L 0.250L
Brain Teaser: 11.7 gm NaCl is dissolved in 500 ml water (Assume density of water =1g/mL). Find
the molality of the solution.
Ans. 0.4 m
1.2 Solubility:
Solubility of a substance is its maximum amount that can be dissolved in a specified amount
of solvent at a specified temperature.

1.3 Solubility of a solid in a liquid :

Every solid does not dissolve in a given liquid.

Example: Sodium chloride and sugar dissolve readily in water, while naphthalene and
anthracene do not. On the other hand, naphthalene and anthracene dissolve readily in
benzene but sodium chloride and sugar do not.

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Liquid Solutions [2]
Reason: A solute dissolves in a solvent if the intermolecular interactions are similar in the
two or we may say ―like dissolves like‖. Hence, Polar solute dissolves in polar solvent and non
polar solute dissolves in non-polar solvent.

When a solid solute is added to the solvent, some solute dissolves and its concentration
increases in solution. This process is known as dissolution. Some solute particles in solution
collide with the solid solute particles and get separated out of solution. This process is known
as crystallisation.

A stage is reached when the two processes occur at the same rate. Under such conditions,
number of solute particles going into solution will be equal to the solute particles separating
out and a state of dynamic equilibrium is reached. At this stage the concentration of solute in
solution will remain constant under the given conditions, i.e. temperature and pressure.
Similar process is followed when gases are dissolved in liquid solvents.

Such a solution in which no more solute can be dissolved i.e which is in dynamic equilibrium
with undissolved solute, is called saturated solution and contains the maximum amount of
solute dissolved in a given amount of solvent at a particular temperature and pressure. The
concentration of solute in such a solution is its solubility.

An unsaturated solution is one in which more solute can be dissolved at same temperature
and pressure.

1.4 Solubility of solid in liquid depends on:

(i) Nature of solute and solvent.

(ii) Temperature:
In general, the dissolution process is endothermic (H > 0), so according to Le Chateliers
Principle, the solubility increases with rise in temperature.
Exception: Dissolution of Ce2(SO4)3 is exothermic (H < 0), hence the solubility decrease with
rise in temperature.

Illustration: What is effect of pressure on solubility of a solid in liquid?

Solution: 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 changes in pressure.

Brain teaser: Give examples of some solids whose solubility in water increases with rise in
temperature.
Ans: NaCl, KCl, Glucose, Sugar
1.5 Solubility of gas in liquid
Solubility of a gas in liquid can be represented by following equilibrium:
H2O(Excess)
O2 (g) O2 (aq)
When dissolved, the gas molecules are present in liquid phase and the process of dissolution
can be considered similar to condensation and heat is evolved in this process.
Dissolution process involves dynamic equilibrium between dissolved and undissolved gases
and thus it follows Le Chatelier's principle. As dissolution is an exothermic process, the
solubility decreases with increase in temperature.

1.6 Effect of pressure on solubility of gas in liquid / Henry’s Law:

At a given temperature, the partial pressure of a gas above solution is proportional to its mole
fraction in solution.

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Liquid Solutions [3]
pgas  Xgas
pgas  KH Xgas
Where,
X gas = Mole fraction of gas at a given temperature as a measure of its solubility.
pgas = Partial pressure of gas in equilibrium with the solution.
KH = Henry‘s law constant

Illustration: What is mole fraction of gas A in liquid B, if KH = 104 bar and the partial pressure of
gas over liquid surface is 2 bar.
Solution: pgas  KH Xgas
2 bar  104 bar Xgas
Xgas  2 104

Brain Teaser: The Henry's law constant for the solubility of gas A in water at 298 K is 1.0 × 10 5
atm. Calculate the moles of A dissolved in 10 moles of water of 298 K and if pressure
of A over water surface is 4 atm.
Ans: ~ 410―4 moles
Note:
(i) If a mixture of gases is brought in contact with solvent each constituent gas dissolves in
proportion to its partial pressure. It means that Henry's law applies to each gas individually,
independent of the pressure of other gas.

(ii) Henry's law can also be applied by expressing the solubility of the gas in terms of mass per
unit volume. Mass of the gas dissolved per unit volume of a solvent at a given temperature is
directly proportional to the pressure of a gas in equilibrium with the solution.
m p, m = K × p
where,
m = mass of gas dissolved in unit volume of solvent.
p = pressure of gas in equilibrium with solution.
Where K is the constant of proportionality that depends on nature of gas and liquid,
temperature & unit of pressure.

1.7 Characteristics of Henry law constant (KH).

(i) Different gas have different value of KH for the same solvent as well as same gas has
different value of KH for different solvent .
(ii) It increase with the increase in temperature.
(iii) Higher the value of KH of a gas in a solvent lower will be its solubility.

1.8 Limitation of Henry's law :

Henry law is valid only if:
(i) The pressure of gas is not too high.
(ii) The temperature is not too low.
(iii) The gas doesn‘t undergo any chemical reaction with the solvent.
(iv) The gas doesn‘t undergo dissociation or association in solution.

1.9 Application of Henry's law :

(i) To increase the solubility of CO2 in soft drinks and soda water the bottle is sealed under
high pressure.
(ii) Scuba divers must cope with high concentrations of dissolved gases while breathing air
at high pressure underwater. Increased pressure increases the solubility of atmosphere

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Liquid Solutions [4]
gases in blood. When the divers come towards surface, the pressure is gradually
decreased. This results into release of the dissolved gases and leads to the formation of
nitrogen bubbles 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. Low blood oxygen causes
climbers to become weak and unable to think clearly, the condition is known as anoxia.

Illustration: When water is heated below its boiling point, some air bubbles appear to emerge from
water. Why?
Solution: Water contains dissolved gas. As temperature increases, solubility of gas decreases in
water and hence the extra dissolved gases escape.

Brain Teaser: Why aquatic animals are more comfortable in cold water than in warm water?

In Chapter exercise – 1 (Henry’s Law)

Subjective:
1. Calculate the mole fraction of glucose in its 2 molal aqueous solution.
Ans: 0.0347
2. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of C2H6O2
by mass.
Ans: 0.068
3. How the solubility of a substance (solid or gas) in liquid affected by temperature.
4. State and explain Henry‘s law.
5. What is effect of temperature on KH.
6. Henry‘s law constant for the solubility 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10–3
7. The air is a mixture of a number of gases. The major components are oxygen and nitrogen
with approximate proportion of 20% and 79% by volume at 298 K. The water is in
equilibrium with air at a pressure of 10 atm. At 298 K if the Henry‘s law constants for oxygen
and nitrogen at 298 K are 3.30 × 107 mm Hg and 6.51×107 mm Hg respectively, calculate
the composition (mole fraction) of these gases in water.
Ans: x O2  4.61105 , x N2  9.22 105
Objective:
1. According to the Henry‘s law solubility of a gas from a mixture of gases in a liquid is directly
proportional to-
(a) volume of the gas over the solvent
(b) pratial pressure of the gas over the solvent
(c) total pressure of the mixture of gases over the solvent
(d) sum of the mole fraction of all gases in mixture over the solvent
[b]
2. KH (Henry‘s constant) of a gas depends on
(a) temperature and pressure of the gas (b) only pressure of the gas
(c) only temperature of the gas (d) volume and pressure of the gas
[C]
3. Solubility of the different gases, at a given temperature and pressure in a given solvent…
(a) is directly proportional to Henry‘s law constant

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Liquid Solutions [5]
(b) is inversely proportional to Henry‘s law constant
(c) is independent of Henry‘s law constant
(d) is proportional to square of Henry‘s law constant
[B]
4. Which of the following curves (isotherms) represents the Henry‘s law? Where m = mass of gas
dissolve in given mass of solvent, P = pressure of the gas over the solution
log m log m log m log m
(a) (b) (c) (d)

log P log P log P log P

SHREE BALAJEE. 314 98[A]
5. According to Henry‘s law, the solubility of a gas in a given volume of liquid increases with
increase in
(a) Temperature (b) Pressure
(c) Both (a) and (b) (d) cannot be predicted
SHREE BALAJEE. 314 99[B]
6. At 300K, 40 mL of O3(g) dissolves in 100g of water at 1.0 atm. What mass of ozone dissolved
in 400 g of water at a pressure of 4.0 atm at 300K?
(a) 0.1 g (b) 1.2 g (c) 0.48 g (d) 4.8 g
SHREE BALAJEE 314 100[B]
7. If N2 gas is bubbled through water at 293K, how many millimoles of N 2 gas would dissolve in
1 litre of water? Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry‘s law
constant for N2 at 293 K is 76.48 k bar.
(a) 0.716 mmol (b) 7.16×10–5 mol (c) 1.29×10–5 mol (d) 1.30×10–4 mol
NCERT 40 EX. 2.4[A]
8. H2S, a 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 Henry‘s law constant
(a) 289 bar (b) 325 bar (c) 225 bar (d) 275 bar
NCERT 41 EX. 2.6[A]
9. Henry‘s law constant for CO2 in water is 1.67×108 Pa at 298K. Calculate the quantity of CO2
in 500 mL of soda water when packed under 2.5 atm CO2 pressure at 298K.
(a) 1.848 g (b) 2.484 g (c) 2. 725 g (d) 1.525 g
NCERT 41 EX. 2.7[A]
10. The partial pressure of ethane over a solution containing 6.56 × 10 –3 g of ethane is 1 bar. If
–2
the solution contains 5.00 × 10 g of ethane, then what shall be the partial pressure of the
gas?
(a) 7.64 bar (b) 1.764 bar (c) 0.283 bar (d) 0.382 bar

AMSWER KEYS
QUE. 1 2 3 4 5 6 7 8 9 10
ANS. B C B A B B A A A A

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Liquid Solutions [6]
2. Vapour Pressure:

The pressure exerted by the vapour (molecules in the vapour phase) over the surface of the
liquid at equilibrium at a given temperature is called the vapour pressure of the liquid.

When a liquid is kept in a closed container, evapouration continues to occur at constant rate
but as time progresses, condensation also occurs. Rate of condensation increases as
molecules in vapour phase increases.

After some time an equilibrium is established where

Rate of evaporation = Rate of condensation

o o o
o o o o o
o oo o o
o o o
o o o o
o o
o o
o Rate of evaporation

Rate
o o o

-------------
o o o o o o o
o o o o o o
----------------------
----------------------
---------------------- Rate of codensation
----------------------
Time
Liquid in a closed container Equilibrium state

Example: When water is kept in a closed container at constant temperature, the following
equilibrium is achieved.
Cons tan t

H2O (l) 
Temperature
 H2O(g)
As gaseous components are involved in reaction, it is convenient to express Keq in terms of
Kp.
K p  pH2O(g )
At equilibrium, the pressure exerted by vapours of liquid on surface of liquid (or wall‘s of
container) is called saturated vapour pressure or vapour pressure of liquid.

Vapour pressure of liquid is equal to equilibrium constant (Kp), hence it depends only on
temperature for a particular liquid.

2.1 Effect of temperature on the vapour pressure of the liquid:

As the temperature increases, Kp increases for above endothermic reaction. Hence vapour
pressure increases and is related as

KP 2 HRe action 1 1
log     (Van‘t hoff equation)
KP 1 2.303R  T1 T2 

Since, Kp = Vapour pressure = P, Hreaction = Hvapourisation

P2 HVapourisation 1 1
log     (Claussius Clapeyron equation)
P1 2.303R  T1 T2 

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Liquid Solutions [7]

Vapour Pressure
Temeperature

Illustration: Vapour pressure of a liquid is 30 mm Hg at 27C. Calculate it‘s vapour pressure at

57C. Enthalpy of vapourisation of the liquid is 1000 Cal/mole.

P2 HVapourisation 1 1 P2 100cal /mol  1 1 

Solution: log      log    
P1 2.303R  T1 T2  30 2.303  2cal /molK  300 K 330 K 

Log P2 = 1.543 , P2 = 34.91 mm Hg

Brain Teaser: Calculate the vapour pressure of water at 27C. If water boils at 100C and enthalpy
of vapourisation of water is 540 cal/g. Ans: 0.0265 atm

2.2 About evapouration:

1. It is a surface phenomenon: A liquid sample consists of molecules having energy

ranging from very low to very high values. When high energy molecules reaches the
surface of liquid, it has tendency to escape the surface.

2. Rate of evaporation: At constant temperature, as the surface area increases, rate of

evaporation increases.

3. It causes cooling: As a liquid evaporates, temperature of liquid or nearby

surrounding decreases because it is an endothermic process and energy required for it
is provided either by bulk of liquid or nearby surrounding.

2.3 Boiling point and volatility:

1. Boiling point: The temperature at which the vapour pressure of the liquid
becomes equal to the external pressure is called its boiling point. Boiling is a bulk
phenomena.
External Pressure

Boiling Point

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Liquid Solutions [8]
The above graph is same as that of Vapour Pressure versus Temperature. Note that
boiling point corresponds to the temperature of liquid itself and external pressure
corresponds to vapour pressure of liquid.

2. Volatility: At constant temperature, the vapour pressure of a liquid depends upon the
strength of intermolecular forces acting between its molecules. A liquid which has
weaker intermolecular forces acting between its molecules has higher tendency to
escape as vapour and therefore such a liquid has higher vapour pressure and is said
to be more volatile.

On the other hand, a liquid which has stronger intermolecular forces acting between
its molecules has lower tendency to escape as vapour and therefore such a liquid has
lower vapour pressure and is said to be less volatile.

Example: Ethyl alcohol has higher vapour pressure because of the weak
intermolecular forces acting between its molecules than water which has stronger
intermolecular forces (H-bond) acting between molecules. A more volatile liquid has
lower boiling point than a less volatile liquid.

In Chapter exercise – 2 (Vapour Pressure)

Subjective :
1. What is vapour pressure?
2. What is effect of temperature on vapour pressure of a liquid?
3. At 27°C, Vapour pressure liquid A is 50 mm Hg and that of liquid B is 500 mm Hg. Which of
the following is more volatile and which has lower boiling point?
4. Define normal boiling point or boiling point of a liquid.
5. What is effect of increasing external pressure on boiling point of a liquid?
6. Account for the following observation
(i) Clothes dry at a faster rate in summer season than in winter season.
(ii) Deserts cooler works better on hot sunny day.
(iii) Water remains cold in an earthen pot.
(iv) Food gets cooked faster in a pressure cooker.
(v) Water boils at lower than 100C in hilly areas.
Objective:
1. The vapour pressure of a given liquid will decrease if:
(a) surface area of liquid is decreased
(b) the volume of liquid in the container is decreased
(c) the volume of the vapour phase is increased
(d) the temperature is decreased
shree balaji 292 1 [d]
2. A liquid is kept in a closed vessel. If a glass plate (negligible mass) with a small hole is kept on
top of the liquid surface, then the vapour pressure of the liquid in the vessel is:
(a) More than what would be if the glass plate were removed
(b) Same as what would be if the glass plate were removed
(c) Less than what would be if the glass plate were removed
(d) none of these
GRB PBAHA 313 2[b]
3. ‗A‘ is in equilibrium with its vapour which relation is correct:
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Liquid Solutions [9]

P4
P2
P3
(Vapour)
P1

(a) P3 = P1 P2 (b) P1 = P2P 3 (c) P1 = P2 = P3>P4 (d) P1 = P2 = P3 = P4

4. For which of the following process H =  ve
(a) eVapouration (b) melting (c) Sublimation (d) Condensation
5. A liquid is introduced in a closed container at room temperature which of the following is true
till the equilibrium is established
(a) rate of eVapouration decreases and rate of condensation remain constant.
(b) rate of eVapouration decreases and rate of condensation increases.
(c) rate of eVapouration remains constant and rate of condensation increases.
(d) rate of eVapouration increases and rate of condensation decreases.
6. Which of the following curve is correct for ln p vs 1/T. Where p = Vapour pressure and T =
Temperature in Kelvin scale

ln p ln p ln p ln p
(a) (b) (c) (d)

1/T 1/T 1/T 1/T

7. Which of the following statement is incorrect?
(a) equilibrium vapour pressure is the maximum vapour pressure of a liquid at a given
temperature.
(b) equilibrium vapour pressure is constant at a given temperature
(c) equilibirum vapour pressure is independent of the amount of liquid as long as there is some
liquid present
(d) equilibrium vapour pressure decreases with increase of temperature
8. The vapour pressure of a volatile substance at 27°C and 127°C are 2 atm and 4 atm
respectively. What will be the magnitude of average molar enthalpy of vapourisation in the
given temperature range (assuming no change in enthalpy of vapourisation in this temperature
range) (Take log 2 = 0.3)
(a) 23.69 R (b) 10.29 R (c) 360 R (d) 829 R
9. The normal boiling point of water is 373 K. Vapour pressure of water at temperature T is 19
mm Hg. If enthalpy of Vapourization is 40.67 kJ/mol, then temperature T would be
(Use : log 2 = 0.3 R : 8.3 JK 1 mol 1)
― ―

(a) 250 K (b) 291.4 K (c) 230 K (d) 290 K

ANSWER KEYS
Que. 1 2 3 4 5 6 7 8 9
Ans. D B C D C D D D B

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Liquid Solutions [10]

3. Raoult’s Law and Vapour Pressure of Solution

For a solution of two miscible liquids, the partial vapour pressure of each liquid is less than
the respective vapour pressure of the pure liquid because of the decrease in volatile nature of
the liquid due to mixing, due to which fewer molecules go into vapour phase.

Raoult‘s law states that, for a solution of miscible volatile liquids, the partial vapour pressure
(PA) of a liquid component is directly proportional to its mole fraction (XA) in solution.

moles of A nA
PA  X A where X A  
moles of A  moles of B nA  nB
PA  kX A … (1)

Where k = proportionality constant and is equal to vapour pressure of pure liquid A at the
same temperature ( k  PA0 ) when it‘s mole fraction (XA) is 1.

Mathematical Expression: Let us assume that a solution has nA moles of liquid A and nB
moles of liquid B. Let PA and PB be the vapour pressure of the pure liquids A and B
respectively.

nA nB
Mole fraction of A, X A  and Mole fraction of B, XB 
nA  nB nA  nB

According to Raoult‘s law,

Partial vapour pressure of liquid A in the solution = PA  PA X A

Partial vapour pressure of liquid B in the solution = PB  PB XB

The total vapour pressure of an ideal solution (PS) containing components A and B is the sum
of partial vapour pressures of all the components (Dalton‘s law of partial pressures)

PS  PA  PB  PA X A  PB XB .

Illustration: A solution has 5 moles of liquid A and 5 moles of liquid B. Let 100 mm Hg be the
vapour pressure of the pure liquid A and 200 mm Hg is the vapour pressure of the
pure liquid B. Calculate the vapour pressure of solution.

Solution: PS  PA  PB  PA X A  PB XB

 5 5 
PS  100   200   mmHg 150 mmHg
 55 55
Brain Teaser:Vapour pressure of Benzene and Toluene mixture at 50°C is given by P = 180 XB + 90,
where XB is the mole fraction of Benzene and pressure in mm of Hg. Calculate:
(a)Vapour pressure of pure liquids.

(b) Vapour pressure of liquid mixture obtained by mixing 12 moles of Benzene and 8
moles of toluene.

Ans: (a) PBenzene = 270 mm ; PToluene = 90 mm (b) PS= 198 mm

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Liquid Solutions [11]

3.1 Composition of the vapour mixture:

The total vapour pressure of solution PS can also be related to the mole fraction YA and YB of
the two components in the vapour phase
PA  YA PS
Y P
From Raoult‘s Law: PA = X A PAo  YAPS  X A  Ao S … (1)
PA
YP
Similarly PB = XB PBo  YBPS  X B  B o S … (2)
PB
YA PS YB PS 1 Y Y 
We know that XA  XB  1  o
 o 1   Bo  Ao 
PA PB  PS PB PA Re member it
Ex. An equimolar mixture of benzene (B) and toluene (T) is prepared the total V.P. of this mixture
as a function of mole fraction of benzene is found to be PS  200  400XB
(a) Calculate composition of vapours of this mixture. [Assume that the number of moles
going into vapour phase is negligible in comparison to number of moles present in liquid
phase]
(b) If the vapour above liquid in part (a) are collected and are condensed into a new liquid
calculate composition of vapours of this new liquid
Sol.(a) PB  600mm of Hg and PT  200 mm of Hg
1 1
PS   600   200  400mm of Hg
2 2
PB  XBPB  YBPS
1/2  600 3
YB    75%
400 4
3 1
YT  1    25%
4 4
75% 25%

Condensate/distillate
(b) (Liquid formed after
condensation of vapours)
(remaining liquid)

3 1 3 / 4  600
PS   600   200  500 mm Hg  YB"   0.9  90%
4 4 500
YT"  1  0.9  0.1  10%

Note: The data shows that, at equilibrium, vapour phase will always be rich in more volatile
component than liquid phase.

Brain Teaser: An equimolar mixture of A & B is prepared, the total V.P. of this mixture as a fraction
of mole fraction of A is found to be : PS  100  200 XA

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Liquid Solutions [12]
(a) Calculate composition of vapours of this mixture. [ Assume that the number of moles
going into vapour phase is negligible in comparison to no. of moles present in liquid
phase ].
(b) If the vapour above liquid in part A are collected & are condensed into a new liquid,
calculate composition of vapours of this new liquid.
Ans: (a) YA=3/4, YB=1/4 (b)YA=9/10, YB=1/10

3.2 For a mixture of Volatile liquid (A) and non volatile solute B:

Partial vapour pressure of liquid A in the solution = PA  PA XA

Partial vapour pressure of component B in the solution = PB  PB X B = 0 ( as PB = 0)
Hence, PS  PA  PB  PA XA  0  PA XA
Graphically:
Vapour pressure Vapour
pressure of
pure solvent

Xsolvent
(Mole fraction of solvent)

When a nonvolatile component is added to a volatile liquid, the vapour pressure of solution is
always less than that of solvent. This decrease in vapour pressure is called Lowering of
vapour pressure (LVP).

Lowering of VP  PA0  PA0 X A  PA0  PS

Illustration: A solution has 5 moles of liquid A and 5 moles of non volatile solute B. Let 100 mm Hg
be the vapour pressure of the pure liquid A. Calculate the vapour pressure of solution
and also the lowering in Vapour pressure.

Solution: PS  PA  PB  PA X A  PB XB (PB  0; as it is non volatile)

 5 
PS  100   0  mmHg  50 mmHg
 55 

Lowering in VP = (100 ― 50 ) mm Hg = 50 mm Hg
Brain Teaser: The vapour pressure of pure water at 30°C is 31.50 mm. When 3 g of a non volatile
solute was dissolved in 54 g H2O , the vapour pressure of solution was found to be
31.30 mm. Calculate the molecular weight of the solute.
Ans: 157.5
3.3 Raoult’s law as a special case of Henry’s law:
According to Raoult‘s law, the vapour pressure of a volatile component (A) in a given solution
is: PA  X A PA0 .
In the solution of a gas in a liquid, the gas present in liquid phase is very low and its
solubility is given by Henry‘s law which states that: p  KH x.

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Liquid Solutions [13]
So we can consider, the component A (gaseous) in the solution is so volatile that it mainly
exists as a gas.

If we compare the equations for Raoult‘s law and Henry‘s law, it can be seen that the partial
pressure of the volatile component (A) or gas is directly proportional to its mole fraction in
solution. Only the proportionality constant PA0 differs from K H .
Thus, Raoult‘s law becomes a special case of Henry‘s law in which K H becomes equal to PA0
3.4 Deviation from Raoult’s Law: Ideality and Non-ideality
Ideal Solution:
An ideal solution may be defined as the one which obeys Raoult‘s law over all concentration
ranges at a given temperature.
PS  PA  PB  PAo X A  PBo XB
Example: Toluene-benzene solution, Ethyl bromide-ethyl iodide solution, Chlorobenzene-
bromobenzene solution.
3.5 Conditions for forming Ideal Solution: Two liquids on mixing form an ideal solution only
when
1. All attractive forces between A and B molecules or between A and A molecules or
between B and B molecules (A–B, A–A and B–B) are nearly identical so that the
escaping tendency of an A or B molecule is independent of whether it is surrounded by
A molecules, B molecules or varying proportions of A and B molecules.
2. Both liquids have similar structures, molecular size and polarity so that they have
similar molecular environment.

Characteristics of Ideal Solution:

1. Hmixing  0  no heat is absorbed or released during dissolution.
2. Vmixing  0  the total volume of the solution is equal to the sum of the volumes of
the pure liquids mixed.
Illustration: What will the change in entropy during formation of an ideal solution.

Solution: Increase in disorderness will increase the entropy. Smixing > 0.

Brain Teaser: What will be change in free energy during formation of ideal solution?
Ans: Gmixing < 0.
Hint – Formation of any type of a stable solution must result in decrease of free energy.
Graphical Representation of Vapour Pressure of Ideal Solution:
1. Straight line I represents the plot of vapour pressure of liquid A (PA ) and its mole
fraction (X A ) . According to Raoult‘s law this should be a straight line,
When XA  0 PA  0
XA  1, PA  PAo

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Liquid Solutions [14]

2. Straight line II represents the plot of partial

vapour pressure of liquid B, PB and its mole PS  PAo  PBo III PBo
fraction (XB ) . According to Raoult‘s law, this
PAo II
should be a straight line.
I
when XB  0 PB  0
XB  1, PB  PBo VP

XA = 1 Mole fraction XA = 0
XB = 0 XB = 1

3. Straight line (III) represents the total vapour pressure P of the solution for any
composition and is the sum of the partial vapour pressures of liquids A and B.
PS  PA  PB

Line (III) is obtained by joining point PAo and PBo . Line (III) also indicates that for an
ideal solution, the vapour pressures at various compositions of solutions are
intermediate between the value PAo and PBo and that these vapour pressure‘s lie on the
straight line joining points PAo and PBo .

3.6 Non-Ideal Solutions

Solutions which do not obey Raoult‘s law over all concentration ranges at constant
temperature are called non-ideal solutions.

The plot of the total pressure of the solution Vs mole fraction is not a straight line but a
curve with a +ve or –ve deviation because

PA  PAo X A and PB  PBo XB

Types of Non-Ideal Solutions

1. Non ideal solutions showing +ve deviation

2. Non ideal solutions showing –ve deviation.

3.7 Positive Deviation from Raoult’s Law:

In a solution showing +ve deviation, the vapour pressure of the solution is higher than
that of an ideal solution of the same composition.

This is because the partial vapour pressure of each liquid is higher than would be expected
on the basis of Raoult‘s law.
PA  PAo XA and P  PBo XB

The reason for solutions showing non-ideal behaviour is that the liquids have different
molecular environments in solution. In a solution showing +ve deviation the attractive forces
between molecules of A and B is less than between A – A molecules or between B – B
molecules. Thus the escaping tendencies of the molecules, as measured by the vapour
pressure of the liquids increases.
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Characteristics of non-deal solution with positive deviation:
1. Hmixing > 0 (Heat is absorbed during mixing)
2. Vmixing > 0 (Volume of the solution formed is more than the sum of the volumes of A
and B mixed)
Illustration: What will the change in entropy during formation of a non ideal solution with positive
deviation?
Solution: Increase in disorderness will increase the entropy. Smixing > 0.
Brain Teaser: What will be change in free energy during formation of a non-ideal solution with
positive deviation?
Ans: Gmixing < 0.
Examples: Ethanol – water, ethanol-acetone, ether-acetone, CS2 -acetone, CCl4 -methanol,
acetone – benzene, CCl4 - CHCl3 .
Reason for positive deviation by ethanol-acetone mixture:
In pure ethanol, ethanol molecules are hydrogen bonded i.e., there are strong attractive
forces between ethanol molecule in liquid ethanol. When liquid acetone is added to ethanol
the acetone molecules get in between the ethanol molecules and thus break up the H-bonds.
This reduces the ethanol ethanol intermolecular attractions and thus escaping tendency of
the ethanol molecules increases. This makes the partial vapour pressure of ethanol higher
than that expected if the solution was ideal. Therefore solution of ethanol and acetone show
non ideal behaviour with +ve deviation from Raoult‘s law.
 –  –  –  –
H O H O H O H O

C2 H5 C2 H5 C2 H5 C2 H5
O O O

H3C CH3 H3C CH3 H3C CH3

Graphical representation of vapour pressure of a non-ideal Solution showing positive

deviation:
The plot of partial vapour pressure of liquid A
1. and its mole fraction is not a straight line but PS  PA  PB
is a curve showing the deviation from Raoult‘s III
I
law
PA  PAo X A

2. The plot of partial vapour pressure of liquid B VP II

and its mole fraction is also not a straight line PB=VP of B PA=VP of (A)
but is a curve (II) showing +ve deviation from
Raoult‘s law.
PB  PBo XB
XA = 1 Mole fraction XA = 0
XB = 0 XB = 1

3. The curve III indicates the total vapour pressure of the solution for any composition.
For the deviation, the total vapour pressure is more than the sum of partial vapour
pressure of liquids A and B if they form ideal solution.

PS  PAo XA  PBo XB .

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Liquid Solutions [16]
3.8 Negative Deviation from Raoult’s Law:
In a solution showing –ve deviation from ideal behaviour, the vapour pressure of the solution
is lower than that of an ideal solution of the same composition. This is because the partial
vapour pressure of each liquid is less than that would be expected on the basis of Raoult‘s
law.
PA  PAo XA , PB  PBo XB

In a solution of liquid A and B showing –ve deviation, the attractive forces between molecules
of A and B is greater than that between A – A molecules or B – B molecules due to formation
of stronger bonds. Thus the escaping tendencies of both the liquids are lowered and hence
their partial vapour pressures are also lower than expected as per Raoult‘s law.

Characteristics of non-deal solution with negative deviation:

1. Hmixing < 0 ( Heat is liberated)
2. Vmixing < 0 (Volume of the solution formed is less than the sum of the volumes of A
and B mixed)
Reason: For a solution showing negative deviation i.e., heat is liberated during formation of
such solutions because the new bonds formed are stronger and there is decrease in volume.

Illustration: What will the change in entropy during formation of a non-ideal solution with negative
deviation?

Solution: Increase in disorderness will increase the entropy. Smixing > 0.

Brain Teaser: What will be change in free energy during formation of a non-ideal solution with
negative deviation?
Ans: Gmixing < 0.
Examples: Phenol – Aniline, Chloroform ― Acetone, Methanol – Acetic acid, water- HNO3 .

Reason for negative deviation by chloroform and acetone mixture: Solution of

chloroform and acetone show –ve deviation from ideal behaviour. When CHCl3 and
CH3COCH3 are mixed together to form a solution, hydrogen bonding occurs between the
molecules of CHCl3 and CH3COCH3 . There are new stronger attractive forces between
chloroform and acetone molecules compared with the attractive forces between
CHCl3 — CHCl3 molecules and CH3COCH3 – CH3COCH3 molecules.

The stronger attractive hydrogen bond between chloroform and acetone decreases the
escaping tendencies of both the chloroform and acetone molecules and make the partial
vapour pressure of each liquid less than that based on Raoult‘s law.
Cl
CH3
Cl C H OC
CH3
Cl

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Liquid Solutions [17]
Graphical representation of vapour pressure of non ideal solution showing negative
deviation:
1. The plot of partial vapour pressure of liquid A PS  PA  PB
and its mole fraction is not a straight line but it III
I
is a curve (I) showing negative deviation from
ideality.
PA  PAo X A
VP II
2. The plot of partial vapour pressure of liquid B is PA=VP of (A)
not a straight line but is a curve (II) showing PB=VP of B
negative deviation from ideality.
PB  PBo XB
XA = 1 Mole fraction XA = 0
XB = 0 XB = 1

3. Curve (III) indicates the total vapour pressure of the solution for any composition. For
-ve deviation, the total vapour pressure of solution is less than the sum of partial
vapour pressures of liquids A and B if they form ideal solution.

3.9 Azeotropes

A solution at certain composition which continues to boil at constant temperature without

change in composition of it‘s liquid and vapour phase is called an Azeotrope or constant
boiling mixture.

Azeotropes are of two types:

1. Azeotropes with maximum vapour pressure and minimum boiling point:

The point of maximum vapour pressure for a non ideal solution with positive deviation
means that the boiling point at this composition will be minimum and constant.

Example of Minimum Boiling Azeotrope

Components Boiling point (K)
A B Mass% of B A B Azeotrope
H2O C2H5OH 95.57 373 351.3 351.10

H2O C3H7 OH 71.69 373 370.0 350.72

CHCl3 C2H5OH 67.00 334 351.3 332.30

2. Azeotropes with minimum vapour pressure and maximum boiling point :

The point of minimum vapour pressure for a non ideal solution with negative deviation
means that the boiling point at this composition will be maximum and constant.

Examples of Maximum Boiling Azeotrope

Components Boiling point (K)

A B Mass% of B A B Azeotrope

H2O HCl 20.3 373 188 383

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H2O HNO3 58.0 373 359 393.5

H2O HClO4 71.6 373 383 476

3.10 Immiscible liquids:

It is probably true that no two liquids are absolutely insoluble in each other, but with certain
pairs, eg. Mercury-water and carbon disulfide-water, the mutual solubility is so small that
the liquids may be regarded as virtually immiscible.

For systems of this type, each liquid exerts its own vapour pressure, independent of the
other, and the total vapour pressure is the sum of the separate vapour pressures of the two
components in the pure state at the given temperature.

The composition of the vapour can be readily calculated by assuming that the gas laws are
obeyed; the number of moles of each component in the vapour will then be proportional to its
partial pressure, that is to say, to the vapour pressure of the substance in the pure state. If
pA and pB are the vapour pressures of the pure liquids A and B, respectively and at the given
temperature, n'A and n'B are the numbers of moles of each present in the vapour phase, total
pressure P at the same temperature is given by:
PS  pA  pB .....................(1)
And the composition of the vapour by :
n'A pA
 ...............................(2)
n'B pB
To express the ratio of A to B in the vapour in terms of the actual weights WA and WB , the
numbers of moles must be multiplied by the respective molecular weights MA and MB : hence,
WA n'A MA pA MA
  ....................(3)
WB n'BMB pB MB

A system of two immiscible liquids will boil, that is, distill freely, when the total Vapour
pressure PS is equal to the atmospheric pressure. The boiling point of the mixture is thus
lower than that of either constituent.

It is seen that chlorobenzene, which has a normal boiling point of 132ºC, can be distilled
with steam at a temperature about 40º lower, the distillate containing over 70 percent of the
organic compound. The process is called steam distillation.

Illustration: Calculate the vapour pressure of equimolar solution of two immiscible liquids A and B
having vapour pressure in their pure states as 100 mm Hg and 200 mm Hg. Also calculate the
change in vapour pressure of solution when solution contains 1 mol A and 3 mol B.
Solution: For immiscible liquids: PS  PA0  PB0  100 mmHg  200 mmHg  300mmHg
There is no change in vapour pressure irrespective of change in composition.

Brain Teaser: Calculate the ratio of moles of A and B in vapour phase for solution of two immiscible
liquids A and B having vapour pressure in their pure states as 100 mm Hg and 200 mm Hg.
Ans: 1/2

*****

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Liquid Solutions [19]
In Chapter exercise – 3 (Raoult’s Law and Deviation from Raoult’s Law)
Subjective :
1. At 40°C the vapour pressures of pure liquids, benzene and toluene, are 160 mm Hg and 60 mm
Hg respectively. At the same temperature, what will be the vapour pressure of an equimolar
solution of the two liquids, assuming the ideal solution.
Ans: 110 mmHg
2. Heptane and octane form an 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 g of octane?
Ans: 73 kPa
3. Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 298 K are 200 mm Hg
and 415 mm Hg respectively.
(i) Calculate the vapour pressure of the solution prepared by mixing 25.5 g of CHCl3 and 40 g
of CH2Cl2 at 298 K.
(ii) mole fractions of each component in vapour phase.
Ans: (i) 347.9 mmHg (ii) y CH2Cl2 = 0.82, y CHCl3 = 0.18
4. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K .
Find out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find
the composition of the vapour phase.
Ans: XA =0.4 , XB =0.6 YA =0.3, YB =0.7
5. 100 g of liquid A (molar mass 140 g mol–1) was dissolved in 1000 g of liquid B (molar mass 180
g mol–1). 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 is 475 torr.

Ans: pA  280.7 torr , pA  32torr
6. 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 mmHg
7. Define with example:
(i) Positive deviation from Raoult‘s law
(ii) Negative deviation from Raoult‘s law
(iii) Azeotrope

8. If two liquids A (PA° = 100 torr) and B (PB° = 200 torr) are completely immiscible with each
other, each one will behave independently of the other, are present in a closed vessel. What will
be the total vapour pressure of the system.
Ans: 300 torr
9. If two liquids A (PA° = 100 torr) and B (PB° = 200 torr) are completely immiscible with each
other. What will be the ratio of moles of A and B in vapour phase of solution made by mixing 2
mole of A and 10 moles of B.
Ans: 1/2
Objective:
1. At 25C, the vapour pressure of pure liquid A (mol. wt. = 40) is 100 torr, while of pure liquid B
is 40 torr, (mol. wt. = 80). The vapour pressure at 25C of a solution containing 20 g of each A
and B is :
(a) 80 torr (b) 59.8 torr (c) 68 torr (d) 48 torr
shree balaji 293 15 [a]
2. For a binary ideal liquid solution, the total pressure of the solution is given as
(a) PS = PA° + (PA° – PB° ) XB (b) PS = PB° + (PA° – PB° ) XA

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Liquid Solutions [20]
(c) PS = PA° + (PB° – PA° ) XA (d) PS = PB° + (PB° – PA° ) XB
TMH9.4 11[b]
3. Mixture of volatile components A and B has total vapour pressure (in torr) PS = 254  119XA
where XA is mole fraction of A in mixture. Hence, poA and poB are (in torr) :
(a) 254, 119 (b) 119, 254 (c) 135, 254 (d) 154, 119

4. At 88°C benzene has a vapour pressure of 900 torr and toluene has a vapour pressure of 360
torr. What is the mole fraction of a benzene in the mixture with toluene that will boil at 88°C at
1 atm pressure, benzene–toluene form an ideal solution?
(a) 0.416 (b) 0.588 (c) 0.688 (d) 0.740
PABAHA 324 54[d]
5. The vapour pressure of ethanol and methanol are 42.0 mm and 88.5 mmHg respectively. An
ideal solution is formed at the same temperature by mixing 46.0 g of ethanol with 16.0 g of
methanol. The mole fraction of methanol in the vapour is:
(a) 0.467 (b) 0.502 (c) 0.513 (d) 0.556
GRB PBAHA 326 50[c]
6. At 40°C, the vapour pressure (in torr) of methyl alcohol (a) and ethyl alcohol (b) solution is
represented by: PS = 120 XA + 138; where XA is mole fraction of methyl alcohol. The value of
Pο Pο
lim B and lim A are:
X A 0 X X B 0 X
B A

(a) 138, 258 (b) 258, 138 (c) 120, 138 (d) 138, 125
GRB PBAHA 324 8[a]
7. At a given temperature, the vapour pressures of pure A and B is 108 and 36 Torr respectively.
What will be the mole fraction of B in the vapour phase which is in equilibrium with a solution
containing equimolar fraction of A and B, under ideal behavior conditions?
(a) 0.25 (b) 0.33 (c) 0.50 (d) 0.60
8. Mole fraction of A vapour above the solution in mixture of A and B (X A = 0.4) will be [ poA = 100
mm poB = 200 mm]
(a) 0.4 (b) 0.8 (c) 0.25 (d) none of these
aritextbookRKG 191 9 [c]
9. For an ideal solution containing a nonvolatile solute, which of the following expressions is
correctly represented?
ΔP ΔP ΔP ΔP
(a)  οA = X A (b)  οA = XB (c)  οA = XB (d)  οA = X A
PA PB PA PB
where the subscripts A and B stand for solvent and solute respectively.
TMH9.4 17[c]
10. For an ideal solution containing a nonvolatile solute, which of the following expressions
represents the vapour pressure of the solution?
(a) P = X2 P2° (b) P = X1 P2° (c) P = X1 P1° (d) P1° – P = X2
where the subscripts 1 and 2 stand for solvent and solute respectively.
TMH9.4 16[c]
11. 6.0 g of urea (molecular weight = 60) was dissolved in 9.9 moles of water. If the vapour
pressure of pure water is Po, the vapour pressure of solution is :
(a) 0.10 P (b) 1.10 P (c) 0.90 P (d) 0.99 P
shree balaji 293 8 [d]
12. When non volatile solute is dissolved in a volatile solvent
(a) vapour pressure will decrease
(b) vapour pressure will increase
(c) vapour pressure will remain same
(d) prediction about vapour pressure is not possible

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A
13. The vapour pressure curves of the same non volatile solute in the same solvent are shown. The
curves are parallel to each other and do not intersect. The concentrations of solutions are in
order of:
1 atm I II III

V.P.( torr)
Pure
solvent

Temperature (°C)
(a) I < II < III (b) I = II = III (c) I > II > III
(d) I > III > II
BALAJI 295 22 [a]
14. Based on the given diagram, which of the following statements regarding the homogenous
solutions of two volatile liquids are correct?
D
H
C
G
[Link].

F
A
E mole fraction B
XA=1 XE=1
(1) Plots AD and BC show that Raoult‘s law is obeyed for the solution in which B is a solvent
and A is the solute and as well as for that in which A is solvent and B is solute
(2) Plot CD shows that Dalton‘s law of partial pressures is obeyed by the binary solution of
components A and B
(3) EF + EG = EH; and AC and BD correspond to the vapour pressures of the pure solvent A and
B respectively.
Select the correct answer using the options given below
(a) only 1 (b) 2 and 3 (c) 1 and 3 (d) all
SHREE BALAJEE 305 19[d]
15. When attraction between A—B is less than that of A—A and B—B, the solution will show .......
deviation from Raoult‘s law:
(a) positive (b) negative
(c) no (d) cannot be predicted.
[a]
16. In a mixture A and B components show negative deviation as
(a) V mix > 0
(b) H mix < 0
(c) A—B interaction is weaker than A—A and B—B interaction
(d) None of the above reason is correct.
328Q162[b]
17. The boiling point of an azeotrope mixture of water–ethanol is less than that of both water and
ethanol. Then:
(a) the mixture will show negtive deviation from Raoult‘s law
(b) the mixture will show positive deviation from Raoult‘s law
(c) the mixture will show no deviation from Raoult‘s law
(d) this mixture cannot be considered as true solution

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18. The azeotropic mixture of water (B.P. = 100°C) and HCl (B.P. = 86°C) boils at about 120°C.
During fractional distillation of this mixture it is possible to obtain:
(a) pure HCl (b) pure H2O
(c) pure H2O as well as pure HCl (d) neither H2O nor HCl

19. An azeotropic mixture of two liquids has a boiling point higher than either of them when it:
(a) shows positive deviation from Raoult‘s law (b) shows negative deviation from Raoult’s law
(c) shows ideal behaviour (d) is saturated

20. Two immiscible liquids A and B had boiling point 100C and 200C. Their mixture will boil at a
temperature
(a) Between 100C and 200C (b) Above 200C
(c) Below 100C (d) Unpredictable

ANSWER KEYS
QUE. 1 2 3 4 5 6 7 8 9 10 11
ANS. a b c d c a a c c c d
QUE. 12 13 14 15 16 17 18 19 20
ANS. a a d a b b b b c

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4. Colligative Properties
The property of a dilute solution which depends upon the number of solute particles and
nature of solvent but not upon the nature of solute is called a colligative property.

There are 4 commonly studied colligative properties:

1. Lowering or relative lowering of vapour pressure
2. Elevation of Boiling point
3. Depression of Freezing point
4. Osmotic Pressure

4.1 Lowering of Vapour pressure (LVP)/Relative lowering of vapour pressure (RLVP):

The vapour pressure of a solvent in solution containing non volatile solute is less than the
vapour pressure of the pure solvent at the same temperature. If PAo is the vapour pressure of
the pure solvent and PA (or PS) that of the solvent in solution, the decrease in vapour
pressure PAo – PA (or PAo – PS ) is called the lowering of vapour pressure (LVP) which is directly
proportional to the mole fraction of the solute in solution.
PS  PA  XA PAo
PS  PA0 (1  XB )  PA0  PA0 XB
PA0  PS  PA0 XB  LVP (Hence PA0  PS  XB )
PAo – PS PA0 XB nB
Relative lowering of vapour pressure = RLVP =   XB 
PAo
PA0
nA  nB

Illustration: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour pressure of
an aqueous solution at 37°C containing 20 g of glucose (non volatile) dissolved in 500
gm of water. Also calculate vapour pressure lowering.

500
Solution: nH2O   27.78 mol
18
20
nglucose   0.11 mol
180
nH2O 27.78 27.78
XH2O     0.996
nH2O  nglu cos e 27.78  0.11 27.89
According to Raoult‘s law,
PS  PHo2O XH2O  47.1 0.996  46.9 torr
LVP = PHo2O – PS  47.1 – 46.9  0.2 torr

Illustration: The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure of a
solution of urea in ethyl alcohol is 51.3 torr. Calculate

(i) mole fraction of urea in the solution

(ii) molality of urea in the solution.

PAo – PS nB 59.2  51.3

Solution: (i)    0.1334
PA0
nA  nB 59.2

(ii) Let ―m‖ be the molality of solution i.e ―m‖ moles of solute in 1 kg of solvent

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Liquid Solutions [24]
o
P – PS n2
A

PA0
n1  n2

59.2 – 51.3 m
  m = 3.347 mol/kg
59.2 1000 m
46

Brain Teaser: The vapour pressure of CS2 at 50°C is 854 mm of Hg. A solution of x g sulphur
(S8) in 100g of CS2 has a vapour pressure of 848.9 mm. Calculate the value of x.
Ans: 2 g

4.2 Measurement of Relative Lowering of Vapour Pressure

Ostwald and Walker Method: In this method a stream of dry air is bubbled successively
through the solution, the solvent and a reagent, that can absorb the vapour of the solvent. As
the solvent is usually water, the reagent is generally anhydrous CaCl2 .

Dry air Dry air

1st bulb 2nd bulb

CaCl2 – drying
Solution Solvent agent

The 1st and 2nd bulb contain a weighed amount of the solution and solvent respectively under
examination. Weighed amount of anhydrous CaCl2 is taken in a U-tube at the end.

All the bulbs must be kept at the same temperature and air must be bubbled gradually to
ensure that it gets saturated with the vapours in each bulb.

The dry air, as it passes through the solution, takes up an amount of vapour which is
proportional to the vapour pressure of the solution at the prevailing temperature. This moist
air passes through water (solvent), it takes up a further amount of vapour which is
proportional to the difference in vapour pressure of the pure solvent and the solution. It is
evident that

Loss in weight of solution  PS (PS = Vapour pressure of solution)

Loss in weight of solvent  P – PS
0
A ( PA0 = Vapour pressure of pure solvent)
(Loss in weight of solution + loss in weight of solvent)  (PA0 – PS  PS )  PA0

The gain in mass of drying agent should be equal to the total loss in weight of the solution
and the solvent which, in turn is proportional to PA0 as shown above.

In other words,
Loss in mass of solvent P0 – P
 A 0 S
Gain in mass of CaCl2tube PA

Thus, knowing the loss in mass of the solvent and gain in the mass of the CaCl2 , it is
possible to calculate the relative lowering of vapour pressure.
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Liquid Solutions [25]
Illustration: During determination of RLVP by Ostwald and Walker Method, Calculate the RLVP if
gain in mass of drying agent is 0.8 g where as loss in mass of solvent is 0.1 g.

PA0 – PS Loss in mass of solvent 0.1g

Solution: RLVP  0
   0.125
PA Gain in mass of CaCl2tube 0.8 g
Brain Teaser: During determination of RLVP by Ostwald and Walker Method, the loss in
weight of solution and solvent is 0.8 g and 0.2 g respectively. What will be the gain
in weight of drying agent if solution container is also replaced by solvent only?
Ans: 1 g
Note: For dilute solution ( nB   nA ), RLVP equation can be modified as

PAo – PS nB n W /MB
RLVP    B  B
PAo
nA  nB nA WA /MA
4.3 Elevation of Boiling Point:

The boiling point of a liquid is the temperature at

which its vapour pressure becomes equal to the
Pure Solvent
atmospheric pressure.
1 atm
When the atmospheric pressure is 1 atm, boiling

Vapour pressure
point is called the normal boiling point.
Solution
The vapour pressure of a liquid decreases when a
non-volatile solute is dissolved in it. The
decreased vapour-pressure means that the
solution would have to be heated to a higher
temperature so that its vapour pressure becomes
equal to the atmospheric pressure. In other Tb0 Tb
Temperture
words, the boiling point of the solution Tb is
higher than the boiling point of the pure solvent Plot of variation of vapour pressure Vs elevation
Tb0. of boiling point.

The difference Tb – Tb0 is called the boiling point elevation.

Boiling point elevation = Tb – Tb0 = Tb

It is found that the elevation of boiling point is directly proportional to molality (m).

Tb  m or Tb  Kb  m

Kb is a constant for a given solvent and is known as boiling-point elevation constant or molal
elevation constant or ebullioscopic constant of solution.

Illustration: Estimate the boiling point of a solution of 25.0 g of urea NH2CONH2 plus 25.0g of
thiourea NH2CSNH2 in 500g of chloroform, CHCl3. The boiling point of pure chloroform
is 61.2°C, Kb of chloroform = 3.63 K kg/mol. .
25.0g 25.0
Solution: Total mole of solute = Mole of Urea + Mole of thio urea    0 .75 mol
60g / mol 76 g/mol
Moles of solute 0.75mol
Molality, m =   1.50m
Mass of solvent in kg (500g /1000g)kg
Tb = Tb – Tb0 = Kbm = 3.63 K m–1 × 1.50 m = 5.44 K = 5.445°C

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Liquid Solutions [26]
Tb = 5.445°C + Tb = 5.445°C + 61.2°C = 66.645°C
0

Brain Teaser: A solution containing 0.512g of naphthalene (molar mass 128.2g mol–1) in 50g
CCl4 yields a boiling point elevation of 0.402K, while a solution of 0.6216g of an
unknown solute in the same mass of the solvent gives a boiling point elevation of
0.647K. Find the molar mass of the unknown solute.
Ans: 96.68 g/mol
4.4 Molal Elevation Constant or Ebullioscopic Constant: When molality of the solution is
1 m, (1 mole of the solute is dissolved in 1 kg of the solvent) the above equation reduces to
Tb  K b 1m  K b
This indicates that molal elevation constant of a liquid (Kb) is equal to elevation of boiling
point when molality of the solution is 1 m. It‘s unit is K kg/mol.

Molal elevation constant is characteristic of a particular solvent and can be calculated as:
RTb2
Kb 
Lv
where R is molar gas constant, Tb is the boiling point of the solvent on Kelvin scale and L v the
latent heat of Vapourization of solvent.
Illustration: Calculate the ebulloscopic constant for water if its latent heat of vapourization
is 540 Cal/g.

R  (Tb )2 2 Cal / (mol  K)  (373K) 2 2 Cal / (mol  K)  (373K) 2

Solution: Kb     0.515K kg / mol
Lv 540Cal / g 540 1000 Cal / kg
Brain Teaser: Calculate the ebulloscopic constant for a liquid having boiling point 127C and
latent heat of vapourization is 42 kJ/mol, and molar weight = 50 g/mol.
Ans: 1.6 K kg/mol

In Chapter exercise – 4 (Colligative Property – RLVP and Elevation in Boiling point)

Subjective :
1. Why is the vapour pressure of an aqueous solution of glucose lower than that of water?
2. Which among the following solute will definitely decrease the vapour pressure of water – Urea,
Glucose, NaCl, Alcohol, Sucrose, CaCl2.
3. Calculate the RLVP if 1 mole of urea is dissolved in 180 g of water.
Ans: 1/11
4. What is the mole fraction of glucose in water to reduce the vapour pressure of water by 20%.
Ans: 0.2
5. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-
electrolyte solid weighing 0.5 g when added to 39.0 g of benzene (molar mass 78 g mol –1).
Vapour pressure of the solution, then, is 0.845 bar. What is the molar mass of the solid
substance?
Ans:170 g/mol
6. The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal
solution of a non-volatile solute in it.
Ans:12.08 kPa
7. 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 the solute?
Ans: 41.35 g/mol

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Liquid Solutions [27]
8. Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which should be dissolved
in 114 g octane to reduce its vapour pressure to 80%.
Ans: 8 g
9. A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour pressure
of 2.8 kPa at 298 K. Further, 18 g of water is then added to the solution and the new vapour
pressure becomes 2.9 kPa at 298 K. Calculate:
(i) molar mass of the solute
(ii) vapour pressure of water at 298 K.
Ans: (i) 34 g/mol, (ii) 3.4 kPa
10. Write the principle involved in determination of RLVP by Ostwald and Walker Method.

11. 18 g of glucose C6H12O6, is dissolved in 1 kg of water in a saucepan. At what temperature will

water boil ? Kb for water is 0.52 K kg mol–1. (Boiling point of water = 373.15 K)
Ans: 373.202K
12. The boiling point elevation constant for benzene is 2.57° C/m. The boiling point of benzene in
81.0°C. Determine the boiling point of a solution formed when 5g of C14H12 is dissolved in 15g
of benzene.
Ans: 85.76°C
13. The boiling point of a solution made by dissolving 12.0 g of glucose in 100g of water is
100.34°C. Calculate the molecular weight of glucose; Kb for water = 0.52° C/m.
Ans:183.5g mol–1
14. A solution containing 0.2563g of naphthalene (molecular mass =128) in 50g of carbon
tetrachloride yields a boiling point elevation of 0.201°C while a solution of 0.6216g of an
unknown solute in the same mass of the solvent gives a boiling point elevation of 0.647°C. Find
the molecular mass of unknown solute.
Ans: 96.44
Objective:

1. The vapour pressure of a solvent decreased by 10 mm Hg when a non volatile solute was added
to the solvent. The mole fraction of solute in solution is 0.2, what would be mole fraction of the
solvent if decrease in vapour pressure is 20 mm of Hg.
(a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2

2. Lowering of vapour pressure due to a solute in 1 molal aqueous solution at 100C is :

(a) 13.44 Torr (b) 14.12 Torr (c) 312 Torr (d) 352 Torr
aritextbookRKG 191 7 [a]
3. Calculate the weight of non-volatile solute having molecular weight 40, which should be
dissolved in 57 gm octane to reduce its vapour pressure to 80% :
(a)47.2 g (b) 5 g (c) 106.2 g (d) None of these
shree balaji 293 12 [b]
4. An ideal solution was found to have a vapour pressure of 80 torr when the mole fraction of a
nonvolatile solute was 0.2. What would be the vapour pressure of the pure solvent at the
same temperature?
(a) 64 torr (b) 80 torr (c) 100 torr (d) 400 torr
shree balaji 293 9 [c]
5. The vapour pressure of an aqueous solution of sucrose at 373 K is found to be 750 mm Hg.
The molality of the solution at the same temperature will be :
(a) 0.26 (b) 0.73 (c) 0.74 (d) 0.039
shree balaji 293 10 [c]

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Liquid Solutions [28]
6. Dry air was passed successively through a solution of 5 g of a solute in 180 g of water and then
through pure water. The loss in weight of solution was 2.50 g and that of pure solvent 0.04 g.
The molecular weight of the solute is:
(a)31.25 (b) 3.125 (c)312.5 (d)None
[a]
7. –1
The molal boiling point constant for water is 0.513 K m . When 0.1 mole of sugar is dissolved
in 200.0g of water, the solution boils under a pressure 1.0 atm at
(a)100.513°C (b) 100.0513°C (c) 100.256°C (d) 101.025°C
KS VERMAP-2.57, 9,-c
8. An aqueous solution of glucose boils at 100.01 °C. The molal elevation constant for water is 0.5
K mol–1 kg. What is the number of glucose molecules in the solution containing 100 g water
(a)1.2 × 1023 (b) 1.2 × 1022 (c) 1.2 × 1021 (d) 3.2 × 1021
PBAHA517 Q51[c]
9. When 1 mole of a solute is dissolved in 1 kg of H 2O, boiling point of solution was found to be
100.5°C. Kb for H2O is:
(a)0.5 (b) 100 (c) 100.5 (d) 95.5
BALAJI 297 39 [a]
10. Chloroform, CHCl3, boils at 61.7°C. If the Kb for chloroform is 3.63°C/molal, what is the boiling
point of a solution of 15.0 kg of CHCl3 and 0.616 kg of acenaphthalene, C12H10?
(a)61.9 (b) 62.0 (c) 52.2 (d) 62.67
BALAJI 297 40 [d]
11. A compound has the empirical formula C10H8Fe. A solution of 0.26 g of the compound in 11.2
g of benzene (C6H6) boils at 80.26°C. The boiling point of benzene is 80.10°C; the K b is
2.53°C/molal. What is the molecular formula of the compound? (At wt of Fe =56)
(a)C30H24Fe3 (b) C10H8Fe (c) C5H4Fe (d) C20H16Fe2
BALAJI 297 41 [d]
12. The boiling point elevation constant for toluene is 3.32 K kg mol –1. The normal boiling point of
toluene is 110.7°C. The enthalpy of Vapourisation of toluene would be nearly:
(a)17.0 kJ mol–1 (b) 34.0 kJ mol–1 (c) 51.0 kJ mol–1 (d) 68.0 kJ mol–1

BALAJI 297 44 [b]

ANSWER KEYS
Que. 1 2 3 4 5 6 7 8 9 10 11 12

Ans. b a b c c a c c a d d b

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Liquid Solutions [29]
5. Depression in Freezing Point
The freezing point of a liquid is the temperature at which it
begins to freeze and the crystallized solid remains in Solid solvent t
solven
equilibrium with liquid.
At freezing point, the vapour pressure of a liquid is equal to solutio
n

the vapour pressure of it‘s solid state.

When a dilute solution is cooled to freezing point, it is

Vapour pressure
assumed that crystals of pure solvent always separate out
first.
The vapour pressure of a liquid decreases when a non- Tfs Tf0
volatile solute is dissolved in it. Therefore, solid liquid Temperature

equilibrium exists at a temperature lower than the normal Plot of variation of vapour
freezing point of the pure solvent i.e. at a lower temperature pressure of a solution with
only, solid has same vapour pressure as that of the solution; temperature and depression
i.e the freezing point is lowered. in freezing point.

If Tf0 is the freezing point of the pure solvent and Tf that of the solution, the difference Tf0 – Tf
is called the freezing point depression.
Freezing point depression = Tf0 – Tf = Tf

It is found that the depression in freezing point is directly proportional molality (m).
Tf = Kfm
Kf is a constant for a given solvent known as molal depression constant or cryoscopic
constant. It‘s unit is K kg/mol.

Illustration: What mass of iodine needed to reduce the freezing point of 1000 g benzene to 3.5°C?
The freezing point and cryoscopic constant of pure benzene are 5.5°C and 5.12
Kkg/mol. respectively.

Solution: Tf = Tf0 – Tf = K m

5.5°C – 3.5°C = 5.12 K/m × m
2 mol mol
m  0.39
5.12 kg kg
mol of solute n
Molality   0.39 mol / kg   n  0.39 mol
Mass of solvent (kg) 1kg
Mass of iodine = 0.39 mol  254 g/mol = 99 g

Brain Teaser: A motor vehicle radiator was filled with 8 litre of water in which 2 litre of
methyl alcohol (density 0.8g/ml) were added. What is the lowest temperature
at which the vehicle can be parked out doors without a danger that water in
radiator will freeze?
Kf for H2O = 1.86° mol kg.
–1

Ans: ―11.625C

5.1 Molal depression Constant or cryoscopic Constant: When molality of the solution is 1 m,
(1 mole of solute is dissolved in 1 kg of solvent) the above equation reduces to

Tf  Kf 1 m  Kf

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Liquid Solutions [30]
This indicates that molal depression constant of a liquid (Kf) is equal to depression in freezing
point when molality of the solution is 1 m. It‘s unit is K kg/mol.

Molal depression constant is characteristic of a particular solvent and can be calculated as:
RTf2
Kf 
Lf
where R is molar gas constant, Tf is the freezing point of the solvent on Kelvin scale and Lf
the latent heat of fusion of solvent.
Illustration: Calculate the cryoscopic constant for water if its latent heat of fusion is 80 Cal/g.

R  (Tf )2 2 Cal /(mol  K)  (273K)2 2 Cal /(mol  K)  (273K)2

Solution: Kf     1.86K kg /mol
Lf 80Cal /g 80 1000 Cal /kg

Brain Teaser:Calculate the ebulloscopic constant for a liquid having freezing point 27C and latent
heat of Vapourization is 2.1 kJ/mol, and molar weight = 50 g/mol.
Ans: 1.8 K kg/mol
5.2 Osmosis:
When a solution is separated from pure solvent by a semi–permeable membrane then it is
observed that the solvent flows from the region of pure solvent into solution in order to
minimize concentration difference.
Similarly, if two solutions of different concentration are separated by a semi–permeable
membrane then the solvent flows from solution of lower concentration into solution of higher
concentration.
The passage of solvent from pure solvent or from solution of lower concentration into solution
of higher concentration through a semipermeable membrane is called osmosis.
Example: When a thistle funnel convered with semi–permeable membrane containing CuSO4
(aq) is placed in a beaker containing pure water, water flows from beaker into funnel and the
level of solution in funnel starts rising.
Copper
sulphate
solution

Semi-permeable
membrane
Water

Initial state After standing

Osmosis
After some time the level of solution in the thistle funnel becomes constant indicating that
process of osmosis has stopped or equilibrium has reached. At this stage hydrostatic
pressure of the column is sufficient to stop inward flow of solvent into solution. The excess
liquid pressure which builds up as a result of osmosis is called osmotic pressure.

Illustration: Why raw mangoes shrivel when prickled in brine (Salt water)?
Solution: Because the water flows from bulk of mangoes (with low salt concentration) to
highly concentrated salt water due to osmosis.
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Liquid Solutions [31]

Brain Teaser: Give reasons:

(i) Blood cell collapse when suspended in saline water.
(ii) Wilted flower revive when placed in fresh water.

5.3 Osmotic Pressure:

Thus, the osmotic pressure () of the solution at a given temperature may be defined as the
excess liquid pressure that builds up when the solution is separated from the solvent by a
semi–permeable membrane.

Let‘s take another example:

Piston

S W
Solution Water

Semi-permeable
membrane
Definition of osmotic pressure
On putting the solution in compartment S and water in the compartment W, the piston will
be displaced upwards due to the movement of water from W to S. To stop this movement of
water, we have to apply mechanical pressure on solution side. The pressure just sufficient to
stop osmosis will be the osmotic pressure.
Thus, the osmotic pressure may also be defined as the excess pressure that must be applied
to the solution side to prevent the passage of solvent into it through a semipermeable
membrane.
Semi–permeable membrane: It is a membrane which allows solvent molecules to pass
through but does not allow the solute particles to pass through it.
Example: Animal bladder, Parchment paper, cellophane, copper ferrocyanide, silicates of
iron, cobalt, etc.
5.4 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.
The process is used in purification of water.
P > Osmotic pressure

Saline Pure
water water

Reverse osmosis
Note: Isotonic, hypertonic and hypotonic solutions:
(i) The two solutions having equal osmotic pressure are called isotonic solutions.
(ii) A solution having higher osmotic pressure than some other solution is said to be
hypertonic with respect to the other solution.
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Liquid Solutions [32]
(iii) A solution having lower osmotic pressure relative to some other solution is called
hypotonic.
5.5 Calculation of osmotic pressure:
The osmotic pressure is a colligative property. For a given solvent the osmotic pressure ()
depends only upon the molar concentration of solute but does not depend upon its nature.
  C (C  Molar concentration)

  T (T  Absolute temperature)

  CRT (R  Ideal solution cons tan t /Universal gas cons tan t  0.082 L  atm/molK)

The equation is called Van‘t Hoff‘s solution equation.

Illustration: Calculate the osmotic pressure of a solution which contains 1 mole urea in 1
litre solution at 25C.
1 mol 0.082 L  atm
Solution:   CRT    298 K  24.6 atm
1L mol K

Brain Teaser: 5 Litre of a solution contains 120 g urea (NH2CONH2) and 360 g glucose (C6H12O6).
Calculate the osmotic pressure at 27C.
Ans: 19.68 atm
Brain teaser: Why calculation of osmotic pressure is best method to determine of molecular
masses solutes especially like proteins, polymers and other macromolecules.

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Liquid Solutions [33]
In Chapter exercise – 5 (Depression in freezing point and osmotic pressure)
Subjective:
1. 45g of ethylene glycol (C2H6O2) is mixed with 600g of water. Calculate (a) the freezing point
depression (Kf of water = 1.86 K kg/mol) (b) the freezing point of the solution.
Ans: (a) 2.2 K, (b) 270.95K
2. 1.00 g of non-electrolyte solute dissolved in 50g of benzene lowered the freezing point of benzene
by 0.40 K. the freezing point depression constant of benzene is 5.12K kg mol –1. Find the molar
mass of the solute.
Ans: 256 g/mol

3. The freezing point of a solution containing 50 cm3 of ethylene glycol (C2H6O2) in 50g of water
is found to be –3.4°C. Assuming ideal behaviour, calculate the density of ethylene glycol (K f for
water =1.86K kg mol–1)
Ans: 1.13 g cm–3.
4. A 5% solution (by mass) of cane sugar (Molar Weight = 342 g/mol) in water has freezing point of
271K. Calculate the freezing point of 5% glucose (Molar Weight = 180 g/mol) in water if freezing
point of pure water is 273.15 K.
Ans: 269.065 K
5. What are factors on which cryoscopic constant of a solvent depends?
6. What is difference between osmosis and diffusion?
7. What is ―semi permeable membrane‖?
8. Calculate the osmotic pressure of a solution which contains 60 g urea (NH 2CONH2) in 1 L water
at 27C.
Ans: 24.44 atm

9. 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic
pressure of such a solution at 300 K is found to be 2.57 bar. Calculate the molar mass of the
protein.
Ans: 61.022 g/mol
10. At certain temperature, 36 g of glucose present in a litre of its solution has an osmotic pressure
of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the same temperature, what
would be its concentration?
Ans: 0.061 M
Objective :
1. During depression of freezing point in a solution, the following are in equilibrium:
(a) liquid solvent, solid solvent (b) liquid solvent, solid solute
(c) liquid solute, solid solute (d) liquid solute, solid solvent
PRADEEP329Q167[a]
2. A solution of 1.25 gram of non–electrolyte in 20 gram of water freezes at 271.94 K. If Kf = 1.86 K
kg mol–1, then the molecular weight of the solute will be
(a) 179.79 g mol–1 (b) 207.8 g mol–1 (c) 209.6 g mol–1
(d) 109.6 g mol–1
PRADEEP334Q266[d]
3. How much ethyl alcohol must be added to 1.0 L of water so that solution will not freeze at –4°F?
(Kf=1.86°C/m)
(a) < 20 g (b) < 10.75 g (c) < 494.5 g (d) > 494.5 g
BALAJI 298 50 [d]

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Liquid Solutions [34]
4. The freezing point of a 4% (by mass) aqueous solution of ‗A‘ is equal to the freezing point of 10%
aqueous solution of ‗B‘. If the molecular weight of ‗A‘ is 60, then the molecular weight of ‗B‘ will
be:
(a) 160 (b) 90 (c) 45 (d) 180
BALAJI 298 59 [a]
5. An aqueous solution boils at 101°C. What is the freezing point of the same solution?
(Given: Kf = 1.86°C/m and Kb = 0.51°C/m)
(a) 3.647°C (b) –3.647°C (c) –0.364°C (d) none of these
BALAJI 304 10 [b]
6. A aqueous solution freezes at –2.55°C. What is the boiling point
(Kb  0.52K m ;Kf  1.86K m1 )?
H2O 1 H2O

(a) 107.0°C (b) 100.6°C (c) 100.1°C (c) 100.7°C

KS VERMAP-2.57, 1,-d
7. For the depression of freezing point experiment. The correct statement(s) is/are:
(a) Vapour pressure of pure solvent is equal that of solution
(b) Vapour pressure of pure solvent is less than that of solution
(c) Only solute molecules solidify at the freezing point
(d) Only solvent molecules solidify at the freezing point.
BALAJI 308 10 [d]
8. The amount of ice that will separate out on cooling a solution containing 50 g of ethylene glycol
in 200 g water to –9.3°C is:
(a) 38.71 g (b) 38.71 mg (c) 42 g (d) 42 mg
PABAHA 324 80[a]
9. The cryoscopic constant value doesn‘t depends upon:
(a) The molar mass of the solute in the solution
(b)The molar mass of the solvent in the solution
(c) The enthalpy of Vapourisation of the solvent
(d)The freezing point of the solvent
BALAJI 308 11 [a]
10. If boiling point of an aqueous solution is 100.1°C, what is its freezing point? Given, latent heat
of fusion and Vapourisation of water are 80 cal g–1 and 540 cal g–1 respectively:
(a) 0.361°C (b) –0.361°C (c) –3.61°C (d) none of these
BALAJI 304 14 [b]
11. A semipermeable membrane used in the measurement of osmotic pressure of a solution allows
the passage of:
(a) solute molecules through it (b) solvent molecule through it
(c) both solvent and solute molecules (d) either solvent or solute
BALAJI 300 77 [b]
12. An unripe mango placed in a concentrated salt solution to prepare pickle, shrinks because
_______.
(a) it gains water due to osmosis. (b) it loses water due to reverse osmosis.
(c) it gains water due to reverse osmosis. (d) it loses water due to osmosis.
Exemplar-12-(d)
13. Consider the Fig. given below and mark the in correct option.
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Piston (A) Piston (B)

SPM

Concentrated
Fresh water Sodium chloride
(A) solution in
water (B)

(a) water will move from side (A) to side (B) if a pressure lower than osmotic pressure is applied
on piston (B).
(b) water will move from side (B) to side (A) if a pressure greater than osmotic pressure is
applied on piston (B).
(c) water will move from side (B) to side (A) if a pressure equal to osmotic pressure is applied on
piston (B).
(d) Both (a) and (b)
-(C)
14. At a given temperature, osmotic pressure of a concentrated solution of a substance
_____________.
(a) is higher than that at a dilute solution.
(b) is lower than that of a dilute solution.
(c) is same as that of a dilute solution.
(d) cannot be compared with osmotic pressure of dilute solution.
(a)
15. 10.0 g of glucose (I), 10.0 g of urea (II), and 10.0 g of sucrose (III) are dissloved in 250.0 mL of
water at 273 K. The relationship between the somotic pressure (of the solution is
(a) 1  2  3 (b) 3  1  2 (c) 2  1  3 (d) 2  3  1
KS VERMAP-2.57, 3,-c
16. 0.6 g of a solute is dissolved in 0.1L of a solvent which develops an osmotic pressure of 1.23atm
at 27°C. The molecular weight of the solute is
(a) 149.5 g mol–1 (b) 120.0 g mol–1 (c) 430.0 g mol–1 (d) none of these
KS VERMAP-2.57, 4,-b
17. 18 g glucose and 6g urea are dissolved in 1L aqueous solution at 26°C. The osmotic pressure of
the solution will be
(a) 8.826 atm (b) 4.926 atm (c) 2.92 atm (d) 4.42 atm
KS VERMAP-2.54, 2.159,-b
18. A solution containing 500 g of a protein per litre is isotonic with a solution containing 3.42 g of
sucrose per litre. The molecular mass of protein is:
(a) 5 (b) 146 (c) 34200 (d) 50000
PABAHA 324 58[d]
19. The osmotic pressure of a 5% (wt./vol.) solution of cane sugar at 150°C is: (M = 342)
(a) 4 atm. (b) 3.4 atm. (c) 5.078 atm. (d) 2.45 atm.
[c]
20. A 5% solution of cane sugar is isotonic with 0.877% solution of urea. Calculate the molecular
mass of urea if the molecular mass of cane sugar is 342
(a) 59.987 (b) 53.231 (c) 60.873 (d) 49.987
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KS VERMAP-2.55, 2.167,-a
21. Osmotic pressure of blood is 7.65 atm at 310 K. An aqueous solution of glucose that will be
isotonic with blood is ... wt./vol.
(a) 5.41% (b) 3.54% (c) 4.53% (d) 53.4%
[Link] 322 Q-14[a]
22. The density of a 9.5% by mass solution of fructose (C 6H12O6) is 1.036 g cm–3 at 293 K.
Calculate the osmotic pressure of the solution.
(a) 12.23 (b) 10.02 (c) 13.16 (d) 0.031
TMH, 359, Q25 [c]
23. Calculate the freezing point of an aqueous solution of non electrolyte having an osmotic
pressure 2.0 atm at 300 K. K´f = 1.86 K mol–1 kg and R = 0.0821 L atm K–1 mol–1.
(a) –0.061°C (b) –1.15°C (c) –0.151°C (d) +0.151°C
525,71 [c]
24. van‘t Hoff proved that osmotic pressure () is a colligative property. For an ideal solution,
W RT
osmotic pressure () is helpful to determine that molecular mass of solute using M B = B .
π·V
Law can be show by the curve (C = concentration):
C = constant C = constant T = constant T = constant
   
(a) (b) (c) (d)

C C
T T

Que. 1 2 3 4 5 6 7 8 9 10 11 12
Ans. A D D A B D D A A B B D
Que. 13 14 15 16 17 18 19 20 21 22 23 24
Ans. D A C B B D C A A C C A

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6. Van’t Hoff Factor (i)

When a substance dissociates or associates in solution, the effective number of moles of particle
increases or decreases respectively and hence observed colligative property is different in
comparison to the one which is theoretically calculated based on moles of particles added in the
solution.

Van't hoff factor (i)

Observed number of solute particles

Theoritical number of solute particles (or number of solute particle added in solution)

Observed colligative properties

=
Theoritical colligative properties

Mass /Observed molar mass of solute


Mass / Theoritical molar mass of solute

Theoritical molar mass of solute


Observed molar mass of solute

Note: Observed , abnormal, experimental or actual values have same meaning.

Expected, theoretical or calculated values have same meaning.

If a solutes undergoes association or dissociation, the actual colligative properties can be

calculated as follows:

PA0  PS i  nB
(i) RLVP  
PA0
nA  i  nB

(ii) Tb  i Kb m

(iii) Tf  i Kf m

(iv)   i CRT

6.1 Calculation of i for dissociation:

Let an electrolyte dissociates as follows having degree of dissociation 

An nA
Number of moles dissolved no 0
Number of moles after dissociation no(1 – ) n(no)
Total number of moles present in solution = no(1 – ) + n(no)

Actual moles of solute present in solution n (1  )  n(no )

i = o  1  (n  1)
Moles of solute dissolved no

Illustration: Calculate the value of i for the following

(i) NaCl (complete dissociation)
(ii) CaCl2 (complete dissociation)
(iii) Al2(SO4)3 (complete dissociation)

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(iv) CH3COOH ( = 0.1)
(v) Na2SO4 ( = 0.8)
Solution: (i) NaCl  Na+ + Cl― (n=2)
i  1  (n  1)  1  (2  1) 1  2

(ii) CaCl2  Ca+ + 2Cl― (n=3)

i  1  (3 1)  1  (3  1) 1  3
(iii) Al2(SO4)3  2 Al3+ + 3 SO42― (n=5)
i  1  (5  1)  1  (5  1) 1  5

(iv) CH3COOH  CH3COO― + H+ (n=2)

i  1  (2  1)  1  (2  1)  0.1  1.1

(v) Na2SO4  2 Na+ + SO42― (n=3)

i  1  (3  1)0.8  1  (3  1)  0.8  2.6

Brain Teaser: Calculate the van‘t hoff factor of Na3[AlF6] assuming complete dissociation.
Ans: 4
Illustration: Calculate osmotic pressure of 1 M NaCl solution at 27C.
Solution: NaCl  Na+ + Cl― (n=2)
i  1  (n  1)  1  (2  1) 1  2
1 mol 0.082 L  atm
  i CRT  2    300K  49.2 atm
L mol K
Brain teaser: Solute A is a ternary electrolyte (produces three ions) and solute B is non–
electrolyte. If 0.1 M solution of solute B produces an osmotic pressure of 2P, then
0.05 M solution of A at the same temperature will produce an osmotic pressure
equal to……..?
Ans: 3P
Illustration: A weak electrolyte, AB, is 5% dissociated in aqueous solution. What is the freezing
point of a 0.100 molal aqueous solution of AB? Kf for water is 1.86 C/molal.

5
Solution: Degree of dissociation, , for AB =  0.05
100
AB A+ + B– (n=2)

i = 1+(n―1)  = 1+ (2―1)0.05 = 1.05

Tf = i Kf m  Tf0 – Tf = 1.86 K/m × 1.050.1 m = 0.1953 deg

Tf = 0°C – 0.1953 = – 1953°C

Brain Teaser: 20 g of a binary electrolyte ([Link]. = 100) are dissolved in 500 g of water. The
freezing point of the solution is –0.74°C, Kf = 1.86 [Link]–1. The degree of
ionisation of the electrolyte is
Ans: 0%
Illustration: The values of observed and calculated molecular weights of silver nitrate are 92.64
and 170 respectively. The degree of dissociation of silver nitrate is
Solution: AgNO3 Ag+ + NO3– (n=2)
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i = 1+(n―1)  = 1+ (2―1)  = 1+

Normal [Link]
i for AgNO3 = =1+
Observed [Link].
170
= – 1 = 0.835 = 83.5 %
92.64

Brain Teaser: A solution is prepared by dissolving 26.3g of CdSO 4 (Molar weight =208.4 g/mol ) in
1000g water. The depression in freezing point of solution was found to be 0.284K.
Calculate the Van‘t Hoff factor and observed molecular weight of CdSO 4. The
cryoscopic constant of water is 1.86K kg solvent mol–1- solute.
Ans:172.23 g/mol

6.2 Calculation of i for association:

Let n moles of the solute, A, associate to form (a)n. If  is the degree of association.
nA An
Number of moles dissolved no 0
Number of moles after association no(1 – ) no/n
Total number of moles present in solution = no (1 – ) + no /n
Actual moles of solute in solution n (1  )  no /n   1  
i  o  1    1 
Moles of solute dissolved in solution no  n  

Illustration :Three particles of a solute, A, associate in benzene to form species A 3.

Calculate the freezing point of 0.25 molal solution. The degree of association of
solute A is found to be 0.80. The freezing point of benzene and its cryoscopic
constant are 5.5°C and 5.12 Km–1 respectively.

Solution: 3A  A3 (n=3)

1  1 
i  1    1   1    1 0.8  0.47
 n   3 

Tf = i Kf m = 0.47  5.12 Km–1 × 0.25 m = 0.6

Tf = Tf0 – 0.6°C = 5.5°C – 0.6°C = 4.9°C

Brain Teaser: Acetic acid (CH3COOH) associates in benzene to form dimer molecules. 1.65 g of
acetic acid when dissolved in 100 g of benzene raised the boiling point by 0.36°C.
Calculate the degree of association of acetic acid in benzene (molal elevation
constant of benzene is 2.57 K kg/mol).
Ans: 98.3%

In Chapter exercise – 6 (Van’t hoff factor)

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Subjective :

1. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K 2SO4 in 2 litre

of water at 25° C, assuming that it is completely dissociated.
Ans: 5.2710–3 atm
2. 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: 3.4 g
3. In comparison to a 0.01 M solution of glucose, how many times will the depression in freezing
point of a 0.01 M MgCl2 solution be?
Ans: 3 times
4. 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.
5. Calculate the depression in the freezing point of water when 10 g of CH 3CH2CHClCOOH is
added to 250 g of water. Ka = 1.4 × 10–3, Kf = 1.86 K kg mol–1. (Consider dilute solution)
Ans: 0.65 K
6. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point of
water observed is 1.00 C. Calculate the van‘t Hoff factor and dissociation constant of
fluoroacetic acid. Density of solution is 1.124 g/mL
Ans: 1.075, 3.0410–3
7. 0.6 mL of acetic acid (CH3COOH), having density 1.06 g mL–1, is dissolved in 1 litre of water.
The depression in freezing point observed for this strength of acid was 0.0205°C. Calculate the
van‘t Hoff factor and the dissociation constant of acid.
Ans: 1.04, 1.7 10–5
8. What is the van‘t hoff factor if A undergoes polymerization as follows: nA  An

Objective :
1. One mole of a solute A is dissolved in a given volume of a solvent. The association of the solute
takes place as follows:
nA  An
If  is the degree of association of A, the van‘t Hoff factor i is expressed as:
α 1
(a) i =1  α (b) i =1  (c) i =1+( -1) (d) i = 1
n n
296 34 [c]
BALAJI
2. The values of Van‘t Hoff factors for KCl, NaCl and K2SO4, respectively, are _____________.
(a) 2, 2 and 2 (b) 2, 2 and 3 (c) 1, 1 and 2 (d) 1, 1 and 1
Exemplar-15-(b)
3. We have three aqueous solutions of NaCl (assuming complete dissociation) labelled as ‗A‘, ‗B‘
and ‗C‘ with concentrations 0.1M, 0.01M and 0.001M, respectively. The value of van‘t Hoff
factor for these solutions will be in the order______.
(a) iA < iB < iC (b) iA > iB > iC (c) iA = iB = iC (d) iA < iB > iC
Exemplar-20-(c)
4. If osomotic pressure of 1 M urea is , what will be the osmotic pressure for 1 M NaCl?
(a)  (b) 0.1  (c) 2  (d) 0.2 
[d]
5. The freezing point of 1 molal NaCl solution assuming NaCl to be 100% dissociated in water is:
(Kf = 1.86 K molality–1)
(a) –1.86°C (b) –3.72°C (c) +1.86°C (d) +3.72°C
[Link] 322Q17[b]
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Liquid Solutions [41]
6. Which one of the following aqueous solutions will exhibit highest boiling point:
(a) 0.015 M urea (b) 0.01 M KNO3 (c) 0.10 M Na2SO4 (d) 0.015 M glucose
BALAJI 297 45 [c]
7. Minimum freezing point will be for 1 molal solution of each compound, assuming complete
ionisation in each case:
(a) [Fe(H2O)6]Cl3 (b) [Fe(H2O)5Cl]Cl2·H2O
(c) [Fe(H2O)4Cl2]Cl·2H2O (d) [Fe(H2O)3Cl3]·3H2O
BALAJI 298 54 [a]
8. Moles of Na2SO4 to be dissolved in 12 mole water to lower its vapour pressure by 10 mm Hg at
a temperature at which vapour pressure of pure water is 50 mm is :
(a) 1.5 mole (b) 2 mole (c) 1 mole (d) 3 mole
shree balaji 297 37 [c]
9. The molal elevation constant of water = 0.52 K, molality 1. The boiling point of 1.0 molal
aqueous KCl solution (assuming complete dissociation of KCl), should be:
(a) 100.52°C (b) 101.04°C (c) 99.48°C (d) 98.96°C
PBAHA 323Q30[b]
10. What is the freezing point of a solution containing 8.1 gram HBr in 100 gram water assuming
the acid to be 90% ionised (Kf for water = 1.86 K kg mol–1)
(a) 0.85°C (b) –3.53°C (c) 0°C (d) –0.35°C
PRADEEP335Q281[b]
11. The degree of dissociation of Ca(NO3)2 in a dilute aqueous solution containing 7 g of salt per
100 g of water at 100 °C is 70%. Calculate the vapour pressure of solution.
(a) 746.32 (b) 786.02 (c) 240.02 (d) 389.02
PBA533 Q89[a]
12. The osmotic pressure of 0.010 M solutions of KI (assuming incomplete dissociation) and of
sucrose (C12H22O11) are 0.432 atm and 0.24 atm respectively. The van‘t Hoff factor for KI is:
(a) 1.80 (b) 0.80 (c) 1.2 (d) 1.0
BALAJI 301 92 [a]
13. A decimolar solution of potassium ferrocyanide K4[Fe(CN)6] is 50% dissociated at 300 K.
Calculate osmotic pressure of the solution. Given S = 8.314 JK–1 mol–1.
(a) 3.24 × 103 Pa (b) 8.92 × 105 Pa (c) 8.06 × 105 Pa (d) 7.48 × 105 Pa
PBAHA526 Q73 [d]
14. Calculate the percentage degree of dissociation of an electrolyte XY2 (Normal molar mass = 164)
in water if the observed molar mass is 65.6:
(a) 75% (b) 25% (c) 65% (d) none of these
BALAJI 297 46 [a]
15. When some NaCl was dissolved in water, the freezing point depression was numerically equal to
twice the molal depression constant. The relative lowering of vapour pressure of the solution is:
(a) 0.117 (b) ~ 0.036 (c) 0.0585 (d) none of these
BALAJI 300 72 [b]
16. The values of observed and calculated molecular weights of calcium nitrate are respectively 65.6
and 164. The degree of dissociation of calcium nitrate will be:
(a) 25% (b) 50% (c) 75% (d) 60%
PABAHA 324 65[c]
17. The freezing point of aqueous solution that contains 5% by mass urea, 1.0% by mass KCl and
10% by mass of glucose is: (Kf H2O = 1.86 K molality–1):
(a) 290.2°C (b) 285.5°C (c) –3.069°C (d) +3.069°C
[Link] 323Q38[c]
18. A substance is completely trimerised on dissolution in a solvent. The Van‘t Hoff‘s factor i for
such change is:
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Liquid Solutions [42]
(a) 1 (b) 2 (c) 3 (d) 1/3
[Link] 323Q29[d]
19. The van‘t Hoff factor i for an electrolyte which undergoes dissociation and association in solvent
are respectively:
(a) greater than one and less than one (b) less than one and greater than one
(c) less than one and less than one (d) greater than one and greater than one
BALAJI 297 35 [a]
20. If benzoic acid (Molecular weight 122) is associated into double molecules when dissolved in
benzene and the osmotic pressure of solution of 5 gm benzoic acid in 100 ml of benzene is 5.73
atm at 10 °C. What is the percentage association?
(a) 89.67 (b) 32.68 (d) 23.66 (d) 79.66
FIITJEE’02L3 [d]
21. One molal solution of carboxylic acid in benzene shows the elevation of boiling point of 1.518 K.
The degree of association for dimerization of the acid in benzene is (K b for benzene = 2.53 K kg
mol–1):
(a) 60% (b) 70% (c) 75% (d) 80%
BALAJI 297 43 [d]
–1
22. Two solvents A and B have Kf values 1.86 and 2.79 K mole kg respectively. A given amount of
substance when dissolved in 500 g of A, it completely dimerizes and when same amount of
substance is dissolved in 500 g of B, the solute undergoes trimerization. What will be the ratio
of observed lowering of freezing points in two cases?
(a) 2 : 3 (b) 1 : 4 (c) 3 : 2 (d) 1 : 1
JRS [d]

Answer Keys
Que. 1 2 3 4 5 6 7 8 9 10 11
Ans. C B C C B C A C B B A
Que. 12 13 14 15 16 17 18 19 20 21 22
Ans. A D A B C C D A D D D

*****

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NEET (PREVIOUS YEARS ASKED QUESTIONS)
Single correct Type Questions
1. An ideal solution is formed when its components c[1988]
(a) have no volume change on mixing (b) have no enthalpy change on mixing 50-[d]
(c) have both the above characteristics (d) have high solubility
2. All form ideal solution except -d[1988]
(a) C6 H6 and C6 H5CH3 (b) CH3I and C2 H5 I
(c) C2 H5Cl and C2 H5 Br (d) C2 H5 I and C2 H5OH
3. The relative lowering of the vapour pressure is equal to the ratio between the number of 57-b[1991]
(a) Solute molecules to the solvent molecules
(b) Solute molecules to the total molecules in the solution
(c) Solvent molecules to the total molecules in the solution
(d) solvent molecules to the total number of ions of the solute.
4. Which of the following aqueous solution has minimum freezing point? -a[1991]
(a) 0.01 m NaCl (b) 0.005 m C2H5OH
(c) 0.005 m MgI2 (d) 0.005 m MgSO4
5. Blood cells retain their normal shape in solution which are 55-b [1991]
(a) hypotonic to blood (b) isotonic to blood
(c) hypertonic to blood (d) equinormal to blood
6. Which one is a colligative property? 54-c[1991]
(a) Boiling point (b) Vapour pressure
(c) Osmotic pressure (d) Freezing point
7. If 0.1 M solution of a glucose and 0.1 M solution of urea are placed on two sides of the semipermeable membrane to
equal heights, then it will be correct to say that 53-a[1992]
(a) There will be no net movement of water across the membrane
(b) Glucose will flow towards glucose solution
(c) Urea will flow towards glucose solution
(d) Water will flow from urea solution to glucose
8. Which of the following salt has the same value of vant's Hoff factor (i) as that of K3[Fe(CN)6 ] ?
(a) Na 2SO4 (b) Al(NO3 )3 (c) Al2 (SO4 )3 (d) NaCl 52-b[1994]
9. At 25C, the highest osmotic pressure is exhibited by 0.1 M solution of -c[1994]
(a) Glucose (b) Urea (c) CaCl2 (d) KCl.
10. How many grams of CH3OH should be added to water to prepare 150 mL solution of 2 M CH3OH ?
(a) 9.6 103 (b) 2.4 103 (c) 9.6 (d) 2.4 50-c[1994]
11. According to Raoult's law, the relative lowering of vapour pressure for a solution is equal to 49-a[1995]
(a) Mole fraction of solute (b) Mole fraction of solvent
(c) Moles of solute (d) Moles of solvent
12. The concentration unit, independent of temperature, would be 48-c[1995]
(a) normality (b) weight volume percent

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Liquid Solutions [44]
(c) molality (d) molarity
13. The relationship between osmotic pressure at 273 K when 10g glucose ( p1 ) to 10 g urea ( p 2 ), and 10 g surcose ( p3 )
are dissolved in 150 mL of water is -a[1996]
(a) p2  p1  p3 (b) p2  p3  p1 (c) p1  p2  p3 (d) p3  p1  p2
14. The vapour pressure of CCl4 at 25C is 143 mm Hg. If 0.5 g of a non-volatile solute (mol. Wt=65) is dissolved in
100 mL CCl4 , the vapour pressure of the solution will be. -c[1996]
(a) 199.34 mm Hg (b) 143.99 mm Hg (c) 141.43 mm Hg (d) 94.39 mm Hg
15. What is the molarity of H2SO4 solution, that has a density 1.84 g/cc at 35C and contains 98% by weight?
(a) 18.4M (b) 18 M (c) 4.18M (d) 8.14M 45-a[1996]
16. Which of the following 0.10 m aqueous solution will have the lowest freezing point? 44-c[1997]
(a) KI (b) C12H22O11 (c) Al2 (SO4 )3 (d) C5H10O5
17. A 5% solution of cane sugar (Mol. Wt. = 342) is isotonic with 1% solution of a substance X. The molecular weight
of X is -a[1998]
(a) 68.4 (b) 6.84 (c) 80 (d) 30
18. The vapour pressure of a solvent decreased by 10 mm of mercury when a non-volatile solute was added to the
solvent. The mole fraction of the solute is 0.2. What should be the mole fraction of the solvent if the decrease in the
vapour pressure is to be 20 mm of mercury? 42-b[1998]
(a) 0.4 (b) 0.6 (c) 0.8 (d) 0.2
19. If 0.15 g of a solute, dissolved in 15 g of solvent, is boiled at a temperature higher by 0.216C, than that of the pure
solvent. The molecular weight of the substance (Molal elevation constant for the solvent is 2.16C) is 1-b[1999]
(a) 10.1 (b) 100 (c) 1.01 (d) 1000
20. How many g of dibasic acid (mol. Weight 200) should be present in 100 mL of the aqueous solution to give strength
of 0.1N? 40-c[1999]
(a) 10 g (b) 2 g (c) 1 g (d) 20 g
21. The vapour pressure of benzene at a certain temperature is 640 mm of Hg. A non-volatile and non-electrolyte solid,
weighing 2.175 g is added to 39.08 of benzene. The vapour pressure of the solution is 600 mm of Hg. What is the
molecular weight of solid substance? 39-a[1999]
(a) 69.5 (b) 59.6 (c) 49.50 (d) 79.8
22. From the colligative properties of solution, which one is the best method for the determination of molecular weight
of proteins and polymers? 38-a[2000]
(a) Osmotic pressure (b) Lowering in vapour pressure
(c) Lowering in freezing point (d) Elevation in boiling point
23. Pure water can be obtained from sea water by 37-c[2001]
(a) Centrifugation (b) Plasmolysis
(c) reverse osmosis (d) sedimentation
24. The beans are cooked earlier in pressure cooker because 36-a[2001]
(a) Boiling point increases with increasing pressure
(b) Boiling point decreases with increasing pressure
(c) Extra pressure of pressure cooker softens
(d) Internal energy is not lost while cooking in pressure cooker.
25. 2.5 litre of 1 M NaOH solution is mixed with another 3 litre of 0.5 M NaOH solution. Then find out molarity of
resultant solution. -c[2002]
(a) 0.80 M (b) 1.0 M (c) 0.73 M (d) 0.50 M
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Liquid Solutions [45]
26. A solution contains non volatile solute of molecular mass M2 . Which of the following can be used to calculate the
molecular mass of solute in terms of osmotic pressure? 34-b[2002]
m   m  RT
(a) M2   2  VRT (b) M2   2 
    V  
m  m  
(c) M2   2  RT (d) M2   2 
 V   V  RT
27. A solution containing components A and B following Raoult's law 33-c[2002]
(a) A–B attraction force is greater than A–A and B–B
(b) A–B attraction force is less than A–A and B–B
(c) A–B attraction force remains same as A–A and B–B
(d) volume of solution is different from sum of volume of solute and solvent
28. A solution of urea (mol. Mass 56 g mol–1) boils at 100.18C at the atmospheric pressure. If Kf and Kb for water are
1.86 and 0.512 K kg mol–1 respectively, the above solution will freeze at 32-b[2005]
(a) 0.654C (b) –0.654C (c) 6.54C (d) –6.54C
29. A solution has 1:4 mole ratio of pentane to hexane. The vapour pressures of the pure hydrocarbons at 20C are 440
mm Hg for pentane and 120 mm Hg for hexane. The mole fraction of pentane in the vapour phase would be-d[2005]
(a) 0.200 (b) 0.549 (c) 0.786 (d) 0.478
30. The vapour pressure of two liquid P and Q are 80 and 60 torr, respectively. The total vapour pressure of solution
obtained by mixing 3 mole of P and 2 mole of Q would be 30-a[2005]
(a) 72 torr (b) 140 torr (c) 68 torr (d) 20 torr.
31. The mole fraction of the solute in one molal aqueous solution is 29-b[2005]
(a) 0.009 (b) 0.018 (c) 0.027 (d) 0.036
32. A solution containing 10 g per dm of urea (molecular mass = 60 g mol–1) is isotonic with a 5% solution of a
3

nonvolatile solute is 28-c[2006]

(a) 200 g mol–1 (b) 250 g mol–1 (c) 300 g mol–1 (d) 350 g mol–1
33. 1.00 g of a non-electrolyte solute (molar mass 250 g mol–1) was dissolved in 51.2 g of benzene. If the freezing point
depression constant, Kf of benzene is 5.12 K kg mol–1, the freezing point of benzene will be lowered by 7-b[2006]
(a) 0.2 K (b) 0.4K (c) 0.3K (d) 0.5K
34. A solution of acetone in ethanol 26-c[2006]
(a) obeys Raoult's law (b) shows a negative deviation from Raoult's law
(c) shows a positive deviation from Raoult's law (d) behaves like a near ideal solution
35. During osmosis, flow of water through a semipermeable membrane is 5-d[2006]
(a) from solution having lower concentration only
(b) from solution having higher concentration only
(c) from both sides of semipermeable membrane with equal flow rates
(d) from both sides of semipermeable membrane with unequal flow rates.
36. Concentrated aqueous sulphuric acid is 98% H2SO4 by mass and has a density of 1.80 g mL–1. Volume of acid
required to make one litre of 0.1 m H2SO4 solution is 24-c[2006]
(a) 16.65 mL (b) 22.20 mL (c) 5.55 mL (d) 11.10 mL
37. 0.5 molal aqueous solution of a weak acid (HX) is 20% ionised. If K f for water is 1.86 K kg mol–1, the lowering in
freezing point of the solution is 23-b[2007]
(a) 0.56 K (b) 1.12K (c) –0.56 K (d) –1.12 K

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Liquid Solutions [46]
38. A 0.0020 m aqueous solution of an ionic compound [Co(NH3 )5 (NO2 )]Cl freezes at –0.00732C. Number of moles
of ions which 1 mol of ionic compound produces on being dissolve in water will be ( Kf  1.86C /m )2-d[2009]
(a) 3 (b) 4 (c) 1 (d) 2
–1
39. A solution of sucrose (molar mass = 342 g mol ) has been prepared by dissolving 68.5 g of sucrose in 1000 g of
water. The freezing point of the solution obtained will be (Kf for water = 1.86 K kg mol–1)
(a) –0.372C (b) –0.520C (c) +0.372C (d) –0.570C 21-a[2010]
40. An aqueous solution is 1.00 molal in KI. Which change will cause the vapour pressure of the solution to increase?
(a) Addition of NaCl (b) Addition of Na 2SO4 20-d[2010]
(c) addition of 1.00 molal KI (d) Addition of water
41. 200 mL of an aqueous solution of a protein contains its 1.26 g. The osmotic pressure of the solution at 300K is found
to be 2.5710–3 bar. The molar mass of protein will be 9-d[2011]
(a) 51022 g mol–1 (b) 122044 g mol–1 (c) 31011 g mol–1 (d) 61038 g mol–1
42. A 0.1 molal aqueous solution of a weak acid is 30% ionized. If K f for water is 1.86C/m, the freezing point of the
solution will be 18-d[2011]
(a) –0.18C (b) –0.54C (c) –0.36C (d) –0.24C
43. The van't Hoff factor i for a compound which undergoes dissociation in one solvent and association in other solvent
is respectively. 7-c[2011]
(a) Less than one greater than one (b) Less than one and less than one
(c) Greater than one and less than one (d) Greater than one and greater than one.
44. The freezing point depression constant for water is –1.86C m–1. If 5.00 g Na2SO4 is dissolved in 45.0 g H2O, the
freezing point is changed by –3.82C. Calculate the van't Hoff factor for Na2SO4. 16-b[2011]
(a) 2.05 (b) 2.63 (c) 3.11 (d) 0.381
45. Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 25C are 200 mm Hg and 41.5 mm Hg
respectively. Vapour pressure of the solution obtained by mixing 25.5 g of CHCl 3 and 40 g of CH2Cl2 at the same
temperature will be [Molecular mass of CHCl3=85 u and molecular mass of CH2Cl2 = 85 u] [2012]
(a) 173.9 mm Hg (b) 615.0 mm Hg (c) 347.9 mm Hg (d) None of these
46. pA and pB are the vapour pressure of pure liquid components, A and B, respectively of an ideal binary solution. If
x A represents the mole fraction of component A, the total pressure of the solution will be
(a) pA  x A (pB  pA ) (b) pA  x A (pA  pB ) 14-d[2012]
(c) pB  x A (pB  pA ) (d) pB  x A (pA  pB )
47. Which condition is not satisfied by an ideal solution? 3-b[2013]
(a) mix V  0 (b) mix S  0
(c) Obeyance to Raoult's Law (d) mix H  0
48. How many grams of concentrated nitric acid solution should be used to prepare 250 mL of 2.0 M HNO3 ? The
concentrated acid is 70% HNO3 . 12-c[2013]
(a) 70.0 g conc. HNO3 (b) 54.0 g conc. HNO3
(c) 45.0 g conc. HNO3 (d) 90.0 conc. HNO3
49. Of the following 0.10 m aqueous solutions, which one will exhibit the largest freezing point depression?
(a) KCl (b) C6H12O6 (c) Al2 (SO4 )3 (d) K2SO4 11-c[2014]
50. Which of them is not equal to zero for an ideal solution? -d[2015]

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Liquid Solutions [47]
(a) Vmix (b) P  Pobserved  PRaoult (c) Hmix (d) Smix
51. Which one of the following electrolytes has the same value of van't Hoff factor (i) as that of Al2 (SO4 )3 (if all are
100% ionised)? 9-b[2015]
(a) Al(NO3 )3 (b) K4 [Fe(CN)6 ] (c) K2SO4 (d) K3 [Fe(CN)6 ]
–1
52. The boiling point of 0.2 mol kg solution of X in water is greater than equimolal solution of Y in water. Which one
of the following statements is true in this case? 8-c[2015]
(a) Molecular mass of X is less than the molecular mass of Y
(b) Y is undergoing dissociation in water while X undergoes no change
(c) X is undergoing dissociation in water.
(d) Molecular mass of X is greater than the molecular mass of Y.
53. What is the mole fraction of the solute in a 1.00 m aqueous solution? 7-c[2015]
(a) 1.770 (b) 0.0354 (c) 0.0177 (d) 0.177
54. At 100C the vapour pressure of a solution of 6.5 g of a solute in 100 g water 732 mm. If K b=0.52, the boiling point
of this solution will be 6-c[2016]
(a) 102C (b) 103C (c) 101C (d) 100C
55. Which of the following statements about the composition of the vapour over an ideal 1:1 molar mixture of benzene
and toluene is correct? Assume that the temperature is constant at 25C. (Given, vapour pressure data at 25C,
benzene 12.8 kPa, toluene = 3.85 kPa) 5-c[2016]
(a) The vapour will contain equal amounts of benzene and toluene
(b) Not enough information is given to make a prediction.
(c) The vapour will contain a higher percentage of benzene
(d) The vapour will contain a higher percentage of toluene.
56. Which one of the following is incorrect for ideal solution? 4-d[2016]
(a) Hmix  0 (b) Umix  0
(c) P  Pobs  Pcalculated by Raoults law  0 (d) Gmix  0
57. The van't Hoff factor (i) for a dilute aqueous solutions solution of the strong electrolyte barium hydroxide is
(a) 0 (b) 1 (c) 2 (d) 3 3-d[2016]
58. Which of the following is dependent on temperature? a[2017]
(a) Molarity (b) Mole fraction (c) weight percentage (d) Molality
59. If molality of the dilute solution is doubled, the value of molal depression constant (Kf) will be 1-c[2017]
(a) Halved (b) Tripled (c) unchanged (d) doubled.

Answer Keys
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. c d b a b c a b c c a a c a c c a b b c
Que. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. a a c a c b c b d a b c b c d c b d a d
Que. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59
Ans. d d c b d d b c c d b c c c c d d a c

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Liquid Solutions [48]
AIIMS (PREVIOUS YEARS ASKED QUESTIONS)
Single correct Type Questions
1. The molality of a solution having 18 g of glucose (mol. Wt. =180) dissolved in 500g of water is
(a) 0.2m (b) 0.1m (c) 2.2 m (d) 0.5m 1-a[1995]
2. The molarity of pure water is 2-c[1995]
(a) 18.36 M (b) 1.16 M (c) 55.56 M (d) 5.56M
3. Which of the following is the correct representation of relative lowering of vapour pressure? 3-d[1996]
P P  P P  P P P P  P
(a)  (b) (c) (d) 
P P P P  P P P
4. The boiling point of a compound is raised by 4-a[1996]
(a) Intermolecular hydrogen bonding (b) volatility of compound
(c) Intramolecular hydrogen bonding (d) non-polarity in the molecules.
5. Vapour pressure of benzene at 30C is 121.8 mm. When 15 g of non-volatile solute is dissolved in 250 g of benzene,
its vapour pressure is decreased to 120.2 mm. The molecular weight of the solute is
(a) 35.67 g (b) 355.5 g (c) 432.8 g (d) 502.7 g 5-b[1997]
6. Which of the following is not affected by the temperature? 6-b[1997]
(a) Molarity (b) Molality (c) Normality (d) Formality
7. Which of the following salt has the same value of van't Hoff factor as that of K3 [Fe(CN)6 ] ? 7-b[1998]
(a) Na 2SO4 (b) Al(NO3 )3 (c) Al2 (SO4 )3 (d) Fe3O4
8. The boiling point of water (100C) becomes 100.52C, if 3 g of a non-volatile solute is dissolved in 200 mL of
water. The molecular weight of solute is ( K b for water =0.6 K/m) -a[1998]

(a) 17.3 g mol1 (b) 15.4 g mol1 (c) 12.2 g mol1 (d) 20.4 g mol1
9. Which of the following is a colligative property? d[1999]
(a) Surface tension (b) viscosity
(c) Refractive index (d) Osmotic pressure
10. The vapour pressure of benzene at a certain temperature is 640 mm of Hg. When a non-volatile and non-electrolyte
solid weighing 2.175 g is added to 39.08 g of benzene, the vapour pressure of the solution becomes 600 mm of Hg.
What is the molecular weight of solid substance? -a[1999]
(a) 69.60 (b) 49.59 (c) 59.60 (d) 108.30
11. Which of the following 0.1 M solution will show maximum boiling point? -d[2000]
(a) Sodium chloride (b) Copper chloride
(c) Magnesium sulphate (d) Chromium sulphate
12. A certain aqueous solution of ..[formula mass = 162] has a density of 1.1 g/mL and contains 20.0% FeCl3 . Molar
concentration of the solution is 12-c[2000]
(a) 0.028 (b) 0.163 (c) 1.357 (d) 1.47
13. How many litres of ammonia gas at STP would be needed to prepare 100 mL of 2.5 M ammonium hydroxide
solution? 13-a[2001]
(a) 5.6 L (b) 0.056 L (c) 11.2 L (d) 0.56 L
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Liquid Solutions [49]
14. Which one of the following statements given below regarding properties of solutions, describes a colligative effect?
(a) Boiling point of pure water decreases by the addition of ethanol 14-d[2003]
(b) Vapour pressure of pure water decreases by the addition of nitric acid
(c) Vapour pressure of pure benzene decreases by the addition of naphthalene
(d) Boiling point of pure benzene increases by the addition of toluene.
15. The average osmotic pressure of human blood is 7.8 bar at 37C. What is the concentration of an aqueous NaCl
solution that could be used in the blood stream? -b[2004]
(a) 0.16 mol/L (b) 0.31 mol/L (c) 0.60 mol/L (d) 0.45 mol/L
16. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K and freezing point of pure water is
273.15 K. The freezing point of a 5% solution (by mass) of glucose in water is 1 6-c[2006]
(a) 271K (b) 273.15K (c) 269.07K (d) 277.23K
17. 1 mol each of the following compounds is dissolved in 1L of solution. Which will have the largest Tb value?
(a) HF (b) HCl (c) HBr (d) HI
18. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-electrolyte solid
weighing 0.5 g is added to 39.0 g of benzene (molar mass 78 g/mol). The vapour pressure of the solution then is
0.845 bar. What is the molecular mass of the solid substance? 18-c[2007]
(a) 58 (b) 180 (c) 170 (d) 145
19. For a dilute solution, Raoult's law states that 19-b[2009]
(a) the relative lowering of vapour pressure proportional to the amount of solute in solution
(b) the relative lowering of vapour pressure is equal to the mole fraction of solute
(c) the lowering of vapour pressure is equal to the mole fraction of the solute
(d) the vapour pressure of the solution is equal to the mole fraction of the solvent.
20. A 0.1 molal solution of an acid is 4.5% ionized. Calculate freezing point. (molecular weight of the acid is 300)
Kf  1.86K mol1 kg. 20-a[2009]
(a) –0.194C (b) 2.00C (c) 0C (d) –0.269C
21. A mixture of two miscible liquids A and B is distilled under equilibrium conditions at 1 atm pressure. the mole
fraction of A in solution and vapour phase are 0.30 and 0.60 respectively. Assuming ideal behaviour of the solution
and the vapour, calculate the ratio of the vapour pressure of pure A to that of pure B.
(a) 4.0 (b) 3.5 (c) 2.5 (d) 1.85 21-b[2009]
22. When 25 g of Na 2SO4 is dissolved in 103 kg of solution, its concentration will be 22-b [2010]
(a) 2.5 ppm (b) 25 ppm (c) 250 ppm (d) 100 ppm
23. Which of the following is true for an ideal solution? A [2013]
(a) H(mix)  0 (b) S(mix)  0 (c) G (mix)  0 (d) None of these

24. Boiling point of benzene is 353.23 K. When 1.8 g of non-volatile solute is dissolved in 90 g of benzene, boiling
point is raised to 354.11 K. If Kb(benzene) = 253 kg mol–1 the molecular mass of non-volatile substance is [2013]
(a) 58 g mol–1 (b) 120 g mol–1 (c) 116 g mol–1 (d) 60 g mol–1
25. The value of Henry's constant KH is 25-b[2014]
(a) Greater for gases with higher solubility (b) Greater for gases with lower solubility

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Liquid Solutions [50]
(c) Constant for all gases (d) Not related to the solubility of gases.
26. The relationship between osmotic pressure at 273 K when 10g glucose (P1), 10g urea (P2) and 10g sucrose (P3) are
dissolved in 250 mL of water is 26-c[2015]
(a) P1  P2  P3 (b) P3  P1  P2 (c) P2  P1  P3 (d) P2  P3  P1
27. Two elements A and B form compounds of formula AB2 and AB4 . When dissolved in 20.0 g of benzene 1.0 g of
AB2 lowers freezing point by 2.3C whereas 1.0 g of AB4 lowers freezing point by 1.3C. The K f for benzene is
5.1. The atomic masses of A and B are 27 -a[2016]
(a) 25, 42 (b) 42, 25 (c) 52, 48 (d) 48, 52.
28. The freezing point of a solution containing 0.2 g of acetic acid in 20.0 g benzene is lowered by 0.45C. The degree
of association of acetic acid in benzene is (Assume acetic acid dimerises in benzene and K f for benzene = 5.12 K kg
mol–1) Mobserved of acetic acid = 113.78. 28 -a[2016]
(a) 94.5% (b) 54.9% (c) 78.2% (d) 100%
29. The depression in freezing point of 0.1 M aqueous solutions of HCl, CuSO4 and K2SO4 are in the ratio
(a) 1 : 1 : 1.5 (b) 1 : 2 : 3 29-a[2017]
(c) 1 : 1 : 1 (d) 2 : 4 : 3
30. When 45 g of solute is dissolved in 600 g water, freezing point gets lowered by 2.2 K, calculate molar mass of
solute. ( Kf  1.86K kg mol1 ) 30 -a[2018]

(a) 63.4 g mol1 (b) 80 g mol1 (c) 90 g mol1 (d) 21 g mol1

31. When pressure is increased at constant temperature -b [2018]
(a) rate of Haber's process decreases
(b) solubility of gas in liquid increases
(c) solubility of solid in liquid increases
(d) 2C(s)  CO2 (g)  2CO(g) reaction moves in the forward direction.
32. 1 g of polymer having molar mass 1,60,000 g is dissolved in 800 mL water. Calculate the osmotic pressure in pascal
at 27C. [ R  8.314J K 1 mol1 ] 32-a[2018]
(a) 19.4 (b) 0.90 (c) 0.50 (d) 1.20
33. Ethylene glycol is used as antifreeze to reduce freezing point of water to –2.4C. What mass of antifreeze is required
for 2 L water? [ Kf water  1.86K kg mol1 ] 33-b[2018]
(a) 16 kg (b) 160 g (c) 1.60 kg (d) 16

ASSERTION AND REASON

Direction:
Each of these questions contains an Assertion followed by Reason. Read them carefully and answer the question on
the basis of following options. You have selected the one that best describes the two statements.
(a) If both assertion and reason are true and reason is the correct explanation of assertion.
(b) If both assertion and reason are true and reason is NOT the correct explanation of assertion.
(c) If assertion is true but reason is false
(d) If both assertion and reason are false.

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Liquid Solutions [51]
34. Assertion: 0.1 M solution of glucose has same depression in the freezing point as 0.1 M solution urea.
Reason: K f for both has same value. 34-b[2000]
35. Assertion: Increasing pressure on pure water decreases its freezing point. 35
-c [2003]
Reason: Density of water is maximum at 273K.
36. Assertion: The molecular weight of acetic acid determined by depression in freezing point method in benzene and
water was found to be different. 36 -a[2005]
Reason: Water is polar and benzene is non-polar
37. Assertion: The water pouch of instant cold pack for treating athletic injuries breaks when squeezed and NH4 NO3
dissolves thus lowering the temperature. 37- a[2006]
Reason: Addition of non-volatile solute into solvent results into depression of freezing point of solvent.
38. Assertion: If red blood cells were removed from the body and placed in pure water, pressure inside the cells
increases. 38-c [2006]
Reason: The concentration of salt content in the cells increases.
39. Assertion: When a concentrated solution is diluted by adding more water, molarity of the solution remains
unchanged. 3 9-d [2008]
Reason: Product of moles of a solute and volume is equal to the molarity
40. Assertion: The molality of the solution doe not change with change in temperature 40-b[2010]
Reason: The molality is expressed in units of moles per 1000 g of solvent.
41. Assertion: A non volatile solute is mixed in a solution then elevation in boiling point and depression in freezing
point both are 2 K. 41-d[2011]
Reason: Elevation in boiling point and depression in freezing point both depend on melting point of non-volatile
solute.
42. Assertion: The solubility of a gas in a liquid increases with increase of pressure. 42-a[2012]
Reason: The solubility of a gas in a liquid is directly proportional to the pressure of the gas.
43. Assertion: In a pressure cooker, the water in brought to boil. The cooker is then removed from the stove. Now on
removing the lid of pressure cooker, the water starts boiling again. 4 3-c[2012]
Reason: The impurities in water bring down its boiling point.
44. Assertion: In ideal solution obeys Raoult's law.
Reason: In an ideal solution, solute-solute as well as solvent-solvent interactions are similar to solute-solvent
interactions.
45. Assertion: Acetone and aniline show negative deviations. 44-a[2014]
Reason: H-bonding between acetone and aniline is stronger than that between acetone-acetone and aniline-
aniline.
46. Assertion: Azeotropic mixtures are formed only by non-ideal solutions and they may have boiling points either
greater than both the components or lesser than both the components. 45-a[2017]
Reason: The composition of the vapour phase is same as that of the liquid phase of an azeotropic mixture.
47. Assertion: The vapour pressure of a liquid decreases if some non volatile solute is dissolved in it.
Reason: The relative lowering of vapour pressure of a solution containing a non-volatile solute is equal to the
mole fraction of the solute in the solution. 47-b[2018]

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Liquid Solutions [52]
48. Assertion: Solubility of gases increases with increase in pressure. 48-b[2018]
Reason: Dissociation of gas in liquid is exothermic.
Answer Keys
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. a c d a b b b a d a d c a d b
Que. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans. c d b b a b b a a b c a a a a
Que. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
Ans. b a b b c a a c d b d a c a a
Que. 46 47 48
Ans. b b b

*****

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Liquid Solutions [53]
BOOKLET SOLUTION
In Chapter exercise – 1 (Henry’s Law)
Subjective:
1. 2 molal aqueous solution means 2 mole of glucose in 1 kg water.
nglu cos e 2
Mole fraction of glucose = X glu cos e    0.0347
nglu cos e  nwater 1000
2
18
2. Basis: 100 g Solution will contain 20 g of ethylene glycol and 80 g of water.
20g
Moles of C2H6O2 =  0.322mol
62g mol1

80g
Moles of water   4.444 mol
18g mol1

moles of C2H6O2 0.322mol

x glycol    0.068
moles of C2H6O2  moles of H2O 0.322  4.444mol

4.444mol
Similarly, x water   0.932
0.322mol  4.444mol
Mole fraction of water can also be calculated as 1–0.068 = 0.932
3. Generally solubility of solid increases while solubility of gas decreases with increase in temperature.
4. Henry’s law: The solubility of a gas in a liquid at a given temperature is directly proportional to the
pressure at which it is dissolved.
pgas  KH Xgas
Where,
X gas = Mole fraction of gas at a given temperature as a measure of its solubility.
pgas = Partial pressure gas in equilibrium with the solution.
KH = Henry’s law constant
5. KH increases with increases in temperature.
6. Here, K H  4.27 105 mm Hg, p= 760 mm Hg
Applying Henry’s law, Pmethane  KH x methane , we have
Pmethnane 760mm
x methane   5
 1.78  103
KH 4.27 10 mm
7. Total pressure of air in equilibrium with water = 10 atm (20% oxygen and 79% nitrogen)

 Partial pressure of oxygen  pO2  

20
10 atm  2atm  2  760mm  1520mm
100

Partial pressure of nitrogen  p N2  

79
10atm  7.9atm  7.9  760mm  6004mm
100

KH  3.30 107 mm, K H  6.51107 mm

O2 N2

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Liquid Solutions [54]
p O2 1520mm
Applying Henry’s law, pO2  K H  x O2 or x O2    4.61105
KH 3.30 107 mm
p N2 6004mm
p N2  K H  x N2 or x N2    9.22  105
KH 6.51 107 mm

Objective:
1 : [b] Henry’s Law:- This law states that at a constant temperature, the solubility of a gas in a liquid is
directly proportional to the partial pressure of the gas.
2 : [c] KH (Henry’s constant) of a gas is a kind of equilibrium constant for the given equilibrium-
undissolved gas over the solution solution of gas in liquid.
Since equilibrium constant depends only on temperature so, KH will also depend only on
temperature.
3 : [b]
4 : [a] According to Henry’s law:-
m = KH × P ---(i)
where m is mass of gas dissolve in given mass of solvent.
P = pressure of the gas over the solution
Taking log in both side in equation (i).
log(m) = log(P) + log KH
y = mx + c
5 : [b]
6 : [b] For O3 gas: PV = nRT
1L
1atm  40ml 
PV 1000 ml w
nO3 (g)   =  w  0.078 g
RT 0.0821 L  atm  300K 48 g /mol
K  mol
In 100 g H2O, O3 dissolved at 1 atm = 0.078 g
400 g H2O, O3 dissolved at 4 atm = 0.07844 g = 1.2 g (Henry’s law: m  P)
p(nitrogen) 0.987bar
7 : [a] x(nitrogen)    1.29  105
KH 76.480bar

As 1 litre (1 kg) of water contains 55.5 mol of it.

nnitrogen nnitrogen
x(nitrogen)    1.29  105 (n +55.55 ≈ 55.55)
nnitrogen  55.5 55.5

Thus nnitrogen = 1.29 × 10–5 ×55.5 mol = 7.16×10–4 mol = 0.716 m mol
8 : [a] Solubility of H 2S gas = 0.195 m = 0.195 mole in 1 kg of the solvent (water)

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Liquid Solutions [55]
1000g
1 kg of the solvent (water) = 1000 g =  55.55 moles
18g mol1

0.195 0.195
 Mole fraction of H 2S gas in the solution (x)    0.0035
0.195  55.55 55.745
Pressure at STP = 1 atm = 1.013 bar
pH2S 1.013 bar
Applying Henry’s law, pH2S  KH  x H2S or K H    289.4 bar
x H2S 0.0035

9 : [a] K H  1.67 108 Pa, pCO2  2.5 atm  2.5 101325 Pa

Applying Henry’s law, pCO2  KH  x CO2

pCO2 2.5  101325Pa n CO2 n CO2

 x CO2    1.517  103 , i.e.,   1.517  103
KH 8
1.67  10 Pa n H2O  n CO2 n H2O

500
For 500 mL of soda water, water present = 500 mL = 500 g =  27.78 moles
18
i.e., n H2O  27.78 moles

n CO2
  1.517  103 or n CO2  42.14 103 mole = 42.14 mmol  42.14 103  44 g  1.854g.
27.78
10 : [a] According to Henry’s law, w  p
w1 p1 6.56  103 g 1 bar
  
w 2 p2 5.0  102 g p2

p2 = 7.64 bar
In Chapter exercise – 2 (Vapour Pressure)
Subjective:
1. The pressure exerted by the vapour (molecules in the vapour phase) over the surface of the liquid at equilibrium at
given temperature is called the vapour pressure of the liquid.

2. As temperature of a liquid is raised, its molecules move more rapidly. This results in an increase in their average
Kinetic Energy. At higher temperature, greater number of molecules possess energies greater than escape energy
and therefore greater number of molecules escape as vapour. This results in increase in vapour pressure of the
liquid.

Mathematically,

HVapourisation 1
log P   ( )  log A
2.303 R T

3. The one with higher vapour pressure is said to be more volatile and have lower boiling point. Hence liquid B is
more volatile and has lower boiling point.
4. Constant temperature at which rapid vaporization of a liquid takes place at 1 atompheric pressure.

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Liquid Solutions [56]
5. Boiling occurs when vapour pressure of a liquid becomes equal to external pressure. So if external pressure is
increased, vapour pressured must be increased by increasing temperature so that it can be equal to external
pressure. Hence boiling point increases as external pressure.
6. (i) Clothes dry due to evaporation of water. As temperature increases, rate of evaporation increases. Summer
season is hotter than winter, hence rate of evaporation in summer season is more than that in winter.
(ii) Deserts cooler works on the principle ―Evaporation causes cooling‖. On hot sunny day, rate of evaporation
and hence rate of cooling is enhanced.
(iii) In earthen pot, water drips from pot to the outer surface. Effective surface area of evaporation and hence rate
of evaporation increases with respect to steel or plastic vessel. Enhanced rate of evaporation causes faster cooling.
(iv) In pressure cooker, external pressure is more i.e. boiling point of water is enhanced i.e. water boils at higher
temperature than 100C. Temperature of water in cooler achieves higher temperature than 100C which enhances
the coking rate.
(v) In hilly areas, external pressure (atmospheric pressure) is low. Hence boiling point of water decreases.
Objective:
1 : [d] Since vapourisation is an endothermic reaction.

liquid + Heat  vapour

Kp = Vapour pressure (V.P.)

Hvap= +ive

 T   Kp   V.P. 
2 : [b] Vapour pressure depends only on temperature.

3 : [c] Pressure applied by vapour in given figure on any boundary in contact with vapour will be similar So, P 1= P2 =
P3, but P4 is the pressure applied by atmosphere, so it will not be equal to any of P1, P2 or P3.

The equality can be written as P1= P2 = P3= {P4+ (Pressure applied by height of mercury

column)}

4 : [d]

[a] Evaporation:– Evaporation is the process of conversion of liquid to gas and this is an endothermic process as
we have to overcome the interaction present in liquid phase to change the given liquid to gas.
[b] Melting:– Melting is the process of conversion of solid to liquid and this is an endothermic
process as we have to overcome the interaction present in solid phase to change the given
solid to liquid.
[c] Sublimation:– Sublimation is the process of conversion of solid directly to gas and this is
an endothermic process as we have to overcome the interaction present in solid phase to
change the given solid to gas.
[d] Condensation:– Condensation is process of conversion of gas to liquid and this is an
exothermic process in this process, molecules come close to each other and new
interaction will develop which will cause of evolution of heat.
5 : [c] Refer graph : Rate of evaporation Vs time in the previous section.

6 : [d]According to clausius– clapeyron equation

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Liquid Solutions [57]
P2 HVapourisation 1 1
log     . The same equation can also be written as
P1 2.303 R  T1 T2 

ΔHvapourisation 1
  lnP=  × +Constant
R T

Comparing with  y = – m.x + C  So, the graph will be linear with negative slope.

7 : [d]

[a] Before the attainment of equilibrium the liquid vapourises to vapour so number of
molecules in vapour phase will increase and hence will cause of increment in pressure at
the given temperature till the equilibrium reached. After the attainment of equilibrium
number of molecules going in vapour phase and number of molecules returning to liquid
phase (in a given time interval) will become same so total number of molecules in vapour
phase at equilibrium at a given temperature will become constant, so vapour pressure will
remain constant till the temperature remain constant.

[b] For liquid  vapour

the equilibrium constant Keq = Pvapour (Vapour pressure) and for a given reaction,

equilibrium constant Keq depends only an temperature so vapour pressure will also

depend only on temperature.

[c] From the above equilibrium constant expression it is clear that vapour pressure will
depend only on temperature and will be independent of any other factor.

P2 HVapourisation 1 1
[d] Clausius Clapeyron equation: log    
P1 2.303 R  T1 T2 

Where,

P1 and P2 = Vapour pressure of liquid at Temperature T1 and T2

 Hv = enthalpy of vapourisation.

The above equation suggests, with raise in temperature vapour pressure will increase.

P2 ΔHv  1 1  4 ΔHv  1 1 
8 : [d]  log       log    
P1 2.303R  T1 T2  2 2.303×R  300 400 

  0.3 × 2.303 × 1200 × R = 1 × Hv Hv= 829.08 × R = 829R

P2 H  1 1 760 40.67  103  1 1 

9 : [b] log =  log = 
P1 2.303 R  T1 T2 
 19 2.303  8.314  T1 373 


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Liquid Solutions [58]
1.6  2.303  8.314 1 1 1 20.001 1
 3
=   =   T = 291.3 K
40.62 10 T 373 T 40670 373

In Chapter exercise – 3 (Raoult’s Law and Deviation from Raoult’s Law)

Subjective:
1. PS = PB0 χB  PT0χ T

1 1
PS = 160   60 
2 2
= 110 mm of Hg
25 1 35
2. nheptane = or ; noctane =
100 4 114
1
4 1 4  114 114
Xheptane = or  =
1 35 4 254 254

4 114
35
35 4  114 140
Xoctane = 114 or  =
1 35 114 254 254

4 114
114
Pheptane =  105.2 kPa = 47.2 kPa
254
140
Poctane =  46.8 kPa = 25.8 kPa
254
Pressure of solution = PS = Pheptane + Poctane = (47.2 + 25.8) kPa = 73.0 kPa
3.(i)
40g
Mole of CH2Cl2 =  0.47 mol
85 g mol1

25.5 g
Mole of CHCl3 =  0.213 mol
119.5 g mol1
Total number of mole = 0.47 + 0.213 = 0.683 mol
0.47 mol
XCH2Cl2   0.688 =XA
0.683mol

XCHCl3  1.00  0.688  0.312 =XB

PS  PA0 XA  PB0 XB  415  0.688  200  0.312  347.9 mm Hg

0
PCH2Cl2 PCH2Cl2
XCH2Cl2 415  0.688
(ii) YCH2Cl2   0 0
  0.82
PS PCH XCH2Cl2  PCH XCH2Cl2 415  0.688  200  0.312
2Cl2 2Cl2

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Liquid Solutions [59]
0
PCHCl3 PCHCl3
XCHCl3 200  0.312
YCHCl3   0 0
  0.18
PS PCH XCH2Cl2  PCH XCH2Cl2 415  0.688  200  0.312
2Cl2 2Cl2

4. Here, PA0  450mm, PB0  700mm, PS  600mm

Applying Raoult’s law, PA  A  PA0

PB  B  PB0  (1  A )PB0

PS  PA  PB  APA0  (1  A )PA0  PB0  (PA0  PB0 )A

100
600 = 700+(450-700)A or 250A  100 or A   0.40
250
Thus, composition of the liquid mixture will be XA =0.40, XB =1-0.40=0.60

 pA  A  p0A  0.40  450mm  180mm, pB  B  pB

0
 0.60  700mm  420mm

pA 180
YA    0.30
pA  pB 180  420

YB = 1–0.30 = 0.70.
5. Let vapour pressure of pure A be P°A.

100 1000
PBο = 500 torr; nA = = 0.714; nB = = 5.55
140 180

0.714
xA = = 0.114; x B = 1  0.114 = 0.886
5.55  0.714

PS=P°AxA + P°BxB  475 (torr)=P°A × 0.114 + 500 × 0.886

 P°A=280.70 torr

PA=280.70 × 0.114 =32 torr

6. P°A = 17.535 mmHg. Let vapour pressure of solution be Ps.

450/18
Ps=P°A × xA =17.535  =17.535 × 0.9945 = 17.438 mmHg 17.44 mmHg
25/180+450/18

7. (i) In a solution showing +ve deviation, the vapour pressure of the solution is higher than that of an
ideal solution of the same composition. Ex- Ethanol – water, ether-acetone.
(ii) In a solution showing –ve deviation from ideal behaviour, the vapour pressure of the solution is lower
than that of an ideal solution of the same composition.
Ex- Methanol – Acetic acid, water- HNO3 , Chloroform ― Acetone.

(iii) A solution at certain composition which continues to boil at constant temperature without change in
the composition of the solution and its vapour is called an AZEOTROPE or constant boiling mixture.
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Liquid Solutions [60]
Ex – Mixture of H 2O and C2 H5OH (95.57%)
8. For completely immiscible liquids A and B
PS  PA0  PB0  100  200  300 torr

9. moles in vapour phase  Vapour pressure in pure state

nA PA0 100 1
  
nB PB0 200 2

Objective:
1 : [a] PS  PA0A  PB0B

2 1
100   40 
3 3
PS = 80 Torr
2 : [b] PS  PA0A  PB0 (1  A ) = PB0  A (PA0  PB0 )

3. [c] When A  0  PS  PB0  254  0  254

when A  1  PS  PA0  265  119  135

4 : [d]PS = 760 torr, because solution boils at 88°C and 1 atm (760 mm of Hg.)

Let mole fraction of C6H6 be XB.

760 = 900 × XB + 360 × (1 –XB)

760=900 XB + 360 – 360 XB XB=0.74

5 : [c] PS = PMeOH +PEtOH

ο ο
PS = PMeOH  XMeOH  PEtOH  XEtOH

 16   46 
 32   
Thus, PS = 88.5     42   46  =29.5+28=57.5
 16  46   16  46 
 32 46   32 46 
ο
PMeOH PMeOH  XMeOH 29.5
YMeOH = =   0.513
PS PS 57.5

6 : [a] If XA  0, then XB  1 and PS  PBο

So,PS = P°B=(120 × 0) + 138 = 138

PBο 138
So, lim = = 138
X A 0 XB 1
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Liquid Solutions [61]
Again, if XB  0, then XA  1 and PTotal  PAο

So,PS = P°A=120 × 1 + 138 = 258

PAο 258
So, lim = = 258
XB  0 X A 1

1 1
7. [a] PS  108   36   72
2 2

PB 1/2  36 1
yB   yB    0.25
PS 72 4

PAο x A 100  0.4 40 40

8: [c] yA = = = = = 0.25
PAο x A  PBο x B 100  0.4  200  0.6 40  120 160

9 : [c] Relative lowering of vapour pressure is given by

PA
 = XB  PA = PS  PAο
PAο

10 : [c] From Raoult’s law,

P = X1P1ο and P1ο  P = P1ο X2

nwater 9.9 9.9

11: [d] Mole fraction of water =  =
nwater  nurea 9.9 + 6/60 10

0
Psolution = Pwater = Pw ·χw

12. [a]

13. [a]
1 atm I II III
V.P. (torr)

Pure
P1
solvent
P2
P3

Temperature (°C)

As concentration increase at a given temperature vapour pressure of the solution decreases.

14.[d] AD plot represent the vapour pressure of B only when B  1  PB0  max. similerly graph BC
represents vapour pressure of A only

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Liquid Solutions [62]
CD curve shows the total pressure developed due to vapours of A and B. Hence for ideal solution we
can apply Dalton’s law of partial pressure.
EH = EF + EG where EH height represents graph CD, EF and EG heights represents graph AD and CB.
15.[a] When attraction between A-B is less than that of A-A and B-B, the solution will show positive
deviation from Raoult’s law because then pressure of solution will be more than expected from
Raoult’s law.
16.[b] When mixture of A and B show negative deviation then H = – ve
17. [b] When azeotrope mixture have less boiling point, then the vapour pressure of mixture must be more than
the individual, this shows positive deviation.
18.[d] Azeotrope mixture have same concentration in liquid as well as in vapour phase when boiled. So not
possible to separate by fractionla distillation.
19.[b] Solution with negative deviation form maximum boiling Azeotrope.
20.[c] Immiscible solution boils at the temperature below boiling point of either of the two components.

In Chapter exercise – 4 (Colligative Property – RLVP and Tb)

Subjective:
1. In pure water, the entire surface is occupied by water molecules which are volatile. On adding glucose (a
non volatile component), some water molecules on the surface are replaced by glucose molecules which
are non-volatile. Hence vapour pressure is lowered.

Mathematically by Raoult’s law:

PSolution  PA0 XA  PB0 XB  PA0 XA (PB0  0)

PSolution  PA0 (XA  1)

2. All non volatile solutes - Urea , Glucose, NaCl, Sucrose, CaCl2. Alcohol is volatile so it may increase or
decrease the vapour pressure pressure when mixed with water.
1 1
3. RLVP  XB  
180 11
1
18
80
4. PS  Pw0   Pw0  0.8
100
PW0  PS Pw0  0.8  Pw0
Xglu cos e    0.2
PW0 Pw0

PA0  PS nB 0.85  0.845 0.5 /MB

5.     MB  170 g /mol
PS nA 0.845 39 /78

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Liquid Solutions [63]
PAο  PS m MA 12.3  PS 1 mol /kg  18 g /mol
6. =    PS  12.0825 kPa
PS 1000 PS 1000

7. Vapour pressure of pure water at the boiling point ( PA0 ) = 1 atm = 1.013 bar

Vapour pressure of solution (Ps)=1.004 bar.

Let mass of solution = 100 g
Mass of solute (wB) = 2g , Mass of solvent = 98 g
PA0  PS nB 1.013  1.004 2/MB
    MB  41.35 g /mol
PS nA 1.004 98 /18
ο
POc tan e  PS n 100  80 wB /40
8. = Solute    wB  8 g
PS noc tan e 80 114 /114

PAο  PS nB PAο  2.8 30 /MB

9. (i) =  = ----(1)
PS nA 2.8 90 /18

Again when 18 g water is added to it, we get

PAο  PS nB PAο  2.9 30 /MB
=  = ------(2)
PS nA 2.9 108 /18

From (1) and (2), we get,

MB=34 g/mol

(ii) Substituting valueof MB In (i), we get

PA0 = 3.4 kPa

10. Loss in weight of solution  PS (PS = Vapour pressure of solution)

Loss in weight of solvent  P – PS0
A
0
( P = Vapour pressure of pure solvent)
A
Gain in weight of drying agent = (Loss in weight of solution + loss in weight of solvent)
 (PA0 – PS  PS )  PA0
18
mol
11. Tb  0.52 Km1  180  0.052 K
1kg

Boiling point of the aqueous solution = 373.15 K + 0.052 K = 373. 202K

5 1
12. Tb  2.57Km1  g /mol 
180 0.015 kg

Tb  4.76K

Boiling point of the solution = 81 + 4.76 = 85.76°C

13. Tb  Kb  m
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Liquid Solutions [64]
12/MB
0.34K  0.52(K m1 )  3
mol Kg 1
100  10

 MB 183.5 g /mol1

14. Tb  Kb  m

0.2563
mol
0.201 K kg /mol  K b  128 3 ---------(1)
50  10 kg

0.6216 g
MB
Also 0.647 K kg/mol = K b  ------(2)
50  103 kg

by solving 1 and 2 we get  MB = 96.4 g mol–1

Objective:

1. [b] PA0 – Ps = PA0  XB  10 = PA0  0.2  PA0 = 50

Again, 20 = PA0  XB  XB = 20/50 = 0.4
Hence, XB = 0.4, so, mole fraction of solvent = XA 1 – 0.4 = 0.6

PA0  PS
2.[a] Since  XB
PA0

Since molality of solution is 1,  1 mol solute (B) in 1000 g water

PA0  PS 1 mol

PA0 (1000/18) mol + 1 mol

1
PA0  PS   PA0
56.5

Since PA0 = 760 mm of Hg, so PA0  PS = 13.45

3.[b] PS = 80% of PA0

PS = 0.8 PA0

PA0  PS WB /40
Since = XB  0.2 =  WB = 5 g
PA0 WB /40 + 1/2

PA  PS
4 : [c] = XB , XB = 0.2, PS = 80 torr
PA

PA  80
= 0.2  80 = 0.8 PA  PA = 100 torr
PA

5 : [c]
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Liquid Solutions [65]
PA  PS mMA m  18 760  750 1
=  = =
PS 1000 1000 750 75

1000 20
 m= = =0.74 m
18  75 27

6[a] According to Ostwald walker method-

PA0  PS WB /MB
 XB 
PA0 WB /MB  WA /MA

5
mol
0.04 MB
   MB  31.25 g / mol
2.50  0.04  5 180 
   mol
 MB 18 
0.1
7. [c] Tb  0.513  K = 0.256 K
0.2
Tb  100  0.256  100.256K

8. [c] Tb  Kb  m

n mol
0.01K  0.5(Km1 ) 
0.1Kg

0.01
n mols
5
0.01 0.01
Number of glucose molecules   NA   6  1023  1.2  1021molecules
5 5
1 mol
9. [a] Tb  Kb  m  0.5K  K b   Kb  0.5K Kg mol1
1 Kg

0.616 /154
10. [d] Tb  K b .m  3.63   1000;  Tb  61.7  0.968  62.67C
15
0.26 /MB
11. [d] Tb  80.26, Tb  0.16;  0.16  256   1000  MB  367
11.20
That is the molar mass of C20H16Fe2.

R  Tb2
12. [b] Kb 
HV

J
8.314  (383.7 K)2
 HV  mol  K  368685 J / kg
K kg
3.32
mol

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Liquid Solutions [66]
3 3
J J 10 kJ 10 kJ
 HV  368685  368685  368685  368685
kg 1000 g 1000 g (1000 /Msolvent ) mol

103 kJ
 HV  368685  33.824 kJ /mol
(1000 /92) mol

In Chapter exercise – 5 (Freezing point depression and Osmotic pressure)

Subjective:
moles of ethylene glycol (45 / 60)mol
1. Molality of ethylene glycol    1.2 mol kg 1
mass of water in kilogram 0.60 kg

[a] Tf  1.86K kg mol1 1.2mol kg 1  2.2K

[b] Freezing point of the aqueous solution =273.15K ― 2.2K = 270.95K.
Wsolute /Msolute 1/MB
2. Tb  K b m  K b  0.4 K  5.12 K kg /mol   MB = 256
WSolvent (kg) 0.05 kg

3. Let d = density of ethylene glycol(g/mL)  weight of ethylene glycol =50 d g

(50  d)
mol
Tf  Kf  m  3.4K  1.86 km1  62  d = 1.13
0.05kg

4. T f = (273.15 – 271.0) k =2.15 K [ melting point of pure water = 273.15 K]

T f =kf ·m
For 5% can solution  5 g can sugar in 95 g water
5
mol
1000
2.15 K = k f × 342 ×      (1)
0.095 kg 95

For 5% glucose solution  5 g glucose in 95 g water

5
mol
Tf =k f × 180 ------- (2)
0.095 kg

2.15 180 2.15  342

From (1) / (2)  = or Tf = or 4.085 K
Tf 342 180

Hence freezing point of 5% glucose solution = (273.15 – 4.085) K = 269.065 K

5. It depends on Freezing point Tf and Latent heat of fusion Lf

RTf 2
Kf 
Lf

6. Osmosis – Spontaneous flow of solvent particle from low to high concentration.

Diffusion – Spontaneous flow of solute particle from high to low concentration.
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Liquid Solutions [67]
7. A semipermeable membrane is a continuous sheet or film of suitable material (natural or synthetic) which
has pores such that solvent molecules can pass through but big molecules of the solute cannot.
(60 /60 mol) L  atm
8.   CRT   0.082  298K
1L mol  K

9. The various quantities known to us are as follows:

  = 2.57 × 10–3 bar; V = 200 cm3 = 0.2 L;

T = 300 K; R = 0.083 L bar mol–1 K–1

Substituting these values in equation,

nB W /MB W
  CRT  RT  B RT  MB  B RT
V V V

1.26 g  0.083 L bar K 1mol1  300 K

we get MB = = 61.022 kg mol–1
2.57 bar  0.200 L

10.  = cRT

1 = c1RT and 2 = c2RT

π1 c 4.98 36 1  36 
or = 1 =   c1 =
π2 c2 1.52 180 c2 180 

1.52  36 1.52
or c2 = = or 0.061 mol L1
4.98  180 24.9
Objective:
1.[a] During the freezing following equilibrium is established:

Solvent( ) Solvent(s)

2.[d] Tf  Kf  m

1.25 g /MB
(273  271.94)K  1.86K kg mol 1   MB  109.6g /mol
0.02kg

3.[d] Tf  Kf  m

C (WB /46) mol C (W /46) mol

4F  1.86   20C  1.86  B  WB = 494.6 g
m 1 kg m 1 kg

(4 /60) mol (10/MB )mol

4.[a] T '  Tf B  Kf  mA  Kf  mB  mA  mB    MB = 150
fA 0.1 kg 0.1 kg

5.[b] Tb  i  Kb  m, Tf  i  Kf  m

Tb K b 1 0.51
 ,   Tf  3.647C
Tf Kf Tf 1.86
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Liquid Solutions [68]
Freezing point = –3.647°C
2.55 K
6 : [d] 2.55K  Kf  m  m 
Kf

2.55 K 2.55 K
Tb  K b  m  K b  Tb  K b  m  0.52 K kg /mol  0.7 K
Kf 1.86 K kg /mol

Tb  100  0.7  100.7K

7.[d] Vapour pressure of pure solvent is more than that of solution

Only solvent molecules solidify at the freezing point

8.[a] Let mass of water remaining = W at –9.3°C.

Tf  Kf  m

(50 /62) mol

9.3K  1.86 K kg mol 1   W = 0.161 kg = 161 g
W kg

Amount of ice separated = 200 g –161 g = 38.71 g

9.[a] Its depends upon

[b] The molar mass of the solvent in the solution

[c] The enthalpy of vaporisation of the solvent

[d] The freezing point of the solvent
10.[b] Given Hf  80cal g 1

Hv  540cal g 1

Tb  Kb  m and Tf  Kf  m;

RTb2 RTf 2
Kb  or K f 
HV Hf

RTb2
Tb K b HV Hf Tb2 80 Cal / g  (373 K)2
      0.2766
Tf Kf RTf 2 HV Tf 2 540 Cal / g  (273 K)2
Hf

Tb 0.1 K 0.1 K

  0.2766   0.2766  Tf   0.361 K
Tf Tf 0.2766

Tf  0.361K  0.361 C  Tf  0.361C

11.[b] Semipermeable membrane allowes only flow of solvent particles.

12.[d] It loses water due to osmosis because the solution in contact with mango is more concentrated.
13.[d] Water will not move from side (B=concentrated solution) to side (A=solvent) if a pressure equal to osmotic
pressure is applied on piston (B)
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Liquid Solutions [69]
14.[a]   CRT,i.e.,  C
15.[c] Since O.P. depends upon number of particles in the system i.e., number of moles so,
10 10
nglucos e, I  mol  0.055 mol ; nurea, II  mol  0.166 mol ;
180 60
10
nsucrose, III  mol  0.029 mol
342
  n  2  1  3

16.[b]   CRT
(0.6 /MB ) L  atm
1.23 atm   0.0821  300K  MB  120g /mol
0.1 L mol  K

17.[b]
6 18
nurea   0.1mole ; nglucos e   0.1mol
60 180
  CRT
(0.1  0.1)moles L  atm
  0.0821  299K  4.9 atm
1L mol  K
3.42g 500g
342 g / mol M B g / mol
18.[d] 1  2  C1  C2    MB = 27500 g/mol.
1l 1L

5 /342 mol L  atm

19.[c]   CRT   0.0821  423K = 5.078 atm
0.1 L mol  K

20.[a] For two solution to be isotonic C1=C2.

W1 /M1 W2 /M2 5g 0.877 g
    M2  59.98
V V 342 g /mol M2 g /mol

21.[a] Let a % (W/V) glucose solution is isotonic with blood  a gram glucose in 100 mL water
  CRT
(a /180)mol L  atm
7.65 atm   0.0821  310K  a = 5.41 %
0.1 L mol  K

22.[c] Let the weight of solution is 100 g, then wet of fructose 9.5 g
100g
Volume of solution   96.52ml
1.036g /ml

9.5g
180 g mol L  atm
  CRT   0.0821  293K = 13.16 atm
0.0965 L mol  K

23.[c]   CRT (Let molality = Molarity for dilute solution)

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Liquid Solutions [70]
2 atm = C × (0.0821 L-atm/mol-K)× 300 K  C = 0.0821 mol/L = 0.0821 mol/kg
Tf  Kf  m = 1.86 K kg/mol  0.0821 mol/kg = 0.151 K

Freezing point = 0 °C – 0.151°C = ―0.151 °C

24.[a] Graph between  VsT should be linear according to equation  = (CR)T
Slope = CR (If C=constant)

In Chapter exercise – 6 (Vant hoff factor)

Subjective:
1. Since K2SO4 is completely dissociated as

K2SO4  2K+ + SO4–2; Thus, i = 3

Now, = i CRT
25×103g
×0.0821L atm K 1mol1×298.15K
174 g /mol
= 3 = 5.27 × 10–3 atm
2L
(WB /MB )  R  T π  MMB  V (L)
2. = i CRT or π = i  or WB =
V (L) iR T

0.75 (atm)  111 (g mol1 )  2.5 (L)

= =3.40 g
2.47  0.0821 (L atm mol1 K 1 )  300.15 (K)

3. For MgCl2  i = 1+(n―1) = 1+ (3―1)1=3

So, depression in freezing point will be three times as that in case of glucose.
4. Colligative property  i   {i  (n  1)}

 = degree of dissociation ()of electrolytes.

Strength of acid and its corresponding degree of ionization ()and hence Tf increases as
H3C—COOH < Cl3C—COOH < F3C—COOH

5. For dilute solution  molarity = molality

nsolute (10 /122.5)mol

Molality    0.33 mol /kg =molarity
Wsolvent (kg) 0.25 kg

Let degree of dissociation of acid be .

Ka 1.4  103
α= = = 0.065
c 0.33
i =1 (n―1)  =1 + (2―1) 0.065 = 1.065
T f =i × Kf × m =1.065 1.86 K kg /mol  0.33 mol /kg = 0.65 K

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Liquid Solutions [71]
(500  19.5) g
6. Volume of solution  =462.18 mL
1.124 g mL1

(19.5 /78) mol

Molarity of solution=  0.54 mol /L
0.462 L

(19.5 /78) mol

Molality of solution=  0.5 mol /kg
0.5 kg

CH2FCOOH  CH2FCOO― + H+

T f =i × Kf × m  0.0205 K = [1+(n―1)]  1.86 K kg/mol  0.5 mol/kg

1 K = [1+  ] 1.86 K kg/mol  0.5 mol/kg   = 0.075

= Ka /c  Ka  C2  0.54  (0.075)2  3.04 103

Wacetic acid 0.6 mL  1.06g mL1

7. Number of moles of acetic acid    0.0106 mol
Macetic acid 60 g mol1

nacetic acid 0.0106mol

Molality =    0.0106mol kg 1
Wwater (kg) 1 kg

Tf  i 1.86 K kg mol1  0.0106mol kg 1

Tf 0.0205 K
i   1.04
K f m 1.86 K kg /mol  0.0106 mol /kg

CH3COOH H  CH3COO

i  1  (n  1)  1.04 = 1 +(2―1)   = 0.04

ka  c2  (0.0106M)  (0.04)2  1.7 105

8. i = 1+ (1/n ―1)
Objective:
1.[c] nA  An
1(1–) /n

nTotal = 1 –  + /n
α
1 α +
n n  1  ( 1  1)α
i= T =
ni 1 n

2.[b] KCl  K   Cl (2ions), i=2

NaCl  Na   Cl (2ions), i=2

K2SO4  2K   SO24 (3ions) , i=3

3.[c] If complete dissociation takes place then

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Liquid Solutions [72]
―i‖ doesn’t depend on the concentration of solution.
4.[c]  = iCRT
1 i1  1
 (For same concentration)  1   2  21
2 i2 2 2

5.[b] Tb  i  Kf  m = 2×1.86 K kg/mol ×1 mol/kg = 3.72 K

Tf = –3.72°C
6 : [c] Tb  (Tb  Tb0 )  (i  m)

For urea  im = 10.015 = 0.015

for KNO3  im = 20.01 = 0.02

for Na2SO4  im = 30.1 = 0.3

for glucose  im = 10.015 = 0.015

Hence Na2SO4 will show maximum boiling point

7.[a] Depression in freezing point is  number of particles furnished by complex compound.

Furnishes for ions [Fe(H2O)6]Cl3

8. [c] Pw = 50 mm of Hg

PS = 40 mm of Hg

Pwo  PS i  nsolute
= ; i = Vant Hoff factor
PS nsolovent

for Na2SO4; i = n = 3 (Since  = 1),

50  40 3  nsolute
=
40 12
10 n 3
= solute
40 12
  nsolute = 1 mole
9.[b] Tb  i  Kb  m  2  0.52 1
Tb  1.04K

Tb = (100+1.04)K
Tb = 101.04K

10.[b] HBr H  Br 

i = 1+(n―1) = 1 + (2―1)0.9 = 1.9

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Liquid Solutions [73]
0.1mol
Tb  iK f  m  1.9  1.86 
0.1kg

Tf  3.53C

Tf = 0–3.53°C = –3.53°C.
11.[a] Ca(NO3 )2  Ca 2  2NO3

i = 1+(n―1) = 1 + (3―1)0.7 = 2.4

PA0  PS (i  nB )

PA0 nA  (i  nB )

760  PS 7g /(40  2  72)g /mol

 2.4 
760 100 /18 mol

PS = 746.32 mm of Hg.
12.[a] = iCRT
0.432 = i × 0.01 × RT . . . (1) For KI solution
0.24 = 0.01 × RT . . . (2) For Sucrose solution
Putting value of RT in equation (1) from (2)
  i =1.8

K 4 [Fe(CN)6 ] 4K   [Fe(CN)6 ]4

13.[d]
0.1(1  0.5) 0.5  4  0.1 0.5  0.1

0.1(0.5)  0.5  4  0.1  0.5  0.1

i
0.1
i=3
  iCRT
3  0.1mol J
 3 3
 8.314  300K
1  10 m mol K

  7.48 105 Pa
14.[a] For XY2:
In dissociation reaction; n = 3
i = 1 + (n–1)
(M)observed
i=
(M)theoretical

(M)observed
= 1 + (3  1)α
(M)theoretical

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Liquid Solutions [74]
164
 1 + 2α = = 2.5
65.6
    = 0.75  75%

15.[b] Tf  i  m  Kf
2K f  2  m  K f
m 1
m=1 means 1 mol solute is in 1 kg of solvent.
PA0  PS (i  nB )

PA0 nA  (i  nB )

PA0  PS 2 1
  0.035
PA0 1000
 2 1
18

Ca(NO3 )2  Ca 2  2NO3
Calculated molecular mass 164
16.[c] i   = 2.5 1 0 0
Observed molecular mass 65.6
1   2

i = 1+ 2 2.5 = 1+2

  = 0.75, or %  = 75%
17.[c] Tf  (i1m1  i2m2  i3m3 )Kf
(i1n1  i2n2  i3n3 )
Tf   Kf
Wsolvent (kg)

Wt. of solvent (if weight of solution is 100g) = 100–5–1–10 = 84g

 2  1 1  10 1  5 
   
 74.4 180 60 
Tf   1.86 K kg /mol  3.06 K
0.084 kg

Freezing point = –3.06°C

18.[d] i  1  (1n  1)  1  (13  1)  1  1/3 ,

19.[a] Observed number of particles increases due to association and decreases due to dissociation.

20.[d] 2C6H5COOH (C6H5COOH)2

  iCRT
5g
122g /mol
5.73atm  i   0.082 L atm  283K
0.1 L mol K

i = 0.6.

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Liquid Solutions [75]
2(C6H5COOH) (C6H5COOH)2
0 0
C(1   ) C /2

 
i  1 ,  1  0.6
2 2
  0.8
%  80%

21.[d] Tb  iKb  m

1.518 = i×2.53 K kg mol–1×1
i = 0.6

2RCOOH (RCOOH)2
1   /2

1   /  /2
 0.6
1

1  0.6,   0.8
2
%   80%

22.[d] Tfa  iA  KfA  m

TfB  iB  KfB  m

TfA i A K fA m
  
TfB iB K fB m

1/2 1.86 TfA

   1
1/3 2.79 TfB

NEET (Previous Years Solution)

1.[c] For ideal solution,
Vmixing  0 and Hmixing  0
2.[d] Because C2 H5 I and C2 H5OH are large dissimilar intraction force.

Psolvent  Psolution
3.[a] 
 x solute
Psolvent
Here, PA  PA (difference in vapour pressure of pure solvent and solution) = Lowering in vapour pressure.
................. (i)
Now, PA  vapour pressure of pure solvent....... (ii)
PA  PA
By dividing (i) and (ii), we get
PA
Which is relative lowering in vapour pressure

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Liquid Solutions [76]
4.[a] Here Tf  i  Kf  m
Van't Hoff factor, i=2 for NaCl, so conc. = 0.02, which is maximum in the present case.
Hence, Tf is maximum or freezing point is minimum in 0.01 m NaCl.
5.[b] Blood cells neither swell nor shrink in isotonic solution.
The solutions having same osmotic pressure are called isotonic solutions.
6.[c] The properties which depends only upon the number of solute particles present in the solution irrespective of their
nature are called as colligative properties. Lowering in vapour pressure, elevation in boiling point, depression in
freezing point and osmotic pressure are colligative properties.
7.[a] There is no net movement of solvent through the semipermeable membrane between two solutions of equal
osmotic pressure.
8.[b] K3[Fe(CN)6 ] 3K   [Fe(CN)6 ]3 and
Al(NO3 )3 Al3  3NO3
Since, both Al(NO3 )3 and K3[Fe(CN)6 ] give the same number of ions, therefore they have the same van't Hoff
factor.
9.[c] In solution, CaCl2 gives three ions, KCl gives two ions while glucose and urea are covalent molecules so they do
not undergo ionisation. Since, osmotic pressure is a colligative property and it depends upon the number of solute
particles (ions), therefore, 0.1 M solution of CaCl2 exhibits the highest osmotic pressure.
n
10.[c] M
VL
w / 32
2
150 /1000
 w  9.6g
11.[a] Since, relative lowering of vapour pressure is a colligative property, therefore it depends upon the number of solute
particles or mole fraction of solute.
12.[c] The molality involves weights of the solute and the solvent. Since, the weight does not change with the
temperatures, therefore molality does not depend upon the temperature.
13.[a] Weight of glucose = 10 g,
Weight of urea = 10 g and
Weight of sucrose = 10g
We know that the number of moles of glucose
Weight 10
(n1 )    0.05
Molecular weight 180
10
Similarly number of moles of urea (n 2 )   0.16 and the number of moles of
60
10
Sucrose (n 3 )   0.03
342
The osmotic pressure is a colligative property and it depends upon the number of moles of a solute. Since,
n 2  n1  n 3 , therefore p2  p1  p3 .
14.[c] Vapour pressure of pure solvent (PA ) = 143 mm Hg, weight of solute (w)=0.5 gram, weight of solvent (W) = 100
grams, molecular weight of solute (m) = 65 and molecular weight of solvent (M) 154.
PA  P wM 143  P
 or
PA mW 143
0.5  154
  0.01 or P  141.31mmHg
65  100
15.[a] We know that 98% H2SO4 by weight means 98 of H2SO4 is present in 100g of solution in water.
Weight of H 2SO4 98
Therefore, its weight is 98 and mole of H2SO4    1 and
Molecular weight 98

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Liquid Solutions [77]
Mass 100 54.35
Volume of solution    54.35mL  L
Density 1.84 1000
Therefore, molarity of H2SO4
Moles of H2SO4 1 1000
   18.4M
Volume (in litres) 54.35
16.[c] Since Al2 (SO4 )3 gives maximum number of ions on dissociation, therefore it will have the lowest freezing point.

17.[a] Cane sugar 'X'

W1  5g W2  1g
V1  100mL V2  100mL
= 0.1 L = 0.1 L
M1  342 M2  ?
For isotonic solutions, 1  2
W1 W2 5 1
  
M1V1 M 2 V2 342  0.1 M 2  0.1
342
 M2   68.4
5
18.[b] x1 (mole fraction of solute) = 0.2
From Raoult's law,
P  Ps 10

 x1    0.2
P P
 P  50mm
Again, when P  Ps  20mm , then
P   Ps 20

 mole fraction of solute   0.4
P 50
 mole fraction of solvent = 1–0.4 = 0.6
19.[b] w = 0.15 g, W = 15 g, Tb  0.216 C
K b  2.16, m  ?
100  K b  w
As Tb 
m W
1000  2.16  0.15
m  100
0.216  15
20.[c] The strength of the solution is 0.1 N
w V N 200
 (Equivalent weight   100 )
E 1000 2
100  0.1100
w  1g
1000
21.[a] P  640mm, Ps  600mm, w  2.175g
W = 39.08 g
From Raoult's law
P  Ps w  M

P Wm
640  600 2.175  78
 
640 39.08  m
 m  69.5

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Liquid Solutions [78]
22.[a] Polymers and proteins are covalent compounds, therefore by measuring osmotic pressure of their solution, the
molecular weight can be determined.
W
PV = nRT or, V  RT
M
WRT CRT
M 
V 
23.[c]
24.[a] More is the pressure, greater will be the boiling point.
25.[c] Molecular weight of NaOH = 40
2.5 litre of 1 M NaOH solution contain
40 2.5 g of NaOH
3 litre of 0.5 M NaOH solution contain
40 0.5  3 g of NaOH
If these two solutions are mixed, the volume of the resultant solution = (2.5 + 3 ) = 5.5 litre.
5.5 litre of the resultant solution contain
40(2.5 + 1.5) g of NaOH
1 litre of the resultant solution contain.
40  4 40  4
g of NaOH  mole of NaOH.
5.5 5.5  40
The molarity of the resultant solution
 0.727  0.73M
26.[b] For dilute solution, the van't Hoff equation is
n
  RT
V
m m RT
V  2 RT  M  2
M V
27.[c] Raoult's law is valid for ideal solution only. The element of non-ideality enters into the picture when the molecules
of the solute and solvent affect each others intermolecular forces. A solution containing components of A and B
behaves as ideal solution when A–B attraction force remains same as A–A and B–B.
28.[b]
Tf  K f m........(1)  Tf K f
  ......(3)
Tb  K b m.......(2)  Tb K b
Tf  depression in freezing point.
Tb  elevation in boiling point.
B.P. of water = 100C; Kf  1.86K kg mol1
B.P. of urea in water = 100.18C
K b  0.512K kg mol1 Tb  0.18
F. P. of water = 0C
F.P. of urea in water = –TC
 Tf  T
T 1.86
 from eq. (3)   T  0.6539
0.18 0.512
 F.P. of urea in water = –0.654C.
n C5H12 1
29.[d] 
n C6H14 4
1 4
 XC5H12  and XC6H14 
5 5
PC5H12  440mmHg; PC6H14  120mm Hg
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Liquid Solutions [79]
 
PT  P C5H12 XC5H12  P
C6H14 XC6H14
1 4
 440   120   88  96  184mm of Hg
5 5
By Raoult's law, PC5H12  PC5H12 XC5H12 ...(1)
XC5H12  mole fraction of pentane in solution.
By Dalton's Law, PC5H12  XC' 5H12 P .......(2)
XC' 5H12 P  mole fraction of pentane above the solution. From (1) and (2),
1
PC5H12  440   88mm of Hg
5
 88  XC5H12 184
'

88
X'  ;X'  0.478
184
30.[a] By Raoult's law
PT  PP XP  PQ XQ
Where PP  80 torr, PQ  60torr,
3 2
X P  , XQ 
5 5
3 2
PT  80   60 
5 5
 48  24  72torr
31.[b] 1 mole of solute present in 1 kg of H 2 O
1000
1 mole of solute present in g mol of H 2 O
18
1
Xsolute 
1000
1
18
18
  0.01768  0.018
1018
32.[c] For isotonic solution, osmotic pressure of urea = osmotic pressure of non volatile solute.
10 5
  m  300g mol1
60 1000 m 100
1000  K f  w 1000  5.12  1
33.[b] m or, 250 
W  T 51.2  T
1000  5.12 1
 T   0.4K
51.2  250
34.[c] Both the components escape easily showing higher vapour pressure than the expected value.
35.[d] Osmosis is the phenomenon of flow of pure solvent from the solvent to the solution or from a less concentrated
solution to a more concentrated solution through a semipermeable membrane. Common semipermeable
membranes are permeable to certain solute particles also. Infact, there is no perfect semipermeable membrane.
Therefore we can say that flow of water through a semiperemable takes place both sides with unequal rates.
36.[c] H2SO4 is 98% by weight.
Weight of H2SO4 = 98 g
Weight of solution = 100 g
mass 100
 Volume of solution   mL
density 1.80

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Liquid Solutions [80]
 55.55mL  0.0555L
Molarity of solution
98
 M  18.02M
98  0.0555
Let V mL of this H2SO4 are used to prepare 1 litre of 0.1 M H2SO4 .
 mM of concentrated H2SO4 = mM of dilute H2SO4
or, V 18.02  1000  0.1
1000  0.1
V  5.55mL
18.02
37.[b] HX H  X
1–  
Total = 1+ 
 i  1    1  0.2  1.2
Tf  i  Kf  m  1.2 1.86  0.5
 1.116K 1.12 K
38.[d] The number of moles of ions produced by 1 mol of ionic compound = i
Applying, Tf  i  Kf  m
0.00732  i 1.88  0.002
0.00732
i  1.96  2
1.86  0.002
39.[a] We know, Tf  Kf m
w 1000 68.5  1000 68.5
m B   
M B WA 342 1000 342
68.5
Tf  1.86   0.372C
342
 Tf  0  0.372C  0.372C
40.[d] Addition of water to an aqueous solution of KI causes the concentration of the solution to decrease thereby
increasing the vapour pressure in the other three options the electrolytes undergo ionization, which leads to
lowering of vapour pressure.
w
41.[d] We know that V  nRT, where n 
M
w
V  RT
M
wRT 1.26  0.083  300
M 
V 200
2.57  103 
1000
1.26  0.083  300
 3
 61038g mol1
2.57  10  0.2
42.[d] We know that Tf  i  Kf  m
Here i is van't Hoff's factor.
i for weak acid is 1  .
30
Here,  is degree of dissociation i.e.,  0.3
100
 i  1    1  0.3  1.3
Tf  i  Kf  m  1.3 1.86  0.1  0.24
 Freezing point = – 0.24.

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Liquid Solutions [81]
43.[c] From value of van't Hoff factor i it is possible to determine the degree of dissociation or association. In case of
dissociation, i is greater than 1 and in case of association i is less than 1.
w  1000
44.[b] We known that Tf  i  K f  B
mB  w A
Given: Tf  3.82, Kf  1.86
w B  5, mB  142, w A  45
T  mB  w A
i
K f  w B  1000
3.82  142  45
  2.63
1.86  5  1000
 
45.[d] PCHCl 3
 200mmHg, PCH 2Cl2
 41.5mmHg
Weight
Moles of CHCl3 =
Molecular weight
25.5
  0.213
119.5
40
Moles of CH 2 Cl2   0.470
85
0.213
XCHCl3   0.31
0.213  0.470
0.470
XCH2Cl2   0.69
0.213  0.470
 
PT  PCHCl X
3 CHCl3
 PCH X
2Cl2 CH2Cl2
 200  0.31  41.5  0.69
 62  28.63  90.63
46.[d] According to Raoult's law,
P  x A pA  x B pB ...................(i)
For binary solutions,
x A  x B  1, x B  1  x A ........(ii)
Putting value of x B from eqn. (ii) to eqn. (i)
P  x a pA  (1  x A )pB  x A pA  pB  x A pB
P  pB  x A (pA  pB )
47.[b] An ideal solution is follow:
 Volume of change (V) of mixing should be zero
 Heat change (H) on mixing should be zero
 Obey Raoult's law at every range of concentration.
W 1000 W 1000
48.[c] Molarity = 2 
Mw  Vsol(mL.) 63 250
63 70 63
W g; Mass of acid  
2 100 2
Mass of acid = 45 g.

49.[c] Tf  i  Kf  m
So, Tf  i(van 't Hoff factor)
Salt i
KCl 2
C6 H12 O6 1

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Liquid Solutions [82]
Al2 (SO4 )3 5
K 2SO4 3.
50.[d] For an ideal solution, Smix  0 while Hmix ,
Vmi x. and P  0 .
51.[b] Al2 (SO4 )3  2Al3  3SO24 , i  5
Al2 (NO3 )3  Al3  3NO3 , i  4
K4 [Fe(CN)6 ]  4K   [Fe(CN)6 ]4 , i  5
K 2SO4  2K   SO42 , i  3
K3[Fe(CN)6 ]  3K   [Fe(CN)6 ]3 ,i  4
52.[c] Tb  iK b m
For equimolal solution, elevation in boiling point will be higher if solution undergoes dissociation i.e. i > 1.
53.[c] 1 molal aqueous solution means 1 mole of solute is present in 1000 g of water.
1 1
 solute    0.0177
1000 56.5
1
18
54.[c] Given: WB  6.5g, WA  100g,
Ps  732mm, Kb  0.52, Tb  100 C,
p  760mm
p   ps n 2

p n1
760  732 n2
 
760 100 /18
28  100
 n2   0.2046mol
760  18
Tb  K b  m
Tb  K b  m
n  1000
Tb  Tb  K b  2
WA (g)
0.52  0.2046  1000
Tb  100 C   1.06
100
Tb  100  1.06  101.06 C
55.[c] PBenzene  x Benzene pBenzene

pTotal  x Toluene pToluene
1 1
For an ideal 1 : 1 molar mixture of benzene and toluene, x Benzene  and x Toluene 
2 2
1 1
pBenzene  pBenzene   12.8kPa  6.4kPa
2 2
1  1
pToluene  pToluene   3.85kPa  1.925kPa
2 2
Thus, the vapour will contain a high percentage of benzene as the partial vapour pressure of benzene is higher as
compared to that of toluene.
56.[d] For an ideal solution, Hmix  0, Vmix  0
Now, Umix  Hmix  PVmix
 Umix  0

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Liquid Solutions [83]
Also, for an ideal solution,
pA  x A pA , pB  x B pB
 P  Pobs  Pcalculated by Raoult 's Law  0
Gmix  Hmix  TSmix
For an ideal solution, Smix  0
 G mix  0
57.[d] Being a strong electrolyte, Ba(OH)2 undergoes 100% dissociation in a dilute aqueous solution,
2 
Ba(OH)2(aq)  Ba (aq)  2OH(aq)
Thus, van't Hoff factor i = 3.
58.[a] The concentraion unit involving volume in its expression depends on temperature.
59.[c] The value of molal depression constant, K f is constant for a particular solvent, thus, it will be unchanged when
molality of the dilute solution is doubled.

AIIMS (Previous Years Solution]

Given mass 18
1.[a] Moles of glucose  
Molecular mass 180

0.1
 Molality   1000  0.2mol kg 1
500
2.[c] In case of pure liquid, the liquid behaves as solute, solvent and solutions.
Density of water = 1 g/cm3 and its molecular weight = 18. Therefore, 1000 cm3 of water will weigh 1000 g of
water. We know that
n
M
VL

1000 /18
  55.56M
1L
3.[d] Relative lowering of vapour pressure is written as:
P P  P

P P
P= Vapour pressure of pure component
P = Vapour pressure of component in solution.
4.[a] Intermolecular H-bonding increases the boiling point of a compound as more energy is required to break the
hydrogen bonding between the molecules.
w

P P m
5.[b] As, 
P w W

m M
P= Vapour pressure of pure component
P = Vapour pressure of component in solution.
w = mass of solute, m = [Link]. of solute.
W = mass of solvent, M= mol. Wt. of solvent.

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Liquid Solutions [84]
15
121.8  120.2 M
   M  355.5g
121.8 15 250

M 78
6.[b] Molality is not affected by temperature because volume does not involve in molality which changes with
temperature.
Moles of solute
Molality =
Weight of solvent (kg)

7.[b] K3[Fe(CN)6 ] on inonsation gives 4 species ( 3K  and 1[Fe(CN)6 ]3 ) and Al(NO3 )3 also gives 4 species give 4
species (1Al3 and 3NO3 ) , thus both will have same value of van't Hoff factor.
8.[a] As elevation in boiling point is given by:
Tb  K b  molality.
Putting the value, we get
3/ M
100.52  100.00  0.6 
200 /1000
 M  17.3g mol1
9.[d] Colligative properties are those properties that depend only on the number of particles (ions, atoms, molecules)
present in the solution e.g., elevation in boiling point, depression in freezing point, osmotic pressure etc.
10.[a] Relative lowering of vapour pressure given by
P  Ps
 x B ; x B  mole fraction of solute
P
P= Vapour pressure of pure component
Ps = Vapour pressure of component in solution.
P  Ps 1
   xB
P 16
1 2.175/ M B
  M B  69.45
16 39.08  2.175
78 MB
11.[d] Sodium chloride : NaCl
Copper chloride : Cu 2 Cl2

Magnesium sulphate : MgSO4

Chromium sulphate : Cr2 (SO4 )3
Maximum number of particles (i.e., ions) will be obtained when Cr2 (SO4 )3 is dissolved in water hence, 0.1 M
solution of chromium sulphate will show maximum elevation in boiling point.
12.[c] 20% FeCl3 solution means 100g of solution contains 20 g FeCl3 .
100g
 Volume of 100 g of solution   90.91mL
1.1g / mL

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Liquid Solutions [85]
20
Moles of 20 g of FeCl3   0.1234mole
162
 Molar concentration of solution
0.1234
  1000  1.357M
90.91
13.[a] Molecular weight of NH4OH  35
Now, 35 g of NH4 OH is needed to prepare 1 M solution in 1 litre.
 35g NH4 OH in 1 L solution = 1 molar solution
 2.5  35g NH4OH in 1L solution = 2.5 molar solution.
2.5  35
 g NH 4 OH in 100 mL solution
10
 2.5 molar solution.
8.75g NH4OH was dissolved.

NH3  H2O  NH4OH

For 35 g NH4OH, NH3 needed = 22.4 L at STP.

 for 8.75 g NH4OH, NH3 , needed

22.4
  8.75L  5.6L
35
14.[d] Boiling point of a pure solvent increases by increase in number of soluble particles present in it. So by addition of
toluene, boiling point of pure benzene increases.
15.[b]   CRT
 7.8
C   0.31mol / L
RT 0.082  310
Tf  W  m
16.[c] K f for water 
1000  w
(where W = wt. of water, w=wt. of cane sugar, m=molecular wt. of can sugar)
2.15  100  342
  14.7
1000  5
Now, for 5% glucose,
K f  1000  w B
Tf 
W  MB

(where, w 2  wt. of glucose, M B =molecular wt. of glucose)

14.7  1000  5
  4.08
100  180
 Freezing point of glucose solution
= 273.15–4.08 = 269.07K

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Liquid Solutions [86]
17.[d] Bond dissociation energy increases in the order : HI < HBr < HCl < HF.
HF is most stable halogen acid and HI is the least. Higher the bond dissociation energy, lower is the degree of
ionisation.
As we known Tb  iK b m .
Hence, Tb value is largest for HI. All colligative properties depend upon number of particles.
18.[c] P = 0.850 bar, Ps  0.845bar

w  0.5g, MB  ?
Weight of solvent (benzene ) = 39.0 g
And molecular weight of benzene = 78 g
P  Ps n
As we know,  xB  B
P nA
w B 0.5
0.850  0.845 M B
  m
0.850 w A 39
MA 78
On solving, we get
Molecular mass of solid structure (m) = 178g.
19.[b]
20.[a] If acid is 4.5% ionized then =0.045.
Tf  molality  Kf 0.11.86  0.186
Texp  Tf (1  )

 0.186(1  0.045)  0.194 C

21.[b] In solution, x 'A  0.30; x B  0.70

In vapour phase, x 'A  0.60; x 'B  0.40
Using Dalton's law and Raoult's law.
pA pA 0.30pA pB pB 0.70pB x 'A 0.60 0.30pA
x 'A  0.60    x 'B  0.40     
P pA  pB 0.30pA  0.70pB P pA  pB 0.30pA  0.70pB x 'B 0.40 0.70pB

pA 0.60  0.70 7

   3.5
pB 0.40  0.30 2
22.[b] When a solute is present in very minute amount (trace quantities), the concentration is expressed in ppm.
mass of component A
ppmof A  106
total mass of solution
0.025
 3
 106  25ppm
10
23.[a] For an ideal solution,
Hmix  0 and Vmix  0
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Liquid Solutions [87]

24.[a] T  353.23K, WB  1.8g,
b

WA  90g, Tb  354.11K,

K b  2.53 kg mol1

Tb  Tb  Tb  354.11  353.23  0.88K

WB  K b 1000 1.8  2.53  1000
MB  
Tb  WA 0.88  90

 57.5  58g mol1

25.[b] p  K H x
Higher the value of K H at a given pressure, lower is the solubility of the gas in the liquid.
w
26.[c] P  RT; since w, V and T are same thus P  (1/ M) .
MV
27.[a] Let the masses of A and B be a and b. the mass of AB2 will be (a + 2b)g mol–1 and AB4 will be (a + 4b)g mol–1.
K f  WB  1000
Tf 
M B  WA

5.1 1 1000
For AB2 , 2.3  .........(i)
(a  2b)  20

5.1 1 1000
For AB4 , 1.3  ..........(ii)
(a  4b)  20
On solving (i) and (ii), we get.
A = 25.59 and b= 42.64.
28.[a] Given: w 2  0.2, w1  20g, Tf  0.45 C
1000  K f  w 2
Tf 
w1  M

1000  5.12  0.2

 0.45 
20  M
 M(observed)  113.78 (acetic acid)

2CH3COOH (CH3COOH) 2
1 0 Before association
1– /2 after association.
(where  is degree of association)
Molecular weight of acetic acid = 60
Normal molecular mass
i
Observed molecular mass

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Liquid Solutions [88]
M(normal) 
 1  
M(observed) 2

60 
Or, 1  
113.78 2
   0.945 or 94.5%
29.[a] Tf  iK f m

Thus, Tf  i (as conc. is same for all solution)

ifor HCl  2, i for CuSO4  2, i for K 2SO4  3
Thus, ratio of depression in freezing point.
= 2 : 2 : 3 = 1 : 1 : 1.5
30.[a] w1  600g, Tf  2.2K

w 2  45g, Kf  1.86K kg mol1

Kf  w 2
M
Tf  w1

1.86  45  1000
  63.4 g mol1
2.2  600
31.[b] Solubility of gas in liquid increases on increasing pressure according to Henry's law.
32.[a]   CRT
1 8.314  300
   19.4Pa
1.6 105
800 106
w
33.[b] Tf  Tf  K f 
[Link].  W
w
2.4  1.86 
62  2
 w  160g
[Mass of 2L of water is 2 kg.]
34.[b] Depression in freezing point is a colligative property which depends on the number of particles present in the
solution. As both 0.1 M solution of glucose and 0.1 M solution of urea contain same number of moles (number of
particles) therefore, both will have same depression in freezing point.
35.[c] Density of water is maximum at 4C i.e., 277K.
36.[a] Depression in freezing point is a colligative property which depends upon the number of particles.
The number of particles are different in case of benzene and water because acetic acid undergoes association in
benzene and dissociation in water. That is why molecular weight of acetic acid determined by depression in
freezing point method is also different.
37.[a] Freezing point of a substance is defined as the temperature at which the vapour pressure of its liquid is equal to the
vapour pressure of the corresponding solid. Since the addition of a non-volatile solute always lowers the vapour
pressure of solvent, therefore it will be in equilibrium with solid phase at a lower pressure and hence at a lower
temperature.

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Liquid Solutions [89]
38.[c] If the red blood cells are placed in pure water, pressure inside the cells increases as the water is drawn in and the
cell swells.
39.[d] Molarity equation is written as
M1V1  M2 V2
Thus if the V2 changes M 2 also changes.

moles of solute
Molarity 
volume of solution in litre
40.[b] Molality does not depend upon volume thus it does not depend on temperature.
41.[d] Elevation in boiling point (Tb )  K b  m depression in freezing point (Tf )  Kf  m Elevation in boiling point
and depression in freezing point are colligative properties i.e., they depends only on the number of particles of the
solute. Value of K b and K f are different, so, Tb and Tf are also different.
42.[a] This is according to Henry's law which states that the solubility of a gas in given volume of a liquid at a particular
temperature is directly proportional to the pressure of gas above the liquid m  p,m  K p where K= Henry's
constant.
43.[c] In pressure cooker, water boils above 100C. When the lid of cooker is opened, pressure is lowered so that boiling
point decreases and water boils again.
44.[a]
45.[a]
46.[b] Non-ideal solutions with positive deviation i.e., having more vapour pressure than expected, boil at lower
temperature while those with negative deviation boil at higher temperature than those of the components.
47.[b] On adding a non volatile solute in a liquid the vapour pressure decreases because some molecules of the solvent on
the surface are replaced by the molecules of the solute.
48.[b]

*****

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