Solution (Booklet)

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.
: Raman Niwas, Near Akashwani, Mahmoorganj, Varanasi, Ph. No. (0542) 2363455, website: www.catjee.in
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.
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 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.
5 5
Ans: x O2  4.61 10 , x N2  9.22 10
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
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
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
(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
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
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
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
9. 8
Henry‘s law constant for CO2 in water is 1.67×10 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
–3
10. The partial pressure of ethane over a solution containing 6.56 × 10 g of ethane is 1 bar. If
the solution contains 5.00 × 10–2g 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
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 
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
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
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
3. ‗A‘ is in equilibrium with its vapour which relation is correct:
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
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
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 1   Bo  Ao 
PAo 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
(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.
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
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.
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?
Brain Teaser: What will be change in free energy during formation of a non-ideal solution with
positive deviation?
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
1. A and its mole fraction is not a straight line PS  PA  PB
but is a curve showing the deviation from III
I
Raoult‘s law
PA  PAo X A
2. The plot of partial vapour pressure of liquid VP II

B and its mole fraction is also not a straight PB=VP of B PA=VP of (A)
line but is a curve (II) showing +ve deviation
from Raoult‘s law.
PB  PBo XB
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 .
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?
Brain Teaser: What will be change in free energy during formation of a non-ideal solution
with negative deviation?
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
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 III
I
it 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 PA=VP of (A)
is not a straight line but is a curve (II) PB=VP of B
showing negative deviation from ideality.
PB  PBo XB
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
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
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
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
(c) PS = PA° + (PB° – PA° ) XA (d) PS = PB° + (PB° – PA° ) XB
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
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
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
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
9. For an ideal solution containing a nonvolatile solute, which of the following expressions is
correctly represented?
ΔPA ΔPA ΔPA ΔPA
(a)  = XA (b)  = XB (c)  = XB (d)  = XA
PAο PBο PAο PBο
where the subscripts A and B stand for solvent and solute respectively.
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
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
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
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
V.Pr.
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
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.
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.
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
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
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
PAo – PS n2

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.
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
Pure Solvent
the atmospheric pressure.
1 atm
When the atmospheric pressure is 1 atm,
boiling point is called the normal boiling point. Vapour pressure
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 Tb0 Tb
Temperture
other words, the boiling point of the solution Tb
is higher than the boiling point of the pure Plot of variation of vapour pressure Vs elevation
solvent 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. .
Solution: Total mole of solute = Mole of Urea + Mole of thio
25.0g 25.0
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
Tb = 5.445°C + Tb0 = 5.445°C + 61.2°C = 66.645°C

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 (K b) 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 Lv
the latent heat of Vapourization of solvent.
Illustration: Calculate the ebulloscopic constant for water if its latent heat of
vapourization is 540 Cal/g.
Solution:
R  (Tb )2 2 Cal / (mol  K)  (373K) 2 2 Cal / (mol  K)  (373K) 2
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
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 C 14H12 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
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
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
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
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
–1
7. 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
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
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
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
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
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
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
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 temperature and depression
solution; 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
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

RTf2
as: K f 
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.
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.
(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.
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 (Kf 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
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
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
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
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
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

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.
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
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
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
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
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.
13. Consider the Fig. given below and mark the in correct option.
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)
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.
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
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
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
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
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.
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
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%
22. The density of a 9.5% by mass solution of fructose (C6H12O6) 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
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
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
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)
(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 (mol.wt. = 100) are dissolved in 500 g of water. The
freezing point of the solution is –0.74°C, Kf = 1.86 K.molality–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)
i = 1+(n―1)  = 1+ (2―1)  = 1+

Normal mol.wt
i for AgNO3 = =1+
Observed mol.wt.
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)
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
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
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
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 
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
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
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
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
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
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
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
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
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
14. Calculate the percentage degree of dissociation of an electrolyte XY 2 (Normal molar mass =
164) in water if the observed molar mass is 65.6:
(a) 75% (b) 25% (c) 65% (d) none of these
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
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%
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

18. A substance is completely trimerised on dissolution in a solvent. The Van‘t Hoff‘s factor i for
such change is:
(a) 1 (b) 2 (c) 3 (d) 1/3
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
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
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%
22. Two solvents A and B have Kf values 1.86 and 2.79 K mole–1 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
*****
JEE MAIN (PREVIOUS YEARS ASKED QUESTIONS)
1. For an aqueous solution, freezing point in –0.186°C. Elevation of the boiling of the same solution is
(Kf = 1.86° mol–1 kg and Kb = 0.512° mol–1 kg)
(a) 0.186° (b) 0.0512° (c) 1.86° (d) 5.12°
2002
2. In a mixture of A and B, components show negative deviation when
(a) A—B interaction is stronger than A—A and B—B interaction
(b) A—B interaction is weaker than A—A and B—B interaction
(c) Vmix > 0, Smix > 0
(d) Vmix = 0, Smix > 0
2002
3. In 0.2 m aqueous solution of weak acid HX, the degree of ionisation is 0.3. Taking kf for water as 1.85
the freezing point of solution will be nearest to:
(a) – 0.480°C (b) – 0.360°C (c) – 0.260°C (d) 0.480°C
2003
4. A pressure cooker reduces cooking time for food because
(a) heat is more evenly distributed in cooking space
(b) boiling point of water involved in cooking is increased
(c) higher pressure inside the cooker crushes food material
(d) cooking involves chemical changes helped by rise in temperature.
2003
5. If liquid A and B form ideal solutions
(a) the enthalpy of mixing is zero
(b) the entropy of mixing is zero
(c) the free energy of mixing is zero
(d) the free energy as well as entropy of mixing are each zero.
2003
6. Which one of the following aqueous solutions will exhibit highest boiling point?
(a) 0.03 M Na2SO4 (b) 0.01 M KNO3
(c) 0.015 M urea (d) 0.015 M glucose.
2004
7. Which of the following pair will show positive deviations from Raoult’s law?
(a) Water – Hydrochloric acid (b) Benzene – Methanol
(c) Water – Nitric acid (d) Acetone – Chloroform.
2004
8. Which of the following statement is false?
(a) Raoult’s law states that vapour pressure of a component over a solution is proportional to its mole
fraction.
(b) Osmotic pressure is given by the expression p = MRT where, M is molarity.
(c) The correct order of osmotic pressures of 0.01 M aqueous solution of each compound is BaCl2 >
KCl > CH3COOH > sucrose.
(d) Two sucrose solutions of same molarity prepared in different solvents will have same freezing
point depressions.
2004
9. If a is the degree of dissociation of Na2SO4, the vant Hoff’s factor (i) used for calculating the molecular
mass is
(a) 1 + 2a (b) 1 – 2a (c) 1 + a (d) 1 – a
2005
10. Benzene and toluene from nearly ideal solutions. At 20°C, the vapour pressure of benzene is 75 torr and
that of toluene is 22 Torr. The partial vapour pressure of benzene at 20°C for a solution containing 78 g
of benzene and 46 g of toluene in Torr is
(a) 37.5 (b) 53.5 (c) 50 (d) 25
2005
11. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The vapour pressure of water for this aqueous
solution at 100°C is:
(a) 759.00 torr (b) 7.60 torr (c) 76.00 torr (d) 752.40 torr
2006
12. A 5.25% solution of a substance is isotonic with a 1.5% solution of urea (molar mass = 60 g mol–1) in the
same solvent. If the densities of both the solutions are assumed to be equal to 1.0 g cm–3, molar mass of
the substance will be
(a) 90.0 g mol–1 (b) 115.0 g mol–1 (c) 105.0 g mol–1 (d) 210.0 g mol–1
2006
13. At 80°C, the vapour pressure of pure liquid ‘A’ is 520 mm Hg and that of pure liquid ‘B’ is 1000 mm
Hg. If a mixture solution of ‘A’ and ‘B’ boils at 80°C and 1 atm pressure, the amount of ‘A’ in the
mixture is (1 atm = 760 mm Hg)
(a) 52 mol percent (b) 34 mol percent (c) 48 mol percent (d) 50 mol percent
2008
14. Two liquids X and Y form an ideal solution. At 300K, vapour pressure of the solution containing 1 mol
of X and 3 mol of Y is 550 mm Hg. At the same temperature, if 1 mol of Y is further added to this
solution, vapour pressure of the solution increases by 10 mm Hg. Vapour pressure (in mmHg) of X and
Y in their pure states will be, respectively :
(a) 200 and 300 (b) 300 and 400 (c) 400 and 600 (d) 500 and 600
2009
15. If sodium sulphate is considered to be completely dissociated into cations and anions in aqueous
solution, the change in freezing point of water (DTf), when 0.01 mol of sodium sulphate is dissolved in
1 kg of water, is (Kf = 1.86 K kg mol–1)
(a) 0.0372 K (b) 0.0558 K (c) 0.0744 K (d) 0.0186 K
2010
16. The degree of dissociation (a) of a weak electrolyte, AxBy is related to van’t Hoff factor (i) by the
expression
i 1 x  y 1 x  y 1 i 1
(a) α= (b) α = (c) α = (d) α =
x  y 1 i 1 i 1 (x  y  1)
2011
17. Ethylene glycol is used as an antifreezee in a cold climate. Mass of ethylene glycol which should be
added to 4 kg of water to prevent it from freezing at –6°C will be :
[Kf for water = 1.86 K kg mol–1, and molar mass of ethylene glycol = 62g mol–1]
(a) 204.30g (b) 400.00 g (c) 304.60 g (d) 804.32g
2011
–1
18. Kf for water is 1.86K kg mol . If your automobile radiator holds 1.0 kg of water, how many grams of
ethylene glycol (C2H6O2) must you add to get the freezing point of the solution lowered to –2.8°C ?
(a) 72g (b) 93g (c) 39g (d) 27g
2012
19. The molarity of solution obtained by mixing 750mL of 0.5(M)HCl with 250 mL of 2(M)HCl will be
(a) 0.875M (b) 1.00M (c) 1.75M (d) 0.975M
2013
20. Consider separate solutions of 0.500M C2H5OH(aq), 0.100M Mg3(PO4)2(aq), 0.250M KBr(aq) and
0.125M Na3PO4(aq) at 25°C. Which statement is true about these solutions, assuming all salts to be
strong electrolytes? (liquid solution)
(a) 0.125 M Na2PO4(aq) has the highest osmotic pressure
(b) 0.500 M C2H5OH(aq) has the highest osmotic pressure
(c) They all have the same osmotic pressure.
(d) 0.100 M Mg3(PO4)2(aq) has the highest osmotic pressure
2014
21. The vapour pressure of acetone at 20°C is 185 torr. When 1.2 g of a non-volatile substance was
dissolved in 100 g of acetone at 20°C, its vapour pressure was 183 torr. The molar mass (g/mol) of the
substance is
(a) 488 (b) 32 (c) 64 (d) 128
2015
22. 18 g glucose (C6H12O6) is added to 178.2 g water. The vapour pressure of water (in torr) for this
aqueous solution at 100°C is
(a) 752.4 (b) 759.0 (c) 7.6 (d) 76.0
2016
23. The freeing point of benzene decreases by 0.45°C when 0.2 g of acetic acid is added to 20 g of benzene.
If acetic acid associates to form a dimmer in benzene, percentage association of acetic acid in benzene
will be. (Kf for benzene = 5.12 K kg mol–1)
(a) 74.6% (b) 94.6% (b) 64.6% (d) 80.4%
2017
24. Two 5 molal solutions are prepared by dissolving a non-electrolyte non-volatile solute separately in the
solvents X and Y. The molecular weights of the solvents are MX and MY, respectively where, the relative
lowering of vapour pressure of the solution in X is ‘m’ times that of the solution in Y. Given that the
number of moles of solute is very small in comparison to that of solvent, the value of ‘MX / MY’ is-
(a) 1/m (b) m (c) 2m (d) 1/2m
2018
25. Which one of the following statements regarding Henry’s law is not correct?
(a) different gases have different KH (Henry’s law constant) values at the same temperature
(b) Higher the value of KH at a given pressure, higher is the solubility of the gas in the liquids
(c) The value of KH increases with increase of temperature KH is function of the nature of the gas
(d) The partial pressure of the gas in vapour phase is proportional to the mole fraction of the gas in the
solution.
2019
Answer Keys
Que. 1 2 3 4 5 6 7 8 9 10 11 12 13
Ans. b a a b a a b d a c d d d
Que. 14 15 16 17 18 19 20 21 22 23 24 25
Ans. c b d d b a c c a b a b
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
p O2 1520mm
Applying Henry’s law, pO2  K H  x O2 or x O2   7
 4.61105
KH 3.30 10 mm
p N2 6004mm
p N2  K H  x N2 or x N2   7
 9.22  105
KH 6.51 10 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, K H 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)
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 1.67  108 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
[51]
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.
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.
[52]
3 : [c] Pressure applied by vapour in given figure on any boundary in contact with vapour will be similar So,
P1= 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
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

[53]
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 T
2.303 R  1 T2 19 2.303  8.314  T1 373 

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
[54]
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
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.
[55]
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.
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
[56]
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   46 
Thus, PS = 88.5     42   16 46  =29.5+28=57.5
 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
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] y A = = = = = 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
[57]
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
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:
[58]
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
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
[59]
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 – PS
0
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
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
[60]
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]
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
[61]
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
J J 103 kJ 103 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
[62]
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.
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
[63]
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
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
[64]
[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)
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
[65]
(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)

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
[66]
(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
(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
[67]
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

―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.
[68]
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

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
[69]
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
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

[70]
  = 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.
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
[71]
%   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
JEE Main (Previous Years Solution)

1: [b] Tb  Kf  m
0.186  1.86  m  m  0.1mol K 1
Tb  K b  m
 0.52  0.1 =0.052
2: [a] It is a required condition along with
V  ve and H  ve
3: [a] T  Kf  molality  (1  )  1.85  0.2(1  0.3)  0.48
 f.pt.  0  0.48  0.48 C
4: [b] Liquid boils at higher temperature if pressure is more.
5: [a] Conceptual question.
6: [a] Tb  Ts  T0
Where Ts = b.pt of solution
T0 = boiling point of pure solvent.
Note: Elevation in boiling point is a colligative property, which depends upon the number of particles. Thus
greater the number of particles, greater is it elevation and hence greater will be its boiling point.
Na 2SO4 2Na   SO42
Since Na2SO4 has maximum number of particles (3) hence has maximum boiling point.
7: [b] Conceptual question.
8: [d] Conceptual question.
9: [a] Na 2SO4 2Na   SO42
1 0 0
1  2 
1    2   1  2
i   1  2
1 1
10: [c] Given, vapour pressure of benzene = 75 torr
Vapour pressure of benzene = 22 torr
Mass of benzene in =78g
78
Hence, moles of benzene   1mole (mol. wt. of benzene =78)
78
Mass of toluene in solution = 46g
46
Hence, moles of toluene   0.5mole
92
[72]
1
Now, partial pressure of benzene Pb .Xb  75   50 torr
1  0.5
P  PS n 18 18
11: [d]    0.01
PS N 180 178.2
760  Ps
  0.01 ( P  760 torr at b.pt. of H2 O)
Ps
PS  752.47 torr
12: [d] Solutions with the same osmotic pressure are isotonic. Let the molar mass of the substance be M.
1  C1RT, C2 RT  2
5.25 15
So, 
M 60
As density of the solutions are same.
5.25 15
So, 
M 60
5.25  60
 M  210
1.5
13: [d] Pm  PA XA  PB .XA  PB .XB
760  520XA  PB (1  XA )
 XA  0.5  50%
14: [c] Initially PM  PX .XX  PY .XY
 1   3 
550  PX .    PY .  
 1 3   1 3 
or PX  3PY  2200 ..........(i)
when 1 mole of y is further added to it.
PM  PX .XX  PY .XY
 1   4 
560  PX   
 1 4   1 3 
 PX  4PY  2800 .................(ii)
By eq. (i) and (ii)
PX  400mm and PY  600mm
15: [b] vant Hoff’s factor i for Na2SO4 = 3
 Tf  i  Kif  molality
0.01
 3 1.86   0.0558K
1
16: [d]  xA y  yBx 
A x By 
Before diss. 1 0 0
After diss. 1  x x
i  1    x  y
or, (i  1)  (x  y  1)
i 1
 
(x  y  1)
17: [d] Given, Kf = 1.86K kg mol–1
[73]
Tf  0  (6)  6C
As we know that Tb  Kf  molality
K f 1000  mass of solute

molar mass of solute  mass of solvent in kg
Substituting given values in formula
1.86 1000  w
6 ; w  0.8kg  800gm
62  4
18: [b] Tb  i  Kf  m
Given, Tb  2.8, Kf  1.86K kg mol1 i  0
(ethylene glycol is a non-electrolyte)
wt. of solvent = 1 kg; Let of wt of solute = x
Mol. wt. of ethylene glycol = 62.
x
2.8  11.86   x  93gm
62 1
19: [a] From Molarity equation:
M1V1 + M2V2 = M×V
0.5  750  2  250  M 1000
 M  0.875mol L1
20: [a]   iCRT
C2H5OH  1 0.500  R  T  0.5RT
Mg3 (PO4 )2  5  0.100  R  T  0.5RT
KBr  2  0.250  R  T  0.5RT
Na3PO4  4  0.125  RT  0.5RT
P0  Ps n1
21: [c] Using relation, 
P0 n2
185  183 1.2 / x
  x  64
185 100 / 58
P0  Ps n1
22: [a] 
P0 n2
Since, at 100 °C the vapour pressure of pure water is 1 atm. i.e., 760 torr.
760  Ps 18 /180
  Ps  752.4 torr
760 178.2 /18
23: [b] Tb  iKf  m
  n   0.2 / 60
0.45K  1    5.12   1    5.12 
 2  W  2  20 /1000
   0.946  94.6%
 nB   nB 
24: [a] RLVP for X = m × RLVP for Y,   for X   m  '  for Y
 nA   nA 
[nA moles of solvent, nB moles of solute. Molality = 5 mole/kg means 5 mole of solute in 1 kg
solvent.]
5 5
  m
1000 / M X 1000 / M Y
 MX  m  MY
[74]
MX
 MX  m  MY   m
MY
25: [b] At constant temperature, solubility of a gas (S) varies inversely with Henry’s law constant (KH)
Pr essure P
KH  
Solubility of a gas in a liquid S
Thus, higher the value of KH at a given pressure, the lower is the solubility of the gas in the liquid.
*****

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Liquid Solutions [1]

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

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

1.3 Solubility of a solid in a liquid :

1.4 Solubility of solid in liquid depends on:

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

1.7 Characteristics of Henry law constant (KH).

1.8 Limitation of Henry's law :

log P log P log P log P

When a liquid is kept in a closed container, evapouration continues to occur at constant

After some time an equilibrium is established where

Rate of evaporation = Rate of condensation

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

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

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

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

Log P2 = 1.543 , P2 = 34.91 mm Hg

2.2 About evapouration:

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

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

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

2.3 Boiling point and volatility:

2. Volatility: At constant temperature, the vapour pressure of a liquid depends upon

(a) P3 = P1 P2 (b) P1 = P2P 3

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

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

3. Raoult’s Law and Vapour Pressure of Solution

According to Raoult‘s law,

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

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

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

Ans: (a) YA=3/4, YB=1/4 (b)YA=9/10, YB=1/10

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

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

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

Characteristics of Ideal Solution:

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

2. Straight line II represents the plot of partial

3.6 Non-Ideal Solutions

PA  PAo X A and PB  PBo XB

Types of Non-Ideal Solutions

1. Non ideal solutions showing +ve deviation

3.7 Positive Deviation from Raoult’s Law:

H3C CH3 H3C CH3 H3C CH3

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

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

Characteristics of non-deal solution with negative deviation:

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

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

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

Azeotropes are of two types:

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

Example of Minimum Boiling Azeotrope

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 :

Examples of Maximum Boiling Azeotrope

H2O HCl 20.3 373 188 383