Chemis try Stu dy mate rial on

SOLUTIONS , STD-XII

P o − Ps
(a) Po
= i.x 2 (b) T = iK .m
b b

(c) Tf = iK f .m (d)  = i CRT

i −1 i −1
(e) = (f)  =
n −1 n −1
1

Calculateed or normal molecular mass M

Van’t hoff factor, i = = C
Observed or Abnormal molecular mass M O

Name:_______________________________________________________
School: _____________________________________________________________
Prepared by:
Dipak Kumar Parida,PGT, Chemistry,
LR DAV Public School, Cuttack

1|Page
Contents:

Part 1: Expressing concentration of solution

Part 2: Henry’s law, Raoult’s law, Ideal and Non

ideal solution

Part 3: Colligative properties

i) Relative lowering in vapour pressure
ii) Elevation in Boilong point
iii) Depression in freezing point
iv) Osmotic pressure

Part 4: Abnormal molecular mass and van’t hoff

factor

2|Page
 Part-1
Introduction:
1. A solution is a homogeneous mixture of two or more components.
2. The size of particles of a solution are less than 1nm in diameter, which are so
small that not able to scatter light passing through the solution.
3. Generally the component which is present in the larger quantity is known as
solvent and which is present in smaller quantity is known as solute.
4. The component which determines the physical state in which the solution exists
is known as solvent and the second component is called solute.
Ex: In the solution which contains 40% water and 60% sugar, water acts as
solvent.
5. The solution can’t be separated by filtration or by settling and hence it is
considered as a single phase containing more than one component.
6. The solution can be classified as binary or ternary or quaternary depending on
the no of components present like 2, 3 or 4 respectively.
7. Again the solutions can be classified as gaseous, liquid or solid solutions
depending on the nature of the solvent where in each case the solute may be
gas or liquid or solid.
Types of solution Solute solvent Example
Gaseous solution Gas Gas O2+N2
Liquid Gas CHCl3 + N2
Solid Gas I2 + Gas
Liquid solution Gas Liquid O2 + H2O
Liquid Liquid C2H5OH + H2O
Solid Liquid NaCl + H2O
Solid solution Gas Solid H2 + Pd
Liquid Solid Hg + Na
Solid Solid Brass( Zn + Cu)
Expressing concentration of solutions:
Qualitatively if less amount of solute is present in the solution then it is called dilute
solution and if more amount of solute is present then it is called concentrated solution.
But the concentration of a solution can be quantitatively expressed by different terms
like:
1. Percentage: It may be mass to mass % or volume to volume % or Mass to
Volume %

3|Page
 i) Mass Percentage (m/m %): The amount of solute in gram present in 100
g of solution is called mass percentage.
w2
So, m/m%=  100
W ( gm)
Where w2= Mass of solute in gm, W= Mass of solution
Mass %( m/m%) is 10 means 10 g of solute is present in 100 g of solution
or 90 g of water.
ii) Volume percentage(v/v %): The volume of solute in ml present in 100
ml of solution is called volume percentage.

So, v/v % = V2
X 100
V (ml )

Where V2= Vol. of solute in ml, V= volume of solution

iii) Mass by volume percentage(m/v%): The mass of solute in gram
present in 100 ml of solution is called mass by volume percentage.
w2
m/v % = X 100
V (ml )
2. Parts per million(ppm): The no parts of the solute present in 1 million parts of
solution is called ppm.
Like percentage it can also may be expressed by mass ppm, volume ppm, mass
by volume ppm.

Mass ppm(w/w%)= w2
X 106
W ( gm)

3. Mole fraction(  ): The ratio of no of mole of the component to the total no of

moles of solution is called mole fraction.

n2 n1
Mole fraction of solutei. e.  2 = , Mole fraction of solvent i. e. 1 =
n1 + n2 n1 + n2

n1 n2  n
So 1 +  2 = + =1, Again 2 = 2
n1 + n2 n1 + n2 1 n1
4. Molarity(M): The no of moles of solute present in one litre of solution is called
molarity.
n2
M= ,Where n2= No of moles of solute
V ( Lit )
w2 1000
So, M =  Where M2 =Molecular mass of solute
M 2 V (ml )

Ex: when molarity = 10 then 10 mole of solute present in 1L=1000ml of solution

4|Page
 For molar solution M=1, For decimolar solution M=0.1, For centimolar solution
M=0.01, For millimolar solution M=0.001
5. Molality(m): The no of moles of solute present in 1 kg of solvent is called
molality.
n2 w 1000
i.e. m = , Or, m= 2  Where w1 = Mass of solvent
w1 ( Kg ) M 2 w1 ( gm)
Ex: When molality is 10 then n2=10 mol and w1=1000 g.
6. Normality: The no gm equivalents of solute present in one litre of solution is
called normality.
w2 1000
N= X , Where E2= Equivalent mass of the solute.
E2 V (ml )

7. Strength(S): The amount of solute in gram present in one litre of solution is

w2
called strength. i.e.S= X 1000 .
V (ml )
Note:
1. The ppm unit is used to express the concentration of very dilute solution.
Ex: The concentration of pollutants in water is expressed in terms of ppm or
 g / ml
2. Molality, mole fraction, mass %, mass ppm are better to express the
concentration of solution as these are independent of temperature because
these are related to mass which doesn’t depend on temperature. Molarity,
normality, v/v %, m/v% are function of temperature as these are related with
volume of solution which depends on temperature.
3. All the conc. terms are intensive properties which don’t depend on amount of
substance.
4. Molarity equation: If a solution having molarity M1 and volume V1 is diluted to
volume V2 having molarity M2, then M1V1 = M2V2, as the no of moles of solute
remain same.
5. If two solutions react completely with each other having molarities and volumes
M1,V1 and M2,V2 then n1M1V1 = n2 M2 V2 , Where n1 and n2 are the total change in

oxidation no of oxidant and reductant in redox reaction or basicity of the acid and
basicity of the base for acid-base reaction.
6. Molarity of the mixture of same substance: If V1 ml of a solution of molarity M1
are mixed with V2 ml of solution of the same substance with molarity M2 the
molarity of the resulting solution is

5|Page
 M 1V1 + M 2V2
M3 =
V1 + V2

Relation between the concentration terms:

1. Relation between strength and molarity:
S = M x M2 i.e Strength = Molarity x molecular mass

Similarly strength = Normality x Equivalent mass

2. Relation between molarity and normality:
S = N x E2 and S = M x M2
So N x E2 = M x M2
N M2 N M2 N
Or, = , Or, = M 2 , Or = n , Or, N = M x n ,
M E2 M n M

Where n= Basicity of acid Or acidity of base Or, Total valency of cation or anion of salt.
3. Relation between molarity and molality:
w2 1000 w 1000
m= X and M = 2 X
M 2 w1 ( gm) M 2 V (ml )

m V m V
= Or, =
M w1 M W − w2

If density of solution = d gm/ml the weight of solution= V x d

m V VM M
= Or, m = , Or, m =
M Vd − n2 M 2 Vd − n2 M 2 d − n2VM 2

1000M 1000 M
Or, m = Or, m =
1000d − n2 XV1000 . M 2 1000d − M . M 2

Relation between molarity and mass %:

Let x= mass % i.e x gm of solute is present in 100 g of solution.
Let d = density of solution
W
So the mass of one litre of solution= (1000 x d) gm (As d = )
V
Mass of solute in one litre of solution= x /100  1000  d = 10d x gm
10dx 10dx
No of moles of solute in one litre of solution= Or, M=
M2 M2

4. Relation between mole fraction and molality:

w 1000
w2
1000 1000 n2 1000  2
m= 2  m=
M2
or m= Or, m= , Or, (As x2/x1 =
M 2 w1 ( gm) w1
M1  M1 M 1n1 M 1 1

M2/M1)

6|Page
 PRACTICE QUESTIONS-1:

1. Which of the following modes of expressing concentration of solution is

independent of temperature:
a. Molarity b. Molality c. Normality d. grams per litre
2. The molarity of a solution obtained by mixing 750 ml of 0.5 M HCl with 250 ml of
2 M HCl will be:
a. 1.00 M b. 1.75 M c. 0.975 M d. 0.875 M
3. What is false for mole fraction: (JEE MAIN)
a. X < 1 b. -2  x  2 c. 0  x  1 d. Always non negative
4. Which of the following dependent on temperature?
a. Molality b. Molarity c. Molefraction d. Weight percentage
5. 6.02x 1020 molecules of urea are present in 100ml of its solution. The
concentration of the solution is: (NEET-2013)
a. 0.02M b. 0.01M c. 0.001M d. 0.1M
6. In one molal solution that contains 0.5 mol of solute, there is: (NEET-2022)
a.500g of solvent b.100ml of solvent c.1000g of solvent d.500ml of solvent
7. Mole fraction of the solute in 1.00 molal aqueous solution is:
a.1.77 b. 0.177 c.0.0177 d. 0.0344
8. What is the mass of ethylene glycol(C2H6O2) required for making 500g of 0.25
molal aqueous solution and 250ml of 0.25 molar aqueous solution? (JEE Main-2023)
a)1:1 b)3:1 c)2:1 d)1:2
9. The mole fraction of a solute in a solution is 0.1. At 298K, molarity of this
solution is the same as its molality. Density of this solution at 298K is 2.0 g/cm-3.
MWsolute
The ratio of the molecular weights of the solute and solvent ( ) is
MWsolvent
__________. (JEE ADV. 2016)
10. Assertion(A): One molar aqueous solution has always higher concentration than
one one molal solution.
Reason(R ): One molar solution contains less solvent than one molal solution.
11. 4L of 0.02M a. solution of NaCl was diluted by adding one lit of water. The
molality of the resulting solution is ________.
12. The molality of sulphuric acid solution in which mole fraction of water is 0.85 is:
a)10.8 b)0.98 c)9.8 d)1.2
Problems solved:
13. Calculate the mole fraction of glucose in a solution having conc. 10% by mass.
Ans: Mass % = 10 means 10 g of solute is present in 100 g of solution.
So w2= 10, w1= 100-10 = 90 g, M2=180, M1 =18
n2
So, Mole fraction of glu cos ei. e.  2 =
n1 + n2

7|Page
 w2 / M 2 10 /180 1 / 18
= = = =1/91=0.010
w1 / M 1 + w2 / M 2 90 /18 + 10 /180 5 + 1 / 18
14. What should be the molarity of conc. nitric acid solution if its density is 1.5 g/ml
and concentration is 68% by mass.
Ans: Mass % is 68 means 68 g of HNO3 is present in 100 g of solution.
So, W2= 68 g, W= 100 g , M2 = 63
Given d=1.5 g/ml
W W 100
So, =1.5  V = = =66.66ml
V 1.5 1.5
w2 1000 68 1000 68000
So, M =  =  = = 16.19 mol/L
M 2 V (ml ) 63 66.66 4199.5

15. Calculate the molality of urea solution having mass to mass % is 20.
Ans: Mass % = 20 means 20 g of solute present in 100 g of solution or 80 g of
solvent. So W2 = 20 g , W1 = 80 g, M2 = NH2CONH2 = 60
w2 1000 20 1000
So, m=  =  = 4.16 mol/kg
M 2 w1 ( gm) 60 80

16. The density of 3 M solution of NaCl is 1.25 g/ml. Calculate molality of solution?
Ans: Molarity is 3 means 3 mol of solute is present in 1L = 1000ml of solution. So n2
= 3 mol, V = 1000ml , M2 = 23 +35.5 =58.5
Given d = 1.25 g/ml
W
 =1.25, Or W = 1.25  1000 =1250 g
V
W2
No of moles of solute(n2) = 3,  =3,  W2 = 3  58.5 =175.5 g
M2

So, W1 = W – W2 = 1250 – 175.5 = 1074.5 g

w2 1000 175.5 1000 175500
So, m=  =  = = 2.79 mol/kg
M 2 w1 ( gm) 58.5 1074.5 62858.25

17. Calculate molarity of an acetic acid solution having molality 4 and d= 1.5 g/ml
Ans: Molality is 4 means 4 mol of solute is present in 1kg = 1000 g of solvent.
So, W1 = 1000 g, n2 = 4 mol,
W2 W
As M2 = 60 g/mol, So = 4,  2 = 4 ,  W2 = 240 g
M2 60

Hence W = W1 + W2 =1000 + 240 =1240 g

W 1240
Given d = 1.5,  =1.5,  V = =826.6 ml
V 1.5

8|Page
 w2 1000 240 1000 240000
So, M =  =  = = 4.83 mol/L
M 2 V (ml ) 60 826.6 49596

ASSIGNMENT-1:
18. Calculate the mole fraction of ethylene glycol(C2H6O2) in a solution containing
20% of C2H6O2 by mass. (Ans: 0.067)

19. Calculate the molarity of a solution containing 5 g of NaOH in 450 ml solution.

(Ans: 0.278)
20. Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
(Ans: 0.55)
21. Calculate the molarity of the solution if 30 ml of 0.5 M H2SO4 diluted to 500 ml.
(Ans:0.03)
22. Calculate a) molality b) molarity and c) mole fraction of KI if the density of 20%
(m/m) aqueous solution of KI is 1.202 g/ml. ( Atomic mass of K = 39 and I=127)
(Ans:1.50, 1.44, 0.0263)
23. What should be the molarity of conc. nitric acid solution if its density is 1.5 g/ml
and concentration is 68% by mass. (Ans: 16.19mol/lit)
24. The solution of glucose in water is labeled as 10% m/m, what would be the
molality and mole fraction of each component in the solution? If the density of
the solution is 1.2 g/ml then what shall be the molarity of the solution?
(m=0.617, M=0.67, X2= 1/91, X1= 90/91)
25. How many ml of 0.1 M HCl are required to react completely with 1 g mixture of
Na2CO3 and NaHCO3 containing equimolar amounts of both? (Ans:159 ml)
26. Define the following terms:
a) Mole fraction b) Molality c) Molarity d) Mass percentage.
27. The density of 3 M solution of NaCl is 1.25 g/ml. Calculate molality of solution?
(Ans: 2.79mol/kg)
28. A solution is obtained by mixing 300 g of 25% solution and 400 g of 40% solution
by mass. Calculate the mass percentage of the resulting solution. (Ans: 33.6%)
29. If the density of some lake water is 1.25 g/ml and contains 92 g of Na + ions per
kg of water, calculate the molality and molarity of Na+ ions in the lake.
(Ans: 4mol/kg, 5 mol/lit)
30. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 ml
of 0.15 M solution in methanol. (Ans: 4.57g)
31. Calculate molarity of a solution which is prepared by adding 20g NaOH in 480g
of water. Density of solution is 1.05g/cm3. Given molar mass of NaOH is
40g/mol. (Ans: 1.05 mol/lit)
32. A sample of drinking water was found to be severely contaminated with
chloroform supposed to be carcinogen. The level of contamination was 15 ppm
by mass.
a.Express this in percent by mass.
b.Determine the m of chloroform in the water sample.(Ans:15 x 10-4 %,1.25 x10-4 m)
9|Page
 33. 20 ml solution is taken out from a flask containing 200 ml of 0.2M
aqueous solution of NaOH. Will it changes the molarity of the two portions?
Explain.
34. Calculate molality of solution containing 2 mol of sodium carbonate in
500ml of solution of density 1.5g/ml. (Ans: 3.71mol/kg)
Part-II
A. Solubility of a gas in a liquid:
All gases are soluble in water to different extent. The solubility of a gas in a liquid
depends on:
(i) Nature of the gas and Solvent:
a) Gases which are easily liquefied are more soluble in common solvent like
water.
b) Gases like H2, He are less soluble in H2O but SO2, CO2 are more soluble
in H2O while O2, N2 are intermediately soluble in water.
c) Gases which form ions in aq. Solution are more soluble in water than
other solvents.
HCl, NH3 are very strongly soluble in water as they react with water
molecules. O2 is less soluble in water but strongly soluble in blood as it
react with Hemoglobin to form oxyhemoglobin.
(ii) Temperature:
a) The solubility of a gas decreases with increase in temperature as the process
is exothermic in nature.
b) Aquatic species are more comfortable in cold water rather than hot water as
solubility of O2 increases with decrease in temperature.
(iii) Pressure:
Henry’s Law:
i) It states that the solubility of a gas in a liquid is directly proportional to partial
pressure of the gas above the surface of the liquid at a given temperature.
ii) It also states that the mole fraction of a gas in solution is directly proportional to
the partial pressure of the gas above the surface of the liquid at a given
temperature.

So,   p ,   = K p
i.e. p =
1
. , or p = KH . 
K
Where KH is called Henry’s law constant

10 | P a g e
Characteristics of KH:
i) It is a function of nature of gas i.e. different gases have different value of K H at
same temperature of same solvent.
ii) When a graph is plotted between  and p then a straight line is obtained having
slope KH.

iii) For a given pressure, higher the value of KH, the lower is the solubility of the gas
in the solution.
Gases: He N2 H2 O2 Ar CO2
KH value at 298K in Kbar : 144 76 69 35 40 1.67

iv) The value of KH increases with increase in temperature because with rise in
temperature the solubility decreases. For O2 the value of KH at 298 K is 35 Kbar
and at 303K it is 47 Kbar respectively
Application of Henry’s law:
1. The bottles of soda water are sealed under high pressure to increases the
solubility of CO2.
2. Scuba divers use diluted He for their respiration instead of air. In high pressure
of deep sea, the gases like N2 and O2 are highly soluble in blood. But the
dissolved gases bubbles in the blood capillaries when the divers come to
atmospheric pressure which is painful and dangerous to life and the disease is
called Bend. To avoid bend air diluted with He (11.7%) is taken by the scuba
divers for respiration because He is very less soluble in blood under high
pressure.

11 | P a g e
 3. At high altitudes people fell weak and don’t think properly and the disease is
called an Anoxia. This is because the PO2 is less at high altitude by which the
conc. of O2 decreases in blood.
B. Solubility of Liquid in Liquid (Vapour Pressure & Raoult’s Law):
The pressure exerted by the vapour molecules on the surface of liquid in
equilibrium state at a given temperature is called vapour pressure.
The vapour pressure depends on:
(i) Nature of liquid: The liquid which have weaker intermolecular force have more
vapour pressure.
(ii) Temperature: The vapour pressure of a liquid increase with increase in
temperature.
Raoult’s law for volatile component:
Statement: The partial vapour pressure of a volatile component of the solution is
directly proportional to its mole fraction in the solution.
Mathematically, p1  x1 and p2  x 2

Or p1 = p10 .x1 and p2 = p2 0 x 2

Where p10 and p20 are the vapour pressure of pure component 1 and 2
respectively.
According to Dalton’s law ,
ptotal = p1 + p2

Or p total = p10 x1 + p 2 0 x 2 ,

Or p total = p10 (1 − x 2 ) + p10 x 2

Or ptotal = p10 − p10 x 2 + p20 x 2

Or ptotal = p10 + x 2 ( p20 − p10 )

If y1 and y2 are the mole fraction of the two components in vapour phase then
accordingly to Dalton’s law. p1 = y1 ptotal and p2 = y2 p total
p1 p
So, y1 = and y2 = 2
Ptotal Ptotal

Graphical representation:
When a graph is plotted between v.p and Mole fraction x 2 or x1 then a straight
line is obtained as p10 and p20 are constants at a particular temperature.

12 | P a g e
Observation:
1. Total vapour pressure over the solution is related to the mole fraction of any one
component.

2. The total vapour pressure over the solution is a linear function of the mole
fraction component A or B.
3. The total vapor pressure over the solution may increase or decrease with
increase in mole fraction of a component.
4. Here with increase in the mole fraction of component A, the total vapour
pressure increase while with decrease in the mole fraction of component B the
total vapour pressure decrease. So component A is more volatile than
component B.
5. The composition of the vapour phase in equilibrium with the solution can be
calculated from the partial pressure of the two components.
Note: Raoult’s law is a special case of Henry’s law.
According to Raoult’s law, p = p10 .x (i)
According to Henry’s law, p = K H .x (ii)
By comparing (i) and (ii) we can write the partial pressure of the volatile liquid or
gas is directly proportional to its mole fraction in solution. Here only the proportionality
constant p0 and KH are differ. Thus Roult’s law is a special case of Henry’s law only
when KH becomes equal to p10.
Ideal and Non-ideal solution:
Ideal Solution:
The solutions which obey Raoult’s law over the entire range of conc. are known
as ideal solution i.e. ideal solution obeys the equation ptotal = p10 x1 + p20 x 2

Conditions:
(i) There will be no change in enthalpy when the two components are mixed i.e.
Hmix = 0 .

13 | P a g e
 (ii) There will be no change in volume when the two components are mixed i.e.
Vmix = 0
(iii) The intermolecular interactions between solute and solvent(A-B interaction) is
same with the intermolecular interaction of the pure components (A - A or B – B
interactions).
Eg: (i) C6 H6 + C6 H5 CH3 (ii) C2 H5Cl + C2 H5Br
(iii). n-Hexane and n-Heptane. (iv) Bromobenzene and chlorobenzene
(iv) n-butyl chloride and n-butyl iodide (v)Ethanol and methanol
Non ideal solution: The solution which doesn’t obey Raoult’s law over the entire range
of conc. is called a non-ideal solution.
For non ideal solution, Hmix  0 , Vmix  0 and the A-B interaction is different

from A-A or B-B interaction.

Non ideal solution is of 2 Types like:
(i) Non-ideal solution showing +ve deviation:
a. The solution shows Positive deviation when the vapour pressure of the solution is
higher than that predicted by Raoult’s law
i.e. Here ptotal > p10x1 + p20x2
so, p1 > p10 . x1 and p2 > p20 . x2
b. Here the interaction between the components (A-B interaction) is less than that of
pure components (A-A or B-B interaction).
c. Here H mix  0 , and Vmix  0 .

E.g: (i) C2 H5OH + CH3COCH3 (ii) CS2 + CH3COCH3 (iii) Ethanol and water
(iv) C6 H6 + CH3COCH3 (v)CCl4 and Toluene (vi)CCl4 and CHCl3

(vii) CHCl3 and ethanol (viii)CCl4 and Methanol (ix)Methanol and water
(x)Ethanol and benzene

14 | P a g e
c.When acetone is mixed with ethanol the hydrogen bonds present between ethanol
molecules break by which A-B interaction is weaker and it exhibits +ve deviation.
(ii) Non-ideal solution showing –ve deviation:
a. Here the v.p. of solution are lower than that predicted by Raoult’s law.
i.e. Here ptotal < p10x1 + p20x2
p1 < p10 . x1 and p2 < p20 . x2
b. In this non-ideal solution the interaction between the components( A- B
interaction) are more than that of pure component (A – A or B – B interaction)
c. Here H mix = − ve, and V = −ve

Ex:
(i)Phenol and aniline (ii) CHCl3 + COCH3 (iii). HNO3 + H2O
(iv) Acetone + Aniline (v)Acetic acid + Pyridine (vi) HCl + H2O
(vii)Acetic acid and methanol (viii)CHCl3 and C6H6 (ix)H2SO4 +H2O
(x) Acetic acid +H2O
The mixture of phenol and aniline shows –ve deviation from Raoult’s law as
the intermolecular hydrogen bonding between phenolic proton and lone pair
on N-atom of aniline is stronger than the respective H-bonding between
similar molecules.
d. The solution of chloroform and acetone shows –ve deviation from Raoult’s
law due to formation of intermolecular hydrogen bonding between the two
molecules.

Azeotropes / Azeotropic Mixtures:

a. The binary mixture having a constant boiling point like pure solvent is called
azeotrope. This is also called constant boiling mixture.
b. Azeotropes have same compositions in liquid and vapour phase and hence
can’t be separated by fractional distillation.
15 | P a g e
It is of 2 types like

(i) Minimum Boiling Azeotropes:

The solutions which show large +ve deviation from Raoult’s law at a specific
composition form minimum boiling azeotropes at a specific composition.
Here the b.p. of azeotrope is less than the b.p. of either of the pure component.
E.g: 95% C2H5OH + H2O . Pure water has B.P. 373K and pure ethanol has B.P.
351.3 K. But the azeotrope has B.P. of 351.15K.
(ii) Maximum boiling azeotrope:
The solutions which show large –ve deviation from Raoult’s law at a specific
composition form maximum boiling azeotrope at a particular composition. Here the b.p.
of azeotrope is higher than the b.p. of either of the pure component.
E.g: 68% HNO3 + H2O . Nitric acid has b.p. of 359 K but this azeotrope has b.p. of
393.5 K
Note: During the preparation of Ideal or non ideal solution the entropy increases
and hence S = +ve
So G = H - T S . For ideal solution H =0, so G =0 – T(+ve) = -ve
For non ideal solution showing –ve deviation, H = -ve, so G = -ve – T(+ve) = -ve
For non ideal solution showing +ve deviation, H = +ve, so G = +ve – T(+ve) = -ve, as
S factor has higher value than H
C. Solubility of a solid in liquid:
The solubility of a solid in a liquid is defined as the maximum amount of the solid
dissolved in a given amount of the solvent to form a saturated solution at a particular
temperature.
Dissolution is the process of increasing the conc. of solution by adding the solute
in the solvent continuously.
Crystallization is the process of separation of solute out of solution due to
collision of some solute particles on the surface of solid solute particles in saturation
solution. A dynamic equilibrium exists between dissolution and crystallization.
⎯⎯
→Solution
Solute + Solvent ⎯
⎯
The solubility of a solid in liquid depends on.
(i) Nature of solute and solvent.
(ii) Temperature
(i) Nature of Solute and Solvent: Like dissolves like i.e. polar solute dissolve in polar
solvent and non polar solute dissolve in non polar solvent.

16 | P a g e
Eg: NaCl is soluble in H2O but insoluble in benzene..
Naphthelene is soluble in C6H6 but insoluble in H2O.
(ii) Temperature: The solubility increases with rise in temp if the dissolution process
is endothermic.
Eg: NaCl, KCl, NaNO3, KNO3
The solubility decreases with rise in temperature if the dissolution process is
exothermic.
Eg: Na2CO3 .H2O, Li2CO3, CeSO4 etc.
The vapour pressure of a solution is always less than that of pure solvent because for a
solution some solute particles are present at the surface of the solution which make
hindrance in the vaporization of the solvent molecules.
Raoult’s law for non-volatile solute:
Statement: The vapor pressure of a solution containing non-volatile solute is directly
proportional to the mole fraction of the solvent at a given temperature,
i.e. ps  x1

or ps = p 0 .x1

Where p0 = the v.p of pure solvent which is constant.

Ps= the vapour pressure of solution
X1= the mole fraction of solvent
PRACTICE QUESTIONS-2:

35. A solution of acetone in ethanol

a. Shows a positive deviation from raoult’s law
b. Behaves like a nearly ideal solution
c. Obey’s Raoult’s law
d. Shows a negative deviation from Raoult’s law.
36. An azeotropic mixture of two liquids has a boiling point higher than either of the
two liquids when it is:
a. Shows large negative deviation from Raoult’s law
b. Shows no deviation from Raoult’s law
c. Shows large positive deviation from Raoult’s law
d. Obey’s Raoult’s law
37. Which of the following pairs will not form an ideal solution? (JEE MAIN-2018)
a. Benzene and Toluene b.Nitric acid and water
c.Hexane and heptanes d. Ethyl chloride and ethyl bromide
38. Which of the following doesn’t show positive deviation from Raoult’s law?
a. Benzene- Chloroform b. Benzene – acetone
17 | P a g e
 c.. Benzene-ethanol d. Benzene-carbon tetra chloride
39. The vapour pressure of two pure liquids (A) and (B) are 100 and 80 torr
respectively. The total pressure of the solution obtained by mixing 2 mol of A and
3 mol of B would be:
a. 20 torr b. 36 torr c. 88 torr d. 180 torr

40. Assertion(A): When methyl alcohol is added to water, boiling point of water
decreases.
Reason(R): When a volatile solute is added to a volatile solvent, elevation in
boiling point is observed.

41. Assertion(A): He is used to dilute oxygen in diving apparatus.

Reason(R): He has high solubility in O2. (NEET-2023)
42. Assertion(A): Azeotropic mixtures are formed only by non-ideal solutions and
they may have boiling points either greater than or less than both the
components.
Reason(R): The composition of the vapour phase is same as that of liquid phase
of the azeotropic mixtures.
43. Assertion(A): Relative lowering in vapour pressure is a colligative property.
Reason(R): Relative lowering in vapour pressure is directly proportional to mole
fraction of solvent.
44. Assertion(A): The solutions which show a large positive deviation from Raoult’s
law form minimum boiling azeotrope at a specific composition.
Reason(R): Azeotropes are binary mixtures and have constant boiling point.
45. An azeotropic solution of two liquids has boiling point lower than either of them
when it:(CBSE-2023)
a)Is saturated
b)shows positive deviation from Raoult’s law
c)shows negative deviation from raoult’s law
d)shows no deviation from Raoult’s law
46. The relative lowering of vapour pressure of an aqueous solution containing non-
volatile solute is 0.0225. The mole fraction of the non-volatile solute is:
a)0.80 b)0.725 c)0.15 d)0.0255
47. Liquids A and B form ideal solution over the entire range of composition. At
temperature T, equimolar binary solution of liquids A and B has vapour pressure
45 Torr. At the same temperature, a new solution of a and B having mole
fractions XA and XB, respectively, has vapour pressure of 22.5 Torr. The value of
XA/XB in the new solution is_________.
(given that the vapour pressure of pure liquid A is 20 Torr at temperature T)
(JEE ADV-2018)
48. Liquids A and B form ideal solution for all compositions of A and B at 250C. two
such solutions with 0.25 and 0.50 mole fractions of A have total vapour pressure
of 0.3 nd 0.4 bar, respectively. What is the vapour pressure of pure liquid B in
bar?(JEE adv-2020)

18 | P a g e
 49. Assertion(A):  mix H and mixV are zero for an ideal solution.
Reason(R): The solution which obeys Raoult’s law over the entire range of
concentration is called an ideal solution.
50. Pure ethanol cannot be prepared by fractional distillation of ethanol-water
mixture. Comment.
51. Shweta mixed two liquids A and B of 10 ml each. After mixing, the volume of the
solution was found to be 20.2ml.
(i) Why was there a volume change after mixing the liquids?
(ii) Will there be an increase or decrease of temperature after mixing?
(iii) Give an example for this type of solution. (CBSE-2023)
52. Account the followings:
(i) The vapour pressure of an aqueous solution of glucose lower than that of
water.
(ii) The solubility of NaCl in water increases with increase in temperature.
53. KH values for Ar, CO2, HCHO, and CH4 are 40.39, 1.67, 1.83 x 10-5 and 0.413
respectively. Arrange the gases in the order of their increasing solubility.
54. If two liquids A and B form minimum boiling azeotrope at some specific
composition then:
(A) A-B interactions are stronger than those between A-A or B-B
(B) Vapour pressure of solution increases because more number of molecules of
liquids A and B can escape from solution.
(C) Vapour pressure of solution decreases because less number of molecules of
only one of the liquid escape from the solution.
(D) A-B interactions are weaker than those between A=A or B-B.
55. The correct option for the value of vapour pressure of a solution at 45 0C with
benzene to octane in molar ratio 3:2 is:
[At 450C vapour pressure of benzene is 280mm Hg and that of octane is 420 mm
Hg. Assume ideal gas]
(a)160 mm (b)168mm (c)336 mm (d)350mm (NEET-2021)
Problems solved:
56. 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 0.2 m, calculate Henry’s law constant.
Ans: Given molality = 0.2, i.e. 0.2 mol of solute is present in 1 kg of solvent.
n2 = 0.2, W1 = 1000 g, M1 = 18
So, n1 = W1/M1 = 1000/18 = 55.55
n2 0.2 0.2
Mole fraction of H 2 S in solution i. e.  2 = = = = 0.0035
n1 + n2 0.2 + 55.55 55.75
At STP, partial pressure is 1 atm
So, p = K H . 

19 | P a g e
 p 1
 KH = = = 285.71 atm
 0.0035

57. 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: Given p10 = 450 mm and p20 = 700 mm, Ptotal = 600 mm
ptotal = p10 x1 + p20 x 2

(
= p10 + x 2 p20 − p10 )
 600 = 450 + x2(700 – 450)
 x2 = 150/250 = 3/5 = 0.6
So, x1 = 1- 0.6 = 0.4
p1 p 0 x 450 x 0.4 180
Mole fraction in vapour phase, y1 = = 1 1= = = 0.3
Ptotal Ptotal 600 600
So, y2 = 1 - 0.3 = 0.7

58. Benzene and toluene form ideal solution over the entire range of composition.
The vapour pressure of pure benzene and toluene at 300 K are 50 mm Hg and
32 mm Hg respectively. Calculate the mole fraction of benzene in vapour phase
if 80 g of benzene is mixed with 100 gm of toluene.
Ans: Given p10 = 50 mm and p20 = 32 mm, W1 = 80 g and W2 = 100 g
M1 ( C6H6 ) = 78, M2(C6H5CH3) = 92
So, n2 = W2/M2 = 100/92 =1.08 and n1 = W1/M1 = 80/78 =1.02
n1 1.02 1.02
So, Mole fraction of benzenein solution i. e. 1 = = = = 0.485
n1 + n2 1.08 + 1.02 2.1

So,  2 = 1- 0.485 = 0.515

So, according to Raoult’s law: ptotal = p10 x1 + p20 x 2

Or, (
= p10 + x 2 p20 − p10 )
= 50 + 0.515(32 – 50)
= 50 + (0.515 x -18) = 50 – 9.27 = 40.73
p1
So, Mole fraction of benzene in vapour phasei. e. y1 = =
Ptotal

p10 x1 50 x 0.485 24.25

= = = 0.595
Ptotal 40.73 40.73

59. Calculate the composition of O2 and N2 in water if their Henry’s law constants at
298 K are 3. 30 x 10 7 mm and 6.51 x 107 mm respectively and total pressure is

20 | P a g e
 10 atm. The composition of O2 and N2 in air at 298 K is 20% and 79%
respectively.
Ans: At constant T and P, V  n
V1 n1 n1 20
So, =  =
V2 n 2 n 2 79
y1 n1 20
So, = =
y2 n2 79
Again Partial pressure = mole fraction x Total pressure
So, The ratio of mole fraction in gaseous phase is same with ratio of
partial pressures if total pressure remains constant.
y1 p1 20
So, = =
y2 p2 79

According to Henry’s law, p = K H . 

p1 K H 1.1 20
So, = =
p2 K H 2 . 2 79

1 p1 K H 2 20 6.51107
 =  = x =130.2/260.7=0.49
 2 p2 K H 1 79 3.30 107
 1 = 0.492

1
As 1 + 2 =1 , So  2 + 0.49 2 =1   2 = = 0.67 and 1 = 0.33
1.49

ASSIGNMENT-2

60. A and B liquids on mixing produced a warm solution. Which type of

deviation is there and why?
61. State Henry’s law about solubility of a gas in a liquid? What is the
significance of Henry’s law constant(KH)?
62. Define azeotropes with examples? What are maximum and minimum
boiling azeotropes? Give suitable example in each case.
63. Vapour pressure of Chloroform(CHCl3) and dichloromethane(CH2Cl2) at
298 K are 200 mm Hg and 415 mm Hg respectively. Calculate the vapour
pressure of solution prepared by mixing 25.5 g of CHCl3 and 40 g of CH2Cl2 at
298 K and mole fraction of each component in vapour phase.
(Ans: 266.65mm, 0.51, 0.49)
64. Accounts for the followings:
a. Aquatic species more comfortable in cold water in comparison to warm water.
b. The mixture of acetone and chloroform form a solution with negative
deviation.
c.. Soda water bottle kept at room temperature fizzes on opening.

21 | P a g e
 d. He is taken by Scuba divers along with air for respiration
e. At high altitudes, the conc. of O2 in blood decreases
f. Addition of methyl alcohol to water decreases the boiling point.
g. Addition of NaCl to water increases the boiling point.
65. State Raoult’s law for i) volatile solute ii) Non volatile solute
66. What is meant by positive and negative deviation from Raoult’s law and
how the sign of H mix related to positive and negative deviations from Raoult’s
law?
67. Heptane(C7H16) and octane(C8H18) form an ideal solution. At 373 K, the
vapour pressure 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 g of heptanes
and 35 g of octane? (Ans: 73.66KPa)
68. The partial pressure of ethane over a solution containing 6.56 x 10 -3 g
of ethane is 1 bar. If the solution contains 5.00 x 10 -2 g of ethane, then what shall
be the partial pressure of the gas. (Ans: 7.62bar)
69. On mixing liquid X and Y, the volume of the resulting solution
increases. What type of deviation from Raoult’s law is shown by the resulting
solution? What change in temperature would be observed after mixing liquids X
and Y?
70. 100 gm of liquid A having molar mass 140 g/mol was dissolved in 1000
g of liquid B having molar mass 180 g/mol. 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: 272.7torr, 30.92 torr)
71. The vapour pressure of ethanol and methanol are 42.0 mm and 88.5mm Hg
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
phase is:
a. 0.467 b. 0.502 c. 0.513 d. 0.556
72. The vapour pressure of a pure liquid solvent(X) is decreased to 0.60 atm from
0.80 atm on addition of a non volatile substance(Y). the mole fraction of (Y) in
the solution is:
a. 0.20 b. 0.25 c. 0.5 d. 0.75
73. At the same temperature, CO2 gas is more soluble in water than O2 gas. Which
one of them will have higher value of KH and why?
74. The vapour pressure of A and B at 250C are 75 mm Hg and 25 mm Hg,
respectively. If A and B are mixed such that the mole fraction of A in the mixture
is 0.4, then calculate the mole fraction of B in vapour phase. (Ans: 0.37)
75. Explain the following phenomena with the help of Henry’s law.
(i) Painful condition known as bends.
(ii) Feeling of weakness and discomfort in breathing at high altitude.
76. What is significance of Henry’s law constant?

22 | P a g e
 Part-III
Colligative properties:
The Properties of the solution which only depends on the no of particles of the
solute dissolved in a specified volume of solvent i.e. conc. of solution, but not on the
nature of solute are called colligative properties.
The colligative properties only depends on conc. of solution.
The colligative properties are used to determine the molecular mass of solute like
proteins, polymers etc.
Colligative properties are observed when
I) A non-volatile solid is dissolved in a volatile liquid
II) A non-volatile liquid is dissolved in another volatile liquid.
The colligative properties are
(i) Relative lowering in vapour pressure
(ii) Elevation in boiling point.
(iii) Depression in freezing point.
(iv) Osmotic pressure.
A. Relative lowering in vapour pressure:
According to Raoult’s law of non volatile solute:
ps = p 0 .x1
Again x1 = 1-x2
So ps = p 0 .(1 − x 2 )

Or, ps = p 0 − p0 .x 2

Or, ps = p 0 − p0 .x 2

p 0 − ps
Or, = x2
p0

Where p 0 − ps = Lowering in vapour pressure

p 0 − ps
= Relative lowering in vapour pressure
p0
n2
Again x2=
n1 + n2

p 0 − ps n2
So, =
p 0
n1 + n2

p 0 − ps w2 / M 2
Or, =
p 0
w1 / M1 + w2 / M 2
23 | P a g e
For dilute solution, n2<<n1, so n2+n1 = n1
n2
So For dilute solution, x2= ,
n1

p 0 − ps w / M2 p 0 − ps w2 M 1
Or, 0
= 2 Or, =
p w1 / M 1 p0 w1M 2

Where w2 = Mass or weight of solute, w1=Mass or weight of solvent

M1= Molecular mass of solvent, M2= Molecular mass of solute
The above equation is used to calculate the molecular mass of solute.
B.Elevation in boiling point:
The temperature at which the vapour pressure of the liquid is equal to the atmospheric
pressure is called boiling point. The boiling point of solution is always higher than the
boiling point of pure solvent. This is because for solution the vapour pressure is less
and in order to boil the solution its vapour pressure must be increased up to
atmospheric pressure by increasing the temp. above the boiling temp. of pure solvent.
The increase in boiling point is denoted by ( Tb ),

Tb =Tbs-Tb0

Where, Tbs = Boiling point of solution, Tb0= Boiling point of pure solvent

For dilute solutions, the curves can be taken as straight lines near the boiling point.
Elevation in boiling point is a colligative properties and it is directly proportional to
molality of solution.
Tb  m

Or, Tb = K b m

24 | P a g e
Where Kb is molal elevation constant or Ebullioscopic constant. It is defined as the
elevation in boiling point in one molal solution.(When m=1, then Kb = Tb )

w2 1000
Tb = Kb .
w1 M 2

Where m= Molality of the solution

Note:
i). The molal elevation constant is characteristic of a particular solvent and can
be calculated by using the relation:
R. M 1.Tb2
Kb=
1000. H vap

Where R=Gas constant, M1= Molecular mass of solvent

Tb=Boiling point of pure solvent. H vap = Enthalpy of vaporization.

ii). The unit of Kb is K.kg.mol-1

Tb
Kb=
M
For, H2O; Kb= 0.52 K.kg. mol-1, Benzene, Kb=2.53, CCl4, Kb=5.03
iii). For a particular conc. (Molality) of solution, the elevation in boiling point
increases with increase in value of Kb.
v) The value of Kb is independent of conc. of solution.
C. Depression in Freezing point:
i). Freezing point of a liquid is defined as the temperature at which the vapour pressure
of the liquid phase is equal to that of solid phase, both liquid and solid co-exist and an
equilibrium exist between them.
ii). When a non volatile solid is added to the solvent then the escaping tendency of the
liquid into solid decreases but the reverse process is not affected. The escaping
tendency of the liquid into the solid increases by decreasing the temperature. So the
freezing point of the solution is always less than pure solvent.
iii). The decrease in freezing point ( T f ) is given as,

T f =Tf0-Tfs

Where Tf0= Freezing point of a pure solvent, Tfs=Freezing point of solution

The graph between vapour pressure and temperature of pure solvent and solution is
given as:

25 | P a g e
For very dilute solutions, the curves are almost straight lines.
Depression in freezing point is a colligative properties as it is directly proportional to
conc. of solution i.e. T f  m

Or, T f = K f m

Where Kf is molal depression constant or cryoscopic constant.

It is defined as the depression in freezing point in one molal solution i.e. when
m=1molal, then K f = T f .

w2 1000
Or, T f = K f .
w1 M 2

Note:
i) The molal depression constant is characteristic of a particular solvent and can be
calculated by using the relation:
R. M1.T f2
Kf= , where Tf=Freezing point of pure solvent.
1000. H fus

H fus = Enthalpy of vaporization.

T f
ii) The unit of Kf is K.kg.mol-1. Because Kf=
m
For, H2O; Kf= 1.86 K.kg. mol-1, For Benzene, Kf=5.12, For CCl4, Kf=31.8,
camphor=39.70 K.kg.mol-1
iii) For a particular conc. (Molality) of solution, the depression in freezing point
increases with increase in value of Kf.
iv) The value of Kf is independent of conc. of solution.
v) Camphor is used to determine the molecular mass of solute as for it, the value of
Kf is highest.

26 | P a g e
 Application of depression in freezing point:
i) For preparation of antifreeze solution: Ethylene glycol is added as
antifreeze solute with water in sub-zero weather condition as it decreases
the freezing point of water.
ii) In melting of ice on the roads: In hills or in winter where it snows heavily,
NaCl or CaCl2 is scattered on the roads to melt the ice. This is because
the mixture of salt and ice has very low freezing point by which the
mixture doesn’t freeze and ice keeps on melting.
D. Osmotic Pressure:
(i) The membrane which allows the solvent molecules to pass through but not the
solute particles is called semi permeable membrane(SPM).
E.g: egg bladder, parchment paper.
Freshly precipitated inorganic compounds like copper ferrocyanide, silicates of
iron, cobalt, nickel etc.
(ii) The spontaneous flow of solvent molecules from the solvent to the solution or
from a lower concentrated solution to a higher concentrated solution through a semi
permeable membrane is called osmosis.
(iii) When the membrane permits the solvent molecules to come out through the
membrane, it is called exomosis and when the membrane permits the solvent
molecules to enter inside is called endosmosis.
(iv) The minimum external pressure applied on the solution to prevent the osmosis
i.e. prevent the flow of solvent molecules from pure solvent into solution through SPM is
called osmotic pressure.
(vi) When a external pressure higher than the osmotic pressure is applied on the
solution, the solvent will flow from the solution into the pure solvent through the semi-
permeable membrane. This process is called reverse osmosis.
The reverse osmosis is applied in the desalination of sea water i.e removal of
salts from sea water.
(vii) The Solutions which have same osmotic pressure at the same temp. are called
isotonic solutions. For isotonic solution, solute and solvent may or may not be same.
The solution which has lower osmotic pressure than another solution is called
hypotonic solution.
The solution which has higher osmotic pressure than another solution is called
hypertonic solution.

27 | P a g e
(viii) Expression for Osmotic Pressure:
Osmotic pressure of a solution is directly proportional to the molar concentration
of th solution and its temperature.
C and T
Or   CT
Or  = R.CT
Or  = CRT
Where R is called solution constant which has same value with gas constant
If a graph is plotted between  vs C then a straight line is obtained having slope RT

If two solutions have osmotic pressures 1 and 2 and conc. C1 and C2 at same temp.

then

1 C1
=
2 C 2

n
Again, C = , n = No of moles of solute, V = Volume of solution in lit.
V
n
So = RT
V
Or V = nRT
w2
But n=
M2

w2 W RT
So V = RT Or,  = 2
M2 M2V

W2 RT
Or M2 = , R = 0.0821 lit. atm. K-1 mol-1 or 1/12 lit. bar K-1.mol-1
V
Where W2 = weight of solute ,M2 = molecular mass of solute.
The above equation is used to calculate the molecular mass of solute if other
values are given.

28 | P a g e
(ix) When a number of solutes are present in the solution and 1 , 2 , 3 are their

individual osmotic pressure then.

Total osmotic pressure 1 + 2 + 3 .

(x) For isotonic solutions, 1 =  2 and T1=T2 So, C1 = C2

Advantages of osmotic pressure than other colligative properties:

Osmotic pressure is preferred than other colligative properties to determine the
molecular mass of solutes like proteins and polymers because:
i) It is measured as room temperature
ii) It has higher value than other colligative properties
iii) It is related to molarity.
Application of Osmosis:
1. Plants absorb water from the soil through their roots due to osmosis.
2. A raw mango placed in concentrated salt solution shrivel into pickle due to loss of
water because of osmosis.
3. A limp carrot becomes firm again when placed in fresh water because water move
into it through osmosis.
4. In RBC the conc. of NaCl solution is 0.9% mass to volume, when the RBC is placed
in a solution with conc. less than 0.9% or in normal water, then they will swell
and burst due to entering of water molecules into the cell(Endosmosis occurs)
through the cell wall. But when RBC is places in a solution of conc. more than
0.9% then it shrink due to exosmosis i.e. flow of water from rbc into the solution.
5. People taking a lot of salt swells and the disease is called edema. This is due to
retention of water in the tissue cells due to osmosis.
6. The preservation of meat by salt or fruits by sugar is because of osmosis. The
bacteria in salted water lose water, shrivel and die.
PRACTICE QUESTIONS-III:

77. A solution of 1 Molal concentration of a solute will have maximum boiling point
elevation when the solvent is:
a. Ethyl alcohol b. acetone c. Benzene d. Chloroform
78. 5 % solution of sucrose is isotonic with 1% solution of a compound A then the
molecular weight of compound A is :
a. 32.4 b. 68.4 c. 121.6 d. 34.2
79. Pure water can be obtained from sea water by:
Centrifugation b. Plasmolysis c. Reverse osmosis d. Sedimentation

80. Osmotic pressure of a solution containing 0.6 g urea and 3.42 g sugar in 100 ml
at 270C
29 | P a g e
 a. 492 atm b. 4.92 atm c. 49.2 atm d. 28.1 atm
81. The average osmotic pressure of human blood is 7.8 bar at 37 0C. what is the
concentration of an aqueous NaCl solution that could be used in the blood
stream:
a. 0.16 mol/l b. 0.32 mol/l c. 0.60 mol/l d. 0.45 mol/l
82. Assertion(A): When NaCl is added to water, a depression in freezing point is
observed.
Reason(R): The lowering of vapour pressure of solution causes depression in
freezing point.
83. Assertion(A): Addition of non-volatile solute to a volatile solvent increases the
boiling point.
Reason(R):Addition of non-volatile solute to a volatile solvent results in lowering
of vapour pressure.
84. Assertion(A): Higher the molal depression of the solvent used, higher the
freezing point of the solution.
Reason(R):Depression in freezing point depend on the nature of the solvent.
85. Assertion(A): Elevation in boiling point is a colligative property.
Reason(R): Elevation in boiling point depends on molality and not upon the
nature of solute.
86. What happens when red blood cells are kept in 0.5%( mass/vol) NaCl solution?
Justify your answer.
87. On mixing 30 ml of phenol with 20 ml of aniline, the total volume of solution is:
(a) Equal to 10ml (b)less than 50ml (c)greater than 50ml (d)equal to 50ml
88. Assertion(A): Cooking time is reduced in pressure cooker.
Reason(R): Boiling point of water inside the pressure cooker is elevated.
89. A solution is prepared by dissolving 5g of a non-volatile solute in 200g of water.
It has a vapour pressure of 31.84 mm Hg at 300K. The molar mass of the solute
is _______.( Vapour pressure of pure water at 300K= 32 mm of Hg)
90. A 1% solution of solute X is isotonic with a 6% solution of sucrose(molar mass=
342g/mol). The molar mass of solute X is ________.
91. When 25.6 g of sulphur as dissolved in 1000g of benzene, the freezing point
lowered by 0.5120C. Calculate the molecular formula of sulphur(Sx)(Kf for
benzene is 5.12 K kg mol-1. Atomic mass of Sulphur =32g mol-1)
92. If molality of a dilute solution is doubled, the value of the molal elevation
constant(Kb) will be:
a)halved b)doubled c)tripled d)unchanged
93. Boiling point of water at 750mm Hg pressure is 99.680C. How much
sucrose(molar mass=342g/mol) is to be added to 500g of water such that it boils
at 1000C? (Kb for water=0.52K. kg mol-1)

30 | P a g e
Problems solved:
94. Vaour pressure of water at 293 K is 17.5 mm. calculate the vapour pressure of
water at 293 k when 25 g of glucose is dissolved in 450 g of water?
Ans: Give W2 = 25 g, M2 = 180 So, n2 = W2/M2 = 25/180 = 0.138 mol
n1 = W1/M1 = 450/18 = 25 mol
p 0 − ps n2 n
So, = = 2
p 0
n1 + n2 n1

Or, 17.5 - ps = 0.138/25 x 17.5

Or, ps = 17.5 – 0.096 = 17.4 mm

95. Calculate the mass of a non volatile solute having molar mass 40 g/mol which
should be dissolve in 114 g octane to reduce its vapour pressure to 80%.?
Ans: Let the v.p. of pure solvent i.e. p0= x , so ps =0.8x
p 0 − ps w2 / M 2
The relative lowering in V.P, =
p 0
w1 / M1 + w2 / M 2

x − 0.8x w2 / 40
Or, =
x 114 /114 + w2 / 40
w2 / 40
Or, 1 – 0.8 = , Or 1 + 40/w2 = 1/0.2 =5
1 + w2 / 40
Or, W2 = 10 g
96. The osmotic pressure of 200 ml of aqueous solution contain 1 gm protein at 27 0
C is 2.020 x 10-1 atm. Calculate the molecular mass of protein.
200 1
Ans: V = 200ml = = = 0.2 lit , W2 = 1 g, T = 270 C = 300K
1000 5
 = 2.0  10−1 atm, R = 0.0821 lit atm k −1mol −1
W2 RT w RT
So = Or, M 2 = 2
M2V V
1 0.0821 300 0.0821 300 2463
= = = = = 615.75 gm / mol
2.0 10−1  0.2 0.2  0.2 4
97. At 300 K, 36 gm of glucose present in a litre has an osmotic pressure of 4.98
bar. If the osmotic pressure of the solution is 1.52 bars at the same temp, What
would be its conc.
1 C1
Ans: At constant temp. =
2 C 2
1 n1 / V1 1 C1
So, = = =
2 C2 2 C 2

31 | P a g e
 36
2 n1 / V1 1.52  (180  1)
 C2 = = = 0.063 mol/L
1 4.98

98. Calculate the boiling point of a solution containing 10 g of glucose in 140 g of

water. Kb of water is 0.52 K.Kg.mol-1
Ans: Given W2 = 10 g, W1 = 140 g, M2( C6H12O6) = 180 g/mol, Kb = 0.52
w2 1000
So, Tb = Kb .
w1 M 2
0.52 x 10 x 1000
= = 0.206
140 180
So, Tb =Tbs-Tb0 = 0.206

Or, Tbs = 0.206 + 373 = 373.206 K

99. Calculate the freezing point of a solution containing 2 g of a urea in 90 g of
water. Kf of water is 1.86 K.Kg.mol-1.
Ans: Given W2 = 2 g, W1 = 90 g, M2( NH2CONH2) = 60 g/mol, Kf = 1.86
w2 1000
So, T f = K f .
w1 M 2

2 1000
Or, T f =1.86  . = 0.68
90 60
Or, Tf0 - Tfs = 0.68
Or, Tfs = 273 - 0.68 = 273.32K

ASSIGNMENT-III

100. The vapour pressure of pure benzene at a certain temp. is 0.850 bar. A
non volatile, non electrolyte solid weighing 0.5 g when added to 39 . 0 g of
benzene, vapour of solution then is 0.845 bar. What is the molar mass of solid
substance? (Ans:170g/mol)
101. 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 waer is then added to
the solution and the new vapour pressure becomes 2.9 KPa. Calculate
i) Molar mass of solute ii)Vapour pressure of water at 298K.
(Ans:34g/mol,3.4KPa)
102. 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 molar mass of solute.
(Ans: 41.34g/mol)
103. The boiling point of benzene is 353.23 K. when 1.80 g of a non volatile
solute was dissolved in 90 g of benzene, the boiling point is raised to 354.11 K.
calculate the molar mass of solute. Kb for benzene is 2.53 K.Kg.mol-1.
(Ans: 57.5g/mol)
104. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate

32 | P a g e
 i) The freezing point depression. ii) The freezing point of the solution.
(Ans:2.25K, 270.75K)
105. 1. 00 g of a non electrolyte solute dissolved in 50 g of benzene lowered
freezing point of benzene by 0.40 K. The freezing point depression constant of
benzene is 5. 12 K. Kg. mol-1. Find the molar mass of solute. (Ans: 256g/mol)
106. Calculate the mass of ascorbic acid (vitamin C, C6H8O6) to be dissolved in
75 g of acetic acid to lower its melting point by 1.5 0C. ( Kf= 3.9 K. Kg. mol-1)
(Ans: 5.07g)
107. A 5 % solution (by mass) of cane sugar in water has freezing point of 271
K. calculate the freezing point of 5% glucose in water if freezing point of pure
water is 273. 15 K. (Ans: 4.08K)
108. Two elements A and B form compounds having formula AB 2 and AB4.
When dissolved in 20 g of benzene, 1 g of AB2 lower the freezing point by 2.3 K
where as 1.0 g of AB4 lowers it by 1.3 K. the molar depression constant for
benzene is 5.1 K. Kg. mol-1. Calculate at. mass of A and B.(Ans: 25.59, 42.64u)
109. Define i) colligative properties ii) Osmosis iii) edema
110. Define i) cryoscopic constant. ii) Ebullioscopic constant iii) osmotic
pressure
111. A solution of glycerol(C3H8O3) in water was prepared by dissolving some
glycerol in 500 g of water. This solution has a boiling point of 100. 42 0C. What
mass of glycerol was dissolved to make this solution. ( Kb for water = 0.512 K.
Kg.mol-1) (Ans: 37.73g)
112. 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 x 10 -3 bar. Calculate the molar mass of the protein. Given R= 0.083 lit. bar
K-1. Mol-1) (Ans: 20.34 x 103 g/mol)
113. Calculate the osmotic pressure in pascals exerted by a solution prepared
by dissolving 1.0 g of polymer of molar mass 185,000 in 950 ml of water at
370C.(Given R= 0.0821 lit atm K-1. mol-1) (Ans: 30.96 Pa)
114. Define i) reverse osmosis ii) Isotonic solution.
115. What is the advantage of using osmotic pressure as compared to other
colligative properties for the determination of molar mass of solute like polymers
in solution?
116. How does sprinkling of salt help in clearing the snow covered roads in
hilly areas? Explain the phenomenon involved in the process.
117. A solution prepared by dissolving 8.95 mg of a gene fragment in 35 ml of
water has an osmotic pressure of 0.335 torr at 250C. Assuming the gene
fragment is non electrolyte, determine its molar mass.
(Given R=0.0821lit atm K-1. mol-1, 1 atm=760 torr) (Ans: 18.67g/mol)
118. How can the direction of osmosis be reversed? Write one use of reverse
osmosis.
119. Why is camphor preferred in the determination of H f ?

120. What happens when blood cells are placed in pure water?

33 | P a g e
 121. How does the size of blood cells change when placed in an aqueous
solution containing more than 0.9% (mass/volume) sodium chloride.
122. A solution containing 2 g of glucose in 100 g of water is prepared at 303K.
if the vapour pressure of pure water at 303K is 32.8mm Hg, what would be the
vapour pressure of the solution. (Ans: 32.814 mm
123. A solution containing 60g of a non-volatile solute in 250g of water freezes
at 270.67K. calculate the molar mass of solute.(Kf of water= 1.86K.kg mol-1)
(Ans: 191.58 g/mol)
124. Account the followings:
(i) When kept in water, raisin swells in size.
(ii) Salt is used to preservation of meat.
Part-IV: Abnormal Molecular Mass and Van’t Hoff Factor:
1. When the molecular mass of a substance determined from the colligative
properties are different than the theoretically calculated or normal value, then the
substance shows abnormal molecular mass.
2. Abnormal molecular mass observed:
(a) When solution is non-ideal i.e. concentric.
(b) When the solute undergoes dissociation in the solution.
(c) When the solute undergoes association in the solution.
3. In higher conc., the solute molecules are so close to each other that there exists
intermolecular force of attraction which brings deviation from ideal behavior.
4. When the solute undergoes dissociation in the solution then no of moles
particles in the solution are more, so the colligative properties are also more and the
molecular mass is less because molecular mass is inversely proportional in colligative
property.
E.g: NaCl, KCl, acetic acid which undergo dissociation in water.
5. When there is association occurs between the molecules then no of moles of
particles in the solution decreases which decrease the colligative properties and hence
increase the molecular mass.
E.g: Acetic acid, benzoic acid in benzene, undergoes dimerisation

(DIMER)
6. Van’t Hoff factor (i) measures the extent of association or dissociation, which is
defined as the ratio of observed or abnormal colligative property to the normal or
calculated value of colligative property.
34 | P a g e
 observed or Abnormal colligative property
i=
Calcuated or normal colligative property
1
But Colligative property 
Molecular mass
Calculateed or normal molecular mass M C
So i= =
Observed or Abnormal molecular mass M O
Total no of moles of particles after association or dissociation
Or i=
No of moles of particles before association or dissociation
7. For dissociation, i > 1
For association, i < 1
For complete or 100% dissociation of a solute, i = n
n = No of ions produced from one molecule of the electrolyte.
Ex: For NaCl, i = 2, For Na2SO4, i = 3, For AlCl3, i = 4
1
For complete or 100% association, i= ,
n
n = No of molecules associated to form one molecule
1 1
. Ex: For 100% dimerisation, i = , for tetramerisation i =
2 4
8. Van’t Hoff factor modifies the expression for colligative properties which are.
P o − Ps
(a) = i.x 2
Po
(b) Tb = i K b .m
(c) Tf = iK f .m
(d)  = i CRT
9. For Weak electrolytes the value of Van’t hoff factor is obtained from the degree of
dissociation or association
Degree of dissociation(  ):
It is defined as the fraction of the total molecules that undergoes dissociation.
no of moles of solute dissociated
i.e. =
Total no of moles taken
Consider an electrolyte A which on dissociation gives n ions, n= n1 + n2 + …
A  n1B + n 2C + .....
Initially 1mol 0
At equilibrium, (1 − ) mol n mol

35 | P a g e
 Total no of moles of particles after dissociation 1 −  + n
So, i = =
No of moles of particles before association 1

 i = 1 +  ( n − 1)

i −1
 = , n = no of ions obtained from one molecule of the electrolyte
n −1
Degree of association(  ): It is defined as fraction of total molecules which exist in the
form of associated molecules.
No of moles associated
=
Total no of moles taken
Consider an electrolyte where n no of molecules undergo association to form one
molecule.

nA ⎯⎯
→ [ − A −]
⎯
⎯ n

Initially, 1mol 0
At equ. (1 − ) mol 
mol
n
Total no of moles of particles after association
So, i =
No of moles of particles before association

1−  +
n  1
Or, i = Or,   1 −  = i - 1
1  n

i −1
 = , where n is the no of molecules associated to form one molecule
1
n − 1

C 2
Note: The Dissociation Constant, Ka =
1− 
Where c = conc. of solution ,  =Degree of dissociation

PRACTICE QUESTIONS-IV:

125. Which of the following salt has same value of Van’t hoff factor as that of
K3[Fe(CN)6]
a. Al2(SO4)3 b. NaCl c. Al(NO3)3 d. Na2SO4 (JEE main-2021)
126. Van’t Hoff factor for acetic acid in aqueous medium at infinite dilution is
a. 1/2 b. 2 c. 1 d. 3 (JEE main-2022)
127. Boiling point of 0.01m AB2 which is 10 % dissociated an aqueous medium
as A2+ and B-( Kb for water is 0.52)
a. 273.006 K b. 373.006 K c. 0.006 K d. 272.006 K

36 | P a g e
 128. If any solute A dimerises in water at 1 atm pressure and the boiling point
of this solution is 100.520C. If 2 moles of A is added to 1 kg of water and Kb for
water is 0.52 0C/molal, calculate the % association of A
a. 50% b. 30% c. 25 % d. 100% (JEE main-2018)
129. Substance A tetramerises in water to the extent of 80%. A solution of 2.5
g of A in 100 g of water lowers the F.P. by 0.30C. the molar mass of A is:
a. 122 b. 31 c. 244 d. 62
130. The freezing point of one molal KCl solution, assuming KCl to be
completely dissociated in water, is ( Kf of water= 1.86K.Kg mol-1)
(A)-3.720C (B)+3.720C (C)-1.860C (D)+2.720C
131. Which of the following aqueous solutions will have the highest boiling
point?
a)1%KCl b)1% glucose c)1% urea d)1%CaCl2
132. When 19.5g of F-CH2-COOH(Molar mass=78g/mol), is dissolved in 500g
of water, the depression in freezing point is observed to be 10C. The degree of
issociation of F-CH2-COOH is ________. (CBSE-2023)
133. 0.3 g of acetic acid(Molar mass 60g/mol) dissolved in 30g of benzene
shows a depression in freezing point equal to 0.450C. calculate the percentage
association of acid if it forms dimer in the solution.(Kf for benzene = 5.12 )

134. We have three aqueous solutions of NaCl labeled as A, B and C with

concentrations of 0.1M, 0.01M and 0.0001M repectively. The value of van’t Hoff
factor for these solutions will be in the order _________.
135. The values of van’t Hoff factors for NaCl, CaCl2 and K2SO4, respectively
are_____________.
136. Which of the following aqueous solutions should have the highest B.P:
(A) 1.0MNaOH (B)1.0M Na2SO4 (C)1.0MNH4NO3 (D)!.0MKNO3
137. Decreasing order of osmotic pressure for 0.01M aqueous solutions of
barium chloride, potassium chloride, sucrose and acetic acid is __________.
138. In comparision to a 0.01M solution of glucose, the depression in F.P. of a
0.01M MgCl2 is:
(A) The same (B)about twice (C)about three times (D)about six times
139. Which of the following aqueous solutions will have the highest F.P?
a)1.0MKCl b)1.0M Na2SO4 c)1.0M Glucose d.1.0M AlCl3
Problems solved:

140. Determine the osmotic pressure of a solution prepared by dissolving 25

mg of K2SO4 in 2 lit of water at 25 0C, assuming that it is completely dissociated.
(R= 0. 0821 L atm k-1mol-1)
Ans: Given W2 = 25 mg = 25 x 10 -3 g, V = 2 L , T = 298 K , R = 0. 0821 L atm k-
1mol-1

K2SO4 ⎯⎯
→ 2 K+ + SO42-
As K2SO4 is completely dissociated, so i = n = 3
The osmotic pressure,  = i CRT ,

37 | P a g e
 W2 RT
Or,  = i.
M2V
3 25  10−3  0.0821 298
Or,  = = 52728 x 10-7 atm
174  2
141. Calculate the Boiling point of a solution containing 4 g of CaCl2(Molar
mass 111) in 90 g of water if CaCl2 is 80% dissociated. Kb of water is 0.52
K.Kg.mol-1
Ans: Given degree of dissociation,  = 80% = 0.8
CaCl2 ⎯⎯
→ Ca2+ + 2 Cl-
Here n = 3
i −1
So For dissociation,  =
n −1
i −1
Or, 0.8 = Or, i = 1 + 1.6 = 2.6
3 −1
The elevation in boiling point, Tb = i K b .m
w2 1000
Or, Tb = i.K b .
w1 M 2
2.6 1.86  4  1000
Or, Tbs-Tb0 = = 1.93
90  111
Or, Tbs = 373 + 1.93 = 374.93 K
142. Calculate the % association of benzoic acid(C6H5COOH) if 2g of it is dissolved
in 25 g of benzene shows a depression in freezing point equal to 1.62 0C. Kf for
benzene is 4.9 k.Kg. mol-1 and benzoic acid form dimer in benzene.

Ans: Given w2 = 2g, w1 = 25 g, Kf = 4.9, T f =1.620C = 1.62 K, M2 = n = 2

The depression in freezing point, Tf = i K f .m

w2 1000
Or, T f = i.K f .
w1 M 2
i 4.9  2 1000
Or, 1.62 =
25 122

1.62  25 122
Or, i = = 0.5041
4.9  2 1000

i −1 0.5041 − 1
So, for association,  = = = 0.9918 = 99.18%
n −1 2 −1
1 1

So degree of association is 99.18%

38 | P a g e
143. Calculate the depression in the freezing point of water when 10 g of
CH3CH2CHClCOOH is added to 250 g of water. Ka = 1.4 x 10 -3, Kf= 1.86 K. Kg.
mol-1.
Ans: CH3CH2CHClCOOH undergoes dissociation in aqueous solution
CH3CH2CHClCOOH ⎯⎯
→ CH3CH2CHClCOO- + H+
So here n=2

w2 1000 10 1000 10000

Concentration (m) = . = . = =0.326 mol/kg
w1 M 2 250 122.5 30625

Given Ka = 1.4 x 10 -3

C 2
 = 1.4 x 10 -3
1− 

 C 2 = 1.4 x 10 -3 (As 1-  =1 because the acid is weak)

1.4 x 10−3
 = 2
=4.2 x 10-4  = 2.04 x 10 -2
0.326

i −1 i −1
For dissociation,  = Or, 0.0204 = , i = 1.0204
n −1 2 −1

So depression in freezing point, Tf = i K f .m

=1.0204 1.86  0.326 = 0.618 K

ASSIGNMENT-IV:

144. Define the term i) Van’t Hoff factor ii) Abnormal molecular mass.
145. 0.6 ml of acetic acid having density 1.06 g/ml, is dissolved in 1 lit of water.
The depression in freezing point observed for this strength of acid was 0.0205
0C. Calculate the van’t Hoff factor and the dissociation constant of acid. (K =
f
1.86 k.kg.mol-1) (Ans: 1.04, 1.69 x 10-3)
146. Calculate the amount of sodium chloride which must be added to one kg
of water so that the freezing point of water is depressed by 3 k. (Given Kf = 1.86
K. Kg. mol-1)
147. Determine the amount of CaCl2 dissolved in 2.5 litre of water such that its
osmotic pressure is 0.75 atm at 27 0C assuming the electrolyte is 60%
dissociated. (Ans: 0.846 g)
148. 19. 5 g of CH2FCOOH is dissolved in 500g of water. The depression in
the freezing point of water observed is 1. 0 0C. Calculate the Van’t Hoff factor
and dissociation constant of fluoroacetic acid. Kf of H2O is 1.86 K. Kg. mol-1.
(Ans: 1.075, 2.8 x 10-3)
149. Calculate the boiling point of a solution prepared by adding 15 g of a NaCl
to 250 g of water. Kb for water is 0.512 K. Kg .mol-1 assuming NaCl is completely
dissociated. (Ans: 274. 05K)

39 | P a g e
 150. Calculate the freezing point of an aqueous solution containing 10. 5 g of
MgBr2 in 200 g of water(Molar mass of MgBr2 =184, Kf of water is 1.86 k. Kg.
mol-1, Assuming MgBr2 to be completely dissociated.) (Ans: 271.41K)
151. Calculate the freezing point depression expected for 0.0711 m aqueous
solution of Na2SO4. If this solution actually freezes at -0.320 0C , what would be
the value of Van’t Hoff factor. ( Kf of water is 1.86 K.kg. mol-1)
(Ans:0.132K, 1.93)
152. 0.1 mol of acetic acid was dissolvd in 1 kg of benzene. Depression in
freezing point of benzene was determined to be 0.256 K. What conclusion can
you draw about the state of the solute( Kf for benzene= 5.12 K. m -1)
(Ans: 0.5, Dimerisation of solute occurs)
153. A 0.561 m solution of unknown electrolyte depresses the freezing point of
water by 2.93 0C. What is Van’t Hoff factor for this electrolyte. ( The Kf for water
is 1.86 k. kg .mol-1). (Ans: 2.8)
154. The boiling point elevation of 0.30 g acetic acid in 100 g benzene is
0.0633 K. Calculate the molar mass of acetic acid from this data. What
conclusion can you draw about the molecular state of the solute in the solution.
Kb for benzene is 2. 53 K. Kg. mol-1. (Ans: 120 g/mol, So dimerization occurs)
155. Why is the molar mass determined measuring a colligative property in
case of some solutes abnormal? Discuss it with the help of Van’t Hoff factor.
156. Accounts:
i) 1m NaCl solution has higher colligative properties than 1 m of glucose solution
ii) Abnormal molecular mass is observed in electrolytic solution.
iii) Equimolar solution of sodium chloride and glucose are not isotonic.
iv) Value of van’t Hoff factor for ethanoc acid in benzene is close to 0.5
157. 1 molal aqueous solution of an electrolyte A2B3 is 60% ionized. Calculate
the boiling point of the solution.(given Kb of water=0.52K kg mol-1)(Ans: 374.768K)
PART-V: Relation among the colligative properties:

P
Relation b/w and Tb : For dilute solution, Relative lowering in vapour pressure,
P0

P w2 M 1 w2 P M 2 w 1000
= ,  = 0  , Elevation in boiling point, Tb = Kb 2 .
P0 w1M 2 w1 P M1 w1 M 2

1000. K b P M 2 1000. K b P
Or, Tb = . 0 Or, Tb = . 0
M2 P M1 M1 P

P
Relation b/w and Tf :
P0

1000. K f P
It can be derived like above T f = . 0
M1 P

40 | P a g e
 P
Relation b/w and  :
P0

P M1
= , d= density of solution
P 0 dRT

Relation b/w  and Tb :

Relation between relative lowering in V.P. and osmotic pressure is,

P M1
= ,
P 0 dRT

Relation between relative lowering in V.P. and elevation in B.P. is,

1000. K b P
Tb = . 0
M1 P

1000. K b  M 1 
Or, Tb = . Or, Tb = 1000 K b .
M1 dRT dRT

Relation b/w  and Tf :


T f = 1000 K f .
dRT

Problems solved:

158. Calculate the V.P. of a solution of glucose at STP if 2 g of it dissolved in

20 g of water. Kb of water is 0.52 K.Kg mol-1 ( NEET-2018)

w2 1000 2 1000
Ans: Tb = i.K b . = 1 0.52 . = 0.28 K
w1 M 2 20 180

At STP, P0 =760 mm

1000. K b P
So, Tb = . 0
M1 P

1000  0.52 P P 0.28 18

So, 0.28 = . 0 Or, = = 0.009
18 P P 0
1000  0.52

Or, P = 0.009  760 ,

Or, P0 - Ps =6.84 Or, Ps = 760 – 6.84 = 753.16 mm

41 | P a g e
 PRACTICE QUESTIONS-V:

159. Vapour pressure of pure water at 298K is 24.8 mm Hg. Calculate the
lowering in vapour pressure of an aqueous solution which freezes at -0.30C. (Kf
of water= 1.86 K kg mol-1) (CBSE-2024)

160. On dissolving 0.5 g of a non volatile non-ionic solute to 39g of benzene,

its vapour pressure decreases from 650 mm Hg to 640 mm of Hg. The
depression in freezing point upon addition of the solute is ________.

( Molar mass of benzene is 76 g/mol and Kf of benzene is 5.12 K kg mol-1)

(JEE ADV P-1, 2019)

ASSIGNMENT: MCQ(Previous year JEE/NEET questions)

1. A 0.002m aqueous solution of an ionic compound Co(NH3)5(NO2)Cl freezes at -
0.00730C. Number of moles of ions which 1 mol of ionic compound produces on
being dissolved in water will be (Kf = 1.86 0C/m)
a. 1 b. 2 c. 3 d. 4
2. 0.5 molal aqueous solution of a weak acid (HX) is 20% ionized. If K f for water is
1.86 K. kg.mol-1, the lowering in freezing point of the solution is:
a. -0. 56 K b. -1.12 K c. 0.56K d. 1.12 K
3. Concentrated aqueous sulphuric acid is 98% H2SO4 by mass and has a density
of 1.80 g/ml. volume of acid required to make 1 litre of 0.1 M H2SO4 solution is:
a. 5.55 ml b. 11.10 ml c. 16.65 ml d. 22 ml
4. A mixture of ethyl alcohol and propylalcohol has a vapour pressure of 290 mm at
300 K. The vapour pressure of propyl alcohol is 200mm. If the mole fraction of
ethyl alcohol is 0.6, its vapour pressure (in mm) at the same temperature will be:
a. 300 b. 700 c. 360 d. 350
5. The density (in g/ml) of a 3.60 M sulphuric acid solution that is 29% H2SO4 by
mass will be:
a. 1.88 b. 1.22 c. 1.45 d. 1.64
6. A 5.25 % solution of a substance is isotonic with a 1.5 % solution of urea in the
same solvent. If the densities of both the solutions are assumed to be equal to
1.0 g/cm3, molar mass of the substance will be:
a. 115.0 g/ mol b. 105.0 g/mol c. 210.0 g/mol d. 90.0 g/mol
7. A 5 % solution by mass of cane sugar in water has freezing point of 271 K and
freezing point of pure water is 273.15 K. the freezing point of a 5 % solution by
mass of glucose in water is:
a. 271 K b. 273.15 K c. 269.07 K d. 277.23 K
8. During osmosis, flow of water through a semipermiable membrane is:
a. From bothsides of semepermiable membrane with equal flow rates
b. From bothsides of semepermiable membrane with unequal flow rates
c. From solution having lower concentration only

42 | P a g e
 d. From solution having higher concentration only
9. Density of a 2.05 M solution of acetic acid in water is 1.02 g/ml. The molality of
the solution is:
a. 1.14 mol/kg b. 3.28 mol/kg c. 2.28 mol/kg d. 0.44 mol/kg
10. 18 g of glucose is added to 178.2 g of water. The vapour pressure of water for
this aqueous solution at 1000C is:
a. 759.00 torr b. 7.60 torr c. 76. 00 torr d. 752. 40 torr
11. A 0.001 molal solution of [Pt(NH3)4Cl4] in water had a freezing point depression
of 0.00540C. Kf for water is 1.8K/m, the correct formulation for the above
molecule is:
a. [Pt(NH3)4Cl3]Cl b. [Pt(NH3)4Cl2]Cl2
c.. [Pt(NH3)4Cl]Cl3 d. [Pt(NH3)4Cl4]
12. In a 0.2 molal aqueous solution of a weak acid HX, the degree of dissociation is
0.3. Taking Kf of water as 1.85, the freezing point of the solution will be nearest
to:
a. -0.4800C b. -0.3600C c. -0.2600C d. +0. 4800C
13. If liquids A and B form an ideal solution,
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 the the entropy of mixing are each zero
14. Which one of the statements given below concerning properties of solutions
describe a colligative effect:
a. Boiling point of pure water decreases by the addition of ethanol.
b. Vapour pressure of pure water decreases by the addition of nitric acid.
c. Vapour pressure of pure benzene decreases by the addition of naphthalene.
d. Boiling point of pure benzene increases by the addition of toluene.
15. Camphor is often used in molecular mass determination because:
a. It has very high cryoscopic constant
b. It is volatile
c. It is solvent for organic substances
d. It is readily available
16. The vapour pressure of two liquids P and Q are 80 and 60 torr, respectively. The
total vapour pressure of solution obtained by mixing 3 mol of P and 2 mol of Q
would be:
a. 68 torr b. 140 torr c. 72 torr d. 20 torr
17. A solution has a 1:4 mole ratio of pentane to hexane. The vapour pressure of the
pure hydrocarbons at 200C are 440 mm Hg for pentane and 120 mm Hg for
hexane. The mole fraction of pentane in the vapour phase would be:
a. 0.200 b. 0.478 c. 0.549 d. 0.786

43 | P a g e
18. A solution containing 10 g per dm3 of urea is isotonic with a 5% solution of a non
volatile solute. The molar mass of this non volatile solute is:
a. 250 g/mol b. 300 g/mol c. 350 g/mol d. 200 g/mol
19. 1.00 g of a non electrolyte solute having molar mass 250 g/mol was dissolved in
51.2 g of benzene. If the freezing point depression constant Kf of benzene is
5.12 K. Kg.mol-1, the freezing point of benzene is lowered by:
a. 0.4 K b. 0.3 K c. 0.5 K d. 0.2 K
20. The relationship between osmotic pressure at 273K when 10 g of glucose(P 1),
10 g urea(P2) and 10 g sucrose(P3) are dissolved in 250 ml of water is :
a. P1 > P2 > P3 b. P3 > P1 > P2 c. P2 > P1 >P3 d. P2 > P3>P1
21. The vapour pressure of an ideal solution having 0.2 mole non volatile solute and
0.8 mole solvent is 60 mm. The vapour pressure of pure solvent at this
temperature will be:
a. 120 mm b. 150 mm c. 60 mm d. 75 mm.
22. Vapour pressure of CCl4 at 250C is 143 mm Hg. 0.5 g of a non volatile solute
having molar mass 65 is dissolved in 100 ml of CCl4. Find the vapour pressure of
the solution if density of CCl4 = 1.58 gm/cm3
a. 141.93 mm b. 94.39 mm c. 199.34 mm d. 143.99 mm
23. The vapour pressure decreases by 10 mm of Hg when solute’s mole fraction in a
solution is 0.2. if the vapour pressure decreases is 20 mm of Hg then the mole
fraction of the solute will be:
a. 0.2 b. 0.4 c. 0.6 d. 0.8
24. The vapour pressure of benzene at a certain temperature is 640 mm of Hg. A
non volatile and electrolytic solid weighting 2.175 g is added to 39.08 g of
benzene. If the vapour pressure of the solution is 600 mm of Hg. What is the
molecular weight of the solid substance?
a. 79.82 b. 65.25 c. 59.60 d. 49.50
25. From the colligative properties of solutions which one is the best method for the
determination of molecular weight of proteins and polymers:
a. Osmotic pressure b. Lowering in freezing point
c.. Lowering in vapour pressure d. Elevation in boiling point
26. A solution contains non volatile solute of molecular mass M2. Which of the
following can be used to calculate the molecular mass of the solute in terms of
osmotic pressure:
m2 m2 RT m2 m2 
a. M 2 = VRT b. M 2 = ( ) c. M 2 =  RT d. M 2 = ( )
 V  V V RT
27. A solution containing components A and B follows Raoult’s law:
a. A-B attraction force is greater than A-A and B-B
b. A-B attraction force is less than A-A and B-B
c. A-B attraction force remains same as A-A and B-B
d. Volume of solution is different from sum of volume of solute and solvent
28. Which of the following solutions would have the highest osmotic pressure:

44 | P a g e
 a. M/10 NaCl b. M/10 urea c. M/10 BaCl2 d. M/10 glucose
29. Which of the following solution has the highest boiling point:
a. 0.1 M glucose b. 0.1 M BaCl2 c. 0.1 M NaCl d. 0.1 M urea
30. How much gram of methanol should be dissolved in water for preparing 150 ml
of 2.0 M CH3OH solution:
a. 9.6 b. 2.4 c. 9.6 x 103 d. 4.3 x 102
31. Acording to Raoult,s law the relative lowering in vapour pressure for a solution is
equal to:
a. Mole fraction of solute b. Mole fraction of solvent
c.. Moles of solvent d. Mole fraction of solute
32. A mixture has 18 g water and 414 g ethanol. The mole fraction of water in
mixture is (assume ideal behavior of the mixture):
a. 0.1 b. 0.4 c. 0.7 d. 0.9
33. The vapour pressure of solvent A is 0.80 atm. When a non volatile substance B
is added to this solvent its vapour pressure drops to 0.6 atm. What is mole
fraction of B in this solution?
a. 0.25 b. 0.50 c. 0.75 d. 0.90
34. 171 g of cane sugar is dissolved in 1 lit of water. The molarity of the solution is:
a. 2.0 M b. 1.0 M c. 0.5 M d. 0.25 M
35. Which of the following doesn’t show negative deviation from Raoult’s law:
a. Acetone – chloroform b. Acetone- Benzene
c. chloroform- ether d. chloroform- benzene
36. The boiling point of an aqueous solution of a non volatile solute is 100.150C.
What is the freezing point of an aqueous solution obtained by diluting the above
solution with an equal volume of water? The value of Kb and Kf for water are
0.512 and 1.86 K/ molality:
a. -0.5440C b. -0.5120C c. -0.2720C d. – 1.860C
37. Insulin(C2H10O5)n is dissolved in a suitable solvent and the osmotic pressure of
the solution of various concentration C is measured at 200C. The slope of a plot
of  against C is found to be 4.65 x 10-3. The molecular weight of the insulin is:
a. 4.8 x 10 5 b. 9 x 105 c. 3 x 105 d. 5.16 x 106
38. An azeotropic solution of two liquids has boiling point lower than either of them
when it:
a. Shows a negative deviation from Raoult’s law
b. Shows no deviation from Raoult’s law
c. Shows positive deviation from Raoult’s law
d. Is saturated
39. What is the freezing point of the solution containing 8.1 gm of HBr in 100 gm of
water assuming the acid to be 100% ionized(Kf for water is 1.86 K.kg.mol-1 ,
atomic mass of Br = 80 )
a.2.72 b. -2.72 c. -3.72 d. 3.32

45 | P a g e
40. How many grams of a non volatile solute having a molecular weight of 90 are to
be dissolved in 97.5 g water in order to decrease the vapour pressure of water
by 2.5 percent:
a. 25 b. 18 c. 12.5 d. 9
41. The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74. The degree of
dissociation is:
a. 91.3% b. 87% c. 100% d. 74%
42. The molecular weight of benzoic acid in benzene as determined by depression
in freezing point method corresponds to:
a. Ionization of benzoic acid b.Dimerisation of benzoic acid
c.. Trimerisation of benzoic acid d. Solvation of benzoic acid
43. Which of the following solutions have the highest boiling point:
a. 1% glucose in water b. 1% sucrose in water
c.. 1% NaCl in water d. 1% urea in water
44. The vapour pressure of acetone at 200C is 185 torr. When 1.2 g of a non volatile
substance was dissolved in 100 g of acetone at 200C, its vapour pressure was
183 torr. The molecular mass of the substance is:
a. 128 b. 488 c. 32 d. 64
45. The boiling point 0.2 mol/kg solution of X in water is greater than equimolar
solution of Y in water. Which one of the following statements is true in this case:
a. Molecular mass of X is less than the molecular mass of Y
b. Y is undergoing dissociation in water while X undergoes no change.
c. X is undergoes dissociation in water
d. Molecular mass of X is greater than the molecular mass of Y.
46. Equal moles of benzene and toluene are mixed. The vapour pressure of
benzene and toluene in pure state are 700 and 600 mm Hg respectively. The
mole fraction of benzene in vapour state is:
a. 0.7 b. 0.47 c. 0.50 d. 0.54
47. The vapour pressure of a solvent decreased by 10 mm of Hg when a non volatile
solute was added to the solvent. The mole fraction of solute in solution is 0.2,
what would be the mole fraction of solute if decreased in vapour pressure is 20
mm of Hg?
A. 0.8 B. 0.6 C. 0.4 D. 0.2
48. Calculate the mole fraction of toluene in the vapour phase which is in equilibrium
with a solution of benzene and toluene having a mole fraction of toluene is
0.5.(The vapour pressure of pure benzene is 119 torr and that of toluene is 37
torr at the same temperature)
a. 0.5 b. 0.75 c. 0.625 d. 0.237
49. K4[Fe(CN)6] is supposed to be 40 % dissociated when 1 M solution prepared. Its
boiling point is equal to another 20% mass by volume of non electrolytic solution
A. considering molality = molarity. The molecular weight of A is:
a. 77 b. 67 c. 57 d. 47

46 | P a g e
50. The freezing point depression constant for water is 1.86 0C/m. if 5 g of Na2SO4 is
dissolved in 45 g water, the freezing point is changed by -3.82 0C. Calculate the
Van’t Hoff factor for Na2SO4.
a. 2.63 b. 3.11 c. 0.381 d. 2.05
51. Which of the following 0.1 M aqueous solutions will have the lowest freezing
point:
a. Potassium sulphate b. sodium chloride c. urea d. glucose
52. Which solutions will exert highest osmotic pressure?
a. 1 M glucose solution b. 1M urea solution
c.. 1 M alum solution d. 1M NaCl solution
53. A 0.004M solution of Na2SO4 is isotonic with a 0.010M solution of glucose at the
250C temperature. What is apparent degree of dissociation of Na2SO4.
a. 25% b. 50% c. 75% d. 85%
54. The value of observed and calculated molecular weight of silver nitrate are 92.64
and 170 respectively. The degree of dissociation of silver nitrate is
a. 60% b. 83.5% c. 46.7% d. 60. 23%
55. 1 mol of liquid A and 2 mol of liquid B make a solution having a total vapour
pressure 40 Torr. The vapour pressure of pure A and pure B are 45 Torr and 30
Torr respectively. The above solution
(a)is an ideal solution (b)Shows positive deviation
(c)Shows negative deviation (d)is a maximum boiling azeotrope.
56. The value of Henry’s constant KH is:
(a) Greater for gases with higher solubility.
(b) Greater for gases with lower solubility.
(c) Constant for all gases (d)Not related to the solubily of gases.
57. Value of Henry’s constant KH is:
(a) Increases with increase in temperature
(b) Decreases with increase in temperature
(c) Remains constant (d)First increases then decreases
Answer kew:
1. B 2. B 3. A 4. D, 5. B 6. C
7. C 8. B 9. C 10. D 11. B 12. A
13. A 14. C 15. A 16. C 17.D 18. B
19. A 20. B 21. D 22. A 23. B 24. B
25. A 26. B 27. C 28. C 29. B 30. A
31. A 32. D 33. A 34. C 35. B 36.C
37. D 38.C 39. C 40. C 41. B 42. B
43. C 44. D 45. C 46. D 47. C 48. D
49. A 50. A 51. A 52. C 53. C 54. B
55. B 56. B 57. A

47 | P a g e
Assertion and Reason type Questions:

A)Both assertion and reason are correct statements and R is the correct explanation of assertion .

B) Both assertion and reason are correct statements ,but R is not the correct explanation of the A

C)Assertion is correct but reason is wrong statement.

D)Assertion is wrong but reason is correct statement.

58. A: Chloroform and acetone shows Positive deviation from Raoult’s law
R: Between the two intermolecular species, Hydrogen bonding exists.
59. A:When RBC’s are placed in 1% NaCl solution, they will swell.
R: 1% NaCl solution is hypertonic solution w.r.t. RBC and plasmolysis occurs.
60. A: The value of KH increases with increase in temperature.
R: The solubility of gas decreases with increase of temperature at the same
pressure.
61. A: Van’t Hoff factor of acetic acid in benzene is less than one but in water
greater than 1.
R: Acetic acid acts as weak electrolyte in benzene but strong electrolyte in water.
62. A:0.1 M HCl solution has higher osmotic pressure than 0.1 M Nacl solution.
R: Cl- ions being common, the small size H+ ions have greater ionic mobility than
larger size Na+ ions.
63. A:If red blood cells were removed from the body and placed in pure water,
pressure inside the cells increases.
R: The concentration of the salt content in the cells increases.
64. A: If on mixing the two liquids, the solution becomes hot, it implies that it shows –
ve deviation from Raoult’s law.
R: Solutions which show –ve deviation are accompanied by decrease in volume.
65. A: Molarity of a solution in liquid state changes with temperature while molality is
independent of temperature.
R: The volume of solution changes with change in temperature but mass is
independent.
66. A: 2m Na2SO4 solution has higher freezing point than 2m glucose solution.
R: Na2SO4 is an electrolyte which undergoes dissociation while glucose is a non
electrolyte.
67. A: Sodium chloride or calcium chloride is used to clear snow from the roads.
R: They decreases the freezing point of water by which it can’t freeze to form ice
easily.
68. A: When a solution is separated from the pure solvent by a semipermiable
membrane, the solvent molecules pass through it from pure solvent side to the
solution side.
R: Diffusion of solvent occurs from a region of high concentration solution to a
region of low concentration solution.
69. A:The vapour pressure of a solution containing non volatile solute is directly
proportional to mole fraction of solvent.
R: Mole fraction of solution is independent of temperature.

48 | P a g e
70. Assertion(A): When NaCl is added to water a depression in freezing point is
observed.
Reason(R ): NaCl undergoes dissociation in water.
71. 50ml of 0.2 molal urea solution(density 1.012 g ml-1 at 300K) is mixed with
250ml of a solution containing 0.06 g of urea. Both the solutions were prepared
in the same solvent. The osmotic pressure in Torr of the resulting solution at
300K is ________. [Molar mass of urea 60g.mol-1, R=62 L Torr K-1 mol-1;
Assume  mix H and mixV are zero] (JEE adv-p-2, 2023)
72. Vessel-1 contains w2 g of a non volatile solute X dissolved in w1g of water.
Vessel-2 contains w2 g of another non volatile solute Y dissolved in w1 g of
water. Both the vessels are at the same temperature and pressure. The molar
mass of X is 80% of that Y. The van’t Hoff factor for X is 1.2 times of that Y for
their respective concentrations. The elevation of boiling point for solution in
vessel-1 is _____% of the solution in vessel-2. (JEE ADV P-2, 2024)
73. If the freezing point of a 0.01molal aqueous solution of a cobalt(III) chloride-
ammonia complex(which behaves as a strong electrolyte) is -0.0558 0C, the
number of chlorides in the coordination sphere of the complex is ______.(Kf of
water=1.86K kg mol-1) (JEE adv,P-1, 2015)
2+ -
74. MX2 dissociates in M and X ions in an aqueous solution, with a degree of
dissociation(  ) of 0.5. The ratio of the observed depression of freezing point of
the aqueous solution to the value of the depression of freezing point in the
absence of ionic dissociation is ________. (JEE adv.)
75. 75.2 g of phenol(C6H5OH) is dissolved in a solvent of Kf=14. If the depression in
freezing point is 7K then find the % of phenol that dimerises. (JEE)
76. The boiling point of water in a 0.1m silver nitrate solution is x0C. to this solution
A, an equal volume of 0.1 molal aqueous barium chloride solution is added to
make a new solution B. the difference in the boiling points of water in the two
solutions A and B is y x 10-2 0C. Te value of X is ____ and y is _______.
(Assume densities of the solutions A and B are the same as that of water and
the soluble salts dissociate completely. Kb of water=0.52 K kg mol-1 and boiling
point of pure water is 1000C.) (JEE adv. 2021)

49 | P a g e