Chemis try Stu dy mate rial on

SOLUTIONS
Name:_______________________________________________________
School: _____________________________________________________________

Po − Ps
(a) Po
= i.x 2 (b) T = iK .mb b

(c) Tf = iK f .m (d)  = i CRT

i −1 i −1
(e) =
n −1
(f)  =
n −1
1

Calculateed or normal molecular mass M

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

STD-XII

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

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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

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 Part-1
Introduction:
1. A solution is a homogeneous mixture of two or more components.
2. 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.
3. 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.
4. 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.
5. The solution can be classified as binary or ternary or quaternary
depending on the no of components present like 2, 3 or 4 respectively.
6. 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 %
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 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: 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: 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

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 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 are function of temperature as these are related with volume of
solution which depends on temperature.
3. 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.
4. If two solutions react completely with each other having molarities and volumes
M1V1 M 2 V2
M1,V1 and M2,V2 then = , Where n1 and n2 are the stochiometric
n1 n2

coefficients of the two solutions in the balanced chemical equation.

5. 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
M 1V1 + M 2V2
M3 =
V1 + V2

Relation between the concentration terms:

1. Relation between strength and molarity:
S = M x M2
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 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
Or, = , Or, = M2 ,
M E2 M n

N
Or = n , Or, N = M x n, Where n= Basicity of acid Or acidity of base
M
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 w1

m V
Or, =
M W − w2

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

m V
=
M Vd − n2 M 2

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

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

1000 M
Or, m =
1000d − M . M 2

4. 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
No of moles of solute in one litre of solution=
M2

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 10dx
Or, M=
M2

5. Relation between mole fraction and molality:

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

Problems solved:
1. 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

w2 / M 2 10 /180 1 / 18
= = = =1/91=0.010
w1 / M 1 + w2 / M 2 90 /18 + 10 /180 5 + 1 / 18

2. 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

3. 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

4. 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

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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

5. Calculate molarity of an acetic acid solution having molality 4 and density

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

MCQ:

6. Which of the following modes of expressing concentration of solution is independent of

temperature:
a. Molarity b. Molality c. Normality d. grams per litre
Ans:
7. 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
Ans:
8. What is false for mole fraction:
a. X < 1 b. -2  x 2 c. 0  x 1 d. Always non negative
Ans:
9. Which of the following dependent on temperature?
a. Molality b. Molarity c. Molefraction d. Weight percentage
Ans:
10. 6.02x 1021 molecules of urea are present in 100ml of its solution. The concentration of the
solution is:
a. 0.02M b. 0.01M c. 0.001M d. 0.1M
Ans:

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ASSIGNMENT-1:
1. Calculate the mole fraction of ethylene glycol(C2H6O2) in a solution containing 20% of C2H6O2 by
mass.
a. Calculate the molarity of a solution containing 5 g of NaOH in 450 ml solution.
2. Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
3. Calculate the molarity of the solution if 30 ml of 0.5 M H2SO4 diluted to 500 ml.
4. Calculate a) molality b) molarity and c) male 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)
5. What should be the molarity of conc. nitric acid solution if its density is 1.5 g/ml and
concentration is 68% by mass.
6. 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?
7. How many ml of 0.1 M HCl are required to react completely with 1 g mixture of Na 2CO3 and
NaHCO3 containing equimolar amounts of both?
8. Define the following terms:
9. a) Mole fraction b) Molality c) Molarity d) Mass percentage.
10. The density of 3 M solution of NaCl is 1.25 g/ml. Calculate molality of solution?
11. 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.
12. 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.
13. Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 ml of 0.15 M
solution in methanol.
14. 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.
15. 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 molality of chloroform in the water sample.

9|Page
 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

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Characteristics of KH:
i) It is a function of nature of gas i.e. different gases have different value of
KH 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:
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

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 taken by the scuba divers for respiration because He is very less soluble
in blood under high pressure.
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 ,
p total = 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

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Graphical representation:
When a graph is plotted between v.p and Mole fraction x2 or x1 then a
straight line is obtained as p10 and p20 are constants at a particular temperature.
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

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

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

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 (iii) C6 H6 + CH3COCH3 (iv) alcohol and water
d. 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) , (ii) CHCl3 + COCH3

(iii). Acetone + Aniline, iv) HNO3 + H2O
d. The mixture of phenol and aniline shows –ve deviation from Raoult’s
law as the 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.
e. The solution of chloroform and acetone shows –ve deviation from
Raoult’s law due to formation of hydrogen bond between the two
molecules.

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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.
It is of 2 types like
(i) Minimum Boiling Azeotropes:
The solutions which show +ve deviation from Raoult’s law form minimum
boiling azeotropes at a specific composition.
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.
Here the b.p. of azeotrope is less than the b.p. of either of the pure
component.
(ii) Maximum boiling azeotrope:
The solutions which show –ve deviation from Raoult’s law form maximum
boiling azeotrope at a particular composition.
E.g: 68% HNO3 + H2O . Nitric acid has b.p. of 359 K but this azeotrope has b.p.
of 393.5 K
Here the b.p. of azeotrope is higher than the b.p. of either of the pure
component.
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.

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 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.
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
Problems solved:
6. 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.

17 | P a g e
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
Mole fraction of H 2 S in solution i. e.  2 =
n1 + n2

0.2 0.2
= = = 0.0035
0.2 + 55.55 55.75
At STP, partial pressure is 1 atm
So, p = K H . 

p 1
 KH = = = 285.71 atm
 0.0035

7. 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

8. 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)
18 | P a g e
 = 50 + (0.515 x -18) = 50 – 9.27 = 40.73
p1 p 0 x 50 x 0.485 24.25
So, Mole fraction of benzene in vapour phasei. e. y1 = = 1 1= = = 0.595
Ptotal Ptotal 40.73 40.73

9. 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 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

MCQ:
10. 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.
11. 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

19 | P a g e
12. Which of the following pairs will not form an ideal solution?
a. Benzene and Toluene
b. Nitric acid and water
c. Hexane and heptanes
d. Ethyl chloride and ethyl bromide
13. Which of the following doesn’t show positive deviation from Raoult’s law?
a. Benzene- Chloroform b. Benzene – acetone
c.. Benzene-ethanol d. Benzene-carbon tetra chloride
14. 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

ASSIGNMENT-2

16. A and B liquids on mixing produced a warm solution. Which type of deviation is there
and why?
17. Define Henry’s law about solubility of a gas in a liquid? What is the significance of
Henry’s law constant(KH)?
18. Define azeotropes with examples? What are maximum and minimum boiling
azeotropes? Give suitable example in each case.
19. Vapour pressure of CHCl3 and dichloromethane 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 CHCl 3
and 40 g of CH2Cl2 at 298 K and mole fraction of each component in vapour phase.
20. Accounts for the followings:
a. Why are aquatic species more comfortable in cold water in comparison to warm wate.
b. The mixture of acetone and chloroform form a solution with negative deviation.
c.. soda water bottle kept at room temperature fizzes on opening?
d. He is taken by Scuba divers along with air for respiration
e. At high altitudes, the conc. of O2 in blood decreases
21. State Raoult’s law for i) volatile solute ii) Non volatile solute
22. 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?
23. Heptane and octane 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?
24. 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.
25. 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?
26. 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.
27. 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

20 | P a g e
 28. 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

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.
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

21 | P a g e
 p 0 − ps w2 / M 2
Or, =
p 0
w1 / M 1 + w2 / M 2

For dilute solution, n2<<n1, so n2+n1 = n1

n2
So For dilute solution, x2= ,
n1

p 0 − ps w / M2
Or, 0
= 2
p w1 / M 1

p 0 − ps w2 M 1
Or, =
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.
[Link] 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.

22 | P a g e
 The  ACE and  ABD are similar:
AC AE
Therefore, =
AB AD
T2 − T0 P0 − P2
 =
T1 − T0 P0 − P1

T2 P2
 =
T1 P1

 T  P --------------------------------(i)

p 0 − ps w2 M 1
From Raoult’s law, =
p0 w1M 2

w2 M 1 0
p0-ps = .p
w1M 2

For a pure solvent, p0 and M1 are constants.

w2
Or, P  --------------------------------------------(ii)
w1M 2

From equation (i) and (ii),

w2
T 
w1M 2

w2
Or, T = K ----------------------------------(iii)
w1M 2

Wherw K is the elevation constant.=M1.P10

w2
If = 1 and w1 = 1000 gm
M2

K
Then T = = Kb
1000
Where Kb is molal elevation constant or Ebullioscopic constant. It is defined as the
elevation in boiling point in one molal solution.
w2
From equation (iii), Tb = 1000 K b
w1M 2

w2 1000
Or, Tb = Kb .
w1 M 2

Or, Tb = Kb m

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:
23 | P a g e
 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 [Link]-1

Tb
Kb=
M
For, H2O; Kb= 0.52 [Link]. 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.
iv) 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:

For very dilute solutions, the curves are almost straight lines:
 BCE and  BFD are similar

24 | P a g e
 CE AC
Therefore, =
BE BD
To − T2 P0 − P2
 =
T0 − T1 P0 − P1

T2 − T1 P0 − P2
 =
T1 − T0 P0 − P1

T2 P2
 =
T1 P1

 T  P ----------------(i)

p 0 − ps w2 M 1
From Raoult’s law, =
p0 w1M 2

w2 M 1 0
p0-ps = .p
w1M 2

For a pure solvent, p0 and M1 are constants.

w2
Or, P  --------------------------------------------(ii)
w1M 2

From equation (i) and (ii),

w2
T 
w1M 2

w2
Or, T = K ----------------------------------(iii)
w1M 2

Where K is the depression constant.=M1.P10

w2 K
If = 1and w1 = 1000 gm , then T = = Kf
M2 1000

Where Kf is molal depression constant or cryoscopic constant. It is defined as

the depression in freezing point in one molal solution.
From equation (II),
w2
T f = 1000 K f
w1M 2

w2 1000
Or, T f = K f . , Or, T f = K f m
w1 M 2

Where m= Molality of the solution

Note:
i). The molal depression constant is characteristic of a particular solvent and can
be calculated by using the relation:

25 | P a g e
 R. M1.T f2
Kf= ,whereTf=Freezing point of puresolvent. H fus = Enthalpy of vaporization.
1000. H fus

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

26 | P a g e
(vi) When a 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.
The solution which has lower osmotic pressure than other is called hypotonic
and which has higher osmotic pressure than other is called hypertonic solution.
(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  = [Link]
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 straightline is obtained having slope RT

If two solutions have osmotic pressures 1 and 2 and conc. C1 and C2 at same
1 C1
temp. then =
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
27 | P a g e
 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.
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.
(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 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% the they will swell and burst
due to entering of water molecules into the cell through the cell wall.
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.

28 | P a g e
Problem solved:
10. 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
11. 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
12. 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
36
2 n1 / V1 1.52  (180  1)
 C2 = = = 0.063 mol/L
1 4.98

13. 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 / M 1 + 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

29 | P a g e
 Or, W2 = 10 g
14. Calculate the boiling point of a solution containing 10 g of glucose in 140 g of water. K b of water
is 0.52 [Link]-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

15. Calculate the freezing point of a solution containing 2 g of a urea in 90 g of water. Kf of water is
1.86 [Link]-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
MCQ:

16. 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
17. 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
18. Pure water can be obtained from sea water by:
Centrifugation b. Plasmolysis c. Reverse osmosis d. Sedimentation

19. Osmotic pressure of a solution containing 0.6 g urea and 3.42 g sugar in 100 ml at 27 0C
a. 492 atm b. 4.92 atm c. 49.2 atm d. 28.1 atm
20. The average osmotic pressure of human blood is 7.8 bar at 370C.
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
ASSIGNMENT-3

27. 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?
28. 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%.

30 | P a g e
29. 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.
30. 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.
31. 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 [Link]-1.
32. 40 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate
i) The freezing point depression. ii) The freezing point of the solution.
33. 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.
34. 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)
35. 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. Kf of H2O is
1.86 K. Kg. mol-1.
36. Two elements A and B form compounds having formula AB2 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 atomic masses of A and
B.
37. Define i) colligative properties ii) Osmosis iii) edema
38. Define i) cryoscopic constant. ii) Ebullioscopic constant iii) osmotic pressure
39. 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. [Link]-1)
40. 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.
41. 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.
42. At 300 K, 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
conc?
43. Define i) reverse osmosis ii) Isotonic solution.
44. What is the advantage of using osmotic pressure as compared to other colligative properties for
the determination of molar mass of solute in solution?
45. How does sprinkling of salt help in clearing the snow covered roads in hilly areas? Explain the
phenomenon involved in the process.
46. A solution prepared by dissolving 8.95 mg of a gene fragment in 35 .0 ml of water has an osmotic
pressure of 0.335 torr at 250C. Assuming the gene fragment is non electrolyte, determine its
molar mass.
47. How can the direction of osmosis be reversed? Write one use of reverse osmosis.

48. Why is camphor preferred in the determination of H f ?

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

31 | P a g e
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.
observed or Abnormal colligative property
i=
Calcuated or normal colligative property
1
But Colligative property 
Molecular mass

32 | P a g e
 Calculateed or normal molecular mass M
So i= = C
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

Total no of moles of particles after dissociation 1 −  + n

So, i = =
No of moles of particles before association 1

 i = 1 +  ( n − 1)
33 | P a g e
 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
Problems:
16. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K 2SO4 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 ,

W2 RT
Or,  = i.
M2V
3 25  10−3  0.0821 298
Or,  = = 52728 x 10-7 atm
174  2
17. Calculate the Boiling point of a solution containing 4 g of CaCl2 in 90 g of water if CaCl2 is 80%
dissociated. Kb of water is 0.52 [Link]-1

Ans: Given degree of dissociation,  = 80% = 0.8

34 | P a g e
 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
18. 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 [Link]. 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%
1
n − 1 1
2 − 1

So degree of association is 99.18%

19. 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 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

35 | P a g e
 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

MCQ:

20. 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
21. Van’t Hoff factor for acetic acid in aqueous medium at infinite dilution is
a. ½ b. 2 c. 1 d. 3
22. 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
23. 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%
24. 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 freezing point by 0.30C. the molar mass of A is:
a. 122 b. 31 c. 244 d. 62
ASSIGNMENT-4:

50. 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression in freezing

point equal1.62 K. Molal depression constant for benzene is 4.9 K Kg. mol-1. What is the
percentage association of acid if it forms dimer in solution?
51. Define the term i) Van’t Hoff factor ii) Abnormal molecular mass.
52. 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. ( Kf = 1.86 [Link]-1)
53. 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)
54. Determine the amount of CaCl2 dissolved in 2.5 litre of water such that its osmotic pressure is
0.75 atm at 27 0C assumiing the electrolyteis 60% dissociated.
55. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K 2SO4 in 2 lit of
water at 25 0C, assuming that it is completely dissociated.(R 0.0821 L atm K-1 mol-1)
56. 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 x 10 -3, Kf= 1.86 K. Kg. mol-1.

36 | P a g e
 57. 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.
58. Calculate the boiling point of a solution prepared by adding 15 g of a NaCl to 250 g of water. K b
for water is 0.512 K. Kg .mol-1 ssuming NaCl is completely dissociated.
59. Calculate the freezing point of an aqueous solution containing 10. 5 g of MgBr 2 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.)
60. Calculate the freezing point depression expected for 0.0711 m aqueous solution of Na 2SO4. If
this solution actually freezes at -0.320 0C , what would be the value of Van’t Hoff factor. ( Kf for
water is 1.86 [Link]. mol-1)
61. 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)
62. 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).
63. 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.
64. 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.
65. Accounts:
i) 1m NaCl solution has higher colligative properties than 1 m of glucose solution
ii) Abnormal molecular mass is observed in electrolytic solution.
Relation among the colligative properties:

P
Relation b/w and Tb :
P0

P w2 M 1
For dilute solution, Relative lowering in vapour pressure, =
P0 w1M 2

w2 P M 2
 = 
w1 P 0 M1

w2 1000
Elevation in boiling point, Tb = K b .
w1 M 2

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

1000. K b P
Or, Tb = . 0
M1 P

37 | P a g e
 P
Relation b/w and Tf :
P0

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

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:

66. 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 [Link] mol-1 ( NEET)

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  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

38 | P a g e
MCQ:
21. A 0.0020 m 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
22. 0.5 molal aqueous solution of a weak acid (HX) is 20% ionized. If Kf for water is 1.86 k. [Link]-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
23. 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
24. 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
25. The density (in g/ml) of a 3.60 M sulphuric acid solution that is 29% H 2SO4 by mass will be:
a. 1.88 b. 1.22 c. 1.45 d. 1.64
26. 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/cm 3, 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
27. 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
28. 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
d. From solution having higher concentration only
29. 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
30. 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
31. 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] e. None of the above
32. 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
33. 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

39 | P a g e
34. 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.
35. 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
36. The mole fraction of solute in one molal aqueous solution is:
a. 0.027 b. 0.036 c. 0.018 d. 0.009
37. 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
38. 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
39. 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
40. 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. [Link]-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
41. 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
42. 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.
43. 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
44. 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
45. 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
46. 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

40 | P a g e
 c.. Lowering in vapour pressure d. Elevation in boiling point
47. 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. M2 = VRT b. M 2 = ( ) c. M 2 =  RT d. M 2 = ( )
 V  V V RT
48. 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
49. Which of the following solutions would have the highest osmotic pressure:
a. M/10 NaCl b. M/10 urea c. M/10 BaCl2 d. M/10 glucose
50. 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
51. How much gram of methanol should be dissolved in water for preparing 150 ml of 2.0 M CH 3OH
solution:
a. 9.6 b. 2.4 c. 9.6 x 103 d. 4.3 x 102
52. 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
53. 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
54. 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
55. 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
56. 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
57. The vapour pressure of pure liquid A is 0.80 atm. When a non volatile solute B is dissolved in A
its vapour pressure becomes 0.60 atm. The mole fraction of B in the solution is:
a. 0.125 b. 0.25 c. 0.50 d. 0.75
58. 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
59. 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 105
60. 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

41 | P a g e
 d. Is saturated
61. 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 [Link]-1 , atomic mass of Br = 80 )
a.2.72 b. -2.72 c. -3.72 d. 3.32
62. 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
63. 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%
64. The molecular weight of benzoic acid in benzene as determined by depression in freezing point
method corresponds to:
a. Ionization of benzoic acid [Link] of benzoic acid
c.. Trimerisation of benzoic acid d. Solvation of benzoic acid
65. 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
66. 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
67. 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.
68. 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
69. 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
70. 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
71. 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
72. 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
73. 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
74. Which solutions will exert highest osmotic pressure?

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 a. 1 M glucose solution b. 1M urea solution
c.. 1 M alum solution d. 1M NaCl solution
75. 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%
76. 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%
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.

77. A: Chloroform and acetone shows Positive deviation from Raoult’s law
R: Between the two intermolecular species, Hydrogen bonding exists.
78. 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.
79. A: The value of KH increases with increase in temperature.
R: The solubility of gas decreases with increase of temperature at the same
pressure.
80. 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.
81. 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.
82. 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.
83. 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.
84. 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.
85. A: When methyl alcohol is added to water, boiling point of water increases.
R: When a volatile solute is added to a volatile solvent, elevation in boiling point
is observed.
86. A: When NaCl is added to water a depression in freezing point is observed.
R: The lowering of vapour pressure of solution causes depression in freezing
point.
87. A: 2m Na2SO4 solution has higher freezing point than 2m glucose solution.
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 R: Na2SO4 is an electrolyte which undergoes dissociation while glucose is a non
electrolyte.
88. A: Elevation in boiling point is a colligative property.
R: Elevation in boiling point depends on molality and not upon the nature of
solute.
89. 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.
90. 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.
91. 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.

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