SOLUTIONS AND

C O L L I G AT I V E
PROPERTIES
1. INTRODUCTION
(a) Solutions are homogenous mixtures of two or more substances.
(b) We call what is being dissolved in the solution as a “solute”: for, it is the active ‘ingredient’ of that particular
solution.
(c) In the same way, in what we are dissolving the solute is termed as a “solvent”: Typically, there is more solvent
than any solute.
(d) Further, solutes and solvents can be technically in any state of matter.
Solutions that contain relatively high concentration of a solute are called concentrated solutions, whereas solutions
that contain relatively low concentration of a solute are called dilute solutions.
Let us now discuss saturated, unsaturated and supersaturated solutions.
Generally by saturated solution we mean a solution, which contains as much solute as it can hold particularly at a
given temperature. Similarly, a solution, which contains comparatively less solute than the quantity of solute it can
actually hold is called a unsaturated solution. Further, a solution is called a supersaturated solution, if it contains
comparatively more solute than the quantity it can actually hold at a particular temperature.
Binary solutions are such solutions that hold only two components.
We now proceed to discuss various types of solutions.

Table 1: Types of Solutions

S. No. Solute Solvent Type of solution Example

SOLID SOLUTIONS (solid solvent)
1. Solid Solid Solid in solid Alloy (brass, German silver, bronze, 22 carat gold, etc.)

2. Liquid Solid Liquid in solid Hydrated salts, amalgam of Hg with Na

3. Gas Solid Gas in solid Dissolved gases in minerals or H2 in Pd

LIQUID SOLUTIONS (liquid solvent)
4. Solid Liquid Solid in solid Salt or glucose or sugar or urea solution in water

5. Liquid Liquid Liquid in solid Methanol or ethanol in water

6. Gas Liquid Gas in solid Aerated drinks, O2 in water

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2 | Solutions and Colligative Properties

S. No. Solute Solvent Type of solution Example

GASEOUS SOLUTIONS (gaseous solvent)
7. Solid Gas Solid in Gas Iodine vapors in air, camphor in N2 gas

8. Liquid Gas Liquid in Gas Humidity air, chloroform mixed with N2 gas

9. Gas Gas Gas in Gas Air (O2 + N2)

Out of the various types of solutions listed in the table given above, the most significant types of solutions are
those which are in liquid phase, i.e., liquid solutions. We therefore confine ourselves to the study of solutions of
solids, liquids or gases in liquids.

2. METHODS FOR EXPRESSING CONCENTRATION OF SOLUTIONS

Mass of solute
1. Mass percentage: % (w/w) Mass percentage of solute = × 100
Mass of solution

Mass of solute
2. Percent mass by volume: % (w/v) = × 100
Volume of solution

Volume of solute
3. Volume percentage: Percent of solute by volume = × 100
Volume of solution

Mass of solute
4. Percentage mass by volume: Percent of solute mass by volume = × 100
Volume of solution
5. Strength of concentration:
Mass of solute in gram Mass of solute in gram
Concentration of solution = = × 1000
Volume of the solution in litres Volume of the solution in mL

Mass of solute
6. Parts per million (ppm): = × 106
Mass of solution

7. Mole Fraction: Let us assume that n moles of solute (A) and N moles of solvent (B) are present in a solution.
n N
Then, mole fraction of the solute = = XA, whereas mole fraction of the solvent = = XB
N+n N+n
Hence, in a binary solution, XA + XB = 1.
Mole fraction is, therefore, independent of temperature of the solution.

Number of moles of solute

8. Molality: Molality (m) =
Number of kilograms of the solvent

Number of moles of solute

9. Molarity: Molarity (M) =
Number of litres of solution

Molarity × Number of liters of solution = Number of mole of solute

Number of gram equivalents of solute

10. Normality: Normality (N) =
Number of litres of the solution

Or Normality × Number of liters of the solution = Number of gram equivalents of the solute.

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Chem i str y | 3

RANKUP CONCEPTS

XB × 1000
Relation between molality and mole fraction =m
(1 − XB )mA

Molality is the most convenient form of representing concentration of a solution as it is independent of

temperature.
1 ρ m
Relation between molality and molarity = − B
m M 1000
where, ρ = density of solution; m = molality; M = molarity and mB = molar mass of a solute.
xB × 1000 × d
Relation between molarity and mole fraction M =
x AmA + xBmB
Relation between normality and strength
wB
Normality × Equivalent mass = = Strength of the solution in g/L
V
Relation between normality and molarity
Normality = n × Molarity
If volume V1 of a solution of normality N1 is mixed with volume V2 of another non-reacting solution of
normality N2, then the normality N3 of the final solution can be calculated as follows:
N1V1 + N2V2 = N3(V1 + V2) or N3 = (N1V1 + N2V2) / (V1 + V2)
Similarly, if molarities are used, then M3 = (M1V1 + M2V2) / (V1 + V2)

Illustration 1: The density of a solution containing 13% by mass of sulfuric acid is 1.09 g/mL. Calculate its molarity.
(JEE MAIN)
Sol: We are provided with strength of solution and density hence for this numerical following formula can be
applied
In solving such problems, the following formula can be applied:
%strength of soln. × density of soln. × 10 13 × 1.09 × 10
Molarity = ;M= = 1.445 M
Mol. mass 98

Illustration 2: The density of a 3M sodium thiosulphate solution (Na2S2O3) is 1.25 g/mL. Calculate (i) the percentage
by mass of sodium thiosulphate, (ii) the mole fraction of sodium thiosulphate and (iii) molalities of Na+ and S2O3
ions. (JEE ADVANCED)

Sol: From the given data determine the strength of the acid. In order to determine the mole fraction we have
to calculate the no of moles of acid and water present in the solution. From the number of moles calculate the
molalities of different ions.
x × d × 10 x × 1.25 × 10
M= ⇒3= ∴ x = 37.92
mA 158
474
No. of moles of Na2S2=
O3 = 3 ; mass of water = (1250 – 474) = 776g
158
776
No. of moles of water
= = 43.1
18

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4 | Solutions and Colligative Properties

3 3
Mole fraction of Na2S=
2 O3 = = 0.065
43.1 + 3 46.1
No. of moles of Na+ ion = 2 × No. of moles of Na2S2O3 = 2 × 3 = 6

No. of moles of Na+ ions 6

Molality of Na+ ion = = × 1000 =7.73 m
Mass of water in kg 776

No. of moles of S2O32– ions = No. of moles of Na2S2O3

3
Molality of S2O32– ions = × 1000 =
3.86 m
776

3. SOLUBILITY
Solubility is defined as the maximum amount of solute that we can dissolve in any given solvent (yielding a
saturated solution). It not only depends on the nature of solute and solvent but also on temperature and pressure.

3.1 Solubility of a Solid in Liquid

Suppose that a solid solute is added continuously to a liquid solvent; then, the solute continues dissolving and
consequently the concentration of the solution increases. We call this process as dissolution. However, ultimately, a
state is reached where no more solute dissolves at the given temperature. This is basically because of the fact that
from the solution, the solute particles keep on colliding on the surface of solid solute particles and ultimately get
separated out of the solution. This process is known as crystallization. Thereafter, no more solute particles dissolve
because the rate of dissolution equalizes the rate of crystallization, i.e., a dynamic equilibrium is attained.
Solute + Solvent → Solution
Further, the solution at this stage is said to be a saturated solution. However, an unsaturated solution is one in
which more solute particles dissolve at the same temperature. Thus, the concentration of such a saturated solution
is called its ‘solubility.’ Now, as per our discussion so far in this regard, we define solubility as follows:
The solubility of a solid in a liquid at any temperature is defined as the maximum amount of the solid
(solute) in grams which can dissolve in 100g of the liquid (solvent) to form the saturated solution at that
particular temperature.
Factors affecting solubility of a solid in a liquid
(a) Nature of Solute and Solvent: Generally, a solid dissolves in a liquid which is chemically similar to it. We
can say this conveniently as ‘like dissolves like.’ In this regard, ionic compounds usually get dissolved in polar
solvents, whereas covalent compounds are soluble in non-polar solvents.

Explanation: For ionic compounds that are being dissolved in polar solvents, the solubility is due to the fact that
there are strong electrostatic forces of attraction between the ions of the crystal and the polar solvent molecules
with the negative ions being attracted with the positive poles of the solvent molecule and positive ions by negative
poles. However, in case of water molecule, the situation can be represented as

-
+
+ -
+
O
+ 104.5o +
Or
+
-+ + - + -+ +- +
H H + + + +
+ - + -+ -
+ - -
+ +
Water molecule - - +
+
- +
(polar molecule) + + + - +
+ - +
- +
- + -
+ + +
+ + -

Figure 1: Dissociation of an ionic compound, like Na+Cl‒, in a polar solvent (H2O)

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Chem i str y | 5

Thus, the water molecules pull apart the ions of the crystal and the electrostatic forces of attraction between the
ions of the crystal are hence cut off. Further, we observe that the ions are surrounded by the water molecules which
act as a sheath (or envelope) around the ions and hence prevent the possible recombination of the ions. Such ions
that are thus moving freely in the solution are said to be hydrated. It is to be noted here that whereas energy is
required for the splitting of the ionic compound into ions (called lattice energy), energy is released when the ions
get hydrated (called hydration energy). It follows then that a substance dissolves if its hydration energy is greater
than its lattice energy, i.e., Dhyd H > Dlattice H.
It may be further mentioned here that whereas water is the best polar solvent (having the highest dielectric constant),
liquid ammonia, liquid hydrogen sulfide and liquid sulfur dioxide are also good solvents for ionic compounds.
In the case of non-polar compounds being dissolved in non-polar solvents, the solubility principle is due to similar
solute–solute, solute–solvent and solvent–solvent interactions.

(b) Temperature: The solubility of solutes is generally dependent on temperature. For example, when a solid
dissolves in a liquid, a change in the physical state of the solid, analogous to melting, takes place. However,
heat is required to break the bonds holding the molecules in the solid together. On the contrary, heat is
liberated during the formation of new solute–solvent bonds.

RANKUP CONCEPTS

Solute + Solvent → Solution. ∆Hsolution = ±x

If ∆Hsolution < 0, i.e., (–ve), then the dissolution is exothermic. In this case, as the temperature increases,
solubility decreases (Le Chatelier’s principle).
If ∆Hsolution > 0, i.e., (+ve), then there is endothermic dissolution. In this case, increase in temperature
increases the solubility (Le Chatelier’s principle).

3.2 Solubility of a Gas in a Liquid

The solubility of any gas in a particular liquid is the volume of the gas in cc (converted to STP) that can dissolve in
unit volume (1 cc) of the liquid to form the saturated solution at the temperature of the experiment and under a
pressure of one atmosphere. This method helps us to express the concentration as an absorption coefficient of the
gas and is usually represent by α.
Further, solubility of a gas in a liquid at a particular temperature is also expressed in terms of molarity (moles of
the gas dissolved per liter of the solvent to form the saturated solution, i.e., in terms of mol L–1) or in terms of mole
fraction (xA) of the gas.

(a) Nature of the gas and solvent: It is to be noted here that gases like H2, O2, N2, etc. dissolve in water only
to a small extent, whereas gases such as CO2, HCl and NH3 are highly soluble. However, the greater solubility
pattern of the latter gases is mainly due to their reaction with the solvent or chemical similarity.

(b) Effect of Temperature: The solubility nature of gases decreases with an increase in temperature as dissolution
is an exothermic process, i.e., it is accompanied by evolution of heat. Thus
Gas + Solvent → Solution + Heat
By applying Le Chatelier’s principle, it is clearly evident that increase of temperature would shift the equilibrium
in the backward direction, i.e., the solubility would decrease.
Exceptions – The solubility of some sparingly soluble gases, such as hydrogen and inert gases, increases
slightly with increase of temperature especially in the case of non-aqueous solvents such as hydrocarbons,
alcohols and acetone.

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6 | Solutions and Colligative Properties

(c) Effect of Pressure (Henry’s law): As the pressure increases, the solubility also increases. We explain this
concept using the following example. As an example
of a solution of a gas in a liquid, consider a system Gaseous w1
as shown in Fig. 2 (a). In this figure, the lower part phase at
is the solution, whereas the upper part is gaseous pressure P,
w1 w2
at pressure p and temperature T. Now, let us temperature T
suppose that the system is in dynamic equilibrium,
i.e., rate of gaseous particles entering and leaving Solution
the solution is the same, which means that rate of phase
dissolution = rate of evaporation. Now, let us a b
increase the pressure over the system as shown in Figure 2: Demonstrating the effect pressure
Fig. 2 (b). Consequently, the gas gets compressed on solubility of a gas in liquid
to a smaller volume. Due to this effect, the total
number of gaseous particles per unit volume tends to increase. Because of this, the total number of gaseous
particles striking at the surface of the solution and hence entering into it also increases. The process is
continuous till a new equilibrium is reestablished. Thus, we learn that upon increase of the pressure of the gas
above the solution, the solubility also increases.
Quantitatively, this fact was also explained by Henry’s law which states that the solubility of a gas in a liquid is
directly proportional to the pressure of the gas over the solution at a definite temperature.
m ∝ P or m = Kp
In this regard, Dalton also concluded independently that, if a mixture of gases is simultaneously is in equilibrium
with the liquid at a particular temperature, then the solubility of any gas in the mixture is directly proportional
to the partial pressure of that gas in the mixture.
By expressing solubility in terms of mole fraction of the gas in the solution, for a gas A, Henry’s law can be
written as XA = K′PA
1 1
However, this can also be written as: PA = X A or PA = KH X A where, KH = is called Henry’s constant.
K' K'
Limitations of Henry’s law
Henry’s law is applicable only when
The pressure of the gas is not too high and temperature is not too low.
The gas should not undergo any chemical change.
The gas should not undergo association or dissociation in the solution.

Illustration 3: Why sealed soda water bottle upon opening shows the evolution of gas with effervescences?
(JEE MAIN)

Sol: CO2 gas is dissolved at high pressure in soda water bottle. On opening the seal, pressure becomes equal to
atmospheric pressure and the dissolved gas comes out from solution with effervescences because solubility of gas
decreases with decrease in pressure.

Illustration 4: NH3 is one of the few gases that do not obey Henry’s law. Suggest a reason. (JEE ADVANCED)

Sol: The solubility of NH3 in water also involves H-bonding and thus, solubility of NH3 in water depends on pressure
as well as tendency to show H-bonding.

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Chem i str y | 7

RANKUP CONCEPTS

Calculation of solubility of a gas at a particular pressure from the known solubility at some other pressure
(but at the same temperature).
From Henry’s law, we know that m = Kp. Hence, if m1 is the solubility of a gas at pressure P1 and m2 is its
m1 P1
solubility at pressure P2, then = .
m2 P2
Thus, by knowing m1 at P1, we can easily calculate m2 at P2. Further, the equation, m = KP also suggests
that the plot of pressure P vs. solubility m will be a straight line passing through the origin with slope = K.
However, the greater the value of K, the greater is the solubility. For example, O2 is more soluble than N2
at the same temperature and pressure as shown in the figure provided.

3.3 Solutions of Liquids in Liquids

Consider the case wherein one liquid dissolves in another. Here, the molecules of the solvent are forced to move
apart so as to accommodate the solute molecules. In the same way, the molecules in the solute must also be
separated so that they can assume their positions in the mixture. However, it is to be noted here that in both these
processes, energy is required. Further, as the molecules of both the solute and the solvent are brought together,
there is release of energy due to the attractive forces between them. Moreover, when the molecules of both the
solute and the solvent are strongly attracted to each other, more energy is released in the final step. There is a
possibility of three cases under such circumstances. Either the overall dissolution process results in evolution of
heat or absorption of heat, or energy is released in the final step of the reaction and is the same as the energy
absorbed in the first two phases, i.e., net change is zero.
Examples
1. Benzene and carbon tetrachloride No evolution or absorption of heat
2. Acetone and water Evolution of heat
3. Ethyl alcohol and water Absorption of heat
However, we must be aware of the fact that a liquid may or may not be soluble in another liquid. Therefore, purely
based upon the relative solubility of a liquid in another, the following three cases are possible:
Miscible liquids form three types of solution, which can be ideal or non-ideal solutions.

Liquids-Liquid System

1. Liquids that are 2. Liquids that are 3. Liquids that are

completely miscible. partially miscible. completely immiscible.
Examples: Examples: Examples:
Benzene and toluene, Ether and water; Benzene and water;
Ethyl alcohol and phenol and water; Carbon tetra-chloride
water, carbon tetra- Nicotine and water. and water; Benzene
chloride and benzene. and alcohol.

Flowchart 1: Types of liquid-liquid system Miscible

liquids form three types of solutions, which can be ideal or non-ideal solutions.

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8 | Solutions and Colligative Properties

4. IDEAL SOLUTION AND RAOULT’S LAW

4.1 Ideal Solution

By an ideal solution, we mean the one that obeys Raoult’s law (we discuss this law hereunder) for a wide range of
concentrations and at a specified temperature. Some examples in this regard include
(1) Mixture of methanol and ethanol;
(2) Mixture of n-hexane and n-heptane and
(3) Mixture of benzene and toluene.

Characteristics
(a) Volume change on mixing should be zero, =
i.e., ∆Vmix 0; VSolvent
= + Vsolute Vsolution
(b) Heat change on mixing should be zero, i.e., ∆Hmix =
0 (heat is neither absorbed nor evolved)
(c) Solute must not undergo association or disociation in solution
(d) There should be no chemical reaction between the solute and solvent

Things to remember
(a) If FA − A is the force of attraction between molecules of A and FB–B is that of molecules of B, then A and B will
form an ideal solution only if, F= A −B F=
A−A FB −B
.
(b) The solution of liquids A and B will be ideal if A and B have similar structures. Further, both methanol and
ethanol have the same functional group and almost same polarity and therefore, form ideal solutions.

4.2 Non-Ideal Solution

A solution which does not obey Raoult’s law is called a non-ideal solution.
For a non-ideal solution.
(a) Raoult’s law is not obeyed, i.e., PA ≠ PA0 x A and PB ≠ PB0 xB .
(b) ∆Hmix ≠ 0 and
(c) ∆V ≠ 0
mix

4.3 Raoult’s Law

This law states that the partial pressure of any volatile constituent of a solution at a constant temperature is equal
to the vapour pressure of pure constituent multiplied by the mole fraction of that constituent in the solution.
Let us assume that a mixture is prepared containing nA and nB moles of liquid A and B, respectively. Further, let PA
and PB be the partial pressures of A and B, respectively and PA0 and PB0 the vapour pressure pure state.
Thus, according to Raoult’s law,
nA
=PA = P0 mole fraction of =
A × PA0 X APA0
nA + nB A
nB
and
= PB = P0 mole fraction of =B × PB0 XBPB0
nA + nB B
If the total pressure be P, then
nA nB
P PA + PB =
= PAo + PBo Thus, =P X APA0 + XBPB0
nA + nB nA + nB
.

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Chem i str y | 9

RANKUP CONCEPTS

This law is an important governing factor in deciding whether a solution is ideal or nonideal. Solutions
obeying Raoult’s law over a wide range of concentrations are ideal; otherwise, they are nonideal.
A non-ideal solution can either show positive or negative deviation from Raoult’s law.

4.4 Ideal and Non-Ideal Solutions

Table 2: Differences between ideal and non-ideal solutions

Ideal solutions Non-ideal solutions

Positive deviation from Raoult’s law Negative deviation from Raoult’s law
1. Obey Raoult’s law at every range of Do not obey Raoult’s law Do not obey Raoult’s law
concentration

2. ∆Hmix = 0; neither heat is evolved ∆Hmix > 0; endothermic dissolution; ∆Hmix < 0; exothermic dissolution;
nor absorbed during dissolution heat is absorbed heat is evolved

3. ∆Vmix = 0; total volume of solution

is equal to sum of volumes of the ∆Vmix > 0; volume is increased after ∆Vmix < 0; volume is decreased
components dissolution during dissolution

4. P = PA + PB = PA0 X A + PB0 XB
0 PA > PA0 X A ; PB > PB0 XB PA < PA0 X A ; PB < PB0 XB
i.e., PA P=
= A X A ; PB PB0 XB
∴ PA + PB > PA0 X A + PB0 XB ∴ PA + PB < PA0 X A + PB0 XB
5. A – A, A – B, B – B interactions
should be same, i.e., ‘A’ and ‘B’ are A – B attractive force should be weaker A – B attractive force should be greater
identical in shape, size and character than A – A and B – B attractive forces. than A – A and B – B attractive forces.
‘A’ and ‘B’ have different shape, size ‘A’ and ‘B’ have different shape, size
6. Escaping tendency of ‘A’ and ‘B’
and character. and character.
should be the same in pure liquid and
in the solution ‘A’ and ‘B’ escape easily showing Escaping tendency of both
higher vapor pressure than the components ‘A’ and ‘B’ is lowered
expected value showing lower vapor pressure than
Examples
expected ideally
Dilute solutions; benzene + toluene
Examples Examples

Acetone + ethanol; acetone + CS2 Acetone + aniline; acetone+

chloroform

4.5 Relation Between Dalton’s Law and Raoult’s Law

In this regard, we can calculate the composition of the vapour in equilibrium with the solution by applying Dalton’s
law of partial pressures. Let us assume that the mole fractions of vapours A and B be YA and YB respectively.
,
Further, let PA and PB be the partial pressures of vapours A and B, respectively and the total pressure be P.
PA = YAP …(i)

PB = YBP …(ii)

PA = X APA0 …(iii)

PB = XBPB0 …(iv)

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10 | Solutions and Colligative Properties

Now, by equating (i) and (iii), we obtain

X APA0 PA
YAP = X APA0 or
= YA =
P P
XBPB0 PB
Similarly, by equating (ii) and (iv), we obtain
= YB = .
P P
Thus, it is clear to us that in the case of an ideal solution the vapor phase is richer with more volatile component,
i.e., the one having relatively greater vapor pressure.

Illustration 5: At 300 K, the vapor pressure of an ideal solution containing one mole of A and 3 moles of B is
550 mm of Hg. At the same temperature, if one mole B is added to this solution, the vapor pressure of solution
increases by 10 mm of Hg. Calculate the VP of A and B in their pure state. (JEE MAIN)

∵ PM0 PA0 ·X A + PB0 ·XB (from Raoult’s law)

Sol: =

 1  0 3 
PA0 × 
Case I: 550 =  + PB   … (i)
1 + 3  1 + 3 
 1  0 4 
PA0 × 
Case II: On addition of one mole of B in liquid mixture 560 =  + PB   … (ii)
1 + 4  1 + 4 
0 0
Solving eqs. (i) and (ii) PA = 400 mm, PB = 600 mm

Illustration 6: The vapor pressure of ethanol and methanol are 44.5 mm and 88.7 mm Hg, respectively. An ideal
solution is formed at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate the total
vapour presure of the solution and the mole fraction of methanol in the vapor. (JEE ADVANCED)

Sol: Total vapour pressure is a sum of of partail preesure of A and B and partial pressure is given by product of
mole fraction and vapour pressure in pure form of A and B. So first we have to find out the mole fraction of A and
B and than partial pressure of A and B.
Mole fraction of a compound in the vapour is given by Partial pressure of that compound divided by total vapour
pressure of the solution.
60
Mol. mass of ethyl alcohol = C2H5OH = 46; No. of moles of methyl alcohol = = 1.304
46
40
Mol. mass of methyl alcohol = CH3OH = 32; No. of moles of methyl alcohol = = 1.25
32
1.304
‘XA’, mole fraction of ethyl alcohol = = 0.5107
1.304 + 1.25
1.25
‘XB’, mole fraction of methyl alcohol = = 0.4893
1.304 + 1.25
Partial pressure of ethyl alcohol = X A ·PA0 = 0.5107 × 44.5 = 22.73 mm Hg
Partial pressure of methyl alcohol = XB ·PB0 = 0.4893 × 88.7 = 43.40 mm Hg
Total vapour pressure of solution = 22.763 + 43.40 = 66.13 mm Hg
Partial pressure of CH3OH 43.40
Mole fraction of methyl alcohol in the vapour = = = 0.6563
Total vapour pressure 66.13

5. THEORY OF FRACTIONAL DISTILLATION

Fractional distillation is the process of separation of one liquid from another (binary mixture) having different
boiling points by distillation. However, the information regarding can a particular solution of two liquids can be
separated by distillation or not, is provided by the study of liquid–vapor equilibrium diagrams at constant pressure,
say, e.g., atmospheric pressure. The separation is possible only when the vapor phase has a composition different
from that of the boiling liquid mixture.

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Chem i str y | 11

5.1 Azeotropes and Azeotropic mixture

Azeotropes are binary mixtures having the same composition both in liquid and vapor phase and boil at a constant
temperature.

Types of Azeotropes
Minimum Boiling Azeotropes: These are the binary mixtures whose boiling point is less than either of their
two components. The non-ideal solutions show a large positive deviation from Raoult’s law for minimum boiling
azeotrope at a specific composition, e.g., a mixture of 94.5% ethyl alcohol and 4.5% water by volume.
Maximum boiling Azeotropes: These are the binary mixtures whose boiling point is more than either of their two
components. The solutions show large negative deviation from Raoult’s law for maximum boiling azeotrope at a
specific composition, e.g., a mixture of 68% HNO3 and 32% H2O by mass.

5.2 Liquid Solutions of Type I (Ideal Solutions)

If a solution of composition x is heated, then
(a) Vapor phase will be richer in B and A will have a composition x1 in
Vapor
the distillate, whereas the residue will become richer in A and let it TA Liquid
have a composition y.

Boiling point
Ty
(b) Now, if this liquid is heated again, the residue will be even more Tx
richer in A and if this process is repeated sufficient number of times, Tz
then pure A will be obtained from the residue. TB

(c) Similarly, if the distillate is recondensed and then heated again, then A 100% y x y1 x1z1 B 100%
the distillate will be richer in B and on continuing the process, pure B 0% Composition A 0%
B will be obtained from the distillate.
Figure 3 a: Composition of solution
(d) Thus, we can separate two liquids that form an ideal solution by showing idea behavior
fractional distillation.

5.3 Type II Solutions (Positive Deviations from Raoult’s Law)

If a mixture of composition x is heated, then
(a) Vapor will have a composition x1 and the composition of residual
liquid will shift toward A while the composition of distillate shifting
toward C
A
Boiling point

Va
p

B
(b) On repeating fractional distillation, pure liquid A is obtained as
or
or

Liq
p
Va

uid
a residue while mixture of composition C (minimum boiling T uid
Liq
azeotropic mixture) is obtained as a distillate. C

B 100%
(c) However, pure B cannot be obtained.
A 100% x x1 y1 y
B 0% Composition A 0%
If a mixture of composition y is heated, then
Figure 3 b: Composition of solution
(i) Vapor will have composition y1 and residual liquid composition showing positive deviation from raoults law
will shift toward C.
(ii) Ultimately, mixture of composition C is obtained as a distillate and pure liquid B is obtained as A residue
(iii) However, it is not possible to obtain pure liquid A.

5.4 Type III Solutions (Negative Deviations from Raoult’s Law)

When a mixture composition‘a’ is taken, then on boiling
(a) Distillate ‘a’ is obtained, which is richer in component A

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2 0 . 1 2 | Solutions and Colligative Properties

(b) Residue hence obtained is ‘b.’ Further, successive distillation D

V
of ‘b’ leads to azeotropic solution D (+ve boiling azeotropic V
mixture). L TB0
B
(c) Successive distillation of ‘a’ will lead to pure (A). TA0 L

When a mixture composition 'c' is taken and boiled, then

a’ a b c c’
(i) Distillate obtained is ‘c’, which is richer in component B and
successive distillation of distillates leads to solution becoming A =1 d e B =1
pure ‘b.’ Mole fraction
Figure 3 c: Mole fraction of solution
(ii) The residue of ‘c’ is ‘e.’ Further, successive distillation of
showing negative deviation from raoults law
‘e’ makes the residue richer in ‘D’ which is +ve boiling
azeotropic mixture.

6. COLLIGATIVE PROPERTIES OF DILUTE SOLUTIONS

A dilute solution is one in which the amount of the solute is very small in comparison to the amount of the solvent.
A dilute solution containing non-volatile solute exhibits some special properties which depends only upon the
number of solute particles present in the solution irrespective of their nature. These properties are termed as
colligative properties and are listed hereunder.
1. Lowering in the vapor pressure,
2. Elevation in the boiling point,
3. Depression in the freezing point and osmotic pressure.
4. Osmotic pressure.
Further, dilute solutions also obey Raoult’s law.

RANKUP CONCEPTS

•• For applying the formulae of colligative properties, the following conditions should be satisfied:
•• The solution should be very dilute.
•• The solute should be nonvolatile.
•• The solute does not dissociate or associate in solution.

6.1 Lowering in the Vapor Pressure

When a non-volatile solute is present in a solution, then the vapor pressure of the solution will be less than the
vapor pressure of pure solvent.
The vapor pressure may be lowered due to the reasons listed hereunder.
(a) Percentage surface area occupied by the solvent decreases. Thus, the rate of evaporation and vapor pressure
decreases. The solute molecules occupy the surface, and therefore the percent surface area occupied by the
solvent decreases.
1
(b) According to Graham’s law of evaporation, rate of evaporation ∝
density
Further, when a non-volatile solute is dissolved in a liquid, its density increases. Thus, both rate of evaporation and
vapor pressure are lowered.

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Chem i str y | 13

Now, let us consider the case in detail.

Only ‘A’ particles
Let there be a solution of solute B in solvent A.
Since ‘B’ is nonvolatile, it would not go to the vapor phase; hence, the Solvent (A)
vapors above the solution will be only due to volatile solvent ‘A.’ Since
Solute (non volatile) (B)
χ APA0 ⇒ PA < PA0 so vapor pressure is lowered.
PA =
Figure 4: Lowering in the Vapor Pressure
For a binary system, χA + χB = 1.
Substituting the value of χA
⇒ PA = PA0 (1 – χB); PA = PA0 – PAoχB
⇒ PA0 χB = PA0 – P = DP (relative lowering in vapor pressure); DP = PA0 χB ⇒ DP ∝ xB
⇒ Lowering in vapor pressure is directly proportional to the mole fraction of a solute. Further, the relative lowering
in vapor pressure is equal to the mole fraction of solute.
∆P PA0 − P nB
= χB , which can also be written as: =
PA0 PA0 nA + nB
or we can rephrase it as ,
P0 − Ps nB
according to Raoult’s law, =
P0 nB + nA
where, P0 = vapor pressure of pure solvent; Ps = vapor pressure of solution;
n2 = number of moles of solute; and n1 = number of moles of solvent.

RANKUP CONCEPTS

•• Lowering in vapor pressure is directly proportional to the mole fraction of solute in the solution.
•• Relative lowering in vapor pressure is equal to the mole fraction of solute.
•• Determination of molecular mass from lowering of vapor pressure.

Po − Ps nB
We know that, according to Raoult’s law, = .
P o nB + nA
If W2 g of the solute is dissolved in W1g of the solvent and if M2 and M1 are their respective molecular masses, then
w w
we have nB = B and nA = A .
MA MA
By substituting these values in the above expression, we obtain
Po − Ps wB / MB
= … (i)
P o w A / MA + wB / MB
However, for a dilute solution, n2 can be neglected in comparison with n1 so that Raoult’s law equation becomes
Po − Ps nB Po − Ps wB / MB Po − Ps wB × MA
≡ or ≡ or =
P o nA P o w A / MA P o w A × MB
From expressions (i) and (ii), it is clear that if w2g of the non-volatile solute is dissolved in w1g of the solvent and the
vapor pressure of the pure solvent (Pº) and that of the solution (Ps) are measured experimentally, then by knowing
the molecular mass of the solvent (M1), that of the solute (M2) can be calculated.

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14 | Solutions and Colligative Properties

Actually, this is not a preferred method because other methods (namely, elevation in boiling point or depression in
freezing point) give results more easily and accurately.

Determination of Relative Lowering in Vapor Pressure

We can determine the relative lowering in vapor pressure by using Ostwald and Walker method. In this method, a
stream of dry air is passed successively through a set of weighed bulbs containing the solution and then through a set
of merged bulbs containing pure solvent and finally through weighed U-shaped tubes containing anhydrous CaCl2.
u2 + Rg u2
<
3g 2g
(a) Let the loss in weight of solution bulbs be w1 gm
(b) Loss in weight of solvent bulbs be w2 gm
(c) Loss in weight of the solution bulbs (w1) ∝ vapor pressure of the solution
(d) Loss in weight of the solvent bulbs (w2) ∝ vapor pressure of the solvent – vapor pressure of the solution.
⇒ Ps ∝ w1 and (P0 – Ps) ∝ w2
Po − Ps w2 Loss in weight of solvent bulbs
⇒ = = = XB
P o w1 + w2 Total loss in weight of soltuion bulbs and solvent bulbs
i.e., mole fraction of the solute.

Vapor Pressure of Liquid and Temperature

Liquid  Vapor ∆Hvap > 0
Basically, vapor pressure of liquid increases with temperature. Here, ∆H is enthalpy of vaporization. We provide a
graphical representation of vapor pressure versus temperature hereunder.
Vapor pressure

log,P

Temperature 1/T

Figure 5: Variation of vapor pressure with temperature

Generally, if vapor pressure of a liquid is known at a temperature, then it can be calculated at another temperature
P  ∆Hvap.  1 1 
using Clausius–Clapeyron equation: log10  2  =  − 
 P1  2.303R  T1 T2 
Here, P1 = vapor pressure at temperature T1 and P2 = vapor pressure at temperature T2.

6.2 Elevation in Boiling Point (Ebullioscopy)

We know that the boiling point of a liquid is the temperature at which its vapor pressure is equal to the atmospheric
pressure. Further, the vapour pressure of a liquid is generally lowered upon addition of a non-volatile solute to it.
Hence, the temperature of the solution when its vapor pressure will be equal to atmospheric pressure will be higher
than the temperature of the pure solvent. In other words, we mean that the boiling point of the solvent is elevated
by the addtion of a non-volatile solute. However, the difference in the boiling point of the solution and the boiling
point of the pure solvent is termed as elevation of the boiling point.

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Chem i str y | 15

Elevation of boiling point, (DT) = Boiling point of the solution – Boiling point of pure solvent
This can be better understood by ploting a graph of vapor pressure vs. temperature for a pure solvent and two
solutions of different concentrations. In such a graph, the curves for solution will always lie below the curves for
pure solvent.
In the graph provided hereunder, P0E represents atmospheric pressure, TB0, T1 and T2 are boiling points for pure
solvent, solution-1 and solution-2, respectively. Similarly, the vapor pressures of solution-1 , solution-2 and pure
solvent at temperatures TB0 are P1, P2 and P0, respectively.
Relationship for elevation in boiling points.

0
P E - Atmospheric Pressure

0 1 atm A D E
P
Vapour
Pressure P TB0=Boiling Point
1
temperature
t
en

1
n-
lv
tio
So

P2 2
n-
lu
So

tio
lu
So

TB0 { T2 T1
TB
Temperature

Figure 6: Elevation in Boiling Point

Let us consider the graph of vapor pressure vs. temperature (in Kelvin scale). Here, triangle ADB and ACE are similar.
Hence,
AD AB
=
AE AC
T1 − T0 P0 − P1
= ⇒ T1 – T0 ∝ P0 – P1
0 0
T2 − T P − P2
⇒ DTB ∝ DP. Also, DP ∝ XB ⇒ DTB ∝ XB
nB nB
DTB ∝ ; DTB ∝ [dilute solutions]
nA + nB nA
WB MA WB
DTB ∝ × ⇒ ∆TB =
Kb
MB WA MB × WA
WB
When = 1 mole and WA = mass of solute in kilogram (kg)
MB
⇒ ∆TB = Kb × m m = molality of solution, Kb = ebullioscopic constant
∆TB ∝ Kb [when concentration is kept constant].
Hence, elevation in boiling point depends upon KB, i.e., nature of solvent.
∆TB ∝ m [when solvent taken is same]
Kb is defined as the elevation in boiling point of a solvent when 1-g mole of a non-volatile solute is dissolved in
1000 g of solvent.
RTb2
Kb = 1v = latent heat of vaporization per gram of the solvent.
1000 lv
RTb2 × M0
Also, Kb = where M0 = molecular weight of solvent
1000 × ∆Hv

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16 | Solutions and Colligative Properties

RANKUP CONCEPTS

Kb Wsolute Kb WB
=∆TB ∆TB
× 1000 = × 1000
Msolute × Wsolvent MB × WA
WB = Wsolute = Mass of solute taken
MB = Msolute = Molecular weight of solute
WA = Wsolvent = Mass of solvent taken in grams
Kb WB
⇒ =
Msolute × 1000
∆TB × WA
TB(1) Kb(1)
Also, = when concentration is same but solvent different
∆TB(2) Kb(2)
∆TB(1) m1
= when solvent is same but concentration different
∆TB(2) m2
∆TB(1) MB(2) 1
= ⇒ DTB ∝ when solvent and amount of solute is same
∆TB(2) MB(1) MB(1)

6.3 Depression in Freezing Point (Cryoscopy)

Freezing point of a substance is defined as the temperature at which the vapor pressure of its liquid is equal to the
vapor pressure of the corresponding solid. This is primarily because the addition of a non-volatile solute always
lowers the vapor pressure of a solvent; therefore, it will be in equilibrium with solid phase at a lower pressure and
hence at a lower temperature. Further, the actual difference between the freezing points of the pure solvent and its
solution is called depression of freezing point. Thus
Depression of freezing point (DT) = Freezing point of the solvent – Freezing point of the solution
Here again,
DTf ∝ DP
DP ∝ molality or DP ∝ XB
nB
DTf ∝ molality DTf ∝ XB ⇒ DTf ∝ for dilute solutions
nA
⇒ DTf = Kf WB when WA is in kilogram ⇒ ∆Tf =
Kfm
MB WA
Kf = molal depression constant or Cryoscopic constant.
Kf is defined as the depression in freezing point of a solvent when 1 g mole of a non-volatile solute is dissolved
RTf2 RTf2 M0
in 1000 g of solvent, i.e., K f = also K f =
1000lf 1000∆Hf
where Tf = freezing point and Tf = latent heat of fusion per gram
RTf × w
Also, ∆Tf
= solute
× 1000
M solute× W solvent

Hence, molecular weight of solute

Kf × W solute
Msolvent
= × 1000
∆Tf × W solvent

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Chem i str y | 17

Since DTf = Kfm ⇒ DTf ∝ Kf [when concentration is same but different solvents are taken]
DTf ∝ m [when solvent is same but different concentration are taken]

6.4 Osmotic pressure

Semipermeable Membrane: We define a semipermeable membrane as “A membrane which allows the solvent’s
molecules to pass through it but prevents the passage of solute molecules through it.”

Osmosis: The phenomenon of osmosis was first observed by Abbe Nollet. It may be defined as a process in
which pure solvent molecules pass through a semipermeable membrane from a solution of low concentration to
a solution of higher concentration.
(a) Further, exosmosis is the mechanism of outward flow of water from a cell containing an aqueous solution
through a semipermeable membrane, e.g., grapes in NaCl solution.
(b) On the other hand, endosmosis is the mechanism of inward flow of water into a cell containing an aqueous
solution through a semipermeable mebrane, e.g., grapes in water.
Therefore, if the solution of density d rises to height h, then osmotic pressure is expressed as
π = h × d × g, where g is the acceleration due to gravity.
Osmotic pressure may also be defined as the excess pressure which must be applied to a solution in order to
prevent flow of solvent into the solution through the semipermeable membrane.
However, we can define osmotic pressure in several other ways also as listed hereunder.
(a) Osmotic pressure is the excess pressure which must be applied to a given solution in order to increase its
vapour pressure until it becomes equal to that of the solution.
(b) Osmotic pressure is the negative pressure when a solution is separated from the solvent by a semipermeable
membrane.
(c) Osmotic pressure is the hydrostatic pressure produced when a solution is separted from the solvent by a
semipermeable membrane.

Differences between Osmosis and Diffusion

Let us now proceed to understand the differences between the processes of osmosis and diffusion as listed
hereunder.
(a) In the process of diffusion, both the solute as well as the solvent molecules flow in opposite directions while
in the process of osmosis the flow of solvent molecules is unidirectional.
(b) For osmosis to take place, a semipermeable membrane is essential while it is not so for diffusion.

6.4.1 Van’t Hoff Theory of Dilute Solutions

Dilute solutions behave like ideal gases and gas laws obeyed by ideal gases are also obeyed by dilute solutions.
We know that
1
V∝ (Boyle–van’t Hoff law); V ∝ T (Charles–van’t Hoff law)
π
V ∝ n (Avogadro–van’t Hoff law)
n× T nRT
⇒ V∝ ⇒ V= R = solution constant (0.0821 it atm K–1 mol–1)
π π
n
⇒ π= RT ⇒ π = CRT
V
Hence, at a given temperature, π ∝ C

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18 | Solutions and Colligative Properties

Pressure–Temperature law (Gay-Lussac–van’t Hoff law)

Concentration remaining same, the osmotic pressure of a dilute solution is directly proportional to its absolute
temperature (T), i.e., π ∝ T
π π
or = constant or = constant
T T

RANKUP CONCEPTS
n
• pV = nRT or pV = nST or π = ST or π = CST
V
where π = osmotic pressure in atmospheres
n = number of moles of the solute present in V liters of the solution
C = concentration of the solution in moles per liter
T = temperature in K
R or S = 0.08211 atm deg–1 mole–1

w  w  wST
• pV = ST  n =  ; M0 = (M0 = molecular weight of solute)
M0  M0  πV
where w = Wt. of solute in g dissolved in V1 of solution.
m = molecular wt. of the solute; π = hdg
• In isotonic solutions, since osmotic pressure p is equal, their concentration (C) must also be equal,
n1 n2 w1 w2
i.e., = ; =
V1 V2 m1 V1 m2 V2
• If a number of solutes is present in the solutions and p1, p2, p3, etc. are their individual osmotic
pressure, then the total osmotic pressure = p1 + p2 + p3 + ….

6.4.2 Reverse Osmosis

Generally, we understand that if a pressure higher than osmotic pressure is applied on a solution, then the solvent
will flow from the solution into the pure solvent through the semipermeable membrane. However, here as the flow
of solvent is in the reverse direction to that observed in the usual osmosis, we call this process as reverse osmosis.
This process is extensively used in the desalination of sea water to obtain pure water.

6.4.3 Isotonic Solutions

A pair of solutions having the same osmotic pressure are known as isosmotic or isotonic solutions. However, if two
such solutions are separated by a semipermeable membrane, then there will be transference of solvent from one
solution to the other. Thus, isosmotic solutions that are separated using a semipermeable membrane are known as
isotonic solutions. Further, isotonic solutios have the same concentration.
For example, 0.85% NaCl solution is found to be isotonic with blood, while 0.9% NaCl solution isotonic with
human RBCs. On the contrary, a solution that is having lower or higher osmotic pressure than the other is said
to be hypotonic or hypertonic, respectively with respect to other solution. (i) When placed in water or hypotonic
solutions, cells swell and burst and this process is known as hemolysis. (ii) When placed in hypertonic solutions,
the fluid from the plant cells comes out and thus the cells contract in size. This process is known as plasmolysis.
Further, when excess of fertilizers (like urea) is applied, then plasmolysis takes place and hence plants dry up (wilt).

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Chem i str y | 19

Illustration 7: Estimate the boiling point of a solution of 25.0 g of urea (NH2CONH2) plus 25.0 g of thiourea
(NH2CSNH2) in 500 g of chloroform, CHCl3. The boiling point of pure chloroform is 61.2°C, Kb of chloroform =
3.63 km–1. (JEE MAIN)

Sol: Molality is given by moles of Solute by mass of solvent in Kg. since here two solute are used we have to first
calculate the mole of urea and thiourea used. The sum of the two solute will give us total moles of solute which can
be used to calculat the molality of the solution.
Mass of urea 25.0g
Moles of urea = = = 0.42 mol
Molecular mass of urea 60g / mol
25.0g
Moles of thiourea = = 0.33mol
76g / mol
\ Total moles of solute = 0.42 + 0.33 = 0.75
Moles of solute 0.75mol
Molality, m = = = 1.50 m
Mass of solvent in kg (500g / 1000g)kg

DTb = Tb – Tbo =Kb.m = 3.63 × 1.50 = 5.44 K = 5.445ºC

Tb = 5.445ºC + Tbo = 5.445ºC +61.2ºC = 66.645ºC

Illustration 8: Consider a vertical tube of cross-section area of 1 cm2. The bottom of the tube is closed with a
semipermeable membrane and 1 g of glucose is placed in the tube. The closed end of the tube is immersed in pure
water. What will be the height of the liquid level in the tube at equilibrium? The density of solution may be taken
as 1 g/cm2. What is the osmotic pressure at equilibrium at 25ºC? Assume negligible depth of immersion of tube.
(JEE ADVANCED)

Sol: Since here we have to calculate the osmotic pressure, we can use the following relation pV = nRT
Volume term is not provided instead cross section area of the tube is given so from this we can calculate the
volume term.
Let height of the tube = h cm
V = (h × 1) cm3 ∵ cross-sectional area = 1 cm2
 h×1  1 134.92
pV = nRT; π ×   = × 0.0821 × 298; π = atm
 1000  180 h

134.92 h×1 9.8

π = h × d × g; = × , 1 atm = 101.325 KPa
h 100 101.325
h = 375 cm = 3.75 m
π = h × d × g = 3.75 × 1 × 9.8 = 36.7 KPa

Illustration 9: A solution containing 0.2563 g of nephthalene (molecular mass = 128) in 50 g of carbon tetrachloride
yields a boiling point elevation of 0.201ºC while a solution of 0.6216 g of an unknown solute in the same mass of
the solvent gives a boiling point elevation of 0.647ºC. Find the molecular mass of the unknown solute.
(JEE MAIN)
∆Tb × W × m
Sol: From the given dataa first calculate Kb by using following formula Kb = ;
1000 × w
Now by using the value of Kb find out the molecular mass of the unknown solute.
We know that,
∆Tb × W × m 0.201 × 50 × 128
Kb = ; for CCl4, Kb = = 5.019
1000 × w 1000 × 0.2563

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20 | Solutions and Colligative Properties

1000 × 5.019 × 0.6216

Kb is now used in the second part of the problem; m = = 96.44
0.647 × 50

Illustration 10: In a cold climate, water is frozen causing damage to radiator of a car. Ethylene glycol is used as an
antifreezing agent. Calculate the amount of ethylene glycol to be added to 4 kg of water to prevent it from freezing
at –6ºC (Kf for water = 1.85 K kg mol–1). (JEE ADVANCED)

Sol: Here we are provided with the value of DT ,W ,m and Kf so we can calculate th weight by using the following
formual:
m × M × ∆Tf m × M × ∆T 62 × 4000 × 6
w= Given, DT = 6ºC, W = 4kg = 4000g, m = 62, Kf = 1.85; w = = = 804.32 g
1000 × K f 1000 × K f 1000 × 1.85

6.5 Abnormal Molar Masses

Association : Association of molecules generally leads to decrease in the number of particles in a solution and
this results in a decrease in the value of colligative property. As we are aware, colligative property is inversely
related to the molecular mass. Therefore, obviously a higher value is obtained for molecular mass. For example,
when ethanoic acid is dissolved in benzene, it undergoes dimerization and shows a molecular mass of 120 (normal
molecular mass is 60).
O --- H – O
2CH3 — COOH H3C – C C — C H3
O – H --- O

Dissociation : In contrast to association, dissociation leads to an increase in the number of solute particles in a
solution and this results in an increase in the value of colligative property. Further, since colligative property is
inversely related to the molecular mass molecular mass of such a substance as calculated from colligative property
will therefore be less than its normal value. For example, we know that KCl is an electrolyte. However, when
it is dissolved in water it dissociates into K+ and Cl– ions and there would be double the number of particles if there
+ −
is complete dissociation. Hence, it is expected to have molecular mass 37.25 g = 74.5/2. KCl  
 K + Cl
To account for the above anomalies, van’t Hoff therefore introduced a factor ‘i’ in the van’t Hoff equation (pV = RT)
of osmotic pressure. Accordingly, the modified equation may thus be written as pV = iRT. The factor ‘i’ is defined
Observed osmotic pressure
by the expression, i =
Normal osmotic pressure
In this regard, the experimental value of i can be obtained by dividing the observed osmotic pressure of the solution
under the study with that of the solution of a normal substance (say, e.g., sucrose) of the same concentration
(molarity) as that of the substance under study.
Now, since osmotic pressure behaves like other colligative properties, the factor i can also be applied to other
colligative properties. Thus, in general,
Actual number of particles Observed colligative property (experimental)
i= ; i=
No. of particle when no ionisation/association Normal colligative property(calculated)

Now, since molecular weight of a solute is inversely proportional to the colligative property the factor ‘i’ may also
be defined in the following way.

Normal molecular wt. (calculated value)

i=
Observed molecular wt.(experimental value)

Evidently, for a normal substance (which neither dissociates nor associates in solution), the factor ‘i’ is always unity.
When the van’t Hoff factor is included, then the colligative properties get modified shown hereunder.

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Chem i str y | 21

(a) Relative Lowering in Vapor pressure

P0 − Ps
= i × XB where i = van’t Hoff factor
P0
P0 − Ps nB
XB = mole fraction of solute for dilute solution = i× ; nB = number of moles of solute; nA = number of
moles of solvent P0 nA

P0 − Ps WB MA
⇒ i×
= × where WB = amount of solute dissolved; WA = amount of solvent taken;
P 0 MB WA
MB = molecular mass of solute; MA = molecular mass of solvent
Elevation in Boiling point
WB
iKbm ; ∆TB = iKb ×
∆TB = × 1000
MB × WA (gms)
Depression in Freezing Point
WB
iK f m ; ∆Tf = iK f ×
∆Tf = × 1000
MB × WA (gms)
Osmotic pressure
pV = inRT; π = iCRT

6.6 Relationship Between van’t Hoff Factor for Dissociation and Association
(a) Dissociation
Degree of dissociation: We define the degree of dissociation as the number of moles dissociated over the initial
concentration taken
Total number of particles at equilibrium
Van’t Hoff factor :
Initial concentration
Let c moles per liter of an electrolyte Axby be taken and let it dissociate
as xA y + & yBx − . ' α ' be degree of dissociation.
∴ No. of solute particle dissociated = Cα
A x By → xA y + + yBx −
Initial conc. C O O
Conc. at equilibrium C – C α   x c α y c α
[(c − cα ) + xcα + Ycα] 1 − α + xα +yα
i= ⇒ i= = 1 + [(x + y) – 1] a
c 1
Let x + y = n = number of particles formed after dissociation
i−1
⇒ i = 1 (n – 1) α; α =
n−1

(b) Association
Degree of Association: The degree of association may be defined as the number of molecules associated over
initial concentration.
number of moles associated Total number of moles of particles at equilibrium
α= ; i=
Initial concentration Initial concentration
Let n molecules of an electrolyte A undergo association
nA → An

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22 | Solutions and Colligative Properties

Let the initial concentration of A = C; the degree of association = a

Cα
when C α moles of A associate, then moles of An are formed
n Cα
Cα C − Cα +
Number of moles of equilibrium (C – Cα) ⇒ i= n
n C
α
1−α+
If C = 1, then i = n ; i = 1 +  1 − 1 α ⇒ α = i − 1
 
1 n  1
−1
n

Illustration 11: The freezing point depression of 0.001m Kx[Fe(CN)6] is 7.10 × 10–3 K. Determine the value of x.
Given, Kf = 1.86 K kg mol–1 for water. (JEE MAIN)

Sol: Dx = i × Kf × m; 7.10 × 10–3 = i × 1.86 × 0.001; i = 3.817

i−1 3.817 − 1
α= ;1= ; x = 2.817 ≈ 3
n−1 (x + 1) − 1
∴ Molecular formula of the compound is K3[Fe(CN)6].

Illustration 12: Three particles of a solute, A, associate in benzene to form species A3. Calculate the freezing point
of 0.25 molal solution. The degree of association of solute A is found to be 0.80, the freezing point of benzene and
its cryoscopic constant are 5.5ºC and 5.12 km–1, respectively. (JEE MAIN)

Sol: 3A
→ A3
No. of moles dissolved 3m(1 – α) 0
No. of moles after dissociation mα/3
Total moles present after dissociation
α  α  2α   3 − 2 × 0.8 
= m(1 – α) + m = m 1 − α +  = m 1 −  = 0.25 m   = 0.177 m
3  3   3   3 
DTf = Kfm or Tf0 – Tf = 5.12 km–1 × 0.117 m = 0.6
Tf = Tf0 – 0.6ºC = 5.5ºC – 0.6ºC = 4.9ºC

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Chem i str y | 23

PROBLEM-SOLVING TACTICS
General Plan for Solving Problems Involving Freezing Point Depression and Boiling Point Elevation

Mass of solute

Convert using the

molar mass of the solute
Amount of solute
in moles
Determine if solute mol particles
m=
is an electrolyte or kg solvent
non-electrolyte

Amount of
Molal concentration
particles
of particles in solution, m
Determine if in solution

Multiply by the molal Multiply by the molal

freezing point boiling point
constant, kf constant, kb

Freezing point Boiling point

depression, Tf elevation, Tb

Add Tf to the normal Add Tb to the normal

freezing point of boiling point of
the solvent the solvent

Freezing point Boiling point

of solution of solution

Figure 7

For example, let us consider the table provided hereunder.

Table: List of freezing point depression and boiling point elevation constant for common solvents.

Solvent Normal f.p. (in ºC) kf (in ºC/m) Normal b.p. (in ºC) kb (in ºC/m)
Acetic acid 16.6 –3.90 117.9 3.07
Camphor 178.8 –39.7 207.4 5.61
Ether –116.3 –1.79 34.6 2.02
Naphthalene 80.2 –6.94 217.7 5.80
Phenol 40.9 –7.40 181.8 3.60
Water 0.00 –1.86 100.0 0.51

Sample Problem 1: What is the freezing point of a solution of 210.0 g of glycerol, HOCH2CHOHCH2OH, dissolved
in 350 g of water?

Sol 1: Analyze

(i) What is given in the problem? The formula and mass of solute and the mass of the water used
(ii) What are you asked to find? The freezing point of the solution

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24 | Solutions and Colligative Properties

Items Data
Identity of solute Glycerol, HOCH2CHOHCH2OH
Particles per mole of solute 1 mol
Identity of solvent Water
Freezing point of solvent 0.00ºC
Mass of solvent 350 g
Mass of solute 210.0 g
Molar mass of solute 92.11 g/mol
Molal concentration of solute particles ?
Molal freezing point constant for water –1.86º C/m
Freezing point depression ?
Freezing point of solution ?

2. Plan
What steps are needed to calculate the freezing point of the solution?
In such cases, use the molar mass of the solute to determine the amount of solute. Then, apply the mass of solvent
to calculate the molality of the solution.
From the molality, now use the molal freeezing constant for water to calculate the number of degrees the freezing
point is lowered. Thereafter, add this negative value ot the normal freezing point.

Freezing point of the glycerol solution

Mass of glycerol in g 6

Multiply by the inverse

Add Tf to the
of the molar mass
normal freezing point
of glycerol
of water

2 5
Amount of glycerol in solution Freezing point elevation, Tf

The solute is a non electrolyte, Multiply by the molal

so the amount of solute freezing point constant
equals the amount Kf of water
of particles in solution
4
Divide the amount
3
of the particles in Molal concentration of
Amount of particles in solution particles in water, m
Solution by the
mass of the solvent
in kilograms
Mass of water in kg

1 kg
Multiply by the conversion factor
1000 g

given
1 kg
gH2O× kg H2O
= Mass of water in g
1000 g
freezing point
1 Calculate depression
molar mass of glycerol above constant freezing po int Calculated
given of H O above
1 mol glycerol 1 −1.86º C 2
g glycerol × × × =∆Tf ; 0.00º C + ∆Tf =tf
92.11 g glycerol kg H2O mol / kg

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Chem i str y | 25

3. Compute
1kg
350 g H2O × = 0.350 kg H2O
1000g
1 mol glycerol 1 −1.86º C
210.0 g glycerol × × × −12.1º C
=
92.11 g glycerol 0.350kg H2O mol / kg

0.00ºC + (–12.1ºC) = –12.1ºC

4. Evaluate

(i) Are the units correct? Yes, units canceled to give Celsius degrees.
(ii) Is the number of significant figure correct? Yes, three significant figures are correct be-
cause the data had a minimum of three signif-
icant figures.
(iii) Is the answer reasonable? Yes, the calculation can be approximated as

200 ÷ [90 × 3(350 ÷ 1000)] × –2 = –400/30 =

–13, which is close to the calculated value.

Sample Problem 2: What is the boiling point of a solution containing 34.3 g of the ionic compound magnesium
nitrate dissolved in 0.107 kg of water?

Sol:
1. Analyze

(i) What is given in the problem? the formula and mass of solute and the mass of the water used
(ii) What are you asked to find? the freezing point of the solution

Items Data
Identity of solute Magnesium nitrate
Equation for the dissociation of the solute Mg(NO3)2 → Mg2+ + 2NO3–
Amount of ions per mole of solute 3 mol
Identity of solvent Water
Boiling point of solvent 100.0ºC
Mass of solvent 0.107 kg H2O
Mass of solute 34.3 g
Molar mass of solute 148.32 g/mol
Molal concentration of solute particles ?m
Molal boiling point constant for solvent 0.51ºC/m
Boiling point depression ?ºC
Boiling point of solution ?ºC

2. Plan
What steps are needed to calculate the freezing point of the solution?
In such a case, use the molar mass to calculate the amount of solute in moles. Then, multiply the amount of solute
by the number of moles of ions produced per mole of solute. Use the amount of ions with the mass of solvent to
compute the molality of particles in solution. Thereafter, use this effective molality to determine the boiling point
elevation and the boiling point of the solution.

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26 | Solutions and Colligative Properties

1 6
Mass of Mg(NO3)2 in g Boiling point the of Mg(NO3)2 in g

Add Tb to the

normal boiling point
of water

5
2 Boiling point elevation, Tb
Amount of Mg(NO3)2 in mol
The solute is an electrolyte, Multiply by the molal
so multiply the amount if boiling point constant
solute by number of Kb of water
particles per mole of solute
4
Divide the amount
3 Molal concentration of
of the particles in
Amount of particles in solution particles in water, m
solution by the
mass of the solvent
in kilograms
Mass of water in kg

1
molal boiling-po int
molar mass of Mg(NO3 )2 given cons tant for water
given
1 mol Mg(NO3 )2 3 mol particles 1 0.51º C
g Mg(NO3 )2 × × × × ∆tb
=
148.32 g Mg(NO3 )2 1 mol Mg(NO3 )2 kg H2O mol / kg

boiling po int Calculate

of H2O above
100.0º C + ∆tb =tb

3. Compute

1 mol Mg(NO3 )2 3 mol particles 1 0.51º C

34.3g Mg(NO3 )2 × × × × 3.31º C
=
148.32 g Mg(NO3 )2 1 mol Mg(NO3 )2 0.107kg H2O mol / kg

100. 0ºC + 3.31ºC) = 103.3ºC

4. Evaluate

(i) Are the units correct? Yes, units canceled to give Celsius degrees.
(ii) Is the number of significant figure correct? Yes, the number significant figures is correct because the boiling point of
water was given to one decimal place.
(iii) Is the answer reasonable? Yes, the calculation can be approximated as
[35 × 3)/150 × 5 = (7/10) × 5 = 3.5, which is given to one decimal place.

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Chem i str y | 27

POINTS TO REMEMBER
P = KHX, where, P = partial pressure of a gas over solution, KH = Henry’s constant,
Henry’s law
X = mole fraction of the gas in solution

0
Raoult’s law P =XA PA + XB PB0 , where, P = total pressure of the solution, XA and XB = mole fraction
0
of substituents A and B. pAo and PB = partial pressure of A and B, respectively

A A X P0
A PB B B X P0 P
YA
Relationship between Dalton’s law= = , YB
= = ,
P P P P
and Raoult’s law
where, YA and YB denotes mole fraction of components A and B in vapor phase

PA0 − P
Lowering of vapor pressure = x B , relative lowering of vapor pressure = mole fraction of solute
PA0

K W
Elevation in boiling point ∆TB = B B × 1000
MB × WA

RTf × wsolute
Depression in freezing point =∆Tf × 1000
Msolute × Wsolvent

Osmotic pressure Osmotic pressure, π =CRT

Normal molecular wt.(calculated value)

van’t Hoff factor, i i=
Observed molecular wt.(experimental value)

van’t Hoff factor in case of i−1

For association, α =
association n−1

i−1
van’t Hoff factor in case of For dissociation, α =
1
dissociation −1
n

Solved Examples

LEVEL 1 Example 2: The osmotic pressure of a solution of an

organic substance containing 18 g in one litre of solution
Example 1: One litre of sea water weighs 1030 g and at 293 K is 2.414 × 105 Nm–2. Find the molecular mass of
contain about 6 × 10–3 g of dissolved O2. Calculate the the substance if S = 8.3 JK–1 per mol.
concentration of dissolved oxygen in ppm. w w
Sol: Applying the equation, PV = · ST or m = · ST
m PV
Sol: Mass of O2 in mg = 6 × 10–3 g × 103 mg/g = 6 mg
Given, P = 2.414 × 105 Nm–2,
ppm of O2 in 1030 g sea water
V = 1.0 liter = 1 × 10–3 m3,
Mass of O2 in mg
= × 106 S = 8.3 JK–1 per mol,
Mass of sea water in mg
6 w = 18 g and T = 293 K
= × 106 = 5.8 ppm
(1030 × 1000)mg

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28 | Solutions and Colligative Properties

18 Example 6: Why does the use of the pressure cooker

m= × 8.3 × 293 = 181.33
5
2.414 × 10 × 1 × 10 −3 reduces cooking time?

Sol: At higher pressure over the liquid (due to weight

Example 3: What is the molality of 40.0 wt% ethylene of the pressure cooker lid) the liquid boils at higher
glycol solution used for automobile antifreeze ? (molar temperaure and cooking occurs faster.
mass of ethylene glycol = 62 g mol–1).

Sol:100 g ethylene glycol solution has Example 7: One liter of a sample of hard water
contains 1 mg of CaCl2 and 1 mg of MgCl2. Find the
= 40 g ethylene glycol total hardness in terms of parts of CaCO3 per 106 parts
60 g water (solvent) has = 40 g ethylene glycol of water by mass.
Or 0.060 kg water has Sol: CaCl2 → CaCO3
40 111 g 100 g
= mole ethylene glycol
62
 100 
mole of solute 40 / 62 \ 1 mg of CaCl2 is equivalent to  × 1  mg CaCO3
∴ Molality = = = 10.75 molal  111 
kg of solvent 0.060
MgCl2 → CaCO3
Example 4: To 500 cm3 of water 3.0 × 103 kg of acetic 95 100
acid is added. If 23% of acetic acid is dissociated, what  1
will be the depression in freezing point ? Kf and density \1 mg of MgCl2 is equivalent to =  2 ×  = 0.82 mg
 3
of water are 1.86 K kg–1 and 0.997 g cm–3, respectively.
 100 100 
Total mass of CaCO3 =  +  mg
Sol: Mass of solute = 3 × 10–3 kg = 3 g  111 95 
Mass of solvent = 500 × 0.997 = 498.5 g = 1.9535 mg

α = 23% = 0.23, Given volume = 1 liter, mass

i = 1 – α + nα= 1 – 0.23 + 2 × 0.23 = 1.23 = 1000 g = 106 mg

DTf = i(molality × Kf ) Thus, 1.9535 mg of CaCO3 is present in 106 mg of H2O.

 3 × 1000  Hardness = 1.9535 ppm

⇒ 1.23 ×   × 1.86 ⇒DTf = 0.229
 60 × 498.5 
Example 8: Vapor pressure of mixtures of C6H6 and
C7H8 at 50ºC are given by PM = 179 XB + 92, respectively
Example 5: Concentration of NaOH solution is 3.0
where XB is the mole fraction of C6H6. Calculate
molal and its denisty is 1.110 g/mL. What is the molarity
of the solution? (a) Vapor pressure of pure liquids.
w 1000 (b) Vapor pressure of liquid mixture obtained by mixing
Sol: Molarity = ×
M V 936g C6H6 and 736 g toluene.
[V = volume of the solution] (c) If the vapors are removed and condensed into liquid
and again brought to the temperture of 50ºC, what
3 mol. of NaOH = 120 g of NaOH
would be the mole fraction of C6H6 in vapor state?
Weight of the solution = [120 + 1000] g
Sol: Given, PM = 179XB+ 92
= 1120 g
For pure C6H6,
1.110 g solution has the volume = 1 c.c.
1 XB, i.e., mole fraction of benzene = 1
∴ 1120 g solution has the volume = × 1120
1.110 \PB0 = 179 + 92 = 271 mm
 w  1000
Hence, molarity =   ×
M  V (a) For pure C7H8; XB = 0
1000 \PT0 = 179 × 0 + 92 = 92 mm
3×
= × 1.110 =
2.9732M
1120

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Chem i str y | 29

936 Example 10: x g of non-electrolytic compound (molar

78 12 mass = 200) is dissolved in 1.0 liter of 0.05 M NaCl
(b)
= XB = = 0.60
936 736 12 + 8 solution. The osmotic pressure of this solution is found
+ to be 4.92 atm at 27ºC. Calculate the value of ‘x.’ Assume
78 92
complete dissociation of NaCl and ideal behavior of
736 this solution.
92 8
XT
= = = 0.40
936 736 12 + 8 Sol: (i) For NaCl; p1 = i(CRT)
+
78 92
p1 = 2 × 0.05 × 0.0821 × 300 ; ⇒ p1 = 2.463 atm
PM = 179 × 0.6 + 92 = 107.4 + 92 = 199.4 mm For unknown compound
(c) Mole fraction of C6H6 in vapor phase of initial mixture x
p2 = CRT ⇒ p2 = × 0.821 × 300 ;
X′B = P′B / PM 200 × 1

∴ X′B = [271 × 0.6] / 199.4 = 0.815 ⇒ p2 = 0.1231 × atm

Similarly, X′T = [92 × 0.4] / 199.4 = 0.185 Total osmotic pressure π = p1 + p2

These fractions of vapors are taken out and condensed 4.92 = 2.463 + 0.1231x; x = 19.959 g
into liquid. The liquid is again brought to 50ºC to get
again vapour–liquid equilibrium.
LEVEL 2
∴ Mole fraction of components in vapor phase of initial
mixture = Mole fraction of components in liquid phase Example 1: Two liquids A and B form ideal solution.
of II mixture. At 300 K, the vapor pressure of a solution containing 1
\PM = PB0 · X′B + PT0 · X′T mole of A and 3 moles of B is 550 mm of Hg. At the same
temperature, if one more mole of B is added to this
= 271 × 0.815 + 92 × 0.185 mm
solution, the vapor pressure of the solution increases
= 220.865 + 17.02 = 237.885 mm by 10 mm of Hg. Determine the vapor pressure of A
and B in their pure state.
Example 9: The solution of a non-volatile solute in
Sol: Let the VP of pure A and B are PA0 and PB0,
water freezes at –0.30ºC. The vapor pressure of pure
respectively.
water at 298 K is 23.51 mm Hg and Kf of water is 1.86
degree/molal. Calculate the vapor pressure of this Total VP of solution (1 mole A + 3 moles B)
solution at 298 K. 1 0 3 0
PM = XAPA0 + XBPB0 ⇒ 550 = P + P
4 A 4 B
Sol: DTf = molality × Kf; 0.30 = molality × 1.86
or PA0 + 3PB0 = 2200 ... (i)
0.30 10 5 n × 1000
molality = = = ⇒ Total VP of solution (1 mole A + 4 moles B)
1.86 62 31 W(gm)
1 0 4 1 0 1 0 4 0
n = moles of solute, W = wt. of solvent PM = P + P ⇒ 560 = P + P
5 A 5 5 B 5 A 5 B
M = mol. wt. solvent, N = mole of solvent
or PA0 + 4PB0 = 2800 … (ii)
n 5
= Solving (i) and (ii)
N × 18 31 × 1000
PA0 = 400 mm of Hg PB0 = 600 mm of Hg
n 5 × 18 9
⇒
= =
N 31 × 1000 3100
Example 2: Two liquids A and B form an ideal solution
N at temperature T. When the total vapor pressure
N 0
∵ PS = P ⇒ n P above the solution is 400 torr, the mole fraction of A
n+N N 0 in the vapor phase is 0.40 and in the liquid phase 0.75.
1+
n What are the vapor pressure of pure A and pure B at
3100 temperature T?

⇒PS = 9 × 23.51 =
23.442 mm
3100 Sol: Mole fraction of A in vapor phase YA = 0.4 and in
1+ liquid phase XA = 0.75
9

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30 | Solutions and Colligative Properties

PTotal = 400 torr (iii) To calculate mole fraction of water

Let VP of pure A and B are PA0 and PB0 Pº − Ps nB
By Raoult’s law, = = xB ,
XAPA0 = YAPTotal Pº nA + nB
mole fraction of solute, i.e.,
YAPTotal 0.4 × 400 160
PA0 = = = Pº − Ps
XA 0.75 0.75 xB = = 0.00351
PA0 = 213.33 torr. Pº
∴ Mole fraction of solvent (water),
PTotal = XAPA0 + (1 – XA)PB0
XA = 1 – xB = 1 – 0.00351 = 0.99649
 160  0
400 = 0.75   PB + (1 – 0.75),
 0.75  Example 5: Ethylene dibromide (C2H4Br2) and
PB0= 960 torr 1,2-dibromo propane form a series of ideal solutions
over the whole range of composition. At 85ºC, the
Example 3: Calculate the freezing point of an aqueous vapor pressure of these two liquids are 173 and
solution of nonelectrolyte having an osmotic pressure 127 torr, respectively. What would be the mole fraction
of 0.2 atmosphere at 300 K. of ethylene dibromide in a solution at 85ºC equilibrated
(Kf = 1.86 K kg mol–1, R = 0.821 liter-atm K–1 mol–1) with 1:1 molar mixture in the vapor?
(assume molarity = molality)
Sol: Suppose the mole fraction of ethylene dibromide in
π 2 the liquid phase = x. Then, mole fraction of 1,2-dibromo
Sol: π = CRT, C = = mol lit–1
RT 0.0821 × 300 propane will be = 1 – x.
In dilute solution, the density of water can be taken as Vapor pressure of ethylene dibromide
1.90 gm cm–3. = x × Pº = x × 173 torr = 173 x torr
Hence, molality ≈ molarity Vapor pressure of 1,2-dibromo propane
2 = (1 – x) × 127 torr
DTf = (molalty × Kf )= × 1.86 ; ⇒DTf = 0.151 K
0.0821 × 300
As they have 1:1 molar ratio in the vapor phase,
∵ (Tf )solution = (Tf ) solvent – DTf = (273 – 0.151)
173 x = (1 – x) × 127 or 173 x = 127 – 127x
(Tf )solution = 272.749 K or –0.151ºC
127
or 300x = 127 or x = = 0.423
300
Example 4: Vapor pressure of water at 293 K is
17.51 mm. Lowering of vapor pressure of a sugar Example 6: Vapor pressure of solution containing 6 g
solution is 0.0614 mm. Calculate (i) relative lowering of of a non-volatile solute in 180 g water is 20.0 torr. If
vapor pressure, (ii) vapor pressure of the solution and 1 mol water is further added vapor pressure increases
(iii) mole fraction of water. by 0.02 torr. Calculate vapor pressure of water
and molecular weight of non-volatile solute with
Sol: Here, we are given that
temperature remaining constant.
vapor pressure of water; (P0) = 17.51 mm
Sol: Let molecular wt. of solute = m
Lowering of vapor pressure
and VP of water (solvent) = P0
(P0 – Ps) = 0.0614 mm
Psolution = 20 torr
(i) Relative lowering of vapor pressure 6
moles of solute, n =
Pº − Ps 0.0614mm m
=
= = 0.00351 180
Pº 17.51mm moles of solvent, N = = 10
18
(ii) Vapor pressure of the solution (Ps)
 N  0
Pº – Ps = 0.0614 mm; Pº = 17.51 mm ∴Ps =  P
n+N
∴ 17.51mm – Ps = 0.0614 mm
 
or Ps = 17.51 mm – 0.0614 mm = 17.4468 mm  10   10m  0
⇒ 20=   P0=  P … (i)
 6 + 10   6 + 10m 
 
m 

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Chem i str y | 31

If 1 mol water is further added, then moles of solvent N Example 8: Calculate the molarity, molality and mole
= 10 + 1 = 11 mol and VP of solution becomes fraction of ethyl alcohol in a solution of total volume
95 mL prepared by adding 50 mL of ethyl alcohol (density
Ps = 20 + 0.02 = 20.02 torr
= 0.789 mL–1) to 50 mL water (density = 1.00 g mL–1).
N 0
⇒Ps = P
n+N Sol: No. of moles of ethyl alcohol
  Vol. × density 50 × 0.789
 11   11m  = = =0.8576
Mol. mass 49
20.02=  = P
0
… (ii)
 6 + 11   6 + 11m  No. of moles of water
 
m 
Vol. × density 50 × 1
Now, divide (2) by (1) = = = 2.7777
Mol. mass 18
20.02 11(6 + 10m) No. of moles
= Molarity = × 1000
20 10(6 + 11m) Vol. of sol. in mL
⇒ m= 54 g 0.8576
= × 1000 = 9.027 M
Put this value of m in (i) or (ii) 95
No. of moles of solute
P0 = 22.22 torr Molality = × 1000
Mass of solvent in grams

Example 7: The density of a solution containing 13% 0.8576

= × 1000 = 17.152 m
by mass of sulfuric acid is 1.09 g/mL. Calculate the 50
molarity and normality of the solution. 0.8576 0.8576
Mole fraction = = = 0.236
0.8576 + 2.7777 3.6353
Sol: Volume of 100 g of the solution
100 100 100 1 Example 9: A current of dry air was bubbled through
= = mL = liter = liter
d 1.09 1.09 × 1000 1.09 × 10 a bulb containing 26.66 g of an organic compound in
200 g of water and then through a bulb at the same
Number of moles of H2SO4 in 100 g of the solution
temperature, containing water and finally through a
13 tube containing anhydrous calcium chloride. The loss
=
98 of mass in bulb containing water was 0.087 g and
No. of moles H2SO 4 gain in mass of the calcium chloride tube was 2.036 g.
Molarity =
Volume of soln. in litre Calculate the molecular mass of the organic substance.
13 1.09× 10 P0 − Ps Loss in mass solvent bulb 0.087
= × = 1.445 M Sol: = =
98 1 P0 Gain in mass of CaCl2 tube 2.036
[Note: In solving such numericals, the following formula
Let the molecular mass of the organic substance be m.
can be applied:]
According to Raoult’s law,
%strength of soln. × density of soln. × 10
Molarity = P0 − Ps
Mol. mass w /m
=
Similarly, normality P0 w W
+
%strength of soln. × density of soln. × 10 m M
=
Eq. mass
26.66
We know that, 0.087 m 26.66
= = ; m = 53.75
Normality = Molarity × n 2.036 26.66 200 200
+ 26.66 + m
m 18 18
= 1.445 × 2
 Mol. mass 98 
n
= = = 2 = 2.89 N Example 10: 2.0 g of benzoic acid dissolved in 25.0 g of
 Eq. mass 49  benzene shows a depression in freezing point equal to
1.62 K. Molal depression constant (Kf ) of benzene is 4.9
K kg mol–1. What is the percentage association of the
acid if it forms dimer in the solution?

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32 | Solutions and Colligative Properties

Sol: Mass of solute (benzoic acid), w2 = 2.0 g 122

= = 0.504
Mass of solvent (benzene), w1 = 25.0 g 242

Observed DTf = 1.62 K If α is the degree of association of benzoic acid, then

we have
Kf = 4.9 K kg mol–1


2C6H5COOH 
(C6H5COOH)2
∴
Observed molar mass of benzoic acid
1000 × K f × w2 Initial moles 1 0
M2 =
∆Tf × w1 After association 1 – a α/2

1000g kg−1 × 4.9 K kg mol−1 × 2.0g ∴ The total number of moles after association
= = 242 g mol–1
1.62K × 25.0g α
=1–α+ = 0.504
Calculated molar mass of benzoic acid 2
α = (1 – 0.504) × 2 = 0.496 × 2 = 0.992
(C6H5COOH) = 72 + 5 + 12 + 32 + 1 = 122 g mol–1
Calculated mol. mass
Or percentage association = 99.2%
van’t Hoff factor, i =
Observed mol. mass

LEVEL 1

Exercise 1 Q.8 A solution of a non-volatile solute in water freezes

at –30.0. The vapour pressure of pure water at 298 K
Q.1 How many grams of H2SO4 are required to prepare is 23.51 mm Hg and Kf for water is 1.86 degree/mol.
250 mL of 0.2 molar solution? Calculate the vapour pressure of this solution at 298 K.

Q.2 A solution contains 23g of ethanol and 72g of Q.9 The vapour pressure of pure benzene at 25ºC is
water. Calculate the mole fraction of ethanol and water. 639.7 mm Hg and the vapour pressure of a solution of
non–volatile solute in benzene at the same temperature
Q.3 2.82 g glucose (mo. mass = 180) are dissolved in is 631.9 mm Hg.
30g of H2O. Calculate the (i) Molality of the solution (ii) Calculate the mole fraction of the solute and the
Mole fraction of glucose and water. molality of the solution. (C = 12, H = 1)

Q.4 Prove that the relative lowering of vapour pressure Q.10 (i) What is osmotic pressure and how is it reached
is equal to the mole fraction of non–volatile solute in to the molecular mass of a non–volatile substance?
the solution.
(ii) What advantage the osmotic pressure method
Q.5 What is the relation between elevation of boiling has over the elevation of boiling point method for
point and osmosis pressure? determining molecular masses?

Q.6 One litre aqueous solution of sucrose (molar mass Q.11 State Raoults’ law for solutions of nonvolatile
= 342 g mol–1) weighing 1015 g is found to record an solute in volatile solvents. Derive a mathematical
osmotic pressure of 4.85 atm at 293 K. What is the expression for this law?
molality of the sucrose solution?
Q.12 What is the molarity of a 13% solution (by weight)
Q.7 A solution containing 12.5 g of a non-electrolyte of sulphuric acid? Its density is 1.020 g cm–1 (Atomic
substance in 175 g of water gave a boiling point masses : H = 1, O = 16, S = 32 amu)
elevation of 0.70 K. Calculate the molar mass of the
substance. (Elevation constant for water is Kb = 0.52 K Q.13 What is the molar concentration of solute particles in
kg mol–1) the human blood if the osmotic pressure is 72 atm at the
body temperature of 37ºC? (R = 0.0821 L atm K–1 mol–1)

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Chem i str y | 33

Q.14 Calculate the molar concentration of urea solution Q.24 Two elements A and B form compound having
if it exerts an osmotic pressure of 2.45 atm at 300K. (R = formula AB2 and AB4. When dissolved in 20g of
0.0821 L atm mol–1 K–1) benzene (C6H6) 1g of AB2 lowers the freezing point by
2.3 K whereas 1.0 g of AB4 lowers by 1.3K. The molar
Q.15 To 500 cm2 of water, 3.0 × 10–5 kg of acetic acid depression constant for benzene is 5.1 K kg mol–1.
is added. If 23% of acetic acid is dissociated, what will Calculate atomic masses of A and B.
be the depression in freezing point? Kf and density of
water are 1.86 K kg–1/mol and 0.997 g cm–1 respectively. Q.25 19.5 g of CH2FCOOH is dissolved in 500g water.
The depression in freezing point of water observed is
Q.16 How many mL of 0.1M HCl are required to react 1.0ºC. Calculate the van’t Hoff factor and dissociation
completely with 1g mixture of Na2CO3 and NaHCO3 constant of fluoroacetic acid.
containing equimolar amount of two?
Q.26 Vapour pressure of pure acetone and chloroform
Q.17 The boiling point of benzene is 353.23K. When at 328K are 741.8 mm Hg and 632.8 mm Hg respectively.
1.80g of a non–volatile solute was dissolved in 90g Assuming that they form ideal solution over the entire
of benzene, the boiling point is raised to 354.11 K. range of composition plot Ptotal , Pchloroform and pacetone as a
Calculate the molar mass of the solute. Kb for benzene function of xacetone. The experimental data observed for
is 2.53K kg mol–1. different compositon of mixture as:

Q.18 1.0 g of a non-electrolyte solute dissolved in 50g 100 × 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1
of benzene lowered the freezing point of benzene Xacetone
by 0.40K. The freezing point depression constant of Pacetone 0 549 110.1 202.4 322.7 405.9 454.1 521.1
benzene is 5.12 K kg mol–1. Find the molecular mass of Pchloroform 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7
the solute.
Plot this data also on the same graph paper. Indicate
Q.19 Calculate the mass of a non–volatile solute (mol whether it has positive deviation or negative deviation
mass = 40) which should be dissolved in 114 g octane from the ideal solution.

to reduce its vapour pressure to 80%.
Q.27 (a) Derive the relationship between relative
Q.20 What is the relation between elevation in boiling lowering of vapour pressure and mole fraction of the
point and molar heat of vapourisation? volatile liquid.

Q.21 (a) The outer shells of two eggs are removed. One (b) (i) Benzoic acid completely dissolves in benzene.
of the egg is placed in pure water and other is placed What will be the vapour pressure of a solution
in saturated solution of sodium chloride. What will be containing 61g of benzoic acid per 500g benzene
observed and why? when the vapour pressure of the pure benzene of the
temperature of experiment is 66.6 torr?
(b) A decimolar solution of potassium ferrocyanide.
K4[Fe(CN)4] is 50% dissociated at 300K. Calculate (ii) What would have been the vapour pressure in the
osmotic pressure of the solution. [R = 8.314 JK–1 mol–1] absence of dissolution?
(iii) Derive a relationship between mole–fraction and
Q.22 Why do calculations based on lowering in vapour pressure of a component of an ideal solution in
freezing points of a solutions sometime give abnormal phase and vapour phase.
molar mass value for solutes? How may the equation
for the related colligative property be modified for Q.28 (a) Which solution has higher concentration:
substance exhibiting abnormal molar mass value? A 1 molar or 1 molal solution of the same solute. Give
solute contains 7.45g KCl per litre of solution. It has reasons.
an osmotic pressure of 4.68 atm at 300K. Calculate the
degree of dissociation for KCl in this solution. (b) 0.5 g KCl was dissolved in 100g of water and the
solution originally at 20ºC, froze at –0.24ºC. Calculate the
Q.23 0.6 mL of acetic acid (CH3COOH) having density percentage ionization of salt. KCl per 1000g water = 1.86.
1.06 g mL–1, in dissolved in 1 litre of water. The
depression in freezing point observed for this strength Q.29 How will you explain Henry’s law in terms of Le
of acid was 0.0205ºC. Calculate van’t Hoff factor and Chatelier’s principle and Kinetic theory of gases? or
dissociation constant of acid. State Henry’s law for the solubility of gases in liquid.
Explain it in terms of Le Chatelier’s theorem.

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34 | Solutions and Colligative Properties

Exercise 2 Q.8 1.0 molal aqueous solution of an electrolyte A2B3 is

60% ionized. The boiling point of the solution at 1 atm
Single Correct Choice Type is Kb(H O) = 0.52 K kg mol–1
2
(A) 274.76 K (B) 377 K (C) 376.4 K (D) 374.76 K
Q.1 Mole fraction of A vapours above the solution in
mixture of A and B (XA = 0.4) will be [Given: PA0 = 100
Q.9 The van’t Hoff factor for a dilute aqueous solution
mm Hg and PB0 = 200 mm Hg]
of glucose is
(A) 0.4 (B) 0.8
(A) Zero (B) 1.0 (C) 1.5 (D) 2.0
(C) 0.25 (D) None of these
Q.10 The correct relationship between the boiling
Q.2 The exact mathematical expression of Raoult’s law is points of very dilute solution of AlCl3 (T1K) and CaCl2
Po − Ps Po − Ps N (T2K) having the same molar concentration is
(A) (B) =
P o P o n (A) T1 = T2 (B) T1 > T2 (C) T2 < T1 (D) T2 ≤ T1

Po − Ps n Po − Ps Q.11 A 0.001 molal solution of a complex [MA3] in water

(C) = (D) = n×N
Ps N Po has the freezing point of –0.0054ºC. Assuming 100%
ionization of the complex salt and Kf for H2O = 1.86
Q.3 A mixture contains 1 mole of volatile liquid km–1, what the correct representation for the complex
A (PA0 = 100 mm Hg) and 3 moles of volatile liquid B (A) [MA8] (B) [MA7]A (C) [MA6]A2 (D) [MA5]A3
(PB0 = 80 mm Hg). If solution behaves ideally, the total
pressure of the distillate is Q.12 The vapour pressure of a solution of a non–volatile
(A) 85 mm Hg (B) 85.88 mm H electrolyte B in a solvent A is 95% of the vapour pressure
of the solvent at the same temperature. If the molecular
(C) 90 mm Hg (D) 92 mm Hg
weight of the solvent is 0.3 times the molecular weight
of solute, the weight ratio of the solvent and solute are
Q.4 Assuming each salt to be 90% dissociated, which of
(A) 0.15 (B) 5.7 (C) 0.2 (D) 4.0
the following will have highest boiling point?
(A) Decimolar Al2(SO4)3 Q.13 The vapour pressure of a saturated solution of
(B) Decimolar BaCl2 sparingly soluble salt (XCl3) was 17.20 mm Hg at 27ºC.
If the vapour pressure of pure H2O is 17.25 mm Hg at
(C) Decimolar Na2SO4 300K, what is the solubility of sparingly soluble salt XCl3
(D) A solution obtained by mixing equal volumes of (B) in mole/litre
and (C) (A) 4.04 × 10–2 (B) 8.08 × 10–2
(C) 2.02 × 10–2 (D) 4.04 × 10–3
Q.5 The vapour pressure of a solvent decreased by
10 mm of Hg when a non–volatile solute was added Q.14 At 300K, the vapour pressure of an ideal solution
to the solvent. The mole fraction of solute in solution containing 3 mole of A and 2 mole of B is 600 torr. At
is 0.2, what would be mole fraction of the solvent if the same temperature, if 1.5 mole of A and 0.5 mole of
decrease in vapour pressure is 20 mm of Hg. C (non–volatile) are added to this solution the vapour
(A) 0.2 (B) 0.4 (C) 0.6 (D) 0.8 pressure of solution increases by 30 torr. What is the
value of PB0?
Q.6 Elevation of boiling point of 1 molar aqueous (A) 940 (B) 405 (C) 90 (D) None of these
glucose solution (density = 1.2 g/mL) is
(A) Kb (B) 1.20 Kb (C) 1.02 Kb (D) 0.98 Kb Q.15 The freezing point depression of a 0.1 M aq.
solution of weak acid (HX) is –0.20ºC. What is the value
of equilibrium constant for the reaction?
Q.7 What will be the molecular weight of CaCl2
determined in its aq. solution experimentally from HX(aq) 1H+ (aq) + X– (aq) [Given: Kf for water = 1.8 kg
depression of freezing point? mol–1 K and Molality = Molarity]

(A) 111 (B) <111 (C) >111 (D) Data insufficient (A) 1.45 × 10–4 (B) 1.35 × 10–3
(C) 1.21 × 10–2 (D) 1.35 × 10–4

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Chem i str y | 35

Q.16 What is the following plots represents an ideal Q.4 25 mL of a solution of barium hydroxide on titration
binary mixture? with a 0.1 molar solution of hydrochloric acid gave
litre value of 35 mL. The molality of barium hydroxide
(A) Plot of Ptotal v/s 1/XB is linear (XB = mole fraction of
solution was (2003)
‘B’ in liquid phase)
(A) 0.07 (B) 0.14 (C) 0.28 (D) 0.35
(B) Plot of Ptotal v/s YA is linear (YB = mole fraction of ‘A’
in vapour phase)
Q.5 Which of the following moles of expressing
1
(C) Plot of v/s YA is linear concentration is independent of temperature? (1988)
Ptotal
(A) Molarity (B) Molality
1
(D) Plot of v/s YB is non–linear
Ptotal (C) Formality (D) Normality

Q.17 Two liquids A and B form an ideal solution. What Q.6 Two solutions of a substance (non-electrolyte) are
is the vapour pressure of solution containing 2 moles mixed in the following manner 480 mL of 1.5M first
of A and 3 moles of at 300K? Vapour pressure of pure solution + 520 mL of 1.2 M second solution. What is
liquid A (PA0) = 100 torr, Vapour pressure of pure liquid the molarity of the final mixture (2005)
B (PB0) = 300 torr/
(A) 1.20 M (B) 1.50 M
(A) 200 torr (B) 140 torr
(C) 1.344 M (D) 2.70 M
(C) 180 torr (D) None of these
Q.7 Increasing the temperature of an aqueous solution
Q.18 The van’t Hoff factor for 1.0 M Ba(NO3)2 solution is will cause (1993)
2.74. The degree of dissociation is
(A) Decrease in molality
(A) 91.3% (B) 87% (C) 100% (D) 74%
(B) Decrease in molarity
(C) Decrease in mole fraction
Previous Years’ Questions (D) Decrease in %w/w

Q.1 The Henry’s law constant for the solubility of N2 gas

in water at 298 K in 1.0 × 105 atm. The mole fraction Q.8 6.02 × 1020 molecules of urea are present in 100 mL of
of N2 in air is 0.8. The number of moles of N2 from its solution. The concentration of urea solution is (2004)
air dissolved in 10 moles of water at 298 K and 5 atm (A) 0.02 M (B) 0.01 M (C) 0.001 M (D) 0.1 M
pressure is (2009)
[Avogadro constant, NA = 6.02 × 10 mol ] 23 –1

(A) 4.0 × 10–4 (B) 4.0 × 10–5

Q.9 To neutralize completely 20 mL of 0.1 M aqueous
(C) 5.0 × 10–4 (D) 4.0 × 10–6
solution of phosphorus acid (H3PO3), the volume of
0.1M aqueous KOH solution required is (2004)
Q.2 The normality of 0.3 M phosphorus acid (H3PO3) is
(1999) (A) 40 mL (B) 20 mL (C) 10 mL (D) 60 mL
(A) 0.1 (B) 0.9 (C) 0.3 (D) 0.6
Q.10 A 5.2 molal aqueous solution of methyl alcohol,
Q.3 With increase of temperature, which of these CH3OH, is supplied. What is the mole fraction of methyl
changes? (2002) alcohol in the solution? (2011)

(A) Molality (A) 0.100 (B) 0.190 (C) 0.086 (D) 0.050

(B) Weight fraction of solute

Q.11 The density of solution prepared by dissolving
(C) Fraction of solute present in water 120 g of urea (mol mass = 60 u) in 1000g water is 1.15
(D) Mole fraction g/mL. The molarity of this solution is (2012)
(A) 0.50 M (B) 1.78 M (C) 1.02 M (D) 2.05 M

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36 | Solutions and Colligative Properties

Q.12 Equimolar solutions in the same solvent have Q.18 Value of gas constant R is (2002)
(2005)
(A) 0.082 litre atm (B) 0.987 cal mol–1K–1
(A) Same boiling point but different freezing point
(C) 8.3 J mol–1 K–1 (D) 83 erg mol–1 K–1
(B) Same freezing point but different boiling point
(C) Same boiling and same freezing point Q.19 During depression of freezing point in a solution
the following are in equilibrium (2003)
(D) Different boiling and different freezing point
(A) Liquid solvent, solid solvent
Q.13 Two liquids X and Y form an ideal solution. At (B) Liquid solvent, solid solute
300K, vapour pressure of the solution containing 1
(C) Liquid solute, solid solute
mol of X and 3 moles of Y is 550 mm Hg. At the same
temperature, if 1 mol of Y is further added to this (D) Liquid solute, solid solvent
solution, vapour pressure of the solution increases by
10 mm Hg. Vapour pressure (in mm Hg) of X and Y in Q.20 The degree of dissociation (α) of a weak electrolyte,
their pure states will be respectively (2009) AxBy is related to van’t Hoff factor (i) by the expression
(A) 200 and 300 (B) 300 and 400 (2011)
i−1 i −1
(C) 400 and 600 (D) 500 and 600 (A) α = (B) α =
(x + y − 1) x + y +1

Q.14 The vapour pressure of water at 20ºC is 17.5 mm x + y −1 x + y +1

(C) α = (D) α =
Hg. If 18g of glucose (C6H12O6) is added to 178.2 g i −1 i −1
of water at 20ºC the vapour pressure of the resulting
solution will be (2005) Q.21 At 80°C , the vapour pressure of pure liquid ‘A’
(A) 15.750 mm Hg (B) 16.500 mm Hg is 520 mm Hg and that of pure liquid ‘B’ is 1000 mm
Hg. If a mixture solution of ‘A’ and ‘B’ boils at 80°C
(C) 17.325 mm Hg (D) 17.675 mm Hg and 1 atm pressure, the amount of ‘A’ in the mixture is
(1 atm = 760 mm Hg) (2008)
Q.15 A mixture of ethyl alcohol and propyl alcohol
(A) 52 mol percent (B) 34 mol percent
has a vapour pressure of 290 mm at 300K. The vapour
pressure of propyl alcohol is 200 mm. If the mole (C) 48 mol percent (D) 50 mol percent
fraction of ethyl alcohol is 0.6, its vapour pressure (in
mm) at the same temperature will be (2007) Q.22 If sodium sulphate is considered to be completely
(A) 350 (B) 300 (C) 700 (D) 360 dissociated into cations and anions in aqueous solution,
the change in freezing point of water ( ∆ Tf ) , when 0.01
mol of sodium sulphate is dissolved in 1 kg of water, is
Q.16 Which of the following liquid pair shows a positive
(Kf = 1.86 K kg mol-1) (2010)
deviation from Raoult’s law (2004)
(A) 0.0372 K (B) 0.0558 K
(A) Water–nitric acid
(C) 0.0744 K (D) 0.0186 K
(B) Benzene–methanol
(C) Water–hydrochloric acid Q.23 Ethylene glycol is used as an antifreeze in a cold
(D) Acetone–chloroform climate. Mass of ethylene glycol which should be added
to 4 kg of water to prevent it from freezing at −6°C will
be: [Kf for water = 1.86 K kg mol-1, and molar mass of
Q.17 A 5.25% solution of a substance is isotonic with
ethylene glycol = 62g mol-1]
1.5% solution of urea (molar mass = 60g mol–1) in the
same solvent. If the densities of both the solutions are (A) 204.30g (B) 400.00 g
assumed to be equal to 1.0 g cm–3, molar mass of the
(C) 304.60 g (D) 804.32g
substance will be (2007)
(A) 90.0 g mol–1 (B) 115.0 g mol–1
(C) 105.0 g mol–1 (D) 210.0 g mol–1

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Chem i str y | 37

Q.24 Kf for water is 1.86 K kg mol-1. If your automobile (C) 0.125 M Na3PO 4( aq) has the highest osmotic
radiator holds 1.0 kg of water, how many grams of pressure.
ethylene glycol (C2H6O2) must you add to get the freezing
(D) 0.500 M C2H5OH( aq) has the highest osmotic
point of the solution lowered to ‒2.8°C? (2012)
pressure.
(A) 72g (B) 93g (C) 39g (D) 27g
Q.26 The vapour pressure of acetone at 20°C is 185 torr.
Q.25 Consider separate solutions of 0.500 M When 1.2 g of a non-volatile substance was dissolved in
100 g of acetone a 20°C, its vapour pressure was 183 torr.
C2H5OH( aq) , 0 . 1 0 0 M Mg3 (PO 4 ) 0.250 M KBr( aq)
2( aq) The molar mass (g mol-1) of the substance is: (2014)
and 0.125 M Na3PO 4( aq) at 25°C . Which statement
(A) 32 (B) 64 (C) 128 (D) 488
is true about these solutions, assuming all salts to be
strong electrolytes? (2014)
Q.27 18 g glucose ( C6H12O6 ) is added to 178.2 g water.
(A) They all have the same osmotic pressure. The vapor pressure of water (in torr) for this aqueous
solution is. (2016)
(B) 0.100 M Mg3 (PO 4 ) has the highest osmotic
2( aq)
pressure. (A) 76.0 (B) 752.4 (C) 759.0 (D) 7.6

LEVEL 2

Exercise 1 Q.7 A solution containing 3.24 of a nonvolatile

nonelectrolyte and 200g of water boils at 100.130ºC at
Q.1 At 25ºC, the vapour pressure of methyl alcohol 1atm. What is the molecular weight of the solute? (Kb
is 96.0 torr. What is the mole fraction of CH3OH in a for water 0.513ºC/m).
solution in which the (partial) vapour pressure of CH3OH
is 23.0 torr at 25ºC? Q.8 The molecular weight of an organic compound is
58.0 g/mol. Compute the boiling point of a solution
Q.2 The vapour pressure of pure liquid solvent A is 0.80 containing 24.0 g of the solute and 600g of water, when
atm. When a non–volatile substance B is added to the the barometric pressure is such that pure water boils at
solvent its vapour pressure drops to 0.60 atm. What is 99.725ºC.
the mole fraction of components B in the solution?
Q.9 An aqueous solution of a non–volatile solute boils
Q.3 The vapour pressure of pure water at 26ºC is 25.21 at 100.17ºC. At what temperature will this solution
torr. What is the vapour pressure of a solution which freeze? [Kf for water 1.86ºC/m]
contains 20.0 glucose, C4H12O6, in 70g water?
Q.10 Find the freezing point of a glucose solution
Q.4 The vapour pressure of pure water at 25ºC is 23.76 whose osmotic pressure at 25ºC is found to be 30 atm.
torr. The vapour pressure of a solution containing 5.40 Kf(water) = 1.86 kg/mol K.
g of a non–volatile substance in 90.0g water is 23.32
torr. Compute the molecular weight of the solute. Q.11 The vapour pressure of an aqueous solution of
glucose is 750 mm Hg at 373K. Calculate molality and
Q.5 What weight of the non–volatile solute, urea needs mole fraction of solute.
to be dissolved in 100g of water, in order to decrease
the vapour pressure of water by 25%? What will be the Q.12 The vapour pressure of pure benzene at 25ºC is
molality of the solution? 639.7 mm of Hg and the vapour pressure of a solution
of a solute in C6H6 at the same temperature is 631.7mm
Q.6 When 10.6 g of a non–volatile substance is dissolved of Hg. Calculate molality of solution.
in 740g of ether, its boiling point is raised 0.284ºC. What
is the molecular weight of the substance? Molal boiling Q.13 The vapour pressure of pure benzene at a certain
point constant for ether is 2.11ºC kg/mol. temperature is 640 mm of Hg. A nonvolatile non-

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38 | Solutions and Colligative Properties

electrolyte solid weighing 2.175 g is added to 39.0 of raised to 25ºC, when the osmotic pressure is found to
benzene. The vapour pressure of the solution is 600 mm be 105.3 mm. Determine extent of dilution.
of Hg. What is molecular weight of solid substance?
Q.23 The freezing point of a solution containing 0.2g
Q.14 The vapour pressure of water is 17.54 mm Hg at of acetic acid in 20.0 g of benzene is lowered by 0.45ºC.
293 K. Calculate vapour pressure of 0.5 molal solution Calculate the degree of association of acetic acid in
of a solute in it. benzene.

Q.15 Benzene and toluene form two ideal solutions A Q.24 0.85% aqueous solution of NaNO3 is apparently
and B at 313K. Solution A (total pressure PA) contains 90% dissociated at 27ºC. Calculate its osmotic pressure.
equal moles of toluene and benzene. Solution B contain (R = 0.082 l atm K–1 mol–1).
equal masses of both (total pressure PB). The vapour
pressure of benzene and toluene are 160 and 60 mm Q.25 A 1.2% solution (w/v) of NaCl is isotonic with 7.2%
Hg respectively at 313K. Calculate the value of PA/PB. solution (w/v) of glucose. Calculate degree of ionization
and Van’t Hoff factor of NaCl.
Q.16 Sea water is found to contain 5.85% NaCl and
9.50% MgCl by weight of solution. Calculate its normal Q.26 Calculate the boiling point of a solution containing
boiling point assuming 80% ionization for NaCl and 0.61g of benzoic acid in 50g of carbon disulphide
50% ionization of MgCl2 [K2(H2O) = 0.51 kg mol–1 K]. assuming 84% dimerization of the acid. The boiling
point and Kb of CS2 are 46.2ºC and 2.3 K kg mol–1,
Q.17 The latent heat of fusion of ice is 80 calories per respectively.
gram at 0ºC. What is the freezing point of a solution
of KCl in water containing 7.45 grams of solute in 500 Q.27 At 25ºC, 1 mol of A having a vapour pressure of
grams of water, assuming that the salt is dissociated to 100 torr and 1 mol of B having a vapour pressure of 300
the external of 95%? torr were mixed. The vapour at equilibrium is removed,
condensed and the condensate is heated back to
Q.18 A complex is represented as CoCl3 · xNH3. Its 0.1 25ºC. The vapours now formed are again removed,
molal solution in aq. solution shows DTf = 0.558ºC. Kf recondensed and analysed. What in the mole fraction
for H2O is 1.86 K mol–1 kg. Assuming 100% ionization of A in this condensate?
of complex and coordination no. of Co is six, calculate
formula of complex. Q.28 Phenol associates in benzene to a certain extent to
form a dimer. A solution containing 20 × 10–3 kg phenol
Q.19 The molar volume of liquid benzene (density in 1kg of benzene has its freezing point depressed
= 0.877 g mL–1) increases by a factor of 2750 as it by 0.69K. Calculate the fraction of phenol that has
vaporizes at 20ºC and that of liquid toluene (density dimerised K for benzene = 5.12 kg mol–1 K.
= 0.867 mL–1) increases by a factor of 7720 at 20ºC.
Solution of benzene and toluene has a vapour pressure Q.29 30 mL of CH3OH (d = 0.7980 gm cm–3) and 70 mL
of 46.0 torr. Find the mole fraction of benzene in vapour of H2O (d = 0.9984 gm cm–3) are mixed at 25ºC to form
above the solution. a solution of density 0.9575 gm cm–3. Calculate the
freezing point of the solution. Kf (H2O) is 1.86 kg mol–1
Q.20 At 100ºC, benzene and toluene have vapour K. Also calculate its molarity.
pressure of 1375 and 558 torr respectively. Assuming
these two form an ideal binary solution, calculate the
composition of the solution that boils at 1 atm and Exercise 2
100ºC. What is the composition of vapour issuing at
these conditions? Single Correct Choice Type

Q.21 At 300K, the solution of glucose in water of Q.1 For an ideal binary liquid solution with PA0 > PB0,
concentration 0.01 M and 0.001M are separated which relation between XA (mole fraction of A in liquid
by semipermeable membrane. Pressure needs to phase) and YA (mole fraction of A in vapour phase) is
be applied on which solution, to prevent osmosis? correct?
Calculate the magnitude of this applied pressure.
(A) YA < YB (B) XA > XB
Q.22 At 10ºC, the osmotic pressure of urea solution is YA XA YA XA
500mm. The solution is diluted and the temperature is (C) > (D) <
YB XB YB XB

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Chem i str y | 39

Q.2 Which of the following aqueous solution will show v2 (10)2

maximum vapour pressure at 300K? (B) tan=
θ = = 1
Rg (10)(10)
(A) 1 M NaCl (B) 1 M CaCl2
(C) θ= tan−1 (1)= 45°
(C) 1 M AlCl3 (D) 1 M C12H22O11
dv
(D) =a
dt
Q.3 At a given temperature, total vapour pressure in
Torr of a mixture of volatile components A and B is
Q.7 FeCl3 on reaction with K4[Fe(CN)6] in aqueous solution
given by PTotal = 120 – 75XB hence, vapour pressure of
given blue colour. These are separated by a semipermeable
pure A and B respectively (in Torr) are
membrane AB as shown. Due to osmosis there is
(A) 120, 75 (B) 120, 95 0.1M 0.01M
(C) 120, 45 (D) 75, 45 K4Fe(CN) 6 FeCl 3

Side x Side y
Q.4 A liquid mixture having
composition corresponding to z 5PM
point z in the figure shown in
subjected to distillation at (A) Blue colour formation in side X
Temp
constant pressure. Which of (B) Blue colour formation in side Y
the following statement is (C) Blue colour formation in both of the sides X and Y
correct about the process xA=0 mole xA=1
yA=0 fraction yA=1 (D) No blue colour formation
(A) The composition of
distillate differs from the mixture Multiple Correct Choice Type
(B) The boiling point goes on changing
Q.8 Acetone and carbon disulphide form binary liquid
(C) The mixture has highest vapour pressure than for solution showing positive deviation from Raoult’s law.
any other composition The normal boiling point (Tb) of pure acetone is less
(D) Composition of an azeotrope alters on changing than that of pure CS2. Pick out the incorrect statement
the external pressure among the following
(A) Boiling temperature of mixture is always less than
boiling temperature of acetone
Q.5 The following graph represents variation of boiling
point with composition of liquid and vapour of binary (B) Boiling temperature of Azetropic mixture is always
liquid mixture. The graph is plotted at constant pressure. less than boiling temperature of acetone
Which of the following statement(s) is incorrect. Here (C) When a small amount of CS2 (less volatile component)
X and Y stands for mole fraction in liquid and vapour is added to excess of acetone boiling point of resulting
phase respectively mixture increases
(D) A mixture of CS2 and CH3COCH3 can be completely
2L separated by simple fractional distillation.
⇒t=
ω2R
(A) Xbenzene = 0.5 and Ytoluene = 0. 2 Q.9 Which of the following would be equal to zero
(B) Xtoluene = 0.3 and Ybenzene = 0. 6 when the liquid pairs form an ideal solution
(C) Xbenzene = 0.3 and Ytoluene = 0. 4 (A) ∆H (B) ∆S (C) ∆G (D) ∆V
(D) Xbenzene = 0.7 and Ytoluene < 0. 3
Q.10 For a non–volatile solute
Q.6 Which of the following represent correctly the (A) The vapour pressure of solute is zero
changes in thermodynamic properties during the (B) Vapour pressure of solution = Vapour pressure of
formation of 1 mol of an ideal binary solution pure solvent
+
(C) Vapour pressure of solution = Vapour pressure of
∆Gmin
T∆Smin solvent in solution
(A) –1
J mol 0
(D) All of the above
– ∆Hmin
Mole fraction

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40 | Solutions and Colligative Properties

Q.11 A difference between diffusion and osmosis is Q.17 Which of the following is/are true?
(A) A semipermeable membrane is required for osmosis (A) For the same solution, elevation in boiling point =
while diffusion requires no semipermeable membrane depression in freezing point
(B) In osmosis movement of molecules is only in one (B) The Van’t Hoff factor for a dilute solution of BaCl2.
direction whereas in diffusion movement is on both sides
(C) The elevation in boiling point is due to increase in
(C) In osmosis only the solvent moves while in diffusion
vapour pressure.
both solute and solvent move
(D) None of the above (D) The depression in freezing point is due to decrease
in vapour pressure.
Q.12 Which of the following statement is/are correct?
Q.18 Which pairs of liquids on mixing is/are expected
(A) The freezing point of water is depressed by the
addition of glucose to show no net volume change and no heat effect?
(B) The degree of dissociation of a weak electrolyte (A) Acetone and ethanol
decrease as its concentration decreases (B) Chloro benzene and bromo benzene
(C) Energy is released when a substance dissolves
in water provided that the hydration energy of the (C) Chloroform and benzene
substance is more than its lattice energy (D) n–Butyl chloride and n–butyl bromide
(D) If two liquids that form an ideal solution are mixed,
the change in entropy is positive Assertion Reasoning Type

Q.13 Which of the following gases are highly soluble Q.19 Statement-I: Addition of ethylene glycol (non–
in water volatile) to water lowers the freezing point of water
(A) HCl (B) SO2 (C) NH3 (D) H2 hence used as antifreezing
Statement-II: Heat must be removed from the water to
Q.14 Which of the following would be equal to zero make it freeze.
when the liquid pairs form an ideal solution.
(A) Statement-I is true, statement-II is true and
(A) ∆H (B) DS (C) ∆G (D) DV statement-II is correct explanation for statement-I
(B) Statement-I is true, statement-II is true and
Q.15 Two miscible liquids A and B having vapour
statement-II is NOT the correct explanation for
pressure in pure state PA0 and PB0 are mixed in mole
statement-I
reaction XA and XB to get a mixture having total vapour
pressure of mixture PM. Which of the following relation (C) Statement-I is true, statement-II is false.
are correct? (D) Statement-I is false, statement-II is true
PM − PB0 X A(  ) PM
(A) X A = (B) =
PA 0 − PB0 X'A(V ) PA 0 Q.20 Statement-I: The freezing of water is an
endothermic process.
X A(  ) PM
(C) = (D) All of these Statement-II: Heat must be removed from the water to
X'A(V) PB0
make it freeze.
(A) Statement-I is true, statement-II is true and
Q.16 Which relations are not correct for aqueous dilute
statement-II is correct explanation for statement-I.
solution of K3PO4 if its degree of dissociation is α?
(B) Statement-I is true, statement-II is true and
∆P Molality × 18 × (1 + 3α ) statement-II is NOT the correct explanation for
(A) =
Pº 1000 statement-I.
∆P πobs × 18 × (1 + 3α ) (C) Statement-I is true, statement-II is false.
(B) =
Pº RT × 1000 (D) Statement-I is false, statement-II is true
∆P ∆Tf obs × 18
(C) =
Pº K f × 1000
(D) Mw of K2PO4 = Mwobs × (1 + 3α)

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Chem i str y | 41

Comprehension Type Match the Columns

The various relations between colligative properties Q.26 PA = partial pressure of components A in liquid
and molecular mass are applicable only to solutions of mixture. PA0 = vapour pressure of A, χA = mole fraction
non–electrolytes and in dilute solutions. Out of various of A in liquid
colligative properties osmotic pressure measurement is
especially suitable for the determination of molecular Column I Column II
masses of proteins whereas freezing point depression (A) C2H5OH + H2O (p) Azeotropic mixture
and other colligative properties are too small. Certain
(B) C2H2Br + C2H5I (q) Obeys Raoult’s law
solutes which dissociate or associate in solution affect
the colligative property and hence molecular mass (C) PA = XAPA0 (r) Non–ideal solution with
determination also. In case of association observed positive deviation
molecular mass is more than normal the correction
(D) H2O + H2SO4 (s) Non–ideal solution with
factor i < 1. For dissociation of solute i > 1 and observed
negative deviation
molecular mass is less than the normal molecular mass
(t) Ideal solution
Q.21 Which of the following 0.1 m aqueous solution
will have the lowest freezing point?
Q.27 Match the following
(A) Al2(SO4)3 (B) C6H12O6
Column I Column II
(C) KI (D) C12H22O11
(A) Urea, glucose, fructose (p) 1 : 0.8 : 1

Q.22 Correction factor for 0.1M ideal solution is (B) NaCl, MgCl2.K2SO4 (q) 1 : 2 : 1

(A) 0.1 (B) 1 (C) 0.01 (D) 2 > 1 (C) Al2(SO4)3, Na3PO4, K3r[Fe(CN)6] (r) 1 : 1 : 1

(D) Glucose, NaCl, CaCl2 (s) 2 : 3 : 3

Q.23 The Van’t Hoff factor for 0.1M Ba(NO3)2 solution is
2.74. The degree of dissociation is
(A) 91.3% (B) 87% (C) 100% (D) 74% Q.28

Column I Column II
Q.24 Which one of the following statements gives
below concerning properties of a solution describe a (A) ppm (p) Van’t Hoff factor
colligative effect? (B) DTb (q) Molal depression
(A) Boiling point of pure water increase by addition of (C) Kf (r) Elevation in boiling point
EtOH
(B) Vapour pressure of pure water decrease by addition (D) i
Mass of solute
of HNO3 (s) × 106
Mass of solution
(C) Vapour pressure of pure benzene decrease by
addition of naphthalene
(D) Boiling point of pure benzene increase by addition
of toluene Previous Years’ Questions

Q.25 After adding a solute, freezing point of water Q.1 An azeotropic solution of two liquids has boiling
decreases to –0.186ºC. What is the value of DT? point lower than either of them when it (1981)
(kb = 0.521; kf = 1.86) (A) Shows negative deviation from Raoult’s law
(A) 0.521 (B) 0.0521 (B) Shows no deviation from Raoult’s law
(C) 1.86 (D) 0.0186 (C) Shows positive deviation from Raoult’s law
(D) Is saturated

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42 | Solutions and Colligative Properties

Q.2 Which of the following 0.1M aqueous solution will In answering the following questions, consider the
have the lowest freezing point? (1989) solution to be ideal dilute solution and solute to be
non–volatile and non–dissociative. (2008)
(A) Potassium sulphate (B) Sodium chloride
(C) Urea (D) Glucose
Q.5 The freezing point of the solution M is
(A) 268.7 K (B) 268.5 K
Q.3 During depression of freezing point in a solution
the following are in equilibrium (2003) (C) 234.2 K (D) 150.9 K
(A) Liquid solvent, solid solvent
Q.6 The vapour pressure of the solution M is
(B) Liquid solvent, solid solute
(A) 39.3 mm Hg (B) 36.0 mm Hg
(C) Liquid solute, solid solute
(C) 29.6 mm Hg (D) 28.8 mm Hg
(D) Liquid solute, solid solvent

Q.4 The freezing point (in ºC) of solution containing Q.7 Water is added to the solution M such that the
0.1 g of K3[Fe(CN6)] (mol. wt. 329) in 100 g of water mole fraction of water in the solution becomes 0.9. The
(Kf = 1.86 K kg mol–1) is (2011) boiling point of this solution is
(A) 380.4 K (B) 376.2 K
(A) –2.3 × 10–2 (B) –5.7 × 10–2
(C) 375.5 K (D) 354.7 K
(C) –5.7 × 10–3 (D) –1.2 × 10–2

Q.8 Following statement is true only under some

Paragraph 3
specific conditions. Write the condition, for it “Two
Properties such as boiling point, freezing point and volatile and miscible liquids can be separated by
vapour pressure of a pure solvent change when solute fractional distillation into pure components”.
molecules are added to get homogeneous solution.
These are called colligative properties. Applications of Q.9 An organic compound (CxH2yOy) was burnt with
colligative properties are very useful in day-to-day life. twice the amount of oxygen needed for complete
One of its examples is the use of ethylene glycol and combustion to CO2 and H2O. The hot gases when
water mixture as anti–freezing liquid in the radiator of cooled to 0ºC and 1 atm pressure, measured 2.24 L.
automobiles. The water collected during cooling weigh 0.9g. The
vapour pressure of pure water at 20ºC is 17.5 mm Hg
A solution M is prepared by mixing ethanol and water.
and is lowered by 0.104 mm when 50g of the organic
The mole fraction of ethanol in the mixture is 0.9.
compound are dissolved in 1000g of water. Give the
Given, freezing point depression constant of water molecular formula of the organic compound. (1983)
(kfwater) = 1.86 K kg mol–1
freezing point depression constant of ethanol (kfethanol) Q.10 The vapour pressure of ethanol and methanol are
= 2.0 K kg mol–1 44.5 and 88.7 mm Hg respectively. An ideal solution
Boiling point elevation constant of water (kbwater) is formed at the same temperature by the mixing 60g
= 0.52 K kg mol–1 of ethanol with 40g of methanol. Calculate the total
vapour pressure of the solution and the mole fraction
Boiling point elevation constant of water (kfethanol)
of methanol in the vapour. (1986)
= 1.2 K kg mol–1
Standard freezing point of water = 273 K
Q.11 The vapour pressure of pure benzene at a certain
Standard freezing point of ethanol = 155.7 K temperature is 640 mm Hg. A non–volatile, non–
Standard boiling point of water = 373 K electrolyte solid weighing 2.175 g is added to 39.0 g of
benzene. The vapour pressure of solution is 600 mm Hg.
Standard boiling point of ethanol = 351.5 K
What is the molecular weight of the solid substance?
Vapour pressure of pure water = 32.8 mm Hg (1990)
Vapour pressure of pure ethanol = 40 mm Hg
Molecular weight of water = 18 g mol–1
Molecular weight of ethanol = 46 g mol–1

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Chem i str y | 43

Q.12 The degree of dissociation of Ca (NO3)2 in a dilute These are called colligative properties. Applications of
aqueous solution, containing 7.0g of the salt per 100g colligative properties are very useful in day-to- day life.
of water at 100ºC is 70%. If the vapour–pressure of One of its examples is the use of ethylene glycol and
water at 100ºC is 760 mm, calculate the vapour pressure water mixture as anti-freezing liquid in the radiator of
of the solution. (1991) automobiles.
A solution M is prepared by mixing ethanol and water.
Q.13 Nitrobenzene is formed as the major product The mole fraction of ethanol in the mixture is 0.9.
along with a minor product in the reaction of benzene
Given: Freezing point depression constant of water
with a hot mixture of nitric acid and sulphuric acid. The
minor product consists of carbon : 42.86%, hydrogen : (K ) = 1.86 K kg mol Freezing point depression
water
f
−1

2.40%, nitrogen : 16.67% and oxygen : 38.07%, constant of ethanol (K ) = 2.0 K kg mol Boiling
ethanol
f
−1

(i) Calculate the empirical formula of the minor product. point elevation constant of water (K )
water
b
(ii) When 5.5g of the minor product is dissolved in 45g = 0.52 K kg mol−1
of benzene, the boiling point of the solution is 1.84ºC
higher than that of pure benzene. Calculate the molar (
Boiling point elevation constant of ethanol Kbethanol )
= 1.2 K kg mol−1
mass of the minor product then determine its molecular
and structural formula. (Molal boiling point elevation In answering the following questions, consider the
constant of benzene is 2.53 K kg mol–1). (1999) solutions to be ideal dilute solutions and solutes to be
non-volatile and non- dissociative. (2008)
Q.14 The vapour pressure of two miscible liquids (A)
and (B) are 300 and 500 mm of Hg respectively. In a flask
Q.17 The freezing point of the solution M is
10 moles of (A) is mixed with 12 moles of (B). However,
as soon as (B) is added, (A) starts polymerizing into a (A) 268.7 K (B) 268.5 K
completely insoluble solid. The polymerization follows (C) 234.2 K (D) 150.9 K
first order kinetic. After 100min, 0.525 mole of a solute is
dissolved which arrests the polymerization completely.
The final vapour pressure of the solution is 400 mm of Q.18 The vapour pressure of the solution M
Hg. Estimate the rate constant of the polymerization (A) 39.3 mm Hg (B) 36.0 mm Hg
and ideal behavior for the final solution. (2001)
(C) 29.5 mm Hg (D) 28.8 mm Hg

Q.15 Consider the three solvents of identical molar

Q.19 Water is added to the solution M such that the
masses. Match their boiling point with their kb values
fraction of water in the solution becomes 0.9. The
(2003)
boiling point of this solution is
Solvents Boiling point kb values (A) 380.4 K (B) 376.2 K
X 100ºC 0.92 (C) 375.5 K (D) 354.7 K
Y 27ºC 0.63
Q.20 The Henry’s law constant for the solubility of N2
Z 283ºC 0.53
gas in water at 298 K is 1.0 × 105 atm. The mole fraction
of N2 in air is 0.8. The number of moles of N2 from air
dissolved in 10 moles of water at 298 K and 5 atm
Q.16 When 20 g of naphthoic acid (C11H8O2) is dissolved
pressure is (2009)
in 50 g of benzene (Kf = 1.72 K kg mol−1), a freezing
point depression of 2 K is observed. The van’t Hoff (A) 4.0 × 10−4 (B) 4.0 × 10−5
factor (i ) is (2007)
(C) 5.0 × 10−4 (D) 4.0 × 10−6
(A) 0.5 (B) 1 (C) 2 (D) 3
Q.21 The freezing point (in oC) of a solution containing
Paragraph for Question Nos. 17 to 19 0.1 g of K3[Fe(CN)6 (Mol. Wt. 329) in 100 g of water
(Kf = 1.86 K kg mol-1) is (2011)
Properties such as boiling point, freezing point and
vapor pressure of a pure solvent change when solute (A) -2.3 × 10-2 (B) -5.7 × 10-2
molecules are added to get homogeneous solution.
(C) -5.7 × 10-3 (D) -1.2 × 10-2

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44 | Solutions and Colligative Properties

Q.22 For a dilute solution containing 2.5 g of a non- Q.24The mole fraction of a solute in a solution is 0.1.
volatile non- electrolyte solute in 100 g of water, the At 298 K, molarity of this solution is the same as its
elevation in boiling point at 1atm pressure is 2°C. molality. Density of this solution at 298 K is 2.0 g cm-3.
Assuming concentration of solute is much lower than The ratio of the molecular weights of the solute and
the concentration of solvent, the vapor pressure (mm  MWsolute 
of Hg) of the solution is (take Kb = 0.76 K kg mol-1) solvent   , is (2016)
(2012)  MWsolvent 

(A) 724 (B) 740 (C) 736 (D) 718 Q.25 Mixture(s) showing positive deviation from
Raoults law at 35οC is (are) (2016)
Q.23 If the freezing point of a 0.01 molal aqueous (A) Carbon tetrachloride + methanol
solution of a cobalt (III) chloride-ammonia complex
(which behaves as a strong electrolyte) is – 0.05580C, (B) Carbon disulphide + acetone
the number of chloride(s) in the coordination sphere of (C) Benzene + toluene
the complex is [Kf of water = 1.86 K kg mol–1]
(D) Phenol + aniline

Rank Essential Questions

LEVEL 1 LEVEL 2

Exercise 1 Exercise 1
Q.2 Q.4 Q.9 Q.6 Q.10 Q.16
Q.14 Q.29 Q.20 Q.21 Q.25

Exercise 2 Exercise 2
Q.2 Q.4 Q.14 Q.6 Q.7 Q.12
Q.17 Q.15 Q.17 Q.25
Q.28
Previous Years' Questions
Q.6 Q.9 Q.11 Previous Years' Questions
Q.16 Q.17 Q.1 Q.13

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Chem i str y | 45

Answer Key

LEVEL 1
Exercise 1
Q.1 4.9 gm Q.2 0.89 Q.3 (i) 0.52m, (ii) 0.99
Q.6 0.2121 m Q.7 53.06g mol–1 Q.8 23.44 mm Hg
Q.9 0.988; 0.156 m Q.121.35 mol/litre; 1.52 mol/kg Q.13 0.283 mol/L
Q.14 0.099 mol L–1 Q.15 0.23 K
Q.16 158.9 mL of 0.1 M HCl Q.17 57.5 g mol–1 Q.18 256 g mol–1
Q.19 10 g Q.21 (b) 7.389 atm
Q.22 Degree of dissociation = 90% Q.23 18.6 × 10–4
Q.24 Atomic mass of A = 25.59; B = 42.64 Q.25 1.0753; 30.68 × 10–4 Q.28 (b) 92%

Exercise 2
Single Correct Choice Type

Q.1 C Q.2 C Q.3 A Q.4 A Q.5 C Q.6 D

Q.7 B Q.8 D Q.9 B Q.10 B Q.11 C Q.12 B
Q.13 A Q.14 C Q.15 B Q.16 C Q.17 D Q.18 B

Previous Years’ Questions

Q.1 A Q.2 D Q.3 C Q.4 A Q.5 B Q.6 C
Q.7 B Q.8 B Q.9 A Q.10 C Q.11 D Q.12 C
Q.13 C Q.14 C Q.15 A Q.16 B Q.17 D Q.18 C
Q.19 A Q.20 A Q.21 D Q.22 B Q.23 D Q.24 B
Q.25 A Q.26 B Q.27 B

LEVEL 2
Exercise 1
Q.1 0.24 Q.2 0.25 Q.3 24.5 torr
Q.4 57.24 g/mol Q.5 111.1 g, 18.52 molal Q.6 106 g/molal
Q.7 64.0 g/mol Q.8 100.079ºC Q.9 –0.62ºC
Q.10 T = -2.28ºC Q.11 0.741m, 0.013 Q.12 0.162 m
Q.13. 65.25 Q.14 17.38 Q.15 0.964
Q.16 Tb = 101.9ºC Q.17 Tf = –0.73ºC Q.18 [Co(NH3)Cl]Cl2
Q.19 0.73 Q.20 xB = 0.2472, yb = 0.4473

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46 | Solutions and Colligative Properties

Q.21 P = 0.2217 atm should be applied Q.22 (Vtotal = 5.Voriginal)

Q.23 94.5% Q.24 4.64 atm Q.25 0.95; 1.95
Q.26 46.33ºC Q.27 x = 0.1 Q.28 a = 0.7333
Q.29 –19.91ºC, 7.63M

Exercise 2
Single Correct Choice Type

Q.1 C Q.2 D Q.3 C Q.4 D Q.5 B Q.6 C

Q.7 D

Multiple Correct Choice Type

Q.8 A, C, D Q.9 A, D Q.10 A, C Q.11 A, B, C Q.12 A, C, D Q.13 A, B, C

Q.14 A, D Q.15 A, B Q.16 A, C, D Q.17 B, D Q.18 B, D

Assertion Reasoning Type

Q.19 C Q.20 D

Comprehension Type

Q.21 A Q.22 B Q.23 B Q.24 C Q.25 B

Match the Columns

Q.26 A → p, r; B → q, t; C → q, t; D → p, s Q.27 A → r; B → s; C → p; D → q

Q.28 A → s; B → r; C → q; D → p

Previous Years’ Questions

Q.1 C Q.2 A Q.3 A Q.4 A Q.5 D Q.6 A

Q.7 B Q.8 Condition Q.9 C5H10O11 Q.10 0.657 Q.11 65.25 Q.12 746.32

Q.13 168 Q.14 1.005 × 10–4 min–1 Q.15 Subjective Q.16 A Q.17 D

Q.18 B Q.19 B Q.20 A Q.21 A Q.22 A Q.23 3

Q.24 9 Q.25 A,B

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