CHEMISTRY

CHAPTER 1: SOLUTIONS
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SOLUTIONS
Introduction:

In this chapter, we will discuss about liquid solutions and their formation. This will be followed by
studying the properties of solutions, like vapour pressure and colligative properties. We will
begin with types of solutions and expressions for concentration of solutions in different units.
Thereafter, we will state and explain Henry’s law and Raoult’s law, distinguish between ideal and
non-ideal solution and deviation of real solutions from Raoult’s law. We will also discuss
abnormal colligative properties alongwith association and dissociation of solute.

Types of Solutions

All the three states of matter (solid, liquid and gas) may behave either as solvent or solute. When
a solution is composed of only two chemical substances, it is termed as binary solution.
Depending upon the state of solute or solvent, binary solutions can be classified as

Some Important Definitions

• Mixture - When two or more chemically non-reacting substances are mixed, they form
mixture.

• Heterogeneous Mixture - It consists of distinct phases, and the observed properties are
just the sum of the properties of individual phases.

• Homogeneous Mixture - It consists of a single phase which has properties that may differ
from one of the individual components.
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• Solution - The homogeneous mixture of two or more components such that at least one
component is a liquid is called solution.

• Solvent - It is the constituent of solution which has same physical state as that of solution
and generally present in greater amount than all the other components.

• Solute - The component of a solution other than solvent is called solute, may or may not
have same physical state as that of solution. Generally it is in smaller amount.

Example - In a sugar syrup (liquid solution) containing 60% sugar (solid) and 40% water
(liquid), water is termed as solvent, due to same physical state as that of solution.
Expressing the Strength of Solution

For a given solution the amount of solute dissolved per unit volume of solution is called
concentration of solute. Strength of solution is the amount of solute in grams dissolved in one
litre of solution. It is generally expressed in g/litre.
Other methods of expressing the strength of solution are:
1. Mass percentage –
Mass of solute
Mass % of solute = × 100
Total mass of solution
Mass of solvent
Mass % of solvent = × 100
Total mass of solution
2. Volume percentage –
Volume of solute
Volume % of solute = × 100
Total volume of solution
Volume of solvent
Volume % of solvent = × 100
Total volume of solution
3. Molality (m) - It is no. of moles of solute dissolved in 1 kg of the solvent.
(Number of moles of solute)
m =
(Mass of solvent {in kg})

4. Molarity (M) - It is no. of moles of solute dissolved in 1 litre of solution.

(Number of moles of solute)
M =
(Mass of soution {in litre})

5. Normality (N) - It is no. of gram-equivalents of solute dissolved in 1 litre of solution

(Number of gram equivalents of solute)
N =
(Volume of solution {in litre)

6. Formality - Ionic solutes do not exist in the form of molecules. These molecular mass is

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expressed as Gram-formula mass. Molarity for ionic compounds is actually called as

formality.

7. Mole fraction –
(Number of moles of solute)
Mole fraction of solute =
(Total moles of solution)
(Number of moles of solvent)
Mole fraction of solvent =
(Total moles of solution)
For a binary solution,
mole fraction of solute + mole fraction of solvent = 1.

8. Parts per million (ppm) –

It is defined in two ways

ppm = mass fraction × 106

ppm = mole fraction × 106

Solubility

Solubility of a substance is its maximum amount that can be dissolved in a specified amount of
solvent at a specified temperature. It depends upon the nature of solute and solvent as well as
temperature and pressure. Let us consider the effect of these factors in solution of a solid or a
gas in a liquid.
1. Solubility of Solid in Liquid
A solute dissolves in a solvent if the intermolecular interactions are similar in them, i.e., like
dissolves like. Polar solute dissolves in polar solvent and non-polar solute in non-polar
solvent. For e.g., sodium chloride and sugar dissolves readily in water and napthalene and
anthracene dissolves readily in benzene.
Solute + Solvent ⟶ Solution
i. Dissolution: When a solid solute is added to the solvent, some solute dissolves and its
concentration increases in solution. This process is called dissolution.
ii. Crystallization: Some solute particles collide with solute particles in solution and get
separated out. This process is called crystallization.
iii. Saturated solution: Such a solution in which no more solute can be dissolved at the
same temperature and pressure is called a saturated solution.
iv. Unsaturated solution: An unsaturated solution is one in which more solute can be
dissolved at the same temperature.
v. Effect of temperature: In general, if in a nearly saturated solution, the dissolution
process is endothermic, the solubility should increase with rise in temperature, if it is
exothermic, the solubility should decrease with rise in temperature.

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vi. Effect of pressure: Solids and liquids are highly incompressible, so pressure does not
have any significant effect on solubility of solids and liquids.
vii. Supersaturated solution: When more solute can be dissolved at higher temperature in
a saturated solution, then the solution becomes supersaturated.
2. Solubility of Gas in Liquid
All gases are soluble in water as well as in other liquids to a greater or lesser extent. The
solubility of a gas in liquid depends upon the following factors Nature of the gas, Nature of
solvent, Temperature and Pressure.
Generally, the gases which can be easily liquified are more soluble in common solvents. For
e.g., CO2 is more soluble than hydrogen or oxygen in water. The gases which are capable of
forming ions in aqueous solutions are much more soluble in water than other solvents. For
e.g., HCl and NH3 are highly soluble in water but not in organic solvents (like benzene) in
which they do not ionize.
i. Effect of temperature: Solubility of most of the gases in liquids decreases with rise in
temperature. In dissolution of a gas in liquid, heat is evolved and thus this is an
exothermic process. The dissolution process involves dynamic equilibrium and thus
follows Le Chatelier’s principle. As dissolution is exothermic the solubility of gas should
decrease with rise in temperature.
ii. Effect of pressure: Henry’s law: At constant temperature, the solubility of a gas in a
liquid is directly proportional to the pressure of the gas.
p = KH x,
KH = Henry’s law constant.
Applications of Henry’s law
1. In manufacture of soft drinks and soda water, CO 2 is passed at high pressure to
increase its solubility.
2. To minimise the painful effects accompanying the decompression of deep sea
divers. O2 diluted with less soluble. He gas is used as breathing gas.
3. At high altitudes, the partial pressure of O2 is less then that at the ground level.
This leads to low concentrations of O2 in the blood of climbers which causes
‘anoxia’.
Vapour Pressure of Solution

It is the pressure exerted by vapour on the surface layer of liquid at equilibrium between
vapour and liquid.

Factors affecting Vapour Pressure

i. Nature of liquid - Liquid with higher intermolecular attraction forces form less amount of
vapour and hence lower vapour pressure and vice-versa.

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ii. Temperature - Vapour pressure increases with temperature of liquid. This is because, as
temperature increases, kinetic energy of the molecules increases, hence, more molecules
leave the surface of the liquid and come into vapour phase.
Raoult’s Law

According to Raoult’s law, for a solution of volatile liquids, the relative lowering of vapour
pressure of solution is directly proportional to its mole fraction of dissolved solvent in solute.

Ideal and Non-Ideal Solution

The binary liquid-liquid solution may be classified into two types :

(1) Ideal solutions

(2) Non-ideal solutions

1) Ideal Solutions
An ideal solution may be defined as the solution which obeys Raoult’s law over the entire range of
concentration.

a) Such solutions are formed by mixing two components which are identical in molecular size, in
structure and have almost identical intermolecular forces.

b)The intermolecular interactions between the components (A – B attractions) are of same

magnitude as the intermolecular interactions in pure components (A- A and B-B attractions).

According to Raoult’s law, the partial vapour pressure of two components of the solution may be
given as :

pA = pA°xA

pB = pB°xB

Total pressure p is given by

p= pA +pB

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p= pA°xA + pB°xB

The ideal solutions have also the following characteristics:

1) Heat change on mixing is zero: Since there is no change in magnitude of the attractive
forces in the two components present, the heat change on mixing i.e. ΔmixingH in such solutions
must be zero.

2) Volume change on mixing is zero: In ideal solutions, the volume of the solution is the sum
of the volumes of the components before mixing i.e. there is no change in volume on mixing or
Δmixing V is zero.

The solutions generally tends to become ideal when they are dilute.

The characteristics of an ideal solution may be summed up as follows

(i) It must obey Raoult’s law.

(ii) Δmixing H should be zero.
(iii) Δmixing V should be zero.

Example of Ideal Solutions

(i) Benzene and toluene

(ii) n-hexane and n-heptane
(iii) Bromoethane and iodoethane
(iv) Chlorobenzene and bromobenene

Solutions which obey Raoult’s law are called ideal liquid solution.

Composition in Vapour Phase

The composition of vapour phase in equilibrium with the solution is determined by the partial
pressure of the components. If y1and y2 are the mole fraction of the two components 1 and 2
respectively in the vapour phase, then according to Dalton’s law of partial pressures:

Partial pressure of a component =Mole fraction of the component x Total pressure

p1= y1 p

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p2 =y2 p

In general, Pi = yi p total

Mole fraction of component 1 in vapour phase y1 = p1/p

Mole fraction of component 2 in vapour phase, y2 = p2 /p

Mole fraction of a component in vapour phase =

Partial vapour pressure of component / Total Vapour Pressure

2) Non-Ideal Solutions
The solutions which do not obey Raoult’s law over the entire range of concentration are called non-
ideal solutions. Therefore, for such solutions

pA ≠ pA° xA

pB ≠ pB° xB

The vapour pressure of such solutions is either higher or lower than that predicted by Raoult’s law.

In non-ideal solutions, there is a noticeable change in volume and heat energy when the two
components are mixed.

Most of the solutions are non-ideal because they deviate from ideal behaviour to more or less
extent.

Thus, for non-ideal solutions,

a) none of the components obey Raoult’s law over the entire composition range, i.e.

pA ≠ pA° xA and pB ≠ pB° xB

b) (i) Δmixing H is not equal to zero

(ii) Δmixing V is not equal to zero

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Ideal solution Non-Ideal solution

The interactions between the The interaction between the components
components are similar to those in the are different from those of the pure
pure components. components.
There is no enthalpy change on mixing. There is no enthalpy change on mixing.
ΔmixingH =0 ΔmixingH ≠ 0
There is no volume change on mixing. There is no volume change on mixing.
Δmixing V =0 Δmixing V ≠ 0
Their components do not obey Raoult’s
Each component obeys Raoult’s law at
law. They show positive and negative
all temperatures and concentrations,
deviations from Raoult’s law.
pA = pA°xA and pB = pB°xB
pA ≠ pA° xA and pB ≠ pB° xB

Types of Non-ideal Solutions

Non-ideal solutions show positive and negative deviations from the ideal behaviour depending
upon their nature.

(1) Non-Ideal solutions showing positive deviations from Raoult’s law

Consider a binary solution of two components A and B.

If the A-B interactions in the solutions are weaker than the A-A and B-B interactions in the two
liquids forming the solution, then the escaping tendency of A and B types of molecules from the
solution becomes more than from pure liquids. As a result, each component of solution has a
partial vapour pressure greater than expected on the basis of Raoult’s law. The total vapour

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pressure will be greater than corresponding vapour pressure expected in case of ideal solution of
the same composition. This type of behaviour of solution is described as positive deviations from
Raoult’s law.

pA >pA° xA and

pB >pB° xB

The total vapour pressure,

p= pA+ pB is always greater than (pA° xA + pB° xB )

Examples of solutions showing positive deviations are :

(i) Ethyl alcohol and cyclohexane

(ii) Acetone and carbon disulphide
(iii) Benzene and acetone
(iv) Carbon tetrachloride and choloroform
(v) Acetone and ethyl alcohol
(vi) Ethyl alcohol and water.

Explanation for positive deviations

In ethyl alcohol, the molecules are held together due to hydrogen bonding. When cyclohexane is
added to ethyl alcohol, the molecules of cyclohexane tend to occupy the spaces between ethyl
alcohol molecules. Consequently, some hydrogen bonds in alcohol molecules break and the
attractive forces in alcohol molecules are weakened. The escaping tendency of alcohol and
cyclohexane molecules from the solution increases. Consequently, the vapour pressure of the
solution is greater than the vapour pressure as expected according to Raoult’s law.

(i) Δmixing H is positive because energy is required to break A-A or B-B attractive forces.
Therefore, dissolution process is endothermic.

(ii) Because of the decrease in the magnitude of intermolecular forces in solutions, the molecules
will be loosely held and, therefore, there will be increase in volume on mixing. Thus, Δmixing V
will be positive.

(iii) Since the dissolution process in endothermic, heating will increase the solubility of such a
solution.

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(2) Non-Ideal solutions showing negative deviations from Raoult’s

law.

In such solutions, the A-B interactions are stronger than the A-A and B-B interactions present in
the two liquids forming the solution. Due to stronger A-B interactions, the escaping tendency of A
and B types of molecules from the solution becomes less than from pure liquids. Consequently,
each component of the solution has a partial vapour pressure less than expected on the basis of
Raoult’s law. As a result , the total vapour pressure becomes less than the corresponding
vapour pressure expected in case of ideal solution.

pA < pA° xA and

pB < pB° xB

p= pA+ pB is always less than (pA° xA + pB° xB )

Examples of Negative Deviation

(i) Acetone and chloroform

(ii) Chloroform and diethyl ether
(iii) Chloroform and nitric acid
(iv) Acetone and aniline
(v) Water and nitric acid
(vi) Diethyl ether and chloroform.

Explanation for Negative Deviations

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When acetone and chloroform are mixed there are new attractive forces due to intermolecular
hydrogen bonding. Thus the attractive forces become stronger and the escaping tendency of each
liquid from the solution decreases. Therefore, the vapour pressure of the solution is less than that
expected for an ideal solution.

(i) ΔmixingH is negative because energy is released due to increase in attractive forces. Therefore,
dissolution process is exothermic and heating the solution will decrease solubility.

(ii)Because of the increase in the magnitude of forces of attraction in solutions, the molecules will
be loosely held more tightly. Therefore, there will be decrease in volume on mixing. Thus,
ΔmixingV will be negative.

Difference between Ideal and Non-Ideal solution

Solution having positive deviation Solution having negative deviation

A-B forces are less than A-A and B-B forces. A-B forces are more than A-A and B-B forces.

pA >pA° xA and pB >pB° xB pA < pA° xA and pB < pB° xB

ΔmixingH is positive ΔmixingH is negative

Dissolution is endothermic Dissolution is exothermic

Heating increases solubility Heating decreases solubility

ΔmixingV will be positive. ΔmixingV will be negative.

a) Some solution exhibit very large positive deviation from Raoult’s law that there is a
maximum in the vapour pressure curve which is above the vapour pressure of either pure
components.

For one of the intermediate composition, the total vapour pressure of such a solution will
be the highest and the boiling point will be the lowest. At this point, the composition of
liquid and vapour phase is same and the liquid mixture boils at constant temperature and
remains unchanged in composition. Therefore, this liquid mixture distills over as if it is a
pure liquid. Solution acquires the property of boiling at constant temperature and remains
unchanged in composition.

The solutions (liquid mixtures) which boil at constant temperature and can distil
unchanged in composition are called azeotropes or azeotropic mixtures. Thus, the

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azeotropes distil over as if it were pure liquids. These types of solutions are
called minimum boiling azeotropes.

For example: Ethanol and water form minimum boiling azeotrope. It has maximum in the
vapour pressure curve and hence a minimum in the boiling point diagram. In this boiling
point diagram, we indicate the composition of the vapour phase by the upper curve and
composition of the liquid phase by the lower curve.

The boiling point diagram shows an azeotropic composition at x(H 2O)=0.056 and
x(C2H5OH) = 0.944 at a temperature.of 351 K (or 78°C) which is lower than that of pure
ethanol 351.5 K (or 78.5°C) and water 378 K (or 100°C).

Fractional distillation of solutions lying on either side of this azeotropic composition is

capable of separating them into at best, one pure component and a azeotropic mixture
having the minimum boiling point.

b) In the case of solutions showing negative deviations, total vapour pressure becomes
less than the corresponding ideal solution of same composition. The boiling points of such
solutions are increased.

For one of the intermediate composition, the total vapour pressure will be the least and
the boiling point will be the highest. At this composition, the solution also boils at constant
temperature without a change in composition. This is also called azeotrope.

The solutions which show negative deviations from Raoult’s law are called maximum
boiling azeotropes because they have a composition having maximum boiling point

For example: hydrochloric acid and water form maximum boiling point azeotrope at the
composition x(H2O)=0.889 and x (HCl)=0.111 (or 20.2% HCl) which boils at 381.6 K (or
108.6°C) which has higher than that of pure water.

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Nitric acid (HNO3) and water also form maximum boiling azeotrope. The azeotrope has the
approximate composition 68% nitric acid and 32% water by mass with a boiling point of
393.5 K.

Thus, the azeotropes are liquid mixtures of definite composition, which boil at constant
boiling point. These cannot be separated into pure components by fractional distillation.

Colligative Properties

The properties of dilute solution which depends only on number of particles of solute
(molecules or ions) present in the solution and not on their nature, are called colligative
properties. The important colligative properties are;
1. Relative lowering of vapour pressure
2. Elevation of boiling point
3. Depression in freezing point
4. Osmotic pressure
i. Relative Lowering of Vapour Pressure
When a non-volatile solute is added to a solvent, its vapour pressure gets lowered. If this
pressure is divided by pressure of pure solvent, this is called relative lowering of vapour
pressure.
According to Raoult’s law,

where, WA = weight of solute

WB = weight of solvent
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MA = molecular weight of solute

MB = molecular weight of solvent
ii. Relative Elevation of boiling point
A liquid boils at the temperature at which its vapour pressure is equal to the atmospheric
pressure. The boiling point of a solution of non-volatile solute is always higher than that of
the boiling point of pure solvent in which the solution is prepared. Similar to lowering of
vapour pressure, the elevation of boiling point also depends on the number of solute
particles rather than their nature.
Let T° be the boiling point of pure solvent and T be the boiling point of solution. The increase
in boiling point ΔTb = T – T° is known as elevation in boiling point.
For dilute solutions, the ΔTb is directly proportional to the molal concentration of the solute
in a solution. Thus
ΔTb ∝ m
ΔTb = Kbm
Kb is molal elevation constant (Ebullioscopic constant). The unit of Kb is K kg mol–1.
Substituting the value of molality in above equation, we get

Where, w1 = mass of solvent, w2 = mass of solute and M2 = molar mass of solute

iii. Depression in freezing point
Freezing point is the temperature at which vapour pressure of liquid phase becomes same
as that of solid phase. The decrease in freezing point of a solvent on the addition of a non-
volatile solute is known as depression in freezing point.
Let T° be the freezing point of pure solvent and T be the freezing point of solution. The
decrease in freezing point ΔTf = T° -T is known as depression in freezing point.
For dilute solutions, the ΔTf is directly proportional to the molal concentration of the solute
in a solution. Thus
ΔTf ∝ m
ΔTf = Kf ⋅ m
Here Kf is molal depression constant or cryoscopic constant
Substituting the value of molality in above equation, we get

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Where, w1 = mass of solvent, w2 = mass of solute and M2 = molar mass of solute

iv. Osmotic pressure
Osmosis is the spontaneous flow of the solvent molecules from a less concentrated solution
(dilute) to a more concentrated solution through a semi-permeable membrane. The driving
force of osmosis is called osmotic pressure. Osmotic pressure may be defined as “the
minimum excess pressure that has to be applied on the solution to prevent the osmosis".
Osmotic pressure of a solution ∝ molar concentration of solute in that solution
π∝c
π = cRT
where, R = Gas constant = 0.0821 lit atm K-1 mole-1
T = Temperature
c = Molar concentration

WB = wt. of solute
MB = Molar mass of solute
van’t Hoff Factor
To calculate the extent of association or dissociation, van’t Hoff in 1886 introduced a factor
‘i’ called van’t Hoff factor. van’t Hoff factor ‘i’ is defined as ratio of the experimental value of
colligative property to the calculated value of colligative property.
Experiment ecolligatival properties
i. e. , i
Calculated ecolligativ properties
Abnormal Molar Masses
Abnormal Molecular Masses
The accurate values of molar masses can be obtained only if the following two conditions are
met.
(i) The solutions should be dilute
The solutions used for measuring colligative properties must not be too concentrated. In the
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concentrated solutions, the particles begin to interact with each other as well as with the
solvent. As a result, the vapour pressure and therefore, other colligative properties depend
upon the nature of the solute and not just on the number of solute particles.
(ii) The solute must not dissociate or associate in solution
The equations derived for measuring the colligative properties are for non-electrolyte solutes
which do not undergo any dissociation or association in the solution.
Discrepancies in determination of molar mass arise when the solute dissociate or associate on
dissolving in a solvent. This is because due to the association or the dissociation of the solute
molecules in the solution, the number of molecules undergo a change.
The discrepancy in molar mass is called abnormal molar mass. The abnormal molar masses is
due to association or dissociation of solute particles.
Association of Solute Particles
In certain solvents, generally non-polar, the solute molecules undergo association i.e. two,
three or even more molecules exist in combination with each other to form bigger molecules.
For example: suppose n simple molecules combine to form an associated molecule as:

nA ⇔ An

Therefore, the total number of molecules in solution become less than the number of
molecules of the substance added and, therefore, colligative properties will be lower. Since the
colligative properties are inversely proportional to the molar mass of the solute, the molar
masses in such cases will be greater than the theoretical values.

For example: In benzene solvent, both ethanoic acid (acetic acid) and benzoic acid exist as
dimers as:

2CH3COOH ⇔ (CH3COOH)2

2C6H5COOH ⇔ (C6H5COOH)2

The molar masses of ethanoic acid and benzoic acid have been found to be nearly 120 and 244
which are about double than their normal values of 60 and 122. The association of solute
molecules in a solution is generally due to the hydrogen bonding between these molecules.

For example: benzoic acid and ethanoic acid exist as dimers due to the formation of hydrogen
bonds. Due to association of ethanoic acid or benzoic acid, the ΔTf or ΔTb value will be about
half of the normal value. Therefore, the molar mass calculated on the basis of ΔT will be about
twice the expected value.

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Dissociation of Solute Molecules

Molecules of certain substances (acids, bases and salts) dissociate or ionise in a solvent to give
two or more particles.

For example: AB dissociates to give double number of particles as:

AB ⇔ A+ + B–

The total number of particles increases in solution and, therefore, the colligative properties of
such solutions will be large. Since colligative properties are inversely proportional to molar
mass, the observed molar mass will be less than the theoretical value.

For example, KCl dissociates to give K+ and Cl– ions.

KCl ⇔ K+ + Cl–

If we dissolve 1 mol of KCl (74.5 g) in water, we expect 1 mol of K+ and 1 mol of Cl– ions to be
produced in the solution. Therefore, there would be 2 mol of particles in the solution instead
of 1 mol. Consequently, the colligative properties would also be about double than expected.

For example: if we ignore interionic attraction, 1 mol of KCl in 1 kg of water would be expected
to increase the boiling point by 2 X 0.52 K (Kb= 0.52 Km-1) = 1.04 K.

Van’t Hoff Factor

In 1886, Van’t Hoff introduced a factor called Van’t Hoff factor, i , to express the extent of
association or dissociation of solutes in solution. It is the ratio of the normal and observed
molar masses (or abnormal molar mass) of the solute, i.e.

Normal molar mass

i=
Observed molar mass

In case of association, observed molar mass being more than the normal, the factor i has a
value less than 1.

But in case of dissociation, the Van’t Hoff factor is more than 1 because the observed molar
mass has a lesser value.

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In case of solutes which do not undergo any association or dissociation in a solvent, the Van’t
Hoff factor i will be equal to 1 because the observed and normal molar masses will be same.

Since the molar masses are inversely proportional to the colligative property. Van’t Hoff factor
may also be expressed as:

Observed colligative property

i=
Normal collegative property

Relative lowering in vapour pressure = i xsolute = Δp / p°

Elevation in boiling point , Δ Tb =i Kb m

Depression in freezing point = Δ Tf = i Kf m

Osmotic pressure π = i cRT

Van’t Hoff Factor and Extent of Dissociation or Association in an Electrolytic

Solution

Van’t Hoff factor can be used to calculate the extent of dissociation or association in terms of
degree of dissociation or association of a substance in solution.

(i) Degree of dissociation: It is defined as the fraction of total substance that undergoes
dissociation into ions, i.e.

Degree of dissociation = No. of moles of the substance dissociated / Total number of moles of
the substance taken

Suppose a molecule of an electrolyte gives n ions after dissociation. Then if we start with 1
mole of the solute, and α is the degree of dissociation, then at equilibrium:

Number of moles of solute left undissociated =1-α

Number of moles of ions formed = nα

Total number of moles of particles 1-α+ nα

Van’t Hoff factor, i =

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Observed number of moles of solute / Normal number of moles of solute

Knowing the value of i from observed molar mass and normal molar mass, degree of
dissociation, α can be calculated.

For the electrolytes of the type AB, such as KCl, NaCl, etc,.the number of particles in solution
i.e. n = 2

For the electrolytes of the type AB, like CaCl2, Ba(NO3)2 etc, the value of n=2, so that

α = ( i-1 ) /2

(ii) Degree of association: It is defined as the fraction of total number of molecules which
combine to form associated molecules, i.e.

No. of moles of the substance associated

Degree of association =
Total number of moles of substance taken

For example: suppose n simple molecules of the solute associate to form the associated
molecule A.

nA= An

If we start with 1 mole of A and α is the degree of association, the concentration of the species
after association is

[An] = α/n

[A] =1-α

Total number of moles after association = 1-α+ α/n

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Thus, the colligative properties will correspond to (1-α+ α/n) mole particles rather than one
mole of particles.

Van’t Hoff factor, i , is : Observed number of moles of solute / Normal number of moles of
solute

= 1-α + α/n / 1

= 1+ α (1/n -1)

α =( i-1 ) /( 1/n -1)

Normal molar mass

I=
Observed molar mass

Knowing n the number of simple molecules which combine to give associated molecule,
observed molar mass, degree of association(α) can be calculated.

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Important Questions
Multiple Choice questions-
Question 1. Which of the following units is useful in relating concentration of solution with its
vapour pressure?

(a) mole fraction

(b) parts per million

(c) mass percentage

(d) molality

Question 2. On dissolving sugar in water at room temperature, solution feels cool to touch.
Under which of the following cases dissolution of sugar will be most rapid?

(a) Sugar crystals in cold water.

(b) Sugar crystals in hot water.

(c) Powdered sugar in cold water.

(d) Powdered sugar in hot water.

Question 3. At equilibrium the rate of dissolution of a solid solute in a volatile liquid solvent is

(a) less than the rate of crystallisation

(b) greater than the rate of crystallisation

(c) equal to the rate of crystallisation

(d) zero

Question 4. A beaker contains a solution of substance ‘A’. Precipitation of substance ‘A’ takes
place when small amount of ‘A’ is added to the solution. The solution is ………………

(a) saturated

(b) supersaturated

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(c) unsaturated

(d) concentrated

Question 5. Maximum amount of a solid solute that can be dissolved in a specified amount of
a given liquid solvent does not depend upon .

(a) temperature

(b) nature of solute

(c) pressure

(d) nature of solvent

Question 6. Low concentration of oxygen in the blood and tissues of people living at high
altitude is due to

(a) low temperature

(b) low atmospheric pressure

(c) high atmospheric pressure

(d) both low temperature and high atmospheric pressure

Question 7. Considering the formation, breaking and strength of hydrogen bond, predict
which of the following mixtures will show a positive deviation from Raoult’s law?

(a) Methanol and acetone.

(b) Chloroform and acetone.

(c) Nitric acid and water.

(d) Phenol and aniline.

Question 8. Colligative properties depend on

(a) the nature of the solute particles dissolved in solution.

(b) the number of solute particles in solution.

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(c) the physical properties of the solute particles dissolved in solution.

(d) the nature of solvent particles.

Question 9.Which of the following aqueous solutions should have the highest boiling point?

(o) 1.0 M NaOH

(b) 1.0 M Na2SO4

(c) 1.0 M NH4NO3

(d) 1.0 M KNO3

Question 10. The unit of ebullioscopic constant is

(a) K kg mol-1 or K (molality)-1

(b) mol kg K-1 or K-1 (molality)

(c) kg mol-1 K-1 or K-1 (molality)-1

(d) K mol kg-1 or K (molality)

Question 11.In comparison to a 0.01 M solution of glucose, the depression in freezing point of
a 0.01 M MgCl2 solution is ………..

(a) the same

(b) about twice

(c) about three times

(d) about six times

Question 12.An unripe mango placed in a concentrated salt solution to prepare pickle shrivels
because ………..

(a) it gains water due to osmosis.

(b) it loses water due to reverse osmosis.

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(c) it gains water due to reverse osmosis.

(d) it loses water due to osmosis.

Question 13. At a given temperature, osmotic pressure of a concentrated solution of a

substance

(a) is higher than that of a dilute solution.

(b) is lower than that of a dilute solution.

(c) is same as that of a dilute solution.

(d) cannot be compared with osmotic pressure of dilute solution.

Question 14. Which of the following statements is false?

(a) Two different solutions of sucrose of same molality prepared in different solvents will have
the same depression in freezing point.

(b) The osmotic pressure of a solution is given by the equation π = cRT (where c is the molarity
of the solution).

(c) Decreasing order of osmotic pressure for 0.01 M aqueous solutions of barium chloride,
potassium chloride, acetic acid and sucrose is BaC l2 > KCl > CH3COOH > sucrose.

(d) According to Raoult’s law, the vapour pressure exerted by a volatile component of a
solution is directly proportional to its mole fraction in the solution.

Question 15.he values of Van’t Hoff factors for KCl, NaCl and K 2SO4, respectively, are

(a) 2, 2 and 2

(b) 2, 2 and 3

(c) 1,1 and 2

(d) 1, 1 and 1

Very Short Question:

Question 1. Define the term – solubility?

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Question 2. What is the effect of pressure on solubility of a gas?

Question 3. State Henry’s Law.

Question 4. State Raoult’s Law.

Question 5. What are the factors on which vapour pressure depends?

Question 6. The vapour pressure of solvent gets lowered, when a non- volatile solute is added
to it. Why?

Question 7. Name two ways by which vapour pressure of a liquid can be lowered.

Question 8. Define solution?

Question 9. Define the following terms:

(a) Molality

(b) Molarity

Question 10. How does change in temperature changes the molarity and molality values?

Short Questions:

Question 1 Find the molality and molarity of a 15% solution of H 2SO4 when its density is

a) 1.10 glcm3 & molar mass = 98 amu.

Question 2. Calculate the mole fraction of ethanol and water in a sample of rectified spirit
which contains 46% ethanol by mass?

Question 3. Calculate the % composition in terms of mass of a solution obtained by mixing

300g of a 25% & 400 g of a 40% solution by mass?

Question 4. One litre of sea water weight 1030g and contains about of dissolved
Calculate the concentration of dissolved oxygen in ppm?

Question 5. The density of 85% phosphoric acid is. What is the volume of a
solution that contains 17g of phosphoric acid?

Question 6. Define the term azeotrope?

Question 7. Obtain a relationship between relative lowering of vapour pressure and

mole fraction of solute?

Question 8. Draw the graphs of both deviations from ideal behaviours?

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Question 9. A weak electrolyte AB in 5% dissociated in aqueous solution? What is the

freezing point of a 0.10 molar aqueous solution of AB? K f = 1.86 deg/molal?

Question 10. Henry’s law constant for the molality of methane in benzene at 298 K is .
Calculate the solubility of methane in benzene at 298 K under 760 mm Hg.

Long Questions:

Question 1.

The vapour pressure of at is 854 mm Hg .A solution of 2.0g sulphur in 100g of

has a vapour pressure of 848.9 mm Hg .Calculate the formula of sulphur molecule

Question 2. Calculate the mass percentage of benzene (C6H6) and carbon tetrachloride (CCl4)
if 22 g of benzene is dissolved in 122 g of carbon tetrachloride.

Question 3. Calculate the mole fraction of benzene in solution containing 30% by mass in
carbon tetrachloride.

Question 4. Calculate the molarity of each of the following

solutions: (a) 30 g of . in 4.3 L of solution (b) 30 mL of 0.5 M H2SO4
diluted to 500mL.

Question 5.Calculate (a)molality (b)molarity and (c)mole fraction of KI if the density of 20%
(mass/mass) aqueous KI is

Assertion and Reason Questions:

1. In these questions, a statement of assertion followed by a statement of reason is given. Choose

the correct answer out of the following choices.

a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.

Assertion: Camphor is used as a solvent in the determination of molecular masses of naphthalene,

anthracene, etc.

Reason: Camphor has high molal elevation constant.

2. In these questions, a statement of assertion followed by a statement of reason is given. Choose

the correct answer out of the following choices.
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a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation for
assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.

Assertion: Reverse osmosis is used in the desalination of sea water.

Reason: When pressure more than osmotic pressure is applied, pure water is squeezed out of
the sea water through the membrane.

Case Study Questions:

1. Read the passage given below and answer the following questions:

The solubility of gases increases with increase of pressure. William Henry made a systematic
investigation of the solubility of a gas in a liquid. According to Henry's law "the mass of a gas
dissolved per unit volume of the solvent at constant temperature is directly proportional to the
pressure of the gas in equilibrium with the solution". Dalton during the same period also
concluded independently that the solubility of a gas in a ti quid solution depends upon the
partial pressure of the gas. If we use the mole fraction of gas in the solution as a measure of its
solubility, then Henry's law can be modified as "the partial pressure of the gas in the vapour
phase is directly proportional to the mole fraction of the gas in the solution"

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Henry's law constant for the solubility of methane in benzene at 298K is 4.27 x 10 5mm
Hg. The solubility of methane in benzene at 298K under 760mm Hg is:

a) 4.27 × 10-5
b) 1.78 × 10-3
c) 4.27 × 10-3
d) 1.78 × 10-5

(ii) The partial pressure of ethane over a saturated solution containing 6.56 × 10-2g of ethane
is I bar. If the solution contains 5.00 × 10-2g of ethane then what will be the partial
pressure (in bar) of the gas?

a) 0.762
b) 1.312
c) 3.81
d) 5.0
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(iii) KH (K bar) values for Ar(g), CO2(g), HCHO(g) and CH4(g) are 40.39, 1.67, 1.83 × 10-5 and 0.413
respectively. Arrange these gases in the order of their increasing solubility. Arrange these
gases in the order of their increasing solubility.

a) HCHO < CH4 < CO2 < Ar

b) HCHO < CO2 < CH4 < Ar
c) Ar < CO2 < CH4 < HCHO
d) Ar < CH4 < CO2 < HCHO

(iv) When a gas is bubbled through water at 298K, a very dilute solution of the gas is
obtained. Henry's law constant for the gas at 298K is 150 kbar. If the gas exerts a partial
pressure of 2 bar, the number of millimoles of the gas dissolved in IL of water is:

a) 0.55
b) 0.87
c) 0.37
d) 0.66

(v) Which of the following statements is correct?

a) KH increases with increase of temperature.

b) KH decreases with increase of temperature.
c) KH remains constant with increase of temperature.
d) KH first increases then decreases, with increase of temperature.

2. Read the passage given below and answer the following questions

Few colligative properties are:

1. Relative lowering of vapour pressure: depends only on molar concentration of solute

(mole fraction) and independent of its nature.
2. Depression in freezing point: it is proportional to the molal concentration of solution.
3. Elevation of boiling point: it is proportional to the molal concentration of solute.
4. Osmotic pressure: it is proportional to the molar concentration of solute

A solution of glucose is prepared with 0.052 g at glucose in 80.2 g of water. (KJ = 1.86K kg mol-
1
and Kb = 5.2K kg mol-1)

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Molality of the given solution is.

a) 0.0052m

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b) 0.0036m
c) 0.0006m
d) 1.29m

(ii) Boiling point for the solution will be.

a) 373.05K
b) 373.15K
c) 373.02K
d) 373.02K

(iii) The depression in freezing point of solution will be.

a) 0.0187K
b) 0.035K
c) 0.082K
d) 0.067K

(iv) Mole fraction of glucose in the given solution is.

a) 6.28 × 10-5
b) 6.28 × 10-4
c) 0.00625
d) 0.00028

(v) If same amount of sucrose (C12 H22 O11) is taken instead of glucose, then.

a) Elevation in boiling point will be higher.

b) Depression in freezing point will be higher.
c) Depression in freezing point will be lower.
d) Both (a) and (b).

Answers key
MCQ answers:
1. Answer: (a) mole fraction

2. Answer: (d) Powdered sugar in hot water.

3. Answer: (c) equal to the rate of crystallisation

4. Answer: (b) supersaturated

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5. Answer: (c) pressure

6. Answer: (b) low atmospheric pressure

7. Answer: (a) Methanol and acetone.

8. Answer: (b) the number of solute particles in solution.

9. Answer: (b) 1.0 M Na2SO4

10. Answer: (a) K kg mol-1 or K (molality)-1

11. Answer: (c) about three times

12. Answer: (d) it loses water due to osmosis.

13. Answer: (a) is higher than that of a dilute solution.

14. Answer: (a) Two different solutions of sucrose of same molality prepared in different
solvents will have the same depression in freezing point.

15. Answer: (b) 2, 2 and 3

Very Short Answers:

1. The maximum amount of a substance that can be dissolved in a specified amount of solvent is
called its solubility.

2. The solubility of a gas increases with increases of pressure.

3. Answer: Henry’s Law states that at a constant temperature the solubility of a gas in a liquid
is directly proportional to the pressure of the gas.

4. Answer: Raoult’s Law states that for a solution of volatile liquids, the partial vapour
pressure of each component in the solution is directly proportional to its mole fraction.

5. Answer: The factors on which vapour pressure depends are –

1) Temperature of the liquid. 2) Nature of the liquid.

6. Answer: When a non-volatile solute is added to a solvent, the surface area for escape of solvent
molecules decreases and vapour pressure gets lowered.

7. Answer: The two ways by which vapour pressure can be lowered are –

1) By decreasing the temperature.

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2) By adding a non- volatile solute.

8. Solutions are homogeneous mixtures of two or more than two components..

9. (a) Molality is defined as the number of moles of the solute per kilogram of solvent.

(b) Molarity (M) = Number of moles of solute dissolved in one litre of solution.

10. As the temperature increases, volume increases and molarity decreases whereas molality does
not change with any change in temperature.

Short Answers:

1. Answer

Volume = mass/density

Molarity =

= .

Molality =

= 1.8 M.

2. Answer:

Mass of ethanol = 46g

Mass of water = 100 – 46 = 54g

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Mole fraction of ethanol,

Mole fraction of water = 1-0.25 = 0.75

Mole fraction of water = 1-0.25 = 0.75

3. Answer:

mass of solute in 400g of 40%

=
Total mass of solute = 160+75 = 235g
Total mass of solution = 400+300 = 700g

Mass% of solute =

Mass % of solvent = 100 – 33.57 = 66.43%

4. Answer:
mass of

ppm of in 1030 g sea water =

5. Answer :
Ans. 85g phosphoric acid is present in 100g of solution.
17g of phosphoric acid is present in

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Volume of 17g of 85% acid =

=

6. Answer

A solution at certain concentration when continues to boil at constant temperature without

change in its composition in solution & in vapour phase is called an azeotrope.

7. Answer:
According to Raoult’s Law –

=
Relative lowering of vapour pressure.

8. Answer:

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9. Answer :
Degree of dissociation of AB = .
AB A+ + B–
M 0 0
No. of moles dissolved
No. of moles after dissociations
m (1- ) m m
0.1 (1 – 0.05)

Total moles = 0.1(1−0.05) + +

= 0.095 + 0.005 + 0.005 = 0.105m

= 0.1953 deg.

10.Answer :

p = 760 mm Hg

According to Henry’s law,

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= (approximately)
Hence, the mole fraction of methane in benzene is .

Long Answers:
1. Answer:

= 854 mm , ,

=
= 254.5 g/mol.

Let the formula = Sx

X=
=7.95
=8.
= Formula = S8

2. Answer:
Mass percentage of

=15.28%

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Mass percentage of =

= 84.72%

Alternatively,

Mass percentage of = (100 – 15.28) %

= 84.72%

3. Answer:
Let the total mass of the solution be 100 g and the mass of benzene be 30g.
∴ Mass of carbon tetrachloride = (100 – 30) g
= 70 g
Molar mass of benzene ( ) = (6 12 + 6 )
= 78

∴ Number of moles of

= 0.3846 mol

Molar mass of carbon tetrachloride ( ) = 1 12 + 4 355

= 154
∴Number of moles of

= 0.4545 mol
Thus, the mole fraction of is given as:

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= 0.458
4. Answer:
Molarity is given by:

(a) Molar mass of 59 + 2 (14 + 3 16) + 6 18

= 291

Therefore, Moles of
= 0.103 mol
Therefore, molarity

= 0.023 M
(b) Number of moles present in 1000 mL of 0.5 M
∴Number of moles present in 30 mL of 0.5 M
= 0.015 mol
Therefore, molarity = 0.03 M
5. Answer:

(a) Molar mass of KI = 39 + 127 = 166

20% (mass/mass) aqueous solution of KI means 20 g of KI is present in 100 g of solution.
That is,
20 g of KI is present in (100 – 20) g of water = 80 g of water
Therefore, molality of the solution=

= 1.506 m
= 1.51 m (approximately)

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(b) It is given that the density of the solution =

Therefore, Volume of 100 g solution =

= 83.19 mL
=
Therefore, molarity of the solution =

(c) Moles of KI =
Moles of water =

Therefore, mole fraction of KI =

=

= 0.0263

Assertion and Reason Answers:

1. (c) Assertion is correct statement but reason is wrong statement.

Explanation:

Camphor has high molal depression constant.

2. (a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.

Explanation:

If a pressure larger than the osmotic pressure is applied to the solution side, the pure solvent
flows out of the solution to the solvent through semi-permeable membrane and this
phenomenon is called reverse osmosis.

Case Study Answers:

1. Answer :

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2. Answer :

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