SOLUTIONS

(Lecture Notes)
 CONTENTS
1. Introduction

2. Types of Solutions

3. Concentration Measurement of Solutions

 Parts per million (ppm)
 Mass percentage (m/m)
 Volume percentage (v/v)
 Mass to volume percentage (m/v)
 Mole Fraction (
 Molarity (M)
 Normality (N)
 Molality (m)

4. Solubility

5. Solubility Laws

6. Solubility Law’s

7. Types of Solutions – Based on Behavior

8. Azeotropic Mixtures

9. Colligative Properties

10. Abnormal Molecular Mass and Van’t Hoff Factor

11. Modified colligative properties

12. Relationship between various Colligative Properties

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INTRODUCTION
Solutions are the substances formed by mixing two or more than two different substances (or
components) together in a homogenous manner. Therefore, Solutions can also be called as
Homogenous Mixtures i.e. their composition remains same throughout the mixture.

The substance present in huge quantity in mixture is considered as Solvent. The nature of
Solvent determines the state in which the Solution exists.

The substance(s) present in less quantity is (are) known as Solute(s). The nature of solution,
amount of solute that dissolves in a given solvent depends on factors such as Temperature,
Pressure.

As the temperature increases, the kinetic energy of the solvent molecules increases thereby
allowing more amount of solute to be dissolved and vice – versa i.e. solubility is directly
proportional to temperature of the solvent.

The effect of pressure can only be observed in case of gases dissolving in liquids and solids.

TYPES OF SOLUTIONS
Depending on the number of solutes present, quantity of solutes present, dissolution of solute
in a solvent, nature of solute and solvent, solutions are classified as:

Based on Number of Components:

Binary Solutions: A solution containing a Solvent and One Solute only i.e. two component
system. Example: Sugar dissolved in Water, toluene dissolved in benzene.

Based on Amount of Solute Present:

Unsaturated Solution: A solution which can dissolve more amount of solute at a given
particular temperature.

Saturated Solution: A solution which can’t dissolve more amount of solute at a given
particular temperature.

In such solutions, if we add more amount of solute, the newly added solute will dissolve
making the already dissolved solute precipitate out. i.e. a dynamic equilibrium exists between
the solute dissolved and the solute being precipitated.

Super Saturated Solutions: A solution made by dissolving more amount of solute than the
maximum amount that can be dissolved either by increasing pressure or temperature. The
excess solute present crystallize out very easily.

On increasing the temperature of a super saturated solution still further, the solution
becomes saturated/ unsaturated.

On decreasing the temperature of a saturated solution, it becomes Super Saturated Solution.

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Based on Amount of Solvent Present:

Concentrated Solutions: A solution that which is near to saturation at a given temperature.

Example: 98% sulphuric acid.

Dilute Solutions: A solution that contains small amount of solute in large amount of solvent
at a given temperature. Example: 1% Sulphuric acid.

Based on Concentration of Solutes in Two Different Solutions:

Isotonic Solutions: The two different solutions containing same amount of solute in a given
amount of solvent. There is no net movement of solute or solvent molecules when both the
solutions are placed together with each other.

Hypertonic Solutions: A solution (1st Solution) kept in another solution (2nd Solution) having
higher concentration of solute in it. This makes the solvent to flow from 1st solution to 2nd
solution. If any biological cells are present in 1st solution, the cells will shrink as a result.

Hypotonic Solutions: A solution (1st Solution) kept in another solution (2nd Solution) having
lower concentration of solute in it. This makes the solvent to flow from 2nd solution to 1st
solution. If any biological cells are present in 1st solution, the cells will swell up as a result
and in some cases they burst out.

Isotonic Solution Hypertonic Solution Hypotonic Solution

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Based on Nature of Solvent and Solute: The solute and solvent can exist in any of the three
states of matter i.e. Solid, Liquid and Gas and accordingly solutions are classified as:

TYPE OF SOLUTION SOLUTE SOLVENT EXAMPLES

Solid Solid Bronze, Brass
Solid Solutions Liquid Solid Moist Solids
Gas Solid Interstitial Hydrides
Solid Liquid Paint, Liquid Ink
Liquid Liquid Milk
Liquid Solutions
Ammonia Gas
Gas Liquid
dissolved in Water
Solid Naphthalene in
Solid Gas
Inert Air
Gaseous Solutions Liquid Gas Clouds
Mixture of any 2
Gas Gas
gases

CONCENTRATION MEASUREMENT OF SOLUTIONS

In order to know the properties of solutions and use them for various purposes, we need to
know the components present in the solution and also quantities of solute and solvent present
i.e. Composition of a given Solution. The different techniques for measuring the amount of
solute present in a given solvent are:

Part per Million (ppm): The ratio of mass of solute present (mg) in a given mas of solution
(kg), when the solute is present in trace quantities.

It is expressed as:

Parts per million (ppm) = =

Mass Percentage (m/m): The ratio of mass of one solute component (g) present in a given
solution to the total mass of solution (g) presents.

Mass % or m/m % =

Volume Percentage (v/v): The ratio of volume of one solute component (ml) present in a
given solution to the total volume of solution (ml) presents.

Volume % or v/v % =

Mass by Volume Percentage (m/v): The mass of solute (g) dissolved in 100ml of the solution.

m/v =

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Mole Fraction ( ): The ratio of number of moles of one component (g) present in a given
solution to the total number of moles of all solute components and solvent present together in
the solution.

Molality (m): The ratio of number of moles of solute present per kilogram of solvent. If w (g)
of a solute with molecular mass W (g) is present in m (g) of a solvent:

Molality =

 Molality is a Temperature Independent Quantity.

Molarity (M): The ratio of number of moles of solute dissolved per litre of solution. If w (g)
of a solute with molecular mass W (g) is present in V (l) of a solution:

Molarity =

 Molarity is a Temperature dependent Quantity as Volume changes with change in

Temperature.

Normality (N): The ratio of number of gram equivalence of solute (equiv.) present in 1000ml
of solution.

Equivalent Mass =

Number of Gram Equivalence =

Normality =

Relationship between Molarity and Normality:

1. If concentrated Nitric acid is 68%, then what should be the molarity of the aqueous
solution of nitric acid, if the density of aqueous solution is 1.504g/cc.
2. Calculate the mole fraction of solute and solvent, molality of the solution formed by
dissolving 3g of urea in 250ml of water.
3. Calculate the molality of iodine dissolved in benzene if the mole fraction of iodine in
benzene is 0.2.
4. One litre sea water of density contains of dissolved nitrogen
gas. Calculate the concentration of nitrogen in ppm.

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SOLUBILITY
Solubility of a substance is the maximum amount of the substance that can be dissolved in a
given amount of solvent at a given temperature.

In general, the amount of a substance (solute) dissolved in 100g of a solvent at a given

temperature is the Solubility of the Substance.

Solubility of the solute depends on many factors such as temperature, pressure, interaction
between solvent and solute particles.

1. Pressure: The effect of pressure on solubility of solids and liquids in liquids is almost
negligible. The effect of pressure can be seen only in case of gases solubility in liquids
at a given temperature and is governed by Henry’s Law.

2. Temperature: The solubility of any substance with variation of temperature is

governed by the thermodynamics.

For solubility of Solids in Liquids:

If heat is liberated in the process (Exothermic Process), then as Temperature
Increases, the Solubility Decreases.

If heat is absorbed in the process (Endothermic Process), then as Temperature

Increases, the Solubility also Increases.

For solubility of Gases in Liquids:

The solubility of a gas in a liquid is an exothermic process and therefore, it decreases
with increase in temperature.

3. Nature of Solvent and Solute: Solvents and solutes can be classified based on polarity
of the bonds present. Therefore, Ionic Solutes are soluble in Polar Solvents and
Covalent Solutes are soluble in in Non – Polar Solvents.

4. Volatility of Substance: Volatility is the measure of the tendency of a substance to

vaporize. Depending on the volatility of the liquids, on mixing two such liquids, their
behavior is governed by Raoult’s Law.

SOLUBILITY LAWS
The solubility of a solute in a liquid mainly depends on temperature and if the solute is a gas,
then Pressure also plays a major rule. So a two components system (one solute and solvent)
is considered as Binary Solution. The laws that govern the solubility are:

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Henry’s Law: The law describes the solubility of a gas in a solvent depending on the
pressure exerted on the liquid. The law states that “the solubility of a solute in a solvent is
directly proportional to the partial pressure exerted over the surface of the liquid, at a
constant temperature”.

where, is the Henry’s Law Constant

Characteristics of :

 It is different for same gas at different temperature.

 It is different for different gases at same given temperature.
 Higher value of indicates less solubility of gas and vice – versa.

The laws governing the solubility of solids and liquids in liquids along with their nature shall
be discussed below:

Liquid in Liquid Solutions:

Vapor Pressure: The pressure exerted by the vapor on the surface of the liquid in a liquid
– vapor mixture system present in a closed container.

If the vapor phase is completely saturated with vapor (no more vapor can be accommodated
in the gas phase), then the pressure exerted by such a vapor on the surface of the liquid is
termed as Saturated Vapor Pressure. In general, it measure at 25C.

Variation of Vapor Pressure with Temperature: Vapor pressure is completely

temperature dependent as vapor is produced only when the vapor pressure equals to
atmospheric pressure (which changes as temperature changes).

The relation between Vapor Pressure and Temperature is given by Clausius – Claypeyron
Equation:

On integrating the above equation, we get:

On comparing Vapor Pressures at two different given temperatures, we get:

( ) ( )

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Raoult’s Law: The law describes the existence and behavior of two non – reacting volatile
liquids when mixed with each other (Binary Solution). The law states that “the partial
pressure of a component in the vapor phase is directly proportional to its mole fraction in
liquid phase when two non – reacting volatile liquids are mixed with each other”.

Consider two liquids A and B (non – reacting & volatile) are mixed with each other. The
solution thus obtained is kept in a closed container. As both liquids are volatile, they start
vaporizing increasing the amount of vapor content with time and vaporization continues till a
dynamic equilibrium is established between the vapor phase and liquid phase.

Two Volatile Non – Reacting Liquids (Benzene & Toluene) mixed with each other

Let the Saturated Vapor Pressure of A and B be and respectively.

Let the total pressure exerted by the vapor present be .

Le the mole fraction of A, B in liquid and vapor phase be , and respectively.

Let the partial pressure of A and B in the vapor phase be and respectively.

As per Raoult’s Law:

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As only two components are present in liquid and vapor phase, using mole fraction concept:

Substituting the values from previous equations:

Using mole fraction of A and B, the equation is modified as:

=  =

=  =

The pressure exerted by all the components in the vapor is equal to the total vapor pressure
according to the Daltons Law of Partial Pressures. Using this law,

= +

Relationship between vapor phase components and liquid phase components:

The variation of total vapor pressures with mole fraction of A and B can be found out and
when plotted on a graph, it would result as:

Total Vapor Pressure vs. Mole Fraction

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Differences between Henry’s Law and Raoult’s Law:
Henry’s Law Raoult’s Law
Explains about dissolution of a gas in a Explains about relationship between Vapor
liquid medium. Pressure of solution and partial pressures of
solutes in the solution.
Amount of gas dissolved in the liquid is Vapor pressure of a component above
directly proportional to partial pressure of solution is directly proportional to mole
gas over the solution. fraction of same in solution.
Constant of proportionality is Henry’s Constant of proportionality is Saturated
Constant. Vapor Pressure.

PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)

1. If the number of moles of dinitrogen and dioxygen in air are and
, calculate the henry’s law constant for the respective gases.

2. Given the Henry’s Law constant for gases P, Q, R and S to be 144.97, 69.16, 76.48
and 88.84 kbar respectively at 298K. Arrange the gases in the order of their solubility.

3. Ethylene glycol and benzene are mixed with each other forming an ideal solution.
Calculate the total vapor pressure of the solution thus formed by mixing 156g of
benzene and 186g of ethylene glycol, if saturated vapor pressure of ethylene glycol
and benzene are 236 mm of Hg and 268 mm of Hg respectively.

4. Two non – reacting, volatile liquids A and B are mixed to form an ideal solution. The
saturated vapor pressure of A and B are 150mm of Hg and 100mm of Hg respectively.
What is the range of the total pressure of the solution formed?

5. Calculate the mole fraction of component B in the vapor phase which is in

equilibrium with an ideal liquid mixture of A and B, with mole fraction of A in liquid
phase as 0.5. Pure vapor pressures of A and B are 119 torr and 37 torr respectively.

Solid in Liquid Solutions:

On dissolving solids in liquids, the surface of solvent is occupied with solute molecules due to
which the amount of solvent converting to vapor phase is reduced. This reduces the exerted
vapor pressure.

The higher the amount of solute added to the solvent, the less the amount of vapor formed. In
other words, the vapor pressure is directly proportional to the mole fraction of solvent
present in the solution.

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TYPES OF SOLUTIONS (BASED ON BEHAVIOR)
All solutions are made by mixing 2 or more components and in this process either there
would be some volume and heat changes or may not be any change observed. Example:

1. In mixing of Acid and Base, heat is evolved.

2. On dissolving any ionic substance in water, heat is absorbed.

Binary Solutions as Ideal and Non – Ideal Solutions: Let us consider two liquids A and B are
present. In liquid A, there would be interactions between the molecules which we are
considered as A – A interactions and similarly in liquid B, there would be B – B interactions.

In the solution formed by mixing liquids A and B, there would be A – B interactions in

addition to A – A and B – B interactions.

Ideal Solutions:
All the Solutions obeying the Raoult’s Law at all concentrations and temperatures are
considered as Ideal Solutions. Ideal Solutions have following properties:

(i) H of Mixing is Zero; i.e. there is no heat evolved or absorbed during the mixing
of liquids.
(ii) V of Mixing is Zero; i.e. there is no change in the volume of solution during the
mixing of liquids.
(iii) A – A, B – B interactions are equal to A – B interactions.

Non – Ideal Solutions:

All the Solutions that DO NOT OBEY Raoult’s Law at any concentration and temperature
are considered as Non – Ideal Solutions. Non – Ideal Solutions have following properties:

(i)
(ii)
(iii) and
(iv) A – A, B – B interactions are either greater than or less than A – B interactions.

Representation of Deviations from Ideal Solutions

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Negative Deviation from Raoult’s Law:

In this type of deviation, A – B interactions are greater than A – A & B – B interactions.

Hence, more amount of A and B components will be present in the liquid phase and therefore,
less amount of vapor would be present. Due to this behavior, there would less total vapor
pressure compared to the ideal total vapor pressure and hence considered as “Negative
Deviation”.

Properties of Negatively Deviated Solutions:

(i) and
(ii) i.e. heat would be liberated in the process.
(iii) i.e. there would be slight decrease in volume after mixing.

Positive Deviation from Raoult’s Law:

In this type of deviation, A – B interactions are less than A – A & B – B interactions. Hence,
less amount of A and B components will be present in the liquid phase and therefore, more
amount of vapor would be present. Due to this behavior, there would more total vapor
pressure compared to the ideal total vapor pressure and hence considered as “Positive
Deviation”.

Properties of Positively Deviated Solutions:

(i) and
(ii) i.e. heat would be absorbed in the process.
(iii) i.e. there would be a slight increase in volume after mixing.

Negative Deviation Positive Deviation

Deviation of Total Vapor Pressure from Ideal Vapor Pressure vs. Mole Fraction

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Differences between Ideal and Non – Ideal Solutions:
Ideal Solutions Non – Ideal Solutions
All interactions appearing among the Different type of interaction arises between
different molecules in solution are identical different types of molecules inside the same
in nature. solution.
Enthalpy change of mixing is Zero. Enthalpy Change of Mixing in Non – Zero.
Volume change of Mixing is Zero. Volume change of Mixing is Non – Zero.
Highly Dilute solutions behave as Ideal Concentrated Solutions behave as Non –
Solutions. Ideal Solutions.

AZEOTROPIC MIXTURES
Azeotropic mixtures are those solutions which boil constantly over a range of temperatures.
i.e. they have a constant composition over an appreciable range of temperatures. Such
azeotropic mixtures boil or distill over completely without a change in composition at a
particular temperature.

In general, the solutions that behave non – ideally and deviate from Raoult’s Law forms such
Azeotropic mixtures.

A solution showing Negative Deviation from Ideal Raoult’s Law has minimum vapor content
and therefore has high boiling points due to which it forms Maximum Boiling Azeotrope.
Example: Mixture of 68% Nitric Acid and 32% Water.

A solution showing Positive Deviation from Ideal Raoult’s Law has maximum vapor content
and therefore has low boiling points due to which it forms Minimum Boiling Azeotrope.
Example: Mixture of Carbon tetrachloride and Alcohol.

Azeotropic Mixtures cannot be separated into their individual components by simple

Fractional Distillation. In order to separate the components in azeotropic mixtures,
additional solutes or solvents should be added.

Deviation from Raoult’s Law and Azeotropic Mixtures vs. Mole Fraction

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 PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)
1. The vapor pressure of pure acetone and pure ether are 300 mm of Hg and 650 mm of
Hg respectively at 30C. A solution formed by these liquids with mole fraction of
acetone 0.2 shows a vapor pressure of 700 mm of Hg. What type of solution is this?

COLLIGATIVE PROPERTIES
The properties that ONLY depend on the number of solute particles present in a given volume
of solvent and NOT on the nature of the solute, are considered as colligative properties.

The properties do depend on the nature of the Solvent. In a pure solvent, when a solute is
added, due to the interactions, the properties of solvent changes slightly to a great extent. The
few such properties are:

Relative Lowering of Vapor Pressure: On addition of a non – volatile solute to a pure

solvent, the vapor pressure of the solvent decreases, known as Relative Lowering of Vapor
Pressure. It is also defined as “the ratio of lowering of vapor pressure to that of vapor
pressure of pure solvent”.

This effect occurs as:

 Solute particles bind themselves very strongly to the solvent particles thereby
hindering them from escaping into vapor phase.
 Formation of a layer by the solute particles on the top layer of the solvent, which also
reduces the escaping of solvent molecules into vapor phase.

Let the Vapor Pressure of Pure Solvent be

Let the Vapor Pressure of Solution be

Let the number of moles of solvent and solute be and respectively.

Let the mole fraction of Solute in the Solution is

Relative Lowering of Vapor Pressure =

From Raoult’s Law,

Substituting the Raoult’s Law equation in Relative Lowering of Vapor Pressure equation, we
get:

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For very dilute solutions ( ):

PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)

1. Calculate the vapor pressure of the solution formed by dissolving 15g of a non –
volatile solute (molar mass = 60g/mol) in 100ml of carbon tetrachloride (density =
1.54g/ml) if the pure vapor pressure of carbon tetrachloride is 143 mm of Hg.
2. If the vapor pressure of 10% aqueous solution of non – volatile substance is 750 mm
of Hg at 373K, calculate the molecular mass of the non – volatile solute.
3. The solution formed by dissolving NaCl in water is found to have vapor pressure of
608 mm of Hg. What should be the amount of NaCl added in 288g of water in order
to produce such vapor pressure?

Elevation in Boiling Point: On addition of a non – volatile solute to a pure solvent, the
boiling point of the solution increases, known as Elevation in Boiling Point which is directly
proportional to molality of the solution.

Boiling point is the temperature at which vapor pressure of the liquid becomes and equal to
atmospheric pressure (or external pressure applied).

Let the Boiling Point of Pure Solvent be

Let the Boiling Point of Solution be

Let the Molality of the Solution be

Elevation in Boiling Point (in K) =

where,  is Molal Elevation Constant or Ebullioscopic Constant

Molal elevation constant is “the elevation in the boiling point produced when 1 mole of a non
– volatile solute is dissolved in 1kg of solvent”.

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Characteristics of molal elevation constant:

 It is constant for a given solvent.

 Using Boiling Point of the solvent ( ) and the latent heat of vaporization per gram of
solvent ( ), it can be theoretically calculated as:

The elevation in boiling point produced for non – associating or non – dissociating solutes
are the same irrespective of solutes.

The elevation in boiling point produced for associating or dissociating solutes are completely
different from one another.

Depression in Freezing Point: On addition of a non – volatile solute to a pure solvent,

the freezing point of the solution decreases (drops down), known as Depression in Freezing
Point which is directly proportional to molality of the solution.

Freezing point is the temperature at which vapor pressure of the liquid becomes and equal to
vapor pressure of solid phase (or external pressure applied).

Let the Freezing of Pure Solvent be

Let the Freezing Point of Solution be

Let the Molality of the Solution be

Depression in Freezing Point (in K) =

where,  is Molal Depression Constant or Cryoscopic Constant

Molal depression constant is “the depression in the freezing point produced when 1 mole of a
non – volatile solute is dissolved in 1kg of solvent”.

Characteristics of molal depression constant:

 It is constant for a given solvent.

 Using Freezing Point of the solvent ( ) and the latent heat of fusion per gram of
solvent ( ), it can be theoretically calculated as:

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The depression in freezing point produced for non – associating or non – dissociating solutes
are the same irrespective of solutes.

The depression in freezing point produced for associating or dissociating solutes are
completely different from one another.

Depression in Freezing Point

Comparison between Elevation in Boiling Point and Depression in Freezing Point

NOTE: and of water are 0.52 K/molal and 1.86 K/molal respectively.

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 PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)
1. The molar enthalpy of sublimation of solid benzene is 20.21 JK/mol. Molar heat of
fusion is 1059 kJ/mol. Calculate the for benzene if boiling point of benzene is
80C.
2. An aqueous solution containing 3.1g of non – electrolyte having the empirical
formulae in 250g water, boils at 100.104C. Find the molecular formulae of the
compound. ( )
3. Calculate of (  
4. The freezing point of pure molten camphor is 178.4C. Calculate
the freezing point of a solution containing 1.5g of an organic compound of molecular
mass 125g/mol in 35g of camphor.
5. A 0.05M aqueous solution of freezes at -0.279C. find the formulae of
the complex by assuming 100% dissociation at the given concentration.
6. Calculate the specific latent heat of fusion of naphthalene, if the freezing point of
molten naphthalene is 80.22C with the value of equal to 6.85 K/mol.

Osmotic Pressure:
Osmosis: Osmosis is a process in which there would be net transfer of solvent molecules from
a higher solvent concentrated region to a lower solvent concentrated region through a semi –
permeable membrane.

This process occurs due to the pressure and concentration difference that exists on either side
of the semi – permeable membrane. In general, atmospheric pressure pushes the solvent
molecules through the membrane.

Process of Osmosis

Osmotic Pressure (): It is the external pressure applied on lower solvent concentration
region to stop the flow of the solvent into it. It is proportional to concentration of the solution
(C) and temperature (T) at which the process is taking place.

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 where, R is Universal Gas Constant and R =

In a solution with many solutes, if are osmotic pressures of n solutes,

then the Total Osmotic Pressure of solution is equal to sum of individual solutes osmotic
pressures.

Reverse Osmosis: Reverse Osmosis is a process in which there would be net transfer of
solvent molecules from a higher solute concentrated region to a lower solute concentrated
region through a semi – permeable membrane on applying external pressure.

It can also be defined as “Flow of solvent molecules from solution region to solvent region
through a semi – permeable region, on applying external pressure greater than osmotic
pressure of the solution”.

Process of Reverse Osmosis

Application of Reverse Osmosis:

 Purification of Contaminated Water. Especially in purification of Brackish Water.

 Removal of contaminated wastes in Industrial and Biological samples.

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 Purification of Brackish Water in Water Treatment Plants using Reverse Osmosis

Differences between Osmosis and Reverse Osmosis:

Osmosis Reverse Osmosis
Occurs due to Potential Gradient. Occurs against Potential Gradient.
Natural and Spontaneous Process. Artificial Process.
Occurs during absorption of water from soil Occurs during purification of waste water.
by roots of plant.

Types of Osmotic Solutions:

Isotonic Solutions: Solutions with same osmotic pressure at same temperature. There is no
flow of solvent between osmotic solutions through the semi – permeable membrane.

Hypertonic Solution: A solution having higher osmotic pressure than the other solution at a
given temperature. There is net flow of solvent from Hypotonic Solution to other Solution.

Hypotonic Solution: A solution having lower osmotic pressure than the other solution at a
given temperature. There is net flow of solvent into Hypotonic Solution from other Solution.

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Differences between Osmotic Solutions:
Isotonic Solutions Hypertonic Solutions Hypotonic Solutions
Solutions have equal Osmotic Solutions have higher Solutions have less Osmotic
Pressure Osmotic Pressure than others Pressure than others
Have equal Solute Have High Solute Have Less Solute
Concentrations Concentrations Concentrations
No effect on Biological Cells Cells will Shrink in Size Cells will Swell in Size
Not helpful in Food Highly Helpful in Food Not Helpful in Food
Preservation Preservation Preservation

PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)

1. An aqueous solution of urea (mol. wt. = 60g/mol) freezes at -0.52C. Calculate the
osmotic pressure of the solution at 37C.
2. The vapor pressure of a solution of urea in water is 736.2 mm of Hg at 100C.
Calculate the osmotic pressure of the solution at 15C by assuming the density of the
solution to be 1g/ml.

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ABNORMAL MOLECULAR MASS
On adding solutes to solvents, solutes sometimes associate, dissociate or remain as they are.
In case of association or dissociation, the properties of solutions changes completely. These
changes are measured using Van’t Hoff Factor.

Van’t Hoff Factor is a measure for the extent of association or dissociation of solute.

Colligative properties and molecular mass of a substance are inversely proportional to each
other. Hence, we use abnormal molecular mass instead of normal molecular mass for
calculation of colligative properties and others whenever solutes associate or dissociate.

Solutes whenever associate, their molecular mass increases and when dissociate, molecular
mass decreases.

In Solutions undergoing dissociation process, i > 1

In Solutions undergoing association process, i < 1

The degree of dissociation (α) and Van’t Hoff factor (i) are related as:

The degree of association (α) and Van’t Hoff factor (i) are related as:

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MODIFIED COLLIGATIVE PROPERTIES
Due to association or dissociation of solutes, the properties of solutions changes and
therefore, the colligative properties can’t be calculated using the same equations. Hence we
use modified equations and are:

Relative Lowering of Vapor Pressure:

Elevation in Boiling Point:

Depression in Freezing Point:

Osmotic Pressure:

PROBLEMS FOR PRACTICE (JEE MAIN & ADV.)

1. Calculate the boiling point of 0.5m aqueous solution of KCl, given that i = 1.85 and

2. Phenol dimerises in benzene. The degree of association is 90%. What weight of

phenol to be added in 2kg of benzene in order to have for the solution as 1.65C?
for the solvent is 5.2K/molal.
3. At 100C, the vapor pressure of solution of calcium nitrate (6.69g in 100g of water) is
746.9 mm of Hg. Calculate the degree of dissociation of the solute.
4. Calculate the boiling point of 0.1M aqueous solution of chloroacetic acid.
and .

RELATION BETWEEN COLLIGATIVE PROPERTIES

In general, for a Solute (B) in a binary solution is:

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For very dilute binary solutions,

Relation between Relative Lowering of Vapor Pressure and Elevation in Boiling Point:

By eliminating “m” from both the above equations, we get:

Similarly,

Relation between Relative Lowering of Vapor Pressure and Depression in Freezing Point:

Relation between Relative Lowering of Vapor Pressure and Osmotic Pressure:

Relation between Elevation in Boiling Point and Osmotic Pressure:

Relation between Depression in Freezing Point and Osmotic Pressure:

Relation between Elevation in Boiling Point and Depression in Freezing Point:

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 Additional Questions for Practise
1. A 20ml sample of copper sulphate solution was evaporated to dryness, leaving 0.319g
of residue. What would be the molarity of the original solution?
2. The concentration of pollutant in ppm that has been measured at 200mg per 50kg of
sample is ……………
3. Calculate the vapor pressure of 0.555molal aqueous solution of urea at 40C, if the
enthalpy of vaporization of water is 10 kcal/mol in the given range of temperature.

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