2.

SOLUTION
2.1 Introduction

Mixture: It is a combination of two or more substances.

Example: Air is a mixture of gases, rock is a mixture of two
or more minerals.

Homogeneous mixture: Mixing of components is

uniform

Heterogeneous mixture: Nonuniform mixing of

components.

Homogenous mixture
(on the basis of size)

Colloids True solution

Colloids • 1 to 1000 nm

True
• < 1nm
solution
Different units to express concentration of solution
Existence of solution:
Molarity (M) Mol/Lit
• Body fluids Normality (N) N
• Industrial processes Molality (m) Moles/ kg
Mole fraction (X) Dimensionless
Definition of solution: The solution is a homogeneous Mass percent (w/w%)
mixture of two or more pure substances. Parts per millions (ppm)
Solute: The minor components in solution, dissolve in
2.3 Capacity of solution to dissolve solute
solvent. A dynamic equilibrium can be reached where the
Solvent: The major component in solution. number of solute molecules leaving the crystal to pass
into solution is equal to the number returning from the
Components of true solution: solution to the crystal.

• Solvent+ one or more solute

• Binary true solutions containing only one solute.
• A saturated solution contains maximum amount
of solute dissolved in a given amount of solvent
2.2 Types of solutions: at a given temperature.
There are nine types of solutions depending on the states • A solution containing greater than the
of solute and solvent. equilibrium amount of solute is said to be
supersaturated solution.
• Such solutions are unstable.
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• The precipitation occurs by the addition of a tiny Polar solutes dissolve in polar solvents. This is because in
crystal of solute and the supersaturated solution these, solute-solute, solute-solvent and solvent-solvent
change saturated solution. interactions are all of similar
magnitude. For example, NaCl dissolves in water. The
strong ion-dipole interactions of Na⊕ and Cl ions with
water molecules, hydrogen bonding between water
molecules and ion-ion attractions between Na⊕ and Cl
ions are comparable.
Nonpolar organic compounds like cholesterol dissolves
in nonpolar solvent such as benzene.
Sugar dissolves in water!
The dissolution of sugar in water is due to intermolecular
hydrogen bonding between sugar and water.
ii. Effect of temperatute on solubility :
Solubility of substance changes with temperature and it
depends on enthalpy of solution.
For Example, KCl, dissolve in water by endothermic
process, that is, with the absorption of heat. When
temperature is increased by adding heat to the system,
the solubility of substance increases according to the Le-
Chatelier principle. Addition of heat causes a stress on
the saturated solution. This stress favor’s endothermic
process.

When the substance dissolves in water by an exothermic

process its solubility decreases with an increase of
temperature. The substances such as CaCl2 and
Li2SO4.H2O dissolve in water releasing heat.

2.4 Solubility : There is no direct correlation between solubility and

• The solubility of a solute is its amount per unit exothermicity or endothermicity. For example,
volume of saturated solution at a specific dissolution of CaCl2 in water is exothermic and that of
temperature. NH4NO3 is endothermic. The solubility of these
• The solubility of a solute is its maximum increases with the temperature.
concentration and expressed in the Figure 2.1 shows the result of experimental
concentration units mol L-1. determination of solubilities of some ionic solids in water
2.4.1 Factors affecting solubility : at various temperatures.
The extent to which a substance dissolves in a solvent
varies greatly with different substances.

i. Nature of solute and solvent :

Compounds with similar chemical character
are more readily soluble in each other
than those with entirely different chemical characters.
The saying that ‘like dissolves like’ guides to predict the
solubility of a solute
in a given solvent.
Substances having similar intermolecular forces are likely
to be soluble in each other.
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Solubility of Increase/Decrease/Changes
NaBr, NaCl and Slightly changes
KCl
KNO3, NaNO3 Increases
and
KBr
Na2SO4 Decreases

The solubility of gases in water usually decreases with

increase of temperature. When gases are dissolved in
water, the gas molecules in liquid phase are condensed.
The condensation is an exothermic process. The
solubility of gases in water must decrease as
temperature is raised.
Classic Henry’s Law Demonstration:

Items: A sealed soda bottle or can.

• Action:
Shake the sealed soda bottle (CO₂ is dissolved under
pressure).
Open it quickly: You will see bubbles rush out as the
pressure above the liquid drops, and the gas (CO₂)
comes out of solution.

• Explanation:
When sealed, the high pressure keeps more
iii. Effect of pressure on solubility gas dissolved.
• Pressure has no effect on the solubilities of solids When opened, the pressure drops and gas
and liquids as they are incompressible. escapes — exactly what Henry’s Law predicts.
• Pressure greatly affects solubility of gases in
liquids. The solubility of gases increases with
increasing pressure. Exceptions to Henry’s law
• The quantitative relationship between gas
solubility in a liquid and pressure is given by Gases like NH3 and CO2 do not obey Henry’s law. The
Henry’s law. reason is that these gases react with water.

Henry’s law:
It states that the solubility of a gas in a liquid is directly
proportional to the pressure of the gas over the solution.

Because of these reactions, NH3 and CO2 gases have

higher solubilities than expected by Henry’s law.
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2.5 Vapour pressure of solutions of liquids in liquids :

Consider a binary solution of two volatile liquids A1 and

A2. When the solution is placed in a closed container,
both the liquids vaporize. Eventually an equilibrium is
established between vapor and liquid phases. Both the
components are present in the vapour phase. The partial
pressure of the components are related to their mole
fractions in the solution. This relationship is given by
Raoult’s law.

2.5.1 Raoult’s law :

It states that the partial vapour pressure of any volatile

component of a solution is equal to the vapour pressure
of the pure component multiplied by its mole fraction in
the solution.

P1 and P2 are their partial vapour pressures and x1 and

x2 are their mole fractions of A1 & A2 in solution
respectively.

P10 and P20 are vapour pressures of pure liquids A1 and

A2, respectively.

According to Dalton’s law of partial pressures,

The composition of vapour in equilibrium with the
solution can be determined by Dalton’s law of partial
pressures.

If we take y1 and y2 as the mole fractions of two

Since x1 = 1- x2, components in the vapour,
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where P1 and P2 are the partial pressures of two
components in the vapour and P is the total vapour
pressure.

1. Ideal solutions

• Obey Raoult’s law over entire range of

concentrations.
• Thus, the enthalpy of mixing is zero.
ΔmixH = 0
• Volume of an ideal solution is equal to the sum
of volumes of two components taken for mixing.
ΔmixV = 0
• In an ideal solution solvent-solute, solute-solute
and solvent-solvent molecular interactions are B. Negative deviations from Raoult’s law
comparable.
• The solutions in which the interactions between
• The vapour pressure of ideal solution always lies
solvents and solute molecules are stronger than
between vapour pressures of pure components.
solute-solute or solvent-solvent interactions,
• Example: benzene + toluene
exhibit negative deviations.
2. Nonideal solutions: • The vapour pressures of such solutions are lower
than those of pure components. The solutions of
• Solutions do not obey Raoult’s law over the phenol and aniline, chloroform and acetone
entire range of concentrations. exhibit negative deviations from the Raoult’s
• Vapour pressures of these solutions can be law.
higher or lower than those of pure components.
• Deviation from the Raoult's law : These solutions
show two types of deviation from the Raoult's
law.

A. Positive deviations from Raoult’s law The solutions in

which solute-solvent

• Intermolecular attractions are weaker than

those between solute-solute molecules and
solvent-solvent molecules, exhibit positive
deviations. The vapour pressures of such
solutions are higher than those of pure
components.
• The solutions of ethanol and acetone, carbon 2.6 Colligative properties of nonelectrolyte solutions :
disulphide and acetone show positive
deviations from the Raoult’s law. Definition: The physical properties of solutions that
depend on the number of solute particles in solutions and
not on their nature are called colligative properties.

Types:

1. vapour pressure lowering

2. boiling point elevation

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3. freezing point depression 2. When nonvolatile solute is dissolved in a solvent,
some of the surface molecules of solvent are
4. osmotic pressure
replaced by nonvolatile solute molecules.
While dealing with colligative properties of 3. These solute molecules do not contribute to
nonelectrolyte solutions, the relatively dilute solutions vapour above the solution.
with concentrations 0.2 M or less are considered. 4. Thus, the number of solvent molecules available
for vaporization per unit surface area of solution
2.7 Vapour pressure lowering : is less than the number at the surface of pure
solvent.
Definition of vapour pressure:
5. As a result, the solvent molecules at the surface
When a liquid in a closed container is in equilibrium with of solution vaporize at a slower rate than pure
its vapours, the pressure exerted by the vapour on the solvent. This results in lowering of vapour
liquid is its vapour pressure. pressure.

2.7.1 Raoult’s law for solutions of nonvolatile solutes

:
Raoult’s law expresses the quantitative relationship
between vapour pressure of solution and vapour
pressure of solvent.
In solutions of nonvolatile solutes, the law is applicable
only to the volatile solvent.

The law states that the vapour pressure of solvent over

When a nonvolatile, nonionizable solid is dissolved in a the solution is equal to the vapour pressure of pure
liquid solvent, the vapour pressure of the solution is solvent multiplted by its mole fraction in the solution.
lower than that of pure solvent. The vapour pressure of
a solvent is lowered by dissolving a nonvoltile solute into
it.

When the solute is nonvolatile it does not contribute to

the vapour pressure above the solution. Therefore, the
vapour pressure of solution is equal to the vapour
pressure of solvent above the solution.

P10 is the vapour pressure of pure solvent

P1 is the vapour pressure of solvent above the solution,

For a binary solution containing one solute,

Why the vapour pressure of solution containing
nonvolatile solute is lower than that of pure solvent?

1. Vapour pressure of a liquid depends on the ease

with which the molecules escape from the
surface of liquid.
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Suppose that we prepare a solution by dissolving W2 g of

a solute in W1 g of solvent. The moles of solute and
solvent in the solution are then,

ΔP depends on x2 that is on number of solute particles.

Thus, ΔP, the lowering of vapour pressure is a colligative
property.

2.7.2 Relative lowering of vapour pressure

The ratio of vapour pressure lowering of solvent divided
by the vapour pressure of pure solvent is called relative Knowing all other quantities, molar mass of solute M2
lowering of vapour pressure. can be calculated.

2.8 Boiling point elevation :

The boiling point of liquid is the temperature at
which its vapour pressure equals the applied pressure.
For liquids in open containers the applied pressure is
atmospheric pressure.

Boiling point of a solvent is elevated by dissolving a

Thus, relative lowering of vapour nonvolatile solute into it. Thus, the
pressure is equal to the mole fraction of solute in the solutions containing nonvolatile solutes boil
solution. Therefore, relative vapour pressure lowering is at temperatures higher than the boiling point
a colligative property. of a pure solvent.
2.7.3 Molar mass of solute from vapour
pressure lowering :
The difference between the boiling point of solution and
that of pure solvent at any given constant pressure is
called the boiling point
elevation.

where n1 and n2 are the moles of solvent and solute

respectively, in the solution.
We are concerned only with dilute solutions hence n1 >>
n2 and n1+n2 ≈ n1.
The mole fraction x2 is then given by
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2.8.1 Boiling point elevation as a consequence of
vapour pressure lowering :
m is the molality of solution. The proportionality
constant Kb is called boiling point elevation constant or
molal elevation constant or ebullioscopic constant.

Ebullioscopic constant is the boiling point elevation

produced by 1 molal solution.

1) At any temperature the vapour pressure of

Reason: We are dealing with the systems whose
solution is lower than that of pure solvent.
temperature is not constant. Therefore, we cannot
2) The vapour pressure-temperature curve of
express the concentration of solution in molarity which
solution (CD) lies below that of solvent (AB).
changes with temperature whereas molality is
3) The difference between the two vapour
temperature independent. Therefore the concentration
pressures increases as temperature and vapour
of solute is expressed in mol/kg (molality) rather than
pressure increase as predicted by the equation,
mol/L (molarity).
2.8.3 Molar mass of solute from boiling
point elevation
4) The intersection of the curve CD with the line
corresponding to 760 mm is the boiling point of
solution. The similar intersection of the curve AB
is the boiling point of pure solvent.
5) boiling point (Tb) of the solution is higher
than that of pure solvent (T0b).
6) At the boiling point of a liquid, its vapour
pressure is equal to 1 atm.
7) In order to reach boiling point, the solution and
solvent must be heated to a temperature at
which their respective vapour pressures attain 1
atm.
8) At any given temperature the vapour pressure of
solution is lower than that of pure solvent.
9) Hence, the vapour pressure of solution needs
higher temperature to reach 1 atm than that
needed for vapour pressure of solvent.

2.8.2 Boiling point elevation and concentration of

solute :
The boiling point elevation is directly proportional to the
molality of the solution.
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The curves AB and CD intersect at
point B where solid and liquid phases of pure solvent are
in equilibrium. The two phases have the same vapour
pressure at B. The temperature corresponding to B is the
freezing point of solvent ( T0f ).
Similarly at E, the point of intersection
of EF and AB, the solid solvent and solution
are in equilibrium. They have the same vapour
pressure at E. The temperature corresponding
2.9 Depression in freezing point to E is the freezing point of solution, Tf .
Freezing point of a liquid is the temperature at which
liquid and solid are in equilibrium and the two phases It is clear from the figure that freezing point of solution
have the same vapour pressure. The freezing point of a Tf is lower than that of pure solvent T0f . It is obvious
solvent is lowered by dissolving a nonvolatile solute into because the vapour pressure curve of solution lies below
it. Thus, freezing point of solution containing a that of solvent.
nonvolatile solute is lower than that of pure
solvent. At the freezing point of a pure liquid the attractive forces
among molecules are large enough to cause the change
of phase from liquid to solid.

2.9.2 Freezing point depression and

concentration of solute :
2.9.1 Freezing point depression as a
consequence of vapour pressure lowering
The effect of dissolution of a nonvolatile solute into a
solvent on freezing point of solvent can be understood in
terms of the vapour pressure lowering.

2.9.3 Molar mass of solute from freezing

point depression

The diagram consists of three curves. AB is the vapour

pressure curve of solid solvent while CD is the vapour
pressure curve of pure liquid solvent. EF is the vapour
pressure curve of solution that always lies below the
pure solvent.
It is important to note that solute does not dissolve in
solid solvent.
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2.10 Osmotic pressure : 2.10.2 Osmotic pressure :
Osmotic pressure is associated with vapour pressure
lowering and can be used to determine molar masses of
dissolved solutes.
Semipermeable membrane :
It is a film such as cellophane which has pores large
enough to allow the solvent molecules to pass through
them. These pores are small enough not to allow the
passage of large solute molecules or ions of high
molecular mass through them. The semipermeable
membrane selectively allows passage of solvent
molecules. Semipermeable membrane is firmly fastened across the
2.10.1 Osmosis : When a solution and mouth of thistle tube. The solution of interest is placed
pure solvent or two solutions of different concentrations inside an inverted thistle tube. This part of the tube and
are separated by a semipermeable membrane, the the membrane are then immersed in a container of pure
solvent molecules pass through the membrane. water.

As a result, some of the solvent passes through the

membrane into the solution. It causes the liquid level in
the tube to rise. The liquid column in the tube creates
hydrostatic pressure that pushes the solvent back
through the membrane into the container. The column
of liquid in the tube continues to rise and eventually
stops rising. At this stage hydrostatic pressure developed
is sufficient to force solvent molecules back through the
membrane into the container at the same rate they enter
the solution.

An equilibrium is thus established where rates of forward

The passage of solvent molecules through the and reverse passages are equal. The height of liquid
semipermeable membrane takes place in both column in the tube remains constant. This implies that
directions, since solvent is on both sides of the the hydrostatic pressure has stopped osmosis.
membrane. the rate of passage of solvent molecules into
the solution or from more dilute solution to more The hydrostatic pressure that stops osmosis is an osmotic
concentrated solution is found to be greater than the pressure (π) of the solution. The hydrostatic pressure is
rate in the reverse direction. This is favourable since the equal to hρg where h is the height of liquid column in the
vapour pressure of solvent is greater than that of tube, ρ is density of solution and g is acceleration due to
solution. The net spontaneous flow of solvent molecules gravity.
into the solution or from more dilute solution to more 2.10.3 Isotonic, hypertonic and hypotonic
concentrated solution through a semipermeable solutions
membrane is called osmosis. i. Isotonic solutions : Two or more solutions having the
As a result of osmosis, the amount of liquid on the pure same osmotic pressure are said to
solvent side or more dilute solution side decreases. be isotonic solutions.
Consequently, the amount of liquid on the other side ii. Hypertonic and hypotonic solutions :
increases. This results in decrease of the concentration If two solutions have unequal osmotic pressures, the
of solution. more concentrated solution with higher osmotic
pressure is said to be hypertonic solution.
The more dilute solution exhibiting lower osmotic
pressure is said to be hypotonic
 2.SOLUTION
solution.

2.10.4 Osmotic pressure and concentration

of solution
For very dilute solutions, the osmotic pressure follows
the equation, 2.10.6 Reverse osmosis :
The direction of osmosis can be reversed by applying a
pressure larger than the osmotic pressure.

While calculating osmotic pressure molarity is used

rather than molality.
Reason is that osmotic pressure measurements are made The pure solvent then flows from solution into pure
at a specific constant temperature. It is not necessary to solvent through semipermeable membrane. This
express concentration in a temperature independent phenomenon is called reverse osmosis.
unit like molality.
Fresh water and salty water are separated by a
2.10.5 Molar mass of solute from osmotic semipermeable membrane. When the pressure larger
Pressure than the osmotic pressure of solution is applied to
solution, pure water from salty water passes into fresh
pure water through the membrane.
2.11 Collgative properties of electrolytes
Experimental observations for the colligative behavior
of electrolytes.
i. The solutions of elctrolytes also exhibit colligative
properties which do not obey the relations of
nonelectrolytes.
ii. The colligative properties of the solutions of
electrolytes are greater than those to be expected for
solutions of nonelectrolytes of the same concentration.
iii. The molar masses of electrolytes in aqueous
solutions determined by colligative properties are found
to be considerably lower than the formula masses.
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Why the colligative properties of electrolyte solutions 2.11.2 van’t Hoff factor and degree of dissociation :
are greater than those for nonelectrolyte solutions of Relation between van’t Hoff factor and degree of
the same concentration? dissociation
Electrolytes dissociate into two or more ions when
dissolved in water whereas nonelctrolytes do not. Stated
differently, one formula unit of electrolyte dissolved in
water produces two or more ions. Consequently,
number of particles in solution increases.
The colligative properties of electrolyte solutions are
thus higher than the nonelectrolyte solutions.
2.11.1 van’t Hoff factor(i)
To obtain the colligative properties of electrolyte
solutions by using relations for nonelectrolytes, van’t
Hoff suggested a factor i. It is defined as the ratio of
colligative property of a solution of electrolyte to the
collogative property of nonelectrolyte solution of the
same concentration.

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2.11.2 Modification of expressions of colligative

properties :