Solutions

• Solutions are homogeneous mixtures of two or

more than two components (composition and
properties are uniform throughout the mixture).

Solvent is the component that is present in the

largest quantity and determines the physical state in
which solution exists.

• Solutes is One or more components present in the

solution and present in the smallest quantity.
Solubility
• Solubility of a substance is its maximum amount that
can be dissolved in a specified amount (mostly 100 g)
of solvent at a specified temperature.
• It depends upon :
1. the nature of solute and solvent
2. temperature
3. pressure.
 Solubility of a Solid in a Liquid
1. Nature of Solute and Solvent
• NaCl dissolve readily in water but in naphthalene and
anthracene do not.
• On the other hand, naphthalene dissolves readily in benzene
but NaCl do not.

• It is observed that polar solutes dissolve in polar

solvents and non polar solutes in non polar solvents.

like dissolves like.

 Polar Non-polar
Water Carbon tetrachloride CCl4
Methanol CH3OH Toluene
Ethanol C2H5OH Hexane, heptane, octane
Acetic acid Benzene
AcetoneCH3COCH3 Oil
Ionic compounds
2. Effect of temperature
• If the dissolution process is endothermic (∆Hsol > 0), the
solubility should increase with rise in temperature and if it is
exothermic (∆Hsol < 0) the solubility should decrease.
3. Effect of pressure
• Pressure does not have any significant effect on solubility of
solids in liquids. This is because solids and liquids are highly
incompressible.
 Solubility of a Gas in a Liquid
1. Nature of Solute and Solvent
• Many gases dissolve in water.
• Oxygen dissolves only to a small extent in water. On the other
hand, hydrogen chloride gas (HCl) is highly soluble in water

(like dissolves like. )

2. Effect of Pressure
• The solubility of gases increase with increase of pressure; by
compressing the gas over liquid, the solubility of the gas will
increase.
Henry’s law.
• “At a constant temperature, the solubility of a gas in a liquid
(the mole fraction of the gas (x) in the solution) is directly
proportional to the partial pressure of the gas present above
the surface of liquid or solution”

p = KH x
Here KH is the Henry’s law constant.

3. Effect of Temperature
Solubility of gases in liquids
decreases with rise in temperature.
 p

k
 Moles of water >>> 𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝑵𝟐
𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝑵𝟐 could be ignored compared to Moles of water

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2
4.67 x 10-4 =
55.51

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁2 = 0.0259 mol

 Liquid - Liquid Solutions

• Consider a binary solution of two volatile liquids as 1 and 2.

• When taken in a closed vessel, both the components would
evaporate and finally an equilibrium would be established
between vapour phase and the liquid phase.

• Vapour pressure p1 and p2 are the partial vapour pressures of

the two liquids respectively.

• Mole fractions x1 and x2 of the two liquids respectively.

• The French chemist, Francois Raoult (1886) gave the
relationship between them.
Raoult’s law
“Partial vapour pressure of each component of volatile liquids of the
solution is directly proportional to its mole fraction present in
solution”.
• Thus, for component 1 p 1 ∝ x1 and p1 = p10 x1
where p1 0 is the vapour pressure of pure component 1.
• Similarly, for component 2 p 2 ∝ x2 p2 = p20 x2
where p20 is the vapour pressure of the pure component 2.
• According to Dalton’s law of partial pressures, the total pressure
(ptotal ) over the solution phase in the container will be

p t= p 1 + p 2
Substituting the values of p1 and p2, we get

pt = x1 p10 + x2 po2
= (1 – x2) p10 + x2 p20
= x1 p10 + (1 – x1) p20

Where:

x1 + x 2 = 1
• Liquid-liquid solutions on the basis of Raoult’s law can be classified
into:

ideal solutions 2. non-ideal solutions

• Ideal solutions
“ The solutions which obey Raoult’s law”.
• The ideal solutions have important properties:
1. The enthalpy of mixing of the pure components to form the
solution is zero. It means that no heat is absorbed or evolved when
the components are mixed. ∆H mix= 0
2. The volume of mixing is also zero, the volume of solution would be
equal to the sum of volumes of the two components. i.e., ∆ V mix = 0
3. At molecular level, ideal behaviour of the solutions can be
explained by considering two components A and B. In pure
components, the intermolecular attractive interactions will be
of types A-A and B-B, whereas in the binary solutions in
addition to these two interactions, A-B type of interactions
will also be present. If the intermolecular attractive forces
between the A-A ≈ B-B ≈ A-B, this leads to the formation of
ideal solution. A perfectly ideal solution is rare but some
solutions are nearly ideal in behaviour.
4. Solution of (n-hexane and n-heptane), (bromoethane and
chloroethane), (benzene and toluene).
 Non-ideal Solutions
“solution does not obey Raoult’s law over the entire
range of concentration”
• The vapour pressure of such a solution is either higher
or lower than that predicted by Raoult’s law.
• If it is higher, the solution exhibits positive deviation
• if it is lower, it exhibits negative deviation from
Raoult’s law.
 Positive Deviation from Raoult’s law
1. A-B intermolecular attractive forces

are weaker than those between

A-A or B-B.
• This means that in such solutions,
molecules of A (or B) will find it easier
to escape than in pure state.
2. Mixtures of ethanol and acetone behave in this manner.
In pure ethanol, molecules held by dipole –dipole interaction and
hydrogen bonded.
In ethanol and acetone:
• break some of the hydrogen bonds between ethanol
molecules.
• Molecules held by dipole –induced dipole interaction (weaker
interactions)
 Negative Deviations from Raoult’s law

1. the intermolecular attractive

forces between A-B are
stronger than those between
A-A and B-B and leads to
decrease in vapour pressure
resulting in negative
deviations.
2. An example is a mixture of chloroform and acetone
forms a solution with negative deviation from Raoult’s
law. This is because chloroform molecule is able to
form hydrogen bond with acetone molecule. This
decreases the escaping tendency of molecules for
each component and consequently the vapour
pressure decreases resulting in negative deviation
from Raoult’s law

Acetone chloroform