SOLUTION

Solubility
It is the maximum amount of solute that can be dissolved in a
specified amount of solvent.
Solubility of a Solid in a Liquid
When a solid solute is added to the solvent, some solute dissolves and
its concentration increases in solution. This process is known as
dissolution.
Some solute particles in solution collide with the solid solute particles
and get separated out of solution. This process is known as
crystallisation.
A stage is reached when the two processes occur at the same rate.
At this stage the concentration of solute in solution will remain
constant under the given conditions, i.e., temperature and pressure.
Such a solution in which no more solute can be dissolved at the same
temperature and pressure is called a saturated solution.
If 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 .
Pressure does not have any significant effect on solubility of solids in
liquids.
Solubility of a Gas in a Liquid
The solubility of gases increase with increase of pressure.
Henry was the first to give a quantitative relation between pressure
and solubility of a gas in a solvent which is known as Henry’s law.
Henry’s law states that “the partial pressure of the gas in vapour
phase (p) is proportional to the mole fraction of the gas (x) in the
solution”
p = KH x
KH is the Henry’s law constant.
Different gases have different KH values at the same Temperature
Higher the value of KH at a given pressure, the lower is the solubility
of the gas in the liquid.
The solubility of gases increases with decrease of temperature. It is
due to this reason that aquatic species are more comfortable in cold
waters rather than in warm waters.
Henry’s law finds several applications :
➢ To increase the solubility of CO2 in soft drinks and soda water,
the bottle is sealed under high pressure.
Scuba divers must cope with high concentrations of dissolved gases
while breathing air at high pressure underwater. Increased pressure
increases the solubility of atmospheric gases in blood.
When the divers come towards surface, the pressure gradually
decreases. This releases the dissolved gases and leads to the formation
of bubbles of nitrogen in the blood. This blocks capillaries and creates
a medical condition known as bends, which are painful and dangerous
to life.
To avoid bends, as well as, the toxic effects of high concentrations of
nitrogen in the blood, the tanks used by scuba divers are filled with air
diluted with helium.
➢ At high altitudes the partial pressure of oxygen is less than that
at the ground level. This leads to low concentrations of oxygen
in the blood and tissues of people living at high altitudes or
climbers. Low blood oxygen causes climbers to become weak
and unable to think clearly, and condition is known as anoxia.
Solubility of gases in liquids decreases with rise in temperature.
Vapour Pressure of Liquid Solutions
(i) liquids in liquids
(ii) solids in liquids
➢ Consider binary solution of two volatile liquids and two
components be 1 and 2.
➢ In a closed vessel, both the components would evaporate and
eventually an equilibrium would be established between vapour
phase and the liquid phase.
➢ Let p1 and p2 be the partial vapour pressures of the two
components 1 and 2.
➢ Ptotal be the total pressure .
➢ x1 and x2 be the mole fraction
➢ According to Raoult’s law which 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.

According to Dalton’s law of partial pressures, the total pressure (p

total ) over the solution phase in the container will be the sum of the
partial pressures of the components of the solution.

Plotting a graph between vapour pressure and mole fraction

 ➢ Assuming component 1 is less volatile than component 2,

➢ Total vapour pressure over the solution can be related to the mole
fraction of any one component
➢ Total vapour pressure over the solution varies linearly with the
mole fraction
➢ Total vapour pressure over the solution decreases or increases
with the increase of the mole fraction of component 1.
➢ The minimum value of ptotal is p10 and the maximum value is p20 .
➢ The composition of vapour phase in equilibrium with the
solution is determined by the partial pressures of the
components.

➢ If y1 and y2 are the mole fractions of the

components 1 and 2 respectively in the vapour phase then, using
Dalton’s law of partial pressures:
p1 = y1 ptotal p2 = y2 ptotal
Raoult’s Law as a special case of Henry’s Law
Comparing the equations for Raoult’s law and Henry’s law, it can be
seen that the partial pressure of the volatile component or gas
is directly proportional to its mole fraction in solution. Only the
proportionality constant KH differs from p10. Thus, Raoult’s law
becomes
a special case of Henry’s law in which KH becomes equal to p10.
Vapour Pressure of Solutions of Solids in Liquids
➢ In a pure liquid the entire surface is occupied by the molecules of
the liquid. If a non-volatile solute is added to a solvent to give a
solution then the vapour pressure of the solution will be from
the solvent alone.
➢ Thus vapour pressure of the solution at a given temperature is
found to be lower than the vapour pressure of the pure solvent at
the same temperature.
This is because the surface of solution has both solute and solvent
molecules; thereby the fraction of the surface covered by the solvent
molecules gets reduced.
➢ Thus the number of solvent molecules escaping from the surface
is reduced, thus, the vapour pressure is also reduced.

➢ The decrease in the vapour pressure of solvent depends on the

quantity of non-volatile solute present in the solution.
Raoult’s law for any solution is stated as
the partial vapour pressure of each volatile component in the solution
is directly proportional to its mole fraction.
Ideal and Non ideal Solutions

On the basis of Raoult’s law Liquid-liquid solutions can be classified

into ideal and non-ideal solutions .

Ideal Solutions

➢ The solutions which obey Raoult’s law over the entire range of
concentration are known as ideal solutions.
No heat is absorbed or evolved when the components are mixed and
no volume change happens for the solution .

• Consider two components A and B.

• the intermolecular attractive interactions for the
components will be of types A-A and B-B.
• when the components are mixed, in addition to these two
interactions, A-B type of interactions will also be present.
• For an ideal solution intermolecular attractive forces
between the A-A and B-B are nearly equal to those
between A-B .
• Example for ideal solutions are Solution of n-hexane and
n-heptane, bromoethane and chloroethane, benzene and
toluene,chlorobenzene and brombenzene.
Non-ideal Solutions
• When a solution does not obey Raoult’s law over the entire
range of concentration, then it is called non-ideal solution.
• The vapour pressure of such a solution is either higher or
lower than that predicted by Raoult’s law.
• If vapour pressure is higher, the solution exhibits positive
deviation and if vapour pressure is lower, it exhibits
negative deviation from Raoult’s law.
For positive deviation from Raoult’s law, A-B(solvent- solute)
interactions are weaker than those between A-A (solvent-solvent)
or B-B (solute-solute).
This will increase the vapour pressure and result in positive deviation.
Example : Mixtures of ethanol & acetone, ethanol & water ,acetone &
benzene ,chloroform & CCl4

For negative deviations from Raoult’s law, the intermolecular

attractive forces between A-A (solvent-solvent) and B-B(solute-
solute) are weaker than those between A-B (solvent- solute) and leads
to decrease in vapour pressure resulting in negative deviations.
Example : mixture of phenol & aniline , chloroform & acetone , nitric
acid & water ,chloroform & benzene .
Azeotropes
• Some liquids on mixing, form azeotropes which are binary
mixtures having the same composition in liquid and vapour
phase and boil at a constant temperature.
• it is not possible to separate the components by fractional
distillation.
• There are two types of azeotropes called
minimum boiling azeotrope
maximum boiling azeotrope.
The solutions which show a large positive deviation from Raoult’s
law form minimum boiling azeotrope at a specific composition.
For example, ethanol-water mixture on fractional distillation gives a
solution containing 95% by volume of ethanol and its boiling point is
351.15 K
The solutions that show large negative deviation from Raoult’s law
form maximum boiling azeotrope at a specific composition.
Nitric acid and water is an example of this class of azeotrope.
Azeotrope has composition, 68% nitric acid and 32% water by mass,
with a boiling point of 393.5 K.
Colligative Properties and Determination of Molar Mass
Properties which depend on the number of solute particles irrespective
of their nature relative to the total number of particles present in the
solution. Such properties are called colligative properties.
These are:
(1) relative lowering of vapour pressure of the solvent
(2) depression of freezing point of the solvent
(3) elevation of boiling point of the solvent and
(4) osmotic pressure of the solution.

Relative Lowering of Vapour Pressure

• The vapour pressure of a solvent in solution is less than that of
the pure solvent.
• lowering of vapour pressure depends only on the concentration
of the solute particles

• The reduction in the vapour pressure of solvent (Δp1) is given by

( )

relative lowering of vapour pressure and is equal to

the mole fraction of the solute
n1 and n2 are the number of moles of solvent and solute
w1 and w2 are the masses and M1 and M2 are the molar masses of the
solvent and solute respectively.
The molar mass of solute (M2) can be calculated.

Elevation of Boiling Point

• The vapour pressure of a liquid increases with increase of
temperature.
• Boiling point is the temperature at which its vapour pressure is
equal to the atmospheric pressure.
• Vapour pressure of the solvent decreases in the presence of non-
volatile solute.
• Hence the boiling point of a solution is always higher than that
of the boiling point of the pure solvent.
• The elevation of boiling point (increase of boiling point )also
depends on the number of solute molecules.
Let Tb0 be the boiling point of pure solvent and Tb be the boiling
point of solution.
The increase in the boiling point ΔTb = Tb − Tb0 is known as
elevation of boiling point.
For dilute solutions the elevation of boiling point (ΔTb) is
directly proportional to the molal concentration of
the solute in a solution.

Where m is molality, Kb is proportionality constant

is also called Boiling Point Elevation Constant or Molal Elevation
Constant (Ebullioscopic Constant)
The unit of Kb is K kg mol-1.

Graphical representation:
Depression of Freezing Point
• The freezing point of a substance is defined as the temperature
at which the vapour pressure of the substance in its liquid phase
is equal to its vapour pressure in the solid phase.
• A solution will freeze when its vapour pressure equals the
vapour pressure of the pure solid solvent
• When a non-volatile solid is added to the solvent its vapour
pressure decreases
• The lowering of vapour pressure of a solution causes a lowering
of the freezing point compared to that of the pure solvent.
• Thus, the freezing point of the solvent decreases.

If Tfo is the freezing point of pure solvent

and Tf be freezing point when non-volatile solute is dissolved in it.
Then decrease in freezing point given as
ΔTf = Tfo − Tf which is known as depression in freezing
point .
For dilute solution depression in freezing point .
is directly proportional to molality.

Where m is molality of the solution

Kf is known as Freezing Point Depression Constant or Molal
Depression Constant or Cryoscopic Constant
The unit of Kf is K kg mol-1.
The values of Kf and Kb, which depend upon the nature of the
solvent.

R and M1 stand for the gas constant and molar

mass of the solvent, respectively and Tf and Tb denote the freezing
point and the boiling point of the pure solvent respectively
ΔHfus and ΔHvap represent the enthalpies for the fusion and
vapourisation of the solvent

Graphical representation:
Osmosis and Osmotic Pressure
The flow of solvent molecules through the semi permeable membrane
from pure solvent to the solution is called osmosis.
The flow of solvent from dilute solution to the concentrated solution
across a semipermeable membrane is due to osmosis.
The flow of the solvent from its side to solution side across a
semipermeable membrane can be stopped by applying pressure on
the solution. This pressure that just stops the flow of solvent is called
osmotic pressure of the solution.
The osmotic pressure has been found to depend on the concentration
of the solution.
Osmotic pressure is a colligative property as it depends on the number
of solute molecules
For dilute solutions, osmotic pressure is proportional to the molarity,
C of the solution at a given temperature T.
𝜋 =CRT
𝜋 = (n2/V)RT
𝜋 V = w2RT/M2
M2 =w2RT/ 𝜋V
Where V is the volume of solution in litres , 𝜋 is osmotic pressure , n2
is no: of moles of solute , M2 is molar mass of solute , w2 is mass of
solute R is gas const , T is temperature

Osmotic pressure method is widely used to determine molar masses

of proteins, polymers , macromolecules
The osmotic pressure method has the advantage over other methods
as pressure measurement is around the room temperature and the
molarity of the solution is used instead of molality.
Isotonic solutions : Two solutions having same osmotic pressure at a
given temperature are called isotonic solutions.
Hypertonic solution : if the concentration is higher than that of the
solution separating it by a semipermeable membrane.
Osmotic pressure associated with the fluid inside the blood cell is
equivalent to that of 0.9% sodium chloride solution, called normal
saline solution
It is safe to inject intravenously.
If we place the cells in a solution containing more than 0.9% sodium
chloride, water will flow out of the cells and they would shrink
solution is called hypertonic.

Hypotonic solution : if the concentration is lower than that of the

solution separating it by a semipermeable membrane.
If the salt concentration is less than 0.9% , the solution is said to be
hypotonic In this case, water will flow into the cells if placed in this
solution and they would swell.
People taking a lot of salt or salty food experience water retention in
tissue cells and intercellular spaces because of osmosis. The resulting
puffiness or swelling is called edema

Reverse Osmosis and Water Purification

If a pressure larger than the osmotic pressure is applied to the solution
side ,then the pure solvent flows out of the solution through the semi
permeable membrane. This phenomenon is called reverse osmosis
Reverse osmosis is used in desalination of sea water.
When pressure more than osmotic pressure is applied, pure water is
squeezed out of the sea water through the membrane.
Porous membrane is a film of cellulose acetate placed over a suitable
support. Cellulose acetate is permeable to water but impermeable to
impurities and ions present in sea water.

Abnormal Molar Masses

Since dissociation of solute into ions and association of solute is not
considered, experimentally determined molar mass is always lower
than the true value.
Molar mass is either lower or higher than the expected or normal
value is called as abnormal molar mass.
van’t Hoff introduced a factor i, known as the van’t Hoff factor, to
account for the extent of dissociation or association.
Inclusion of van’t Hoff factor modifies the equations for colligative
properties as :
Relative lowering of vapour pressure of solvent,

Elevation of Boiling point =

Depression of Freezing point =

Osmotic pressure of solution 𝜋 = i (n2/V)RT