SOLUTION

Solution: It is a homogeneous mixture of two or more chemically non reacting

substances whose composition is same throughout.

 The component which is present in the largest quantity is called the solvent
while the component which is present in lesser quantity is termed the solute.

SOLUBILITY OF GASES AND SOLIDS IN LIQUIDS-

 Solubility of a substance expresses the maximum amount of it which can be

dissolved in a specific amount of solvent at a specified temperature.
 The concentration of the solute has the highest value in a saturated solution.
 “Like dissolves like.” This means that ionic (or polar) compounds dissolve
more readily in polar solvents. Similarly, non-polar (covalent or organic)
compounds are soluble in non-polar solvents like benzene, ether.
 The effect of pressure on the solubility of solids in liquids is generally very
small or insignificant.
 The solubility of a gas decreases with increase of temperature. Because, in
general, gases dissolve in a liquid with the evolution of heat i.e., exothermic
process.
 The solubility of gases increases with increase of pressure.

HENRY’S LAW:-
The law states that the mass of a gas dissolved per unit volume of the solvent at a
constant temperature is directly proportional to the pressure of the gas in
equilibrium with the solution.
x∝ p p=partial pressure

x=K ' p KH= Henry’s Law constant (atm or bar)

1 X= mole fraction of solute

p= x
K'

p=K H x
From these values, it may be concluded that-

(i) Henry's law constant, KH depends upon the nature of the gas.
(ii) Higher the value of KH at a particular pressure, the lower is the solubility of
the gas in the liquid.
(iii) The value of KH increases with increase in temperature indicating that the
solubility of gases decreases with increase of temperature.
(iv) KH value is maximum for helium at a given temperature & helium gas has
very low solubility.

ΔS = -ve (gas dissolved in solution is less random, entropy decreases)

ΔG = -ve (dissolution of a gas is spontaneous in a liquid)

ΔH = -ve (as only then ΔG can be -ve according to the equation: ΔG = ΔH – TΔS).
Hence the dissolution of a gas in water is always exothermic.

Limitation of Henry’s law: - It has been observed that Henry’s law is valid if

(i) Pressure is low. At high pressure, the law becomes less accurate and the
proportionality constant shows considerable deviations.
(ii) The temperature is not too low.
(iii) The gas is not highly soluble and
(iv) The gas neither reacts chemically with the solvent nor dissociates or
associates in the solvent.

VAPOUR PRESSURE OF LIQUID SOLUTIONS:

The pressure exerted by the vapours above the liquid surface in equilibrium with
the liquid at a given temperature is called vapour pressure.

RAOULT’S LAW:- At a given temperature, for a solution of volatile liquids, the

partial vapour pressure of each component in solution is equal to the product of
the vapour pressure of the pure component and its mole fraction.
The vapour pressures of the components are linear functions of their mole
fractions.

 Thus, the plot of pA against xA should give a straight line passing through pA°
(when xA = 1) and 0 (when xA = 0). This is shown by line I in Fig. 7.
 It is clear from the curve that when the liquid is pure (xA = 1), its vapour
pressure is equal to pA°.
 As component B is added to component A (xA decreases), the vapour pressure
decreases along the line I till it becomes zero (xA = 0).
  Similarly, the variation of partial pressure of component B (pB) with its mole
fraction (xB) is represented by the plot from xB = 0 (i.e., pB = pB° × 0 = 0) to xB =
1 (i.e., pB = pB° × 1 = pB°). It is shown by line II.
 The total vapour pressure p, exerted by the solution as a whole at any
composition is given by the sum of partial vapour pressures according to
Dalton’s law of partial pressures.
Thus, p = pA + pB = pA°xA + pB°xB This is shown by line III.

Q) Why less vapour is formed when we add non-volatile solute?

Ans- The vapour pressure depends on the escape of solvent molecules from the
surface of the liquid. The non-volatile molecules also occupy a surface area
therefore, the surface has both solute and solvent molecules; and the fraction of
surface covered by solvent molecules gets reduced. As a result, lesser number of
solvent molecules will escape into vapours.

Another form of Raoult’s Law-

For Non-
Volatile solute
IDEAL AND NON-IDEAL SOLUTIONS:-
1. Ideal solutions: Ideal solution may be defined as the solution which obeys
Raoult’s law exactly over the entire range of concentration.
P=P A + PB =P A X A + P B X B
0 0

(i) ∆ H mix=0
(ii) ∆ V mix=0

Eg, (a) Chlorobenzene & bromobenzene (c) n-hexane and n-heptane

(b) Bromoethane and iodoethane (d) Benzene and toluene

2. Non-Ideal Solution: The solutions which do not obey Raoult’s law over the entire
range of concentration are called non-ideal solutions.
(i) P ≠ P A + PB ≠ P A X A + P B X B
0 0

(ii) ∆ H mix ≠ 0
(iii) ∆ V mix ≠ 0
Non-ideal solutions showing positive deviations from Raoult’s law-
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 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.
P> P A + P B > P A X A + PB X B
0 0 PA> P A X A
0

A few 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.
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. The solutions
are said to have negative deviations from Raoult’s law
P< P A + P B < P A X A + PB X B
0 0 PA< P A X A
0

A few examples:
(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.
 Azeotropes or Constant Boiling Mixtures-
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. In such
cases, it is not possible to separate the components by fractional distillation.
(i) Minimum boiling azeotropes: The solutions which show a large positive
deviation from Raoult's law. For example, ethanol-water mixtures (obtained
by fermentation of sugars) are rich in water.
(ii) Maximum boiling azeotropes: The solutions which show negative deviation
from Raoult's law form maximum boiling azeotrope at a specific composition.
For example, nitric acid (HNO3) and water form maximum boiling azeotropes.
The azeotrope has the approximate composition 68% nitric acid and 32%
water by mass with a boiling point of 393.5 K

COLLIGATIVE PROPERTIES:-
The properties of the solutions which depend only on the number of solute
particles but not on the nature of the solute are called colligative properties. The
four important colligative properties are:

(i) Relative lowering of vapour pressure

(ii) Elevation in boiling point
(iii) Depression in freezing point
(iv) Osmotic pressure
RELATIVE LOWERING IN VAPOUR PRESSURE:-
xA-mole fraction of
the solvent

xB-mole fraction of
the solute

pA°-vapour
pressure of the
pure solvent

p-vapour pressure
of solution.

ELEVATION IN BOILING POINT-

The boiling point of a liquid is the temperature at which its vapour pressure
becomes equal to the atmospheric pressure.

The vapour pressure of the pure solvent or solution increases with rise in
temperature. The curve AB gives the vapour pressure for the pure solvent and the
curve CD gives the vapour pressure for the solution at different temperatures. The
curve CD representing the vapour pressure of the solution at different
temperatures lies below the curve AB which corresponds to the vapour pressure
of the pure solvent. This is because of the fact that the vapour pressure of the
solution is less than that of the pure solvent at all temperatures. It is clear from
the figure that the vapour pressure of the pure solvent becomes equal to
atmospheric pressure at X (corresponding to temperature Tb°) while the vapour
 pressure of the solution becomes equal to atmospheric pressure at Y
(corresponding to temperature Tb). Thus, the boiling point of the pure solvent is
Tb - while that of the solution is Tb. Since Tb is greater than Tb - there is an
elevation or increase in boiling temperature of the solution as compared to that
of the solvent. Mathematically,
∆Tb = Tb – Tb°
It has been found out experimentally that the elevation in the boiling point (∆Tb)
of a solution is proportional to the molal concentration of the solution,
i.e., ∆Tb ∝ m
or ∆Tb = Kbm (where m is the molality of the solution and represents moles of
solute in 1 kg of solvent)
 Kb is molal boiling point elevation constant or ebullioscopic constant(Kb)
 Kb- is defined as the elevation in boiling point for 1 molal solution i.e., a
solution containing 1 gram mole of solute dissolved in 1000 g of the solvent.
 Elevation in boiling point —As, Kb is constant, so that ∆Tb ∝ m. Thus, elevation
in boiling point is directly proportional to the molal concentration of the solute
(i.e., number of molecules) and therefore, it is a colligative property.

Determination of Molar Mass of Solute from Elevation in Boiling Point –

Let wB gram of a non-volatile solute is dissolved in wA grams of the solvent and MB is

the molar mass of the solute.
DEPRESSION IN FEEEZING POINT-
Freezing point is the temperature at which the solid and the liquid states of the
substance have the same vapour pressure.

In the figure, the curve BC gives vapour pressure of the pure solvent. We know
that the addition of a non-volatile solute lowers the vapour pressure and the
curve DE gives the vapour pressure curve for the solution at different
temperatures. The curve AB corresponds to the vapour pressure of the solid at
different temperatures. The temperature corresponding to the point B where the
solid and liquid solvent meet (i.e., solid and liquid states have the same vapour
pressure) represents the freezing point temperature of pure solvent (Tf °). The
temperature corresponding to the point D where the solid solvent and liquid
solution meet (i.e., solid and liquid states have the same vapour pressure)
represents the freezing point temperature of the solution (Tf ). Since Tf is less than
Tf °, this shows that the freezing temperature of the solution is less than that of
pure solvent and the depression in freezing temperature (∆Tf ) is given as :

∆Tf = Tf ° – Tf

It has been determined experimentally that the depression in freezing point of a

solution is proportional the molal concentration of the solution i.e,

∆Tf ∝ m = Kf m

 The units of Kf are degree/molality i.e. Km–1, °C m–1 or K kg mol–1

 Kf is the molal freezing point depression constant. It is also called molal
cryoscopic constant(Kf).
 Molal freezing point depression constant is defined as the depression in
freezing point for 1 molal solution i.e., a solution containing 1 gram mole of
solute dissolved in 1000 g of solvent.
 The depression in freezing point temperature is directly proportional to the
molal concentration of the solute (i.e., number of molecules) and therefore,
it is a colligative property.
 Osmosis and Osmotic pressure:-
 The phenomenon of the flow of solvent through a semipermeable membrane
from pure solvent to the solution is called osmosis.
 The solvent molecules move from the less concentrated solution (low solute
concentration) to a more concentrated solution (higher solute concentration)
through a semipermeable membrane.
 Osmotic pressure may be defined as the minimum excess pressure which must be
applied to a solution to prevent the passage of solvent into it through a
semipermeable membrane. It is generally denoted by π.
#TYPES OF SOLUTION-
1. If a solution has more osmotic pressure than some other solution, it is called
hypertonic. It is more concentrated.
2. A solution having less osmotic pressure than the other solution is called
hypotonic. It is less concentrated.
3. The solutions having same osmotic pressure at the same temperature are
called isotonic solutions or isosmotic solutions.

From the equation, π = cRT, it is clear that if two solutions have same
concentrations, they must have same osmotic pressure at the same temperature.

Thus, solutions of equimolar concentrations at the same temperature have

same osmotic pressure, i.e., are isotonic.

However, the solutions having concentration more or less than 0.91% (mass/
volume) are not safe as explained below:

(i) A pure sodium chloride solution with salt concentration less than 0.91% is
said to be hypotonic solution. When red blood cells are placed in this
solution, water flows into the cells and they swell or burst.
(ii)A pure sodium chloride solution with salt concentration more than 0.91% is
said to be hypertonic solution. When red blood cells are placed in this
solution, water flows out of the cells and they shrink or collapse due to loss
of water by osmosis.
(iii) People taking a lot of salt or salty food experience water retention in
tissue cells and intercellular spaces because of osmosis. The swelling or
puffiness is called edema. When red blood cells are placed in this solution,
water comes out of the cells and they shrink.

The process of osmosis can be reversed if a pressure larger than the osmotic
pressure is applied on the solution side. As a result, the solvent starts moving
from solution towards the pure solvent through the semipermeable
membrane. This process of movement of solvent through a semipermeable
membrane from the solution to the pure solvent by applying excess pressure
on solution side is called reverse osmosis.
DIFFERENCE BETWEEN OSMOSIS AND DIFFUSION:-
OSMOSIS DIFFUSION
(i) The process of osmosis takes No semi-permeable membrane is
place through a semi-permeable needed for the diffusion process.
membrane.
(ii) The osmosis involves the In diffusion, both the solute and
movement of the solvent the solvent molecules can move.
molecules only.
(iii) In osmosis, molecules of In diffusion, the molecules move
solvent move from a region of from a region of higher
lower concentration of solution concentration into the region of
into a region of higher lower concentration.
concentration.
(iv) Osmosis is limited to Diffusion is common in gases as
solutions only. well as in liquids.
(v) Osmosis can be stopped or It cannot be stopped or reversed
reversed by applying additional
pressure on the higher
concentration side.
ABNORMAL MOLAR MASS:-