Solutions

 A solution is a homogeneous mixture of two or more pure

substances, the relative ratio of which can be changed
within certain specified limit.
Components of a solution: (i) Solvent
(ii) Solute(s)
Thus,
Solution = Solute(s) + Solvent

Depending on the number of constituents, solutions are

called Binary (2 constituents), Ternary (3 constituents),
Quarternary (4 constituents), etc.

 Solvent(A): It is the component of the solution

which is present in a relatively large proportion and
whose physical state is same as that of the solution.
 Solute (B): It is the component of the solution which
is present in relatively small proportion.

 Types of solutions:
Solid solutions
Solid in solid copper dissolved in gold
Liquid in solid Na-Hg amalgam
Gas in solid H2 gas in Pd
 Liquid solutions
Solid in liquid Glucose dissolved in water
Liquid in liquid alcohol dissolved in water
Gas in liquid oxygen dissolved in water

Gaseous solutions
Solid in gas camphor in nitrogen gas
Liquid in gas chloroform mixed with N2
Gas in gas mixture of O2 and N2

 Saturated solution: A solution in which no more solute

can be dissolved at a given temperature and pressure. Such
a solution is in dynamic equilibrium with undissolved
solute.
 Note: The concentration of a solute in its saturated solution
is its solubility.

 Unsaturated solution: An unsaturated solution is one in

which more solute can be dissolved at the same
temperature.
 Solubility: The solubility of a substance is its maximum
amount that can be dissolved in a specified amount of
solvent (100 g) at a given temperature.
Factors affecting solubility:
(i) Nature of solute and solvent
(ii) Temperature
(iii) Pressure
 Factors influencing solubility of a solid in a liquid:

Nature of solute and solvent: A solute generally dissolves in a solvent

if intermolecular interactions are similar in the two or we may
dissolves Thus naphthalene and anthracene dissolve in
benzene but not in water whereas salt and sugar dissolve in water
but not in benzene.
Temperature: Temperature significantly affects the solubility of a
solid in a liquid. If in a nearly saturated solution (in equilibrium state),
dissolution process is exothermic, the solubility decreases with rise
in temperature and if the process is endothermic then solubility
increases with rise in temperature.

Pressure: Since solids and liquids are highly incompressible so

pressure does not have any significant effect on solubility of solids in
liquids.

 Factors affecting solubility of a gas in a liquid:

Nature of the gas: Easily liquefiable gases (having higher critical

temperature) are generally more soluble in common solvents

Nature of the solvent: Water can easily dissolve many gases because
ion formation occurs easily in the aqueous solutions of gases. In other
solvents, ion formation is not an easy process.
Temperature: As dissolution is an exothermic process, the solubility of
a gas in a liquid decrease with increase of temperature. It is for this
reason that we are more comfortable in cold waters rather than in
warm waters.
Pressure: Pressure is an important factor affecting the
solubility of gases in liquids. This is governed by Henry’s law.
 Henry’s Law: It states that at a constant temperature, solubility
of a gas in a liquid is directly proportional to the pressure of the
gas.

The most commonly used form of Henry’s Law States that:

the partial pressure (p) of a gas in vapour phase is
proportional to the mole fraction of the gas (x) in the
solution.

Thus, p = KH x, where KH is the law constant.

A graphical plot of partial pressure of a gas versus its

mole fraction becomes a straight line passing through the
origin. KH value depends on nature of the gas.

 Applications of Henry’s law:

(i) To increase the solubility of CO2 in soda water and
soft drinks, the bottle is sealed under high
pressure.
(ii) To avoids 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 .
(11.7% He, 56.2% N2 and 32.1% O2)
(iii) Due to low concentration of oxygen in the blood
and tissues, people living at high altitudes or
climbers become weak and unable to think
clearly, which are the symptoms of a condition
known as anoxia.
  Note: Due to high pressure underwater, the solubility of
atmospheric gases in blood increases. When the scuba 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 blood capillaries
and creates the symptoms of a medical condition known as
decompression sickness or bends, which are painful and
dangerous to life.

 Methods of expressing concentrations of solutions:

(a) Mass percentage (w/W): The mass percentage may be

defined as mass of solute per 100 g of the solution.
Mass % of solute = Mass of solute X 100 /Mass of the solution
(b) Volume percentage (v/V): It may be defined as:
Volume % of solute = Volume of solute x 100 / Volume
of the solution
(c) Mass by volume percentage ( w/V ) : It is defined as the
mass of solute per 100 mL of the solution.
Mass by volume % = Mass of solute X 100/ Volume of the
solution.
(d) Parts per million (ppm) : It denotes the number of parts of
a component per million (106 ) parts of the solution. ppm =
Number of parts of the component X 106 / Total number of
parts of all components in the solution.

(e) Mole fraction (x) : Mole fraction of a component = No. of

moles of the component / Total number of moles of all the
components
 Mole fraction of solute (xB): nB / nA + nB
Mole fraction of solvent (xA): nA / nA + nB
Thus, xA + xB = 1 (For a binary solution having two components)

(f) Molarity (M) = No. of moles of solute/ Volm of the solution in L

(Unit: mol L- or M)
M = w2 x 1000 / M2 x Vm L
Molarity of a solution depends on temperature as volume of a
solution changes with change of temperature.

g) Molality (m) = No. of moles of solute/ Mass of solvent in kg.

(Unit: mol/kg or m)
m = m = w2 X 1000 / w1 X M2
Molality of a solution is independent of temperature.
 Vapour pressure of pure liquid and solution:

When a liquid substance or solution is heated in a closed

vessel, a part of the liquid evaporates and its vapours
occupy the vacant space available within the container. As
the vessel is closed, the vapours cannot escape and rather
show a tendency to condense into liquid form. Equilibrium
is established between liquid and vapours when the rate of
condensation equals the rate of evaporation. Vapour
pressure of a liquid may be defined as the pressure exerted
by the vapours above the liquid surface in equilibrium with
the liquid phase at a given temperature. The vapour
pressure of a liquid depends on (i) nature of the liquid and
(ii) temperature.

 Vapour pressure of liquid-liquid solution:

:
It states that for a solution of volatile liquids, the partial
vapour pressure of each volatile component of the solution
is directly proportional to its mole fraction present in
solution.

Thus, pA xA or pA= pA xA

pB xB or pB=pB xB

pA , pB denote the vapour pressures of pure components A

and B. pA and pB denote the partial vapour pressure of
components A and B in the solution.
 total vapour pressure over the solution phase is equal to
the sum of the partial vapour pressure of both the volatile
components.

Hence, ptotal = pA + pB

= pA xA + pB xB

= pA ( 1- xB ) + pB xB

= pA + (pB - pA ) xB

= pB + ( pA - pB ) x A

 Conclusions :
(i) Total vapour pressure over the solution can be
related to the mole fraction of any one or both the
components.

(ii) Total vapour pressure over the solution varies linearly

with the mole fraction of the component B.

(iii) Vapour pressure over the solution decreases or

increases with the increase in mole fraction of component A
depending on the vapour pressures of pure components A
and B

(iv) Partial vapour pressure of each volatile component in

gaseous phase can be related to the total vapour pressure
over the solution as : p = x ( mole fraction ) X ptotal

Vapour pressure Vs Mole fraction

( Graphical representation ) : Refer textbook.

 Raoult’ law as a special case of law: According to
law, pA = p x , where p is the vapour pressure
A A A
of the pure component which is constant at a given
temperature.

According to law : p = KH x , where KH is a constant.

Thus, law is a special case of law in which

KH becomes pA

 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 (solid) is
added to make a solution, the vapour pressure of the
solution is solely from the solvent alone. The vapour
pressure of the solution at a given temperature is less than
the vapour pressure of the pure solvent at the same
temperature. In the solution, the surface has both solute
and solvent molecules due to which the fraction of the
surface covered by the solvent molecules gets reduced.
Consequently, the number of molecules escaping from the
surface decreases and hence the vapour pressure also
decreases. The decrease in vapour pressure of solvent
depends on the quantity of non-volatile solute present in
the solution, irrespective of its nature.

 Note: Lowering of V.P = V.P of the pure solvent

( pA ) V.P of the solution (pS)

 Relative lowering of V.P (RLVP) = Lowering of V.P / V.P of
the pure solvent

-volatile solute
in a volatile solvent: Relative lowering of vapour pressure is
equal to the mole fraction of the non-volatile solute in the
solution.

 General form of law For any solution, the partial

vapour pressure of each volatile component in the solution
is directly proportional to its mole fraction.

Note: In a binary solution, when the solute is non-volatile,

only the solvent molecules in vapour phase contribute to
vapour pressure.

So the vapour pressure of the solvent, pA = p A x A

A plot between the V.P of the solvent (in solution) and mole
fraction of the solvent is a straight line passing through the
origin.

 Ideal and non-ideal solutions : Those solutions which obey

called ideal solutions. In ideal solutions, solvent-solvent (A-

A) interactions are almost similar to solvent-solute (A-B)
interactions. Liquids having similar nature and structure are
likely to form ideal solutions. These solutions satisfy the
following requirements and show ideal behaviour.

(a) mixH = 0 (b) mix V=0

 Examples:

(i) Mixture of hexane and heptane

(ii) Mixture of methanol and ethanol
(iii) Mixture of benzene and toluene
(iv) Mixture of chlorobenzene and bromobenzene
(v) Mixture of ethyl chloride and ethyl bromide.

Note: For ideal solutions, ptotal= pA + pB

 Non-ideal solutions: When a solution does not obey

law over the entire range of concentration, then it is called non-
ideal solution. In these solutions, solvent- solute (A-B)
interactions are different from solvent- solvent (A-A) and
solute-solute (B-B) interactions. For non- mix

mix - ideal solutions show either positive

or negative deviation from ideal behaviour. For non-ideal
solutions,

ptotal pA + pB

Examples of non-ideal solutions:

(i) Ethanol + cyclohexane mixture

(ii) Ethanol + acetone mixture
(iii) Ethanol + water mixture
(iv) Acetone + benzene mixture
(v) Acetone + carbon disulphide mixture
(vi) Chloroform + carbon tetrachloride mixture
(vii) Phenol + aniline mixture
(viii) Acetone + chloroform mixture

Examples of non-ideal solutions showing positive

deviations:

(i) Mixture of ethanol and acetone

(ii) Mixture of acetone and carbon disulphide
(iii) Ethanol + cyclohexane mixture
(iv) Ethanol + water mixture
(v) Acetone + benzene mixture

Examples of non-ideal solutions showing negative

deviations:

(i) Phenol + aniline mixture

(ii) Chloroform + acetone mixture
(iii) Sulphuric acid + water mixture
(iv) Nitric acid + water mixture
(v) Chloroform + benzene mixture
(vi) Acetone + aniline mixture
Causes of deviations of non-ideal solutions from ideal behaviour:
The cause for these deviations lie in the nature of interactions at the
molecular level.
In case of positive deviation from raoult’s law, -B interactions are
weaker than those between A-A or B-B, i.e. intermolecular attractive forces
between the solvent- solute molecules are weaker than those between the
solute-solute and solvent-solvent molecules. This means that in such
solutions, molecules will find it easier to escape than in pure state and
consequently, the vapor pressure will increase and positive deviation will
be observed. Mixture of ethanol and acetone shows positive deviation. In
pure ethanol, molecules are hydrogen bonded. On adding acetone, its
molecules break some of the hydrogen bonds present between the
molecules of ethanol. Due to this, the mixture shows positive deviation
from Raoult’s law in a solution formed by adding carbon disulphide and
acetone, dipolar interactions between the solute-solvent molecules are
weaker than the respective interactions among the solute-solute and
solvent-solvent molecules. This solution also shows positive deviation.

In case of negative deviation from Raoult’s Law, the

intermolecular attractive forces between A-A and B-B are weaker
than those between A-B and leads to decrease in vapor pressure
resulting in negative deviations. An example of this type is a mixture
of phenol and aniline. In this case the intermolecular hydrogen
bonding between phenolic proton and lone pair on nitrogen atom
on aniline is stronger than the respective hydrogen bonding
between similar molecules. Similarly, a mixture of chloroform and
acetone shows negative deviation because chloroform molecules
form hydrogen bonds with acetone molecules. This decreases the
escaping tendency of molecules of each component and
consequently the vapour pressure decreases resulting in negative
deviation law.
 Azeotropes or azeotropic mixtures: An azeotrope is a
binary mixture having the same composition in liquid and
vapour phase and boils at a constant temperature like a
pure solvent.

Types of azeotropes:

(a) Minimum boiling azeotropes These azeotropes

have boiling point lower than each of the
individual component. The solutions which show
positive
law form minimum boiling
azeotrope at a specific composition, e.g. a mixture of
95% ethanol and 5% water by volume.
(b) Maximum boiling azeotropes These azeotropes
have boiling point higher than each of the
individual component. The solutions which show
negative

azeotrope at a specific composition, e.g. a mixture of

68% HNO3 and 32% H2O by mass.

Note: An azeotrope has the same composition in the

liquid and vapour phase and both the components boil at
the same temperature. So it is not possible to separate
the components by fractional distillation.