2.

SOLUTIONS
Solutions are homogeneous mixtures containing two or more components. Generally, the
component that is present in larger quantity is called solvent. Solvent determines the physical
state of the solution. One or more components present in the solution other than solvent are
called solutes. [Or, the substance which is dissolved is called solute and the substance in
which solute is dissolved is called solvent].
Solutions containing only two components are called binary solutions. Here each component
may be solid, liquid or in gaseous state. Based on this, solutions are of the following types:

Types of Solution Solute Solvent Examples

Gaseous solutions Gas Gas Mixture of O2 and N2
Liquid Gas Chloroform mixed with nitrogen gas, water-vapour in
air
Solid Gas Camphor in nitrogen gas, naphthalene in air
Liquid solutions Gas Liquid Oxygen dissolved in water, soda water
Liquid Liquid Alcohol dissolved in water, dilute acids and alkalies
Solid Liquid Salt in water, glucose in water
Solid solutions Gas Solid Hydrogen in Pd, Pt, Ni etc
Liquid Solid Amalgam of mercury with sodium
Solid Solid Gold ornaments, alloys of metals

Concentration of Solutions
Composition of a solution can be expressed in terms of concentration. Concentration is
defined as the number of moles of solute present per litre of the solution. The concentration
of a solution can be expressed by several ways.
(i) Mass percentage (w/w): The mass percentage of a component in a solution is defined as
the mass of the component present in 100 parts by mass of the solution.

Mass of the component ∈the solution

Mass % of a component = x 100
Total mass of the solution

For e.g. 10% aqueous solution of glucose by mass means that 10 g of glucose is dissolved in
90 g of water resulting in a 100 g solution.
Concentration described by mass percentage is commonly used in industrial chemical
applications.

(ii) Volume percentage (v/v): The volume percentage is defined as the volume of a
component present in 100 parts by volume of the solution.

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 Volume of the component
Volume % of a component = x 100
Total volume of solution
For example, 10% ethanol solution in water means that 10 mL of ethanol is dissolved in 90
mL of water such that the total volume of the solution is 100 mL.
Concentration of solutions containing liquids is commonly expressed in this unit.

(iii) Mass by volume percentage (w/v): It is the mass of solute dissolved in 100 mL of the
solution .It is commonly used in medicine and pharmacy.

Mass of the component ∈the solution

Mass/volume % of a component = x 100
Total volume of solution
(iv) Parts per million (ppm): When a solute is present in trace quantities (i.e. very small
amounts), its concentration is expressed in parts per million (ppm). It is defined as the
number of parts of a particular component in million parts of the solution.

Number of parts of the component

ppm = × 106
Total number of parts of all t h e components of t h e solution

Concentration in parts per million can be expressed as mass to mass, volume to volume and
mass to volume.
The concentration of pollutants in water or atmosphere is expressed in terms of μg mL –1 or
ppm.
(v) Mole fraction (x): It is defined as the ratio of the number of moles of a particular
component to the total number of moles of solution.

Number of moles of the component

Mole fraction of a component =
Total number of moles of all t h e components

For example, in a binary solution, if the number of moles of A and B are nA and nB
respectively,
nA
Then, the mole fraction of A ( x A) =
n A + nB

nB
and that of the component B ( x B ) =
n A + nB
x A +¿ x B = 1
i.e. in a given solution sum of the mole fractions of all the components is unity.
If there are i components,then
x1 + x2 + x3+ .................. + xi = 1
Mole fraction is useful in describing the calculations involving gas mixtures.

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(vi) Molarity (M): It is defined as the number of moles of solute dissolved per litre of
solution.
Number of moles of solute ( n )
i.e. Molarity (M) =
❑
Volume of solution∈litre ( V )

W B X 1000
Molarity (M) =
M B X V (ml)

For example, 0.25 M solution of NaOH means that 0.25 mol of NaOH is dissolved in one
litre of solution.

(vii) Molality (m): It is defined as the number of moles of the solute present per kilogram
(kg) of the solvent.
Number of moles of solute (n)
i.e. Molality (m) =
❑
Mass of solvent ∈kg (WA)

W B X 1000
Molality (m) =
M B X W A (g)

For example, 1 molal (m) solution of KCl means that 1 mol (74.5 g) of KCl is dissolved in 1
kg of water.
1Molar solution is more concentrated than 1molal solution when the density of solvent is 1g /
mL. 1m solution has 1mole of solute dissolved in 1000g or 1000ml of solvent. 1M solution
contains 1 mole of solte in 1000g of solution which is the volume of both solute and
solvent . Therefore the solvent present in 1M solution is less compared to 1m solution and
concentration is more.
Normality (N): It is defined as the no. of gram equivalents of solute present per litre of the
solution.
Number of gram equivalents of solute
i.e., Normality (N) =
❑
Volume of solution∈litre

Mass of solute x 1000

Normality (N) =
quivalent mass of solute x Volume of solution∈mL

Mass %, ppm, mole fraction and molality are independent of temperature; whereas molarity,
normality and volume % are depend on temperature. This is because volume depends on
temperature and the mass does not.

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SOLUBILITY
Solubility of a substance is its maximum amount that can be dissolved in a specified amount
of solvent. It depends upon the nature of solute and solvent, temperature and pressure.
Solubility of a Solid in a Liquid
It is observed that polar solutes dissolve in polar solvents and non polar solutes in non polar
solvents. In general, a solute dissolves in a solvent if the intermolecular interactions are
similar in the two or the general principle related to solubility is that “like dissolves like”.
Saturated and Unsaturated solutions
A solution in which no more solute can be dissolved at the same temperature and pressure is
called a saturated solution. Here there is a dynamic equilibrium between the dissolved solute
and the undissolved solute. A solution in which more solute can be dissolved at the same
temperature is called an unsaturated solution.
Effect of temperature
The solubility of a solid in a liquid mainly depends on temperature. Since the dissolution of a
solid in a liquid is an equilibrium process, it follows Le Chateliers Principle. In general, if in
a nearly saturated solution, the dissolution process is endothermic (Δsol H > 0), the solubility
should increase with rise in temperature and if it is exothermic (Δsol H > 0) the solubility
should decrease with temperature.
Effect of pressure
Since solids and liquids are highly incompressible, pressure does not have any significant
effect on solubility of solids in liquids.
Solubility of a Gas in a Liquid
Solubility of gases in liquids is greatly affected by pressure and temperature. The solubility
of a gas increases with increase of pressure.
A quantitative relation between pressure and solubility of a gas in a liquid was first given by
Henry, which is known as Henry’s law. “The law states that at a constant temperature, the
solubility of a gas in a liquid is directly proportional to the pressure of the gas”.
Or, “the partial pressure of the gas in vapour phase (p) is proportional to the mole fraction
of the gas (x) in the solution” and is expressed as:
p = KH x
Here KH is the Henry’s law constant.
*The value of KH depends on the nature of the gas and temperature.
*As the value of KH increases, the solubility of the gas in the liquid decreases.
A graph of partial pressure (p) of the gas against mole fraction (x) of the gas in solution is a
straight line as follows. (Fig 2.2)
*The slope of the graph gives the value of KH.

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*As the temperature increases solubility of a gas in a liquid decreases as the dissolution of
gases in liquid is exothermic. It is due to this reason that aquatic species are more
comfortable in cold waters rather than in warm waters.

Applications of Henry’s law

1. To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under
high pressure.
2. Scuba divers carry oxygen cylinders to breath under deep sea. At high pressure under
water, the solubility of atmospheric gases in blood increases. 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. To avoid bends the cylinders used by scuba divers are filled with
air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen) because of lower
solubility of He than N2 .
3. 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. This condition is known as anoxia.
Effect of Temperature
Solubility of gases in liquids decreases with rise in temperature, as dissolution is an
exothermic process.
Vapour Pressure of Liquid Solutions
In liquid solutions, the solvent is always a liquid. The solute can be a gas, a liquid or a solid.
Generally, the liquid solvent is volatile. The solute may or may not be volatile. Based on the
volatility of solute, the vapour pressure of the solution is greater or less than that of the
solvent.
Vapour Pressure of Liquid-Liquid Solutions – Raoult’s Law
It 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.
Consider a binary solution of two volatile liquids A and B.
Let pA and pB be the partial vapour pressures of the two components A and B respectively and
ptotal be the total vapour pressure.
Let xAand xBbe the mole fractions of the two components A and b respectively.
Then according to Raoult’s law,
for component A,
p A α xA or, p A = p0A xA
for component B,
pB α xB or, pB = p0B xB

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According to Dalton’s law of partial pressures, the total pressure (p total) will be the sum of
the partial pressures of the components of the solution.
So, ptotal = pA + pB
Substituting the values of pA and pB, we get
ptotal = p0A xA + p0B xB
Plots of pA or pB against the mole fractions xA and xB give straight lines .

The composition of vapour phase in equilibrium with the solution is determined from the
partial pressures of the components.
If yA and yB are the mole fractions of the components A and B respectively in the vapour
phase then, using Dalton’s law of partial pressures:
pA = yA ptotal and
pB = yB ptotal
In general, pi = yi ptotal

Raoult’s Law as a special case of Henry’s Law

According to Raoult’s law, the vapour pressure of a volatile component in a solution is given
by pi = xi p0i .
According to Henry’s law, solubility of a gas in a liquid is given by p = KH x.
If we compare the equations for Raoult’s law and Henry’s law, we can see 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 p0i . Thus, Raoult’s law becomes a
special case of Henry’s law in which KH becomes equal to p0i .
Vapour Pressure of Solutions of Solids in Liquids
The vapour pressure of a liquid is the pressure exerted by the vapour in equilibrium with its
own liquid. If a non-volatile solute is added to a pure solvent, the vapour pressure of the
resulting solution is always lower than that of the pure solvent. This is because in a pure
solvent, there are only solvent molecules, which can vapourise. But when a non-volatile
solute is added to the solvent, a fraction of the surface is occupied by solute molecules. So
the number of solute molecules passing to the vapour phase decreases and hence the vapour
pressure also decreases. The decrease in the vapour pressure of solvent depends on the
quantity of non-volatile solute present in the solution and not on its nature.
6
 For such a solution the Raoult’s law can be stated as, for any solution, the partial vapour
pressure of each volatile component in the solution is directly proportional to its mole
fraction.
Consider a binary solution containing a solvent A and solute B. Since the solute is non-
volatile, only the solvent molecules are present in vapour phase and contribute to vapour
pressure.
Let pA be the vapour pressure of the solvent, xA be its mole fraction, p0A be its vapour pressure
in the pure state. Then according to
Raoult’s law, pA α xA
or, p A = p0A xA
A graph between the vapour pressure and the mole fraction of the solvent is linear. (Fig 2.5)

Ideal and non-ideal solutions

Liquid – liquid solutions can be classified into ideal and non-ideal solutions on the basis of
Raoult’s law.

1. Ideal solutions:
*These are solutions which obey Raoult’s law over the entire range of concentration.
*The A-A and B-B interactions are nearly equal to the A-B interaction, i.e. solvent-solvent
interactions and solute-solute interactions are nearly equal to solute-solvent interaction
* for an ideal solution, , p A = p0A x A and pB = p0B x B
*ΔH mix = 0 and ΔV mix = 0
A perfectly ideal solution is rare. But some solutions are nearly ideal in behaviour.
E.g. solutions of n-hexane and n-heptane, bromoethane and chloroethane, benzene and
toluene etc

2. Non-ideal solutions:
These are solutions which do 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 and if it is lower, it
exhibits negative deviation from Raoult’s law.

Positive deviation Negative deviation

A‐B interaction is weaker than A‐A and B‐B A‐B interaction is stronger than A‐A and B‐B
p A > p0A x A p A < p0A x A
p A > p0B x B pB < p0B x B
ΔH mix > 0 ie positive ΔH mix < 0 ,ie negative
ΔV mix> 0 ie positive ΔV mix < 0 , ie negative
E.g. Ethylalcohol and water E.g. Chloroform&acetone, HCl & water

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Acetone & CS2 , CCl4 & benzene phenol & aniline

Azeotropes
They are binary mixtures having the same composition in liquid and vapour phase and boil at
a constant temperature. For such solutions, it is not possible to separate the components by
fractional distillation. There are two types of azeotropes: minimum boiling azeotrope and
maximum boiling azeotrope.
The solutions which show a large positive deviation from Raoult’s law form minimum
boiling azeotrope at a particular composition. Such azeotropes have boiling points lower than
either of the components,
E.g. 95% ethanol solution by volume.
The solutions which show large negative deviation from Raoult’s law form maximum boiling
azeotrope at a particular composition. Such azeotropes have boiling points higher than either
of the components.
E.g. a mixture of 68% Nitric acid and 32% water by mass forms a maximum boiling
azeotrope at 393.5 K.

COLLIGATIVE PROPERTIES AND DETERMINATION OF MOLARMASS

The properties which depend only on the number of solute particles and not on their nature
are called Colligative properties. The important colligative properties are: Relative lowering
of Vapour pressure, Elevation of Boiling point, Depression of Freezing point and Osmotic
Pressure.

1. Relative lowering of Vapour Pressure

When a non-volatile solute is added to a pure solvent, the vapour pressure of the resulting
solution is lower than that of the pure solvent. The difference between the vapour pressure of
pure solvent and that of the solution is called lowering of vapour pressure .
Consider a binary solution containing a non-volatile solute B dissolved in a solvent A.

8
Then according to Raoult’s law,
p A = p0A xA

= p0A ( 1- x B )
= p0A - p0A x B

p 0A− P
xB = 0
A

P A
0
p A− PA
0
is called relative lowering of vapour pressure.
PA
It is defined as the ratio of the lowering of vapour pressure to the vapour pressure pure
solvent.
nB
But xB =
n A +n B

Where nA and nB are the number of moles of solvent and solute respectively.
For dilute solutions, nB << nA and hence nB in the denominator can be neglected.
So, xB = nB/nA

WB X M p 0A− P
MB X W A
A
= 0
A

PA

2. Elevation of Boiling Point (ΔTb)

Boiling point of a liquid is the temperature at which its vapour pressure becomes equal to the
atmospheric pressure.
When a non-volatile solute is added to a pure solvent, the boiling point of the resulting
solution is always greater than that of the pure solvent. The difference between the boiling
point of solution (Tb) and that of the pure solvent (T 0b) is called elevation of boiling point
(ΔTb).
i.e. ΔTb = Boiling point of solution – Boiling point of pure solvent
Or, ΔTb = Tb – T b
0

If we plot a graph between the vapour pressure and temperature, we get the following graphs
for the pure solvent and the solution.

9
ΔTb α m
ΔTb = Kb m
Where Kb is a constant called Boiling Point Elevation Constant or Molal Elevation Constant
or Ebullioscopic Constant.
Kb is defined as the elevation of boiling point for 1 molal solution.
The unit of Kb is K kg/mol. For water, Kb = 0.52K kg/mol.
W B X 1000
ΔTb = Kb MB X W A

3. Depression of Freezing point (ΔTf)

Freezing point is the temperature at which the solid phase and liquid phase of a substance has
the same vapour pressure.
According to Raoult’s law, when a non-volatile solute is added to a pure solvent, its vapour
pressure decreases. Now it would become equal to that of solid solvent at lower temperature.
Thus the freezing point of the solvent decreases. The difference between the freezing point of
pure solvent (T 0f )and that of the solution (Tf) is called depression of freezing point (ΔTf).
i.e. ΔTf = T f - T f
0

The vapour pressure – temperature graph representing the freezing point of pure solvent and
solution is as follows:

For dilute solutions, it is found that the depression of freezing point (ΔTf) is directly
proportional to molality (m) of the solution.
Thus ΔTf α m
Or , ΔTf = Kf.m
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Where Kf is a constant called Freezing Point Depression Constant or Molal Depression
Constant or Cryoscopic Constant.
It is defined as the depression of freezing point for 1 molal solution.
The unit of Kf is K kg/mol. For water, Kf = 1.86 K kg/mol.
W B X 1000
We know that molality m =
MB X W A

W B X 1000
ΔTf = Kf. MB X W
A

4. Osmosis and Osmotic Pressure

Osmosis is the process of flow of solvent molecules from pure solvent to solution through a
semipermeable membrane. Or, it is the flow of solvent molecules from lower concentration
side to a higher concentration side through a semi-permeable membrane (SPM).
A membrane that allows the passage of solvent molecules only is called a semi-permeable
membrane. E.g. egg membrane, all animal and plant membrane. Cellulose acetate is an
example for artificial SPM.
Osmotic pressure is defined as the excess pressure that must be applied on solution side to
stop osmosis. Or, it is the pressure that just stops the flow of solvent molecules. It is denoted
by π. It is a colligative property, since it depends on the number of solute molecules and not
on their nature.
For dilute solutions, osmotic pressure is proportional to the molarity (C) and temperature (T).
i.e. π = CRT
Here R is the universal gas constant. (R= 0.0821 Latm/K/mol or R = 0.083Lbar/K/mol).
But C = nB/V, the concentration of the solution.
Therefore, π = nB.RT/V
Or, πV = nBRT

W B RT
Or, πV =
MB

Where V is the volume of the solution, wB is the mass of solute and MB is the molar mass of
solute.
Thus by knowing all other values, we can calculate the molar mass of the unknown solute by
the equation:
W B RT
MB =
πV

Advantages of osmotic pressure measurement over other colligative property measurement

1. Osmotic pressure measurement can be done at room temperature.

11
2. Here molarity of the solution is used instead of molality, which can be determined easily.
3. The magnitude of osmotic pressure is large even for very dilute solutions.
4. This method can be used for the determination of molar masses of biomolecules (which
are generally not stable at higher temperatures) and for polymers (which have poor
solubility).
Examples for osmosis:
a) Raw mango placed in concentrated salt solution loses water and shrink.
b) Wilted flowers revive when placed in fresh water
c) Blood cells collapse when suspended in saline water.
d) The preservation of meat by salting and fruits by adding sugar protect against bacterial
action. Through the process of osmosis, a bacterium on salted meat or candid fruit loses
water, shrinks and dies.
Isotonic, hypertonic and hypotonic solutions
Two solutions having same osmotic pressure at a given temperature are called isotonic
solutions.
When such solutions are separated by a semi-permeable membrane, no osmosis occurs.
For e.g. our blood cells are isotonic with 0.9% (mass/volume) sodium chloride solution,
called normal saline solution. So it is safe to inject intravenously.
A solution having higher osmotic pressure than another is called hypertonic solution. While
a solution having lower osmotic pressure than another is called hypotonic solution.
If we place our blood cells in a solution containing more than 0.9% (mass/volume) sodium
chloride solution, water will flow out of the cells and they would shrink. On the other hand, if
they are placed in a solution containing less than 0.9% (mass/volume) NaCl, water will flow
into the cells and they would swell.
Reverse osmosis and water purification
The direction of osmosis can be reversed if a pressure larger than the osmotic pressure is
applied to the solution side. Now the pure solvent flows out of the solution through the semi
permeable membrane. This phenomenon is called reverse osmosis and is used in desalination
of sea water.
ABNORMAL MOLARMASS
The molar mass obtained by colligative property measurement is incorrect, if there is
association or dissociation of particles. Such molar masses are called abnormal molar masses.
For e.g. acetic acid dimerises in benzene due to hydrogen bonding. So the number of
molecules in solution decreases and hence the colligative property decreases and molecular
mass increases.
In order to correct the abnormal molar masses, van’t Hoff introduced a factor called van’t
Hoff factor (i). It is defined as:

Normal Molar mass

i=
Abnormal molar mass

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 Observed colligative property
Or, i =
Calculated colligative property

Total number of moles of particles after association/dissociation

Or, i =
Number of moles of particles before association/dissociation

In the case of association, the value of i < 1 and in dissociation, the value of i > 1.

Thus for NaCl, i =2, for K2SO4, i = 3, for CaCl2, i = 3 and for acetic acid in benzene, i =1/2

i −1
α= n−1 where α is the degree of dissociation , i is van’t Hoff factor , n is the no. of ions
produced per formula of the compound.
i−1
α= 1
−1 where α is the degree of association , i is van’t Hoff factor , n is the no. of solute
n
molecules that associate to form a molecule.
Inclusion of van’t Hoff factor modifies the equations for colligative properties as follows:
p 0A− P
1. Relative lowering of vapour pressure, 0
A
=i x B
P A

2. Elevation of Boiling point (ΔTb) = i.Kb.m

3. Depression of freezing point (ΔTf) = i.Kf.m
4. Osmotic Pressure (π) = i.CRT

1.Given reason for the following :–

(a) Aquatic species are more comfortable in cold waters than in warm waters.
(b) To avoid bends scuba divers use air diluted with helium.
(c) Cold drinks bottles are sealed under high pressure of CO2
(e) CaCl2 is used to clear snow from roads in hill stations.
(f) Ethylene glycol is used as antifreeze solution in radiators of vehicles in cold countries.
(g) The freezing point depression of 0.01 m NaCl is nearly twice that of 0.01 m glucose
solution.
(h) RBC swell up and finally burst when placed in 0.1% NaCl solution.
(i) When fruits and vegetables that have been dried are placed in water, they slowly swell and
return to original form.
(j)A and B liquids on mixing produce a warm solution. Which type of deviation from
Raoult’s law is there?

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