Chapter -2

SOLUTIONS
 Solutions
a homogenous mixture of 2 or more substances

Solvent
the
substance
Solute present in the
larger amount
is(are) the
substance(s)
present in the
smaller
amount(s)

When the solvent is water the solution is said to be aqueous

 Some Definitions

A solution is a homogeneous mixture

of 2 or more substances in a single
phase.
One constituent is usually regarded as
the SOLVENT and the others as
SOLUTES.
 Parts of a
SOLUTE – the part
Solution
of a solution that Solute Solvent Example
is being dissolved
(usually the lesser solid solid Cu dissolved in Au
amount)
SOLVENT – the solid liquid Glucose in water

part of a solution gas solid Solution of

that dissolves the Hydrogen and Pd
solute (usually the liquid liquid Ethanol in water
greater amount)
Solute + Solvent gas liquid Oxygen in water
= Solution
gas gas Mixture of O2 and
N2
 Expressing Concentration
QUANTITATIVELY QUALITATIVELY
Mass percentage * Dilute
Volume percentage * Concentrated
Mass by volume percentage
Parts per million
Mole Fraction (χ)
Molarity (M)
Molality (m)
 Mass percentage
Mass percentage (w/w): The mass percentage of a component
of a solution is defined as:
Mass % of a component
= Mass of the component in the solution ×100
Total mass of the solution
Example
What is the mass percent of 500g of water containing
6.50g of potassium nitrate?

Solution: 6.5 KNO3 x 100 =

(500g +6.5g) soln

Ans: 1.28 %

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 Volume percentage
The volume percentage is defined as:

Volume % of a component = Volume of the

compone×100
Total volume of
solution
Mass by volume percentage
Another unit which is commonly used in medicine
and pharmacy is mass by volume percentage. It is
the mass of solute dissolved in 100 mL of the
solution.
 Parts per million
When a solute is present in trace quantities, it
is convenient to express concentration in parts
per million (ppm) and is defined as:
ppm = Number of parts of the component ×106
Total number of parts of all components
of soln
 Mole Fraction (χ)
Commonly used symbol for mole fraction is x
and subscript used on the right hand side of x
denotes the component. It is defined as:
Mole fraction of a component =
Number of moles of the component
Total number of moles of all the
components
Example
Deepak puts 76.0g of sodium iodide in 500g of water. What is the mole fraction of
the solution?

Solution: 76.0g NaI x 1 mol NaI =0.507 mols NaI( Atomic mass of Na=23,I=127)
150g NaI

500g H2O x1 mol H2O = 27.8 mols H2O

18g H2O

.507 =
(.507 +27.8)

Ans: .018

12
 Molarity
Number of moles of
solute per litre of the Assumptions you can make:
solution
A 5.0 Molar Solution =
M = moles solute 5 moles solute
liters solution 1 liter solution
Example
Calculate the molarity of a solution that contains 5.8g KCl in 550mL
of solution.

Solution: 5.8g KCl x 1 mol KCl = 0.078 mol KCl

74.55g KCl

0.078 mol KCl =

0.55L solution

Ans: 0.14M
 Molality
Number of moles Assumptions you
of solute per Kg can make:
of the solvent A 5.0 molal
m = moles solute solution =
kg solvent 5.0 moles solute
1 kg solvent
Example
Calculate the molality of a solution prepared by placing 10.3g of
MgCl2 in 200g of water.

Solution: 10.3g MgCl2 x 1mol MgCl2 =.108mol MgCl2

95.2g MgCl2

.108g MgCl2 =
.2 kg H2O

Ans: .54 m
 Solubility
Solubility of a substance is its maximum
amount that can be dissolved in a specified
amount of solvent.
1.Solubility of a Solid in a Liquid

2.Solubility of a Gas in a Liquid

 Solubility
Solubility of a Solid in a Liquid
polar solutes dissolve in polar solvents and non polar
solutes in nonpolar solvents.
In general, a solute dissolves in a solvent if the
intermolecular interactions are similar in the two or
we may say like dissolves like.
 Classification Based on solubility
An unsaturated solution is one in which more
solute can be dissolved at the same temperature.

A saturated solution is one in which more

solute can not be dissolved at the same
temperature.

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Factors affecting solubility

1. Temperature
2.Pressure
3. Inter molecular forces of
attraction
Solubilities of Solids vs Temperature

Solid solubility generally

increases with increase in
temperature.
But if dissolution of solute is
exothermic, solubility decreases

21
Solid solubility and Pressure
Pressure does not have any significant
effect on solubility of solids in liquids. It is
so because solids and liquids are highly
incompressible and practically remain
unaffected by changes in pressure.

22
 Solubility of a Gas in a Liquid
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.

Solubility of gases in liquids is greatly affected

by pressure and temperature.

23
The solubility of gases DECREASES at
Temperature & the Solubility of Gases

higher temperatures

24
 Pressure and Solubility of Gases
The solubility of a gas in a liquid is
proportional to the pressure of the gas over
the solution (Henry’s law).

low P high P

low c high c

25
 Henry’s Law
in terms of partial pressure and mole fraction
“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
Here KH is the
Henry’s law constant.
KH Increases Solubility
decreases 26
APPLICATIONS OF Henry’s Law

27
VAPOUR PRESSURE OF BINARY
SOLUTIONS
 Vapour Pressure of Liquid- Liquid Solutions
Consider a binary solution of two Mixtures of Volatile Liquids
Both liquids evaporate & contribute to the vapor pressure
volatile liquids A and B. When taken in a
closed vessel, both the components
would evaporate and eventually an
equilibrium would be established
between vapour phase and the liquid
phase. Let the total vapour pressure at
this stage be ptotal and pA and pB be the
partial vapour pressures of the two
components A and B respectively. These
partial pressures are related to the mole
fractions xA and xB of the two
components A and B respectively.
29
Raoult’s Law
Raoult’s law 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 in the
solution.
Thus, for component A,
P1 α c1
P1 = P°1.c1
P1 = vapour pressure of solvent A above the
solution
c1 = mole fraction of the solvent A in the solution
P°1 = vapour pressure of pure solvent A
30
Since BOTH liquids are volatile
and contribute to the vapour, the
total vapor pressure can be
represented using Dalton’s Law:

PT = P 1 + P 2
The vapor pressure from each
component follows Raoult’s
Law:
PT = P°1c1 + P°2c2
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Also, c1 + c2 = 1 (since there are
2 components)
c1 = 1 – c2
PT = P°1c1 + P°2c2 can be

written as

PT = P°1(1-c2)+ P°2c2
PT = P°1- P°A1.c2 + P°1c2

PT = P°1 + c2 (P°2 - P°1 )

Partial pressure in vapour phase

32
 Raoult’s Law as a special case of Henry’s Law
Henry’s law p = KH .x
Raoult’s law p= p0 .x

Thus Rault’s law becomes a special case of

Henry’s law when KH becomes equal to p0

33
Vapour Pressure of Solutions of Solids in Liquids
Vapour pressure of a solution
is lower than that of the
solvent.
Raoult’s law in its general
form can be stated as,
for any solution thepartial
vapour pressure of each
volatile component in the
solution is directly
proportional to its mole
34
 Vapour Pressure of Solutions of Solids in
Liquids
When the solute is non-volatile, only the solvent
molecules are present in vapour phase and
contribute to vapour pressure.

Let p1 be the vapour pressure of the solvent, x1 be its

mole fraction, p10 be its vapour pressure in the pure
state. Then according to Raoult’s law

p1 α x1 and
p1 = p1 0 .x1

A plot between the vapour pressure and the mole

fraction of the solvent is linear

35
IDEAL AND NON-IDEAL SOLUTION
 Ideal solutions
The
 In solutions
pure which obey
components, the
Raoult’s law over the entireattractive
intermolecular
range of concentration
interactions will be are
of types A-A
known
and B-B,as ideal solutions.
whereas in the binary
The ideal solutions
solutions haveto
in addition two
these two
other important properties.
interactions, A-B The
type of
enthalpy of mixing
interactions of the
will also bepure
present. If
components to form the solution
the intermolecular attractive
is zero and the volume of mixing
forces between
is also zero, i.e.,
the A-A and B-B
are nearly equal to those
between A-B, this leads to the
ΔHmix = 0, ΔVmix = 0
formation of ideal solution.
37
 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 it is higher, the
solution exhibits positive
deviation and if it is lower, it
exhibits negative deviation
from Raoult’s law.
NON-IDEAL WITH POSITIVE DEVIATION
NON-IDEAL SOLUTION WITH NEGATIVE DEVIATION
AZEOTROPIC
MIXTURE
 AZEOTROPIC MIXTURE
Azeotropes are binary mixtures having the same composition in liquid
and vapour phase and boil at a constant temperature
COLLIGATIVE PROPERTIES
 Colligative Properties

Colligative Properties are properties of a

liquid that change when a solute is added.

The magnitude of the change depends on the

number of solute particles in the solution,
NOT on the nature of the solute particles.

45
COLLIGATIVE PROPERTIES

Relative Lowering of Vapor-Pressure

Elevation of Boiling-Point

Depression of Freezing-Point

Osmotic Pressure (p)

46
Vapor Pressure Lowering

 The presence of a non-volatile solute means that

fewer solvent particles are at the solution’s
surface, so less solvent evaporates! 47
According to Rault’s law, P1 = P°1.c1
Relative Lowering of Vapor-Pressure

Relative lowering of vapour pressure ,

Δ p1 = p10-p1
p10-p1 = p10- p10. c1
= p10 (1- c1)
p10-p1 = p10. c2 (as (1-
c1)= c2 )
p10-p1 = c2
p10 48
 c2= n2
n1+n2
p10-p1 = n2 = n2/ n1 (for dilute solution n2
is negligible)
p10 n1+n2

p10-p1 = w2/M2
p10 w1/M1
w1 and w2 are the masses and M1 and M2 are the molar
masses of the solvent and solute respectively
49
Elevation of Boiling-Point
B.P Iis the temperature at which vapour
pressure becomes equal to atmospheric
pressure.
When a non-volatile solute is added to a
volatile solvent its B.P INCREASES
Elevation of boiling point ΔTb =Tb−Tb0
Tb0 -Boiling point of pure solvent
Tb -Boiling point of solution
ΔTb α m m-molality
ΔTb =Kb m
Kb - Boiling Point Elevation constant or
Molal Elevation Constant (Ebullioscopic
Constant)
 m= w2/M2
w1/1000

ΔTb = Kb.w2. 1000

w1.M2

M2 = 1000.Kb.w2
ΔTb w1
 DEPPRESSION IN FREEZING POINT
FP is the temperature at which solid and liquid have same vapour pressure

The freezing point of a solution is LOWER than that of the pure solvent
Depression of Freezing Point

depression of freezing point ΔTf

=Tf0−Tf
Tf0 -freezing point of pure solvent
Tf -freezing point of solution
ΔTf α m m-molality
ΔTf =Kf m
Kf - Freezing Point Depression
Constant or Molal Depression
Constant or Cryoscopic Constant
 m= w2/M2
w1/1000

ΔTf = Kf.w2. 1000

w1.M2

M2 =.Kf.w21000.
ΔTf. w1
OSMOTIC PRESSURE
Osmotic pressure
Osmosis is the spontaneous
movement of solvent across a
semi-permeable membrane
from an area of low solute
concentration to an area of
high solute concentration
Osmotic Pressure - The
Pressure that must be
applied to stop osmosis
Osmosis
 Osmotic Pressure (p)
Osmosis is the selective
passage of solvent
molecules through a
porous membrane from a
dilute solution to a more
concentrated one.

A semipermeable
membrane allows the
passage of solvent
molecules but blocks
more the passage of solute
dilute
concentrated molecules.

Osmotic pressure (p) is the pressure required to stop osmosis.

Osmotic pressure
osmotic pressure П is proportional to the molarity, C
of the solution at a given temperature T.
П α CT
П =RCT R- gas constant
C=n2/V
П =n2RT
V
ПV = n2RT But n2 =w2/M2
ПV =w2RT or M2= w2RT
M2 ПV
Measurement of osmotic pressure is widely
used to determine molar masses of proteins,
polymers and other macromolecules.
Two solutions having same osmotic
pressure at a given temperature are
called isotonic solutions.
No osmosis occurs when such solutions are
separated by semi-permeable membrane.

61
 Osmosis and Blood Cells
(a) A cell placed in an isotonic solution. (0.9%
(mass/volume) sodium chloride solution, called normal saline
solution)The net movement of water in and out
of the cell is zero because the concentration
of solutes inside and outside the cell is the
same.
(b) In a hypertonic solution, (more than 0.9%)the
concentration of solutes outside the cell is
greater than that inside. There is a net flow
of water out of the cell, causing the cell to
dehydrate, shrink, and perhaps die.
(c) In a hypotonic solution, (less than 0.9%) the
concentration of solutes outside of the cell is
less than that inside. There is a net flow of
water into the cell, causing the cell to swell
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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. That is, now the
pure solvent flows out of the solution through
the semi permeable membrane. This
phenomenon is called reverse osmosis and is
of great practical utility.
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. The
pressure required for the reverse osmosis is
quite high.
 Abnormal Molar Mass
For compounds which
dissociate or associate in
solution, the molar mass
will be either lower or
higher than the expected
or normal value is called
as abnormal molar mass.
e.g. for NaCl or KCl, the
value will be about half
for acetic acid, which
associates, the value will
be twice.
64
 Van’t Hoff Factor
In 1880 van’t Hoff introduced a factor i,
known as the van’t Hoff factor, to
account for the extent of dissociation
or association. This factor i is defined
as:
Jacobus
Normal molar mass
i= Henricus
Abnormal molar mass van 't Hoff
Nobel prize 1901
=
Observed colligative property
Calculated colligative property

Total number of moles of particles after

association/dissociation
=
Number of moles of particles before
association/dissociation
The value of i for
aqueous KCl solution,
which dissociates into 2
is close to 2,
The value for acetic
acid in benzene, which
dimerises is nearly 0.5.

66
Colligative Properties of Electrolyte Solutions

Relative lowering of V.P. p10-p1 = i. n2

p10 n1+n2
Boiling-Point Elevation DTb = i Kb m

Freezing-Point Depression DTf = i Kf m

Osmotic Pressure (p) p = i.n2.R.T/V