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Solutions and
colligative properties
 Solution

By convention

Constituent present in
Solvent
the largest amount.

Constituents present in
Homogeneous mixture relatively small Solute
i.e., a single phase amounts.
containing more than one
component dispersed on
a molecular scale.

+ =

Solute Solvent Solution

 Note

If one of the components of a

solution is water, it will always be
considered as a solvent even
when it is present in a very less
amount.

Solvent determines the physical

state in which the solution
exists.
 Types of solutions

Binary solution
2

Number of
constituents 3
Ternary solution

Quaternary solution
 Liquid solutions

Gas in liquid Liquid in liquid

e.g., alcohol and Solid in liquid
e.g., carbonated
water e.g., salt in
drinks
water
 Composition of a solution
can be described by
expressing its concentration.

Concentration can be expressed either

qualitatively or quantitatively.

Concentrated
Concentration
Or,
Terms
Dilute
 Percentage Concentration Terms

% w/w % w/V % V/V

Amount of solute in Amount of solute in Volume of a solute

grams dissolved grams dissolved (in mL) dissolved per 100 mL
per 100 g of per 100 mL of of solution.
solution. solution.

Weight of solute (g) × 100 weight of solute (g) ×

% w/w = % w/V = volume of solute (mL)
% V/V = × 100
Weight of solution (g) Volume of solution (mL) Volume of solution (mL)
100
 Other Concentration
Terms

Strength
(S)
Molarity
(M)
Molality
(m)
Normality
(N)
ppm

Mole fraction ( 𝞆
)
 Strength
(S)

Weight of solute
(in gram) per
litre (1000 mL) of
solution.

Strength (S) =
Weight of solute (g)
Volume of solution
(L)
 Molarity Molality (m)
(M)

Number of Number of moles

moles of solute of solute per 1000
per litre of g or 1 kg
solution. of solvent.

No. of moles of solute No. of moles of solute

M = (n) Volume of solution
m = (n) Mass of solvent
(L) (kg)
 Normality
(N)

Number of gram equivalents of

Normality = solute Volume of solution (L)

Number of gram
equivalents of solute
Number of gram Mass of the
dissolved per litre of
solution. equivalents = species Gram
equivalent mass

Mass of the
= species
Molar mass
n - factor
 ‘n’ - factor

For
oxidising/ For For
reducing acid / salt
agents base
For Oxidising/Reducing Agents

Number of electrons
involved in oxidation/
reduction half reaction
per mole of oxidising/
reducing agent.

2
5e‒+ 8H+ + MnO4 Mn+ +
H2O
‒
n-factor =
5
 For Acid/Base and Salts

Number of moles For simple salts,

of H+ ions n-factor is a total
displaced/OH− ions charge on cations
displaced per mole or a total charge
of acid/base. on anions.

Example: H2SO4 Example: NaOH Example: Al2(SO4)3

n-factor = charge on
n-factor = 2 n-factor = the cation
1 =2×3=6
 Parts per Million (ppm)

Weight of solute
ppm = (g)
Weight of solution
×
(w/w) 106
(g)

The number
Weight of solute
of parts of
solute present
ppm = (g)
Volume of solution
×
(w/V) 106
in 1 million (mL)
parts of solution.

ppm Moles of solute

(moles/moles) = Moles of solution
×
106
 Mole Fraction
(𝓧)
For a binary
solution,

Ratio of the Moles of solute n

number of moles 𝓧solute = Total moles in = n +
of a particular solutions N
component to the
total number of
moles of all the Moles of solvent N
components. 𝓧solvent = Total moles in = n +
solutions N

𝓧solute + 𝓧solvent = 1
 Based on the amount
of the solute
dissolved

Unsaturated Saturated Supersaturated

A solution which contains

It is a solution in A solution in which no more amount
which more amount more solute can be of the dissolved solute
of solute can be dissolved at a than in the saturated
dissolved at a particular temperature. solution at a particular
particular temperature. temperature and
pressure.
 Solubility

Solubility of one substance

into another depends on:

Solubility of a substance
is its maximum amount
that can be dissolved in a 1 Nature of the solute and
specified amount of solvent
solvent (generally 100 g of
solvent) at a specified
temperature 2 Temperature
to form a saturated
solution.
3 Pressure
 1. Nature of Solvent & Gas

Like dissolves like

When a gas undergoes
ionisation in a solvent,
then it is highly soluble
in that solvent. Polar gases dissolve in polar
solvents and non-polar
gases in non-polar solvents.
E.g., HCl is
highly soluble in
water.
 2. Effect of Temperature

Generally, Oxygen dissolves only to a small extent

in water. It is this dissolved oxygen
Dissolution of gas which sustains all aquatic life.
in liquid is
exothermic
Temperature

Solubility
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.
 3. Effect of Pressure (Henry’s Law)

� ∝ P
�

P=
The solubility of KH 𝓧
a gas in a liquid at
a P is the partial pressure of gas
given temperature is in equilibrium with the
directly proportional solution.
to its partial
pressure, at which, it K H is Henry’s law constant.
is
dissolved.
𝓧 is the mole fraction of the
unreacted gas in the
solution.
 P Increase in
pressure increases
solubility

Movable frictionless piston

Gas
⇌

P Decrease in
Liquid pressure decreases
solubility

Gas is in equilibrium
with the liquid
solution
 Characteristics of Henry’s Law Constant

a Same unit as that of K H value increases with increase

d
pressure: torr or in temperature.
bar

b Different gases have different KH Higher the value of K H of a

e
for the same solvent. gas,
lower will be its solubility.

P
c K H value of gas is different
in different solvents.
Since, � = KH
�
 Graphical Analysis (Henry’s Isotherm)

Plot of P vs 𝓧 is a straight line passing

through the origin with slope equal to T1
KH.

Partial pressure
T2
T3

(P)
Partial pressure

Mole fraction (𝓧)

Slope = T1 > T2 > T3

KH
(P)

K >
H1 KH 2 KH 3
>
Mole fraction
(𝓧)
 Note

If a mixture of gases is brought in contact

with a solvent, each constituent gas
dissolves in proportion to its partial
pressure.

Henry's law applies to each gas

independent
of the pressure of other gas.
 Application of Henry’s Law

To increase the solubility

of CO2 in soft drinks and At high altitudes, the partial
(a
soda water, the bottle is (b pressure of oxygen is less
) sealed under high than that at the ground
)
pressure. level.

Scuba diving tanks are

(c diluted with helium.
)

Low blood oxygen

level causes
anoxia.
 Application of Henry’s Law

The bubble blocks the capillaries and

Scuba divers must cope with high
creates a medical condition known as
concentration of dissolved gases
bends that are painful and dangerous to
while, breathing air at high
life.
pressure.

Increased pressure increases solubility of

To avoid bends as well as toxic effects
atmosphere gases in the blood which are
of high concentration of nitrogen in
released when the diver comes towards
blood, tanks used by scuba divers are
the surface. The pressure decreases and filled with air diluted with helium.
results in formation of nitrogen bubbles
in blood.
 Limitations of Henry’s Law

Henry’s law is valid only under the

following conditions:

1 Pressure of the gas is not too

high.

2 Temperature is not too

low.

The gas should not undergo any

3
chemical reaction with the
solvent.

4
The gas should not undergo dissociation
in solution.
 Vapour Pressure

Evaporation of a Liquid in a Closed Container

Some of the more

energetic particles on the
surface of the liquid move
fast enough to escape from
the attractive forces
holding the liquid together.

As the gaseous particles bounce

around, some of them will hit the
surface of the liquid again, and be
trapped there.
 Evaporation and Condensation

An equilibrium is set up rapidly in which,

the number of particles leaving the surface
is exactly balanced by the number
rejoining it.
Rate of evaporation
At equilibrium,
Rate of Rate of
evaporation = condensation
Rate

Rate of condensation
H2O (l) ⇌ H2O
(g)
Kp = Peq (H2O (g))
Time
KP = V.P.
 Vapour Pressure of Solution

Vapour pressure of a liquid

(a
Vapour Pressure does not depend on:
)

Pressure exerted
by the vapour 1 Amount of liquid taken
of solvent 'A'
and solute 'B' in
equilibrium with
2 Surface area of the liquid
the liquid phase.

3 Volume or shape of the

container
 Vapour Pressure of Solution

It depends upon the

(b
nature of the liquid
)

Intermolecular Vapour Boiling

attractive forces pressure point

Loosely held molecules escape

more easily into the vapour
phase.
 Boiling Point

Temperature at which the

vapour pressure of a liquid is
equal to the external pressure.

At normal b.p., the vapour

pressure of the pure = 1
atm
liquid
 Vapour Pressure of Solution

(c Temperature
) Temperature at which the
vapour pressure of a liquid is
equal to the external pressure.

Vapour
Temperature
pressure At normal b.p., the vapour
pressure of the pure = 1
atm
liquid

More molecules from the liquid

have enough K.E. to escape
from the surface of the liquid.
 V.P.

K.E
.

Temperature K.E. of
particles
As the temperature of a liquid increases, the kinetic energy of its molecules also
increases. As the kinetic energy of the molecules increases, the number of molecules
transitioning into a vapor also increases, thereby increasing the vapor pressure. In
the first container (extreme left) the temperature is lowest and in the third one
(extreme right) the temperature is maximum, consequently the number of
molecules shown in the container is also maximum.
 Temperature

H2O (l) ⇌ H2O

ΔH > 0

(g)

According to
Le Chatelier principle,
increasing the temperature of
a system in a dynamic
equilibrium favours the
endothermic change.
 Raoult’s Law

PA ∝ �A
�
PA = o
𝓧A PA

In the solution of
volatile liquids, the
partial vapour
pressure of each PA Partial vapour pressure
of component 'A'
component is
directly proportional
to its mole fraction.
Mole fraction of
�A
component ‘A’ in solution
�

Vapour pressure of pure

o
PA component ‘A’ at a
given temperature
 For Binary Solutions of A & B

PA = 𝓧A P A
o PB = o
𝓧B PB

PT = PA + PB

A 𝓧
o

B PT = o
A
P A + 𝓧BPB

A+
B
Solutions which obey Raoult’s law
𝓧B over the entire range of
concentration are called ideal
𝓧A solutions.
 Relation between Total Pressure vs Mole Fraction

𝓧A Po + 𝓧 P o
PT = A
B
𝓧A B = 1
B +𝓧

PT = ( P o - Poo ) 𝓧
+ P A B
A
o B
PT PA
This represents equation
o
PB PA of a straight line of PT A
vs 𝓧
A is more
PB If P > P
o o
volatile than
A
B B

𝓧A = 𝓧A =
b.p. of < b.p. of
A B
0𝓧B = 1B =
𝓧
1 0
 Composition of Vapour Phase

Mole fraction of A in
yA
vapour phase above the PA = yAP Dalton’s Law
T
solution PA

yB
Mole fraction of B in
PA = 𝓧A PA
o
Raoult’s Law
vapour phase above the
PA
solution
Similarly,

PB = yB P = o
𝓧B PB
T
 P T in Terms of Composition of Vapour Phase

𝓧A + = 1 1 yA yB
𝓧B PT = o
+
o
PA PB

yAPT yBPT

P oA
+ P oB
= 1 yA 1-
yA o
=
o

+
PA + PB

1 yA yB
=
o o
~ PT PA
o +
P oB
PA PB
PT = o o
P A + (PB - PA ) A
o

y
P T in Terms of Composition of Vapour Phase

o
PA

PT
o osition
omp
PB our c
Va p

0 Mole fraction of 1
A
 Did You Know?

Compositions of the liquid and

vapour that are in mutual
equilibrium are not necessarily the
same.

The vapour will be richer in the more

volatile component, if the mole fraction of
components in liquid phase is comparable.
 Characteristics of ideal solution

(i Ideal Solutions obey Raoult's law

over the entire range of concentration
)
o
PA PT = P A + (ii
PB If the forces of attraction between
) A—A, B—B is similar to A—B, then A
PoB
and B will form ideal solution.

PB PA
(iii Δ mix H = 0, i.e., there should not
) an enthalpy
be change when components
of ideal solutions are mixed.
𝓧A = Mole Fraction 𝓧A =
1 0
𝓧B = 𝓧B = (iv
0 1 Δ mix V = 0, (1L + 1L = 2L)
) there
i.e., should not be a
change in volume on
mixing.
 Characteristics of ideal solution

(v (Δ S) >0 (vi -qsys

) mix sys
⇒randomness
increases on )
T
=
mixing. (ΔmixS)surr = 0⇒(ΔmixS)surr = 0

(vii
) (Δamixspontaneous
S)univ > 0 ⇒process
Mixing
is

Probability of picking a red ball

is less as it has more
randomness
 Examples

n-Hexane and
n-Heptane Benzene and Toluene

Ethyl bromide and Ethyl Chlorobenzene and

iodide Bromobenzene
 Non-Ideal Solution

Characteristics:
Solutions that do not obey Raoult's law
over the entire range of concentration

1 Raoult's law is not

obeyed.
If the forces of attraction between A—
A, B—B is different from A—B, then A 2 ΔHmix ≠ 0
and B will form non-ideal solution.

3 ΔVmix ≠ 0
 Non-ideal Solutions

Positive deviation from Negative deviation

Raoult’s Law from Raoult’s Law
Non-Ideal with Positive Deviation

If the forces of attraction

between
A—A, B—B is stronger than A—B

Partial pressure of each component

A and B is higher than that
calculated from Raoult's law.

Hence, the total pressure over

the solution is also higher
than the solutions, if were
ideal.
 Non-Ideal with Positive Deviation

Vapour pressure
of solution
o Dashed lines represent vapour
PA pressures and total pressure
corresponding to ideal solution
o
PB

PB
PA
V.P. B.P.

𝛘A = Mole fraction 𝛘A =
1 0
𝛘B =
0
𝛘B =
1
b.p. of
solution
< b.p. of both A and
B
 Characteristics

1 Raoult's law is not

obeyed. 3 ΔH mix > 0

2 ΔV m i x > 0 (1L + 1L >

2L)
When the liquids are mixed, less heat
is evolved when the new attractions
are set up
Intermolecular forces between than was absorbed to break the
molecules of A and B are original ones.
weaker than those in the pure
liquids.
 Characteristics

Examples

4 (ΔmixS)sys > 0 ⇒
randomness increases on Water and ethanol
mixing.

-qsys-q Chloroform and water

5 sys <
(ΔmixS)surr = 0⇒ (ΔmixS)suTrr = 0
T

Ethanol and acetone

6 (ΔmixS)univ > 0~ Mixing is a

spontaneous process

Methanol and chloroform

Non-Ideal with Negative Deviation

If the forces of attraction between

A—A, B—B are weaker than A—B

Partial pressure of each component

A and B is lower than that
calculated from Raoult's law.

Hence, the total pressure over

the solution is also lower than
the solutions, if were ideal.
 Non-Ideal with Negative Deviation

Vapour pressure
o
PA of solution Dashed lines represent vapour
pressures and total pressure
corresponding to ideal solution.
o
PB
PA
PB

V.P. B.P.

𝛘A = Mole fraction 𝛘A =
1 0

>
𝛘B = 𝛘B =
B.P. of solution B.P. of both A and
0 1
B
 Characteristics

1 Raoult's law is not

obeyed.
3 ΔH mix < 0

2 ΔV m i x < 0 (1L + 1L <

2L)
When the liquids are mixed, more heat
is evolved when the new attractions are
set up than was absorbed to break the
original ones.
Intermolecular forces between
molecules of A and B are
stronger than those in the pure
liquids.
 Characteristics

Examples

Chloroform and
4 (ΔmixS)sys > 0 ⇒ randomness acetone
increases on mixing.
Chloroform and methyl
acetate

5 -qsys H 2O and
> HCI
mix
(Δ surr
S) =0 ⇒ mix
(Δ S)surr T 0
= H2O and HNO3

Acetic acid and

6 Mixing is a pyridine
(ΔmixS)univ > 0 ⇒
spontaneous process
Phenol and aniline
 Comparing Ideal & Non-Ideal
Solutions
Non-ideal solutions
Ideal solutions
Positive deviation Negative deviation

o o o
P = 𝓧 P + 𝓧o P > o𝓧 P + 𝓧 P < o𝓧 P + 𝓧
P P P
T A A B B T A A B T A A B
B B

A-A & B-B A-A & B-B A-A & B-B

molecular molecular molecular
interaction are interaction are interaction are
similar as A-B stronger than A-B weaker than A-B

∆mixH = 0 ∆mixH > 0 ∆mixH < 0

∆mixV = 0 ∆mixV > 0 ∆mixV < 0

 Non-ideal solutions
Ideal solutions
Positive Negative
deviation deviation

(∆mixS)sys > 0 (∆mixS)sys > 0 (∆mixS)sys > 0

(∆mixS)surr = 0 (∆mixS)surr < 0 (∆mixS)surr > 0

(∆mixS)univ > 0 (∆mixS)univ > 0 (∆mixS)univ > 0

(∆mixG)sys < 0 (∆mixG)sys < 0 (∆mixG)sys < 0

 Azeotropic Mixtures

Liquid mixtures which boils at a constant

Very large deviations from ideality temperature and can be distilled
lead to a special class of mixtures without any change in the composition.
known as azeotropes, azeotropic
mixtures,
or constant-boiling mixtures.
A boiling liquid mixture at the azeotropic
composition produces vapours of exactly
the same composition as that of the
liquid.
Composition of liquid mixtures at
which, distillation cannot separate
the two liquids because the Azeotropes are of two types:
condensate has the same
composition as that of the 1. Maximum boiling azeotropes
azeotropic liquid. 2. Minimum boiling azeotropes
 Minimum Boiling Azeotropes
Non-ideal solutions showing large
positive deviation from Raoult's law, form
minimum boiling azeotropes that boil
at a temperature lower than the
boiling points of its components 'A' and
'B'.
Ethanol - water mixture containing
≈ 95% by volume of ethanol
Chloroform - methanol mixture
containing 87.4% chloroform and
12.6% methanol by weight
Minimum Boiling Azeotropes
Non-ideal solutions showing large
negative deviation from Raoult's
law,
form maximum boiling azeotropes that boil
at a temperature higher than the boiling
points of its components 'A' and 'B'.
A mixture of HNO3 and H2O containing
≈68% HNO3 and 32% water by mass
Formic acid - water mixture containing
77.6% formic acid and 22.4% water by
mass.
 Minimum Boiling Azeotropes Maximum Boiling Azeotropes

Constant pressure Constant Pressure

P = 101.325 kPa P = 101.325 kPa
Vapour composition
Vapour only (Dew point curve)

Temperature [K]
Temperature [K]

Vapour s
se
Co ph
a Azeotrope
composition
ex
ent
ist (Dew point
en xist
tp curve) e
ha Co
se Liquid composition
Liquid s
(Bubble point
composition curve)
(Bubble
point curve) Liquid only
Azeotrope
0 Mole fraction of 1 1
Pure Pure 0 Pure Mole fraction of formic Pure
chloroform
methanol chloroform water acid formic
acid
 Minimum Boiling Azeotropes Maximum Boiling Azeotropes

Constant Temperature Azeotrope

Constant Temperature
T = 298.15 K T = 298.15 K
Liquid Liquid only
composition
(Bubble

Pressure [kPa]
Pressure [kPa]

point Liquid composition

s
se
ha

curve) (Bubble point

tp
en

curve)

s
se
ist

ha
ex

tp
Co

en
a

ist
ex
p Azeotrope

Co
o
u
Vapour composition
r
(Dew point curve)
0 Mole fraction of 1
o 0 Pure Mole fraction of formic Pure 1
Pure chloroform Pure
methanol n chloroform
water acid formic acid
l
y
 Dissolution & Crystallisation

When a solid solute is added to the At equilibrium

solvent, some solute dissolve and its
concentration increases in the
solution.
Rate of Rate of
dissolution = crystallisation

Some solute particles in the solution Solute + Solution

collide with the other solid solute particles Solvent
and get separated out of the solution.
 Equilibrium

At this stage, the concentration

of solute in solution will
remain
constant under the given temperature and
pressure conditions.

Such a solution is said to be

saturated with the given
solute.
 Factors affecting Solubility of Solid in liquid

Nature of
the solvent Temperature Pressure
& the
solute
 1. Nature of Solvent & Solute

Sodium chloride dissolves readily

Like dissolves like in water, whereas naphthalene and
anthracene do not.
Polar solutes dissolve in polar
solvents and non-polar solutes
dissolve in non-polar solvents.

Naphthalene and anthracene

dissolve readily in benzene
but sodium chloride do not.
 2. Effect of Temperature

Solute + Solution Solute + Solution

Solvent Solvent

If dissolution If dissolution
ΔH < ΔH >
is exothermic is endothermic
0 0

By Le Chatelier's By Le Chatelier's
principle, principle,

T Solubility T Solubility
 3. Effect Of Pressure

Pressure does not have any signifficant

effect on the solubility of solids in
liquids.

Solids and liquids are highly

incompressible, and practically remain
unaffected by changes in the pressure.
 Colligative Properties

Relative lowering
The properties of the solution of the vapour
that are dependent only on pressure
the total number of solute
particles relative to Elevation in the boiling
solvent/solution are known as point
colligative properties. Colligative
Properties
Depression in the
freezing point
They are not dependent
on the nature of particle
i.e., shape, size, charge, Osmotic pressure
etc.
 Abnormal Colligative Property

For electrolytic solutes,

If solute gets associated or dissociated in the number of
solution, then experimental/observed/actual particles
value of colligative property will be would be different from the
different from the theoretically predicted number of particles
value. actually added due to
dissociation or association
of the solute.

Abnormality in colligative NaCl (s) + H2 O (l Na+ (aq) + Cl‒ (aq)

property can be calculated )
in terms of van’t-Hoff
factor.
Example: On adding 1 mole of NaCl in
excess water gives 1 mole of Na+ and 1 mole
of Cl‒ ions
i.e. 2 moles of solute.
 van’t Hoff Factor
(i)

The actual extent

of dissociation/ Observed colligative property
association can i = Calculated colligative property
be expressed with
a correction factor
known as van’t
Hoff factor (i).

Moles of solute particles in solution after dissociation/

i = association
Moles of solute particles before
association/dissociation
 van’t–Hoff Factor
(i)

Dissociation
>1

i No
=
1 dissociation/
association

<1

Association
 i for Dissociation of Electrolyte

AxBy (aq) xAy+ yBx–

+
t= C 0 0
0

t= C(1 xC yC
teq - 𝜶) 𝜶 𝜶
At equilibrium, Net concentration = C – C𝜶 + xC𝜶 +
yC𝜶

= C[1+(x+y- = C[1+(n-1
1 ) 𝜶] ) 𝜶]
n Number of particles in which 1 molecule of electrolyte
dissociates
 i for Dissociation of Electrolyte

Examples

C[1+(n -1
i = ) 𝜶]
C NaCl (100% i = 2
ionised) 1

i = 1+(n -1
BaCl2 (100% ionised) i = 3
)𝜶
 i for Association of Electrolyte

nA An

t= C 0
0

C
t= C(1
At equilibrium, 𝜷
teq - 𝜷)
n
C
Net concentration = C – C𝜷
+
𝜷
n

= C 1
1
- �
�
+ 1
n
 i for Association of Electrolyte

Examples

C 1 – 1
1
i = +
n
𝜷 Dimerisation of
CH3 COOH in benzene i = 01
C (100 %) .5

Dimerisation of
C6H5COOH in benzene i = 0.
(100 %) 5
i = 1
1
– 1
+ 𝜷
n
 1. Relative
lowering of vapour
pressure

2. Elevation in
boiling point
Colligative
Properties
3. Depression
in freezing
point

4. Osmotic pressure
1. Relative Lowering of Vapour Pressure
(RLVP)

V.P. of a solution
containing a non-
volatile solute (solid
solute)
is always found to
be less than the V.P.
of the pure solvent.
 1. Relative Lowering of Vapour Pressure
(RLVP)

V.P. of a solution containing a non-volatile solute (solid solute)

is always found to be less than the V.P. of the pure solvent.

P1 P2 P1 P2

Pure
P1 =P 2
Pure
Solution P1 < P 2
Pure
(non-volatile solute
solvent solvent solvent
in solvent A)
A A A
Reason Some of the solute
molecules will occupy some
surface area of the solution.

Tendency of the solvent

particles to go into the vapour
phase slightly decreases.

Hence, P 0 > PS, where P 0

is V.P. of the pure solvent and
Solvent P S is the V.P. of the solution.
Solution
Lowering in V.P. = P o - PS = ΔP

Relative lowering ΔP
in vapour = Po

pressure
 Note

Raoult’s Law (For

non–volatile solutes)
Vapour pressure
The vapour pressure of a solution of a
of pure solvent
non-volatile solute is equal to the
vapour pressure of the pure solvent at

Vapour pressure
that
temperature multiplied by its mole
fraction.
PS = 𝓧solvent P o = ( 1 - 𝓧solute)
Po
P o - PS n
RLVP n +
= Po = 𝓧solute
N 0
Mole fraction of
1

=
n = Number of moles of non-volatile solute
solvent
𝓧solvent
N = Number of moles of solvent in the
solution
 1. Relative Lowering of Vapour Pressure

n+ N P o - PS w
Po
P - PS
o
= N = 1+
PS
= M
solvent
n n solute x wsolvent

Msolute
N PS w solute
n = Po
P - PS
o — = Po ‒ P S = xM x
1000
1 1000
Msolute solvent

wsolvent

P o ‒ PS n
PS = N
w = Weight of species
M = Molar mass of
species
 1. Relative Lowering of Vapour Pressure

P o - PS wsolute 100 If the solute gets associated

Msolvent
PS = M solute x w0 x 100
or dissociated
solvent
0
P o - PS
i
Po = xn
P o - PS Msolvent ixn +
PS = Molality x 100
0
N
P o - PS ix M solvent
PS = n = i x Molality x 100
N 0
 Boiling Point

Temperature at which the V.P. of a

liquid is equal to the external pressure
present at the surface of the liquid.
External
pressure
Vapour
pressure

At normal B.P., V.P.

of the pure liquid = 1
atm
2. Elevation in Boiling Point

When a non-volatile solute

is added into a volatile liquid
to form solution, V.P.
decreases.

The solution need to be

heated to a higher
temperature to boil it, so that
V.P. becomes equal to external
pressure.
 For Vapour pressure of an aqueous solution
example, of
sucrose is less than 1.013 bar at 373.15
Atmospheric Atmospheric K.
pressure pressure
To make this solution boil, its vapour
pressure must be increased to 1.013 bar by
raising the temperature above the boiling
Lower vapour temperature of the pure solvent (water).
pressure

Thus,

The boiling point The boiling point of

Pure
Solution
of a solution > the pure solvent
(with
solvent solute)
 Tb = B.P. of solution
Tbo(K)
= B.P. of pure solvent
(K)

V.P. of solution < V.P. of pure solvent

1
atm
e nt
lv
So

Vapour pressure
n
t io
Hence, to make the V.P. equal to Pext, o lu
S
we have to heat the solution by a
greater amount in comparison to pure ΔTb
solvent.

T ob Tb
Temperature
(K)
 2. Elevation in Boiling Point

o
ΔTb = Tb - Tb ΔTb = Kb m

ΔTb ∝ m
K b = B.P. elevation constant
or, Molal elevation constant or,
Ebullioscopic constant
m Molality
 Kb o2

RTb M
It is equal to elevation in
Kb = 1000 x vap
boiling point of 1 molal ΔH
solution.

o
● T is B.P. of pure solvent (K)
b

Units K/m or ● M is the molar mass of solvent in

°C/m or K g/mol
vap
kg mol–1 ΔH is the molar
● vapourisation enthalpy
of the of
solvent
(J/mol)
● R = 8.314 J/mol-K
 Note

If solute gets
1
associated/dissociated then
ΔTb = i × K b × Molality

2 K b is the property of
solvent

Elevation in B.P. is proportional

3
to the lowering of vapour
pressure.

ΔTb ∝ ΔP
 Freezing Point (F.P.)

Temperature at which, the vapour

pressure of a solid becomes equal to
the vapour pressure of liquid at 1 atm
is called normal freezing point.
 3. Depression in Freezing Point

When a non-volatile solute is

dissolved in the solvent, the V.P. of
the solvent in the solution decreases. Liquid n t
lve
so
Solid re
Pu

Pressure
1 atm
tion
olu
S
V.P. of solid and liquid solvent Gas
ΔTf
will become equal at a
lower Temperature (K)
temperature, i.e., F.P. of solution is lower
than that of a pure solvent.
 3. Depression in Freezing Point

ΔTf o
ΔTf = Tf -
Tf
The difference between
o
F.P. of a pure solvent Tf ΔT f ∝ m
and F.P. of its solution
Tf.

ΔTf = Kf m

m Molality

Kf is equal to the depression in Kf = F.P. depression constant or molal

freezing point of 1 molal depression constant or cryoscopic
 Cryoscopic Constant (Kf)

2
RTfo M
K/m or
Kf = 1000 x fus Units
°C/m or K
ΔH
kg mol–1

o
● Tf is F.P. of pure solvent (K)
● M is the molar mass of solvent in
g/mol
● ΔHfus is the molar enthalpy
of fusion of the solvent
(J/mol)
● R = 8.314 J/mol-K
 Note

Depression in freezing point is proportional

1 to the lowering of
vapour pressure i.e. ΔTf ∝ ΔP

If solute gets
2 associated/dissociated then
ΔTf = i × Kf × Molality

At freezing point or below it,

3 only solvent molecules will
freeze & not solute
molecules.
 Osmosis

The spontaneous flow of solvent

particles from solvent side to solution
side, or from solution of low
concentration side to
solution of high concentration side
through a semi-permeable membrane
(SPM).

Solution Solvent

C1 SPM
 Semi-permeable Membrane (SPM)

Natural
A membrane
that allows only
solvent particles
SPM
to move across
it.
Artificial
 Semi-permeable Membrane (SPM)

Natural SPM Artifficial SPM

Animal/plant cell Cu2[Fe(CN)6]

membrane formed just & Silicate of
below the outer skins. Ni, Fe, Co
can act as
SPM.
 Example of Osmosis

People taking a lot of salt,

A raw mango placed in a experience water retention in tissue
i concentrated salt solution loses ii cells. This results in puffiness or
water & shrivel into pickle. swelling called edema.
 4. Osmotic Pressure
(𝚷)
Pext

The external
pressure that Solution Solvent
must be applied
on the solution
side to just
stop the
C1 SPM
process of
osmosis.

Pext = 𝚷
 4. Osmotic Pressure
(𝚷)

𝚷 ∝
Concentration � = CRT
(Molarity) �

● 𝚷 = Osmotic pressure
𝚷 ∝ T ● C = Concentration
(mol/L)
● R= Universal gas
constant
● T = Temperature (K)
 4. Osmotic Pressure
(𝚷)

If more than one type of

solute particles are
𝚷 = CRT
present.

CT = C1 + C2 + C3 +
……..
n
𝚷 = V RT n1 + n2 + n3 +
= …….. V

𝚷 = CTRT
 4. Osmotic Pressure
(𝚷)

If two solutions of concentration C1 & C2

are kept separated by SPM, and C1 > C2,
then the solvent particle movement take
Solution Solution 2 place
1 from lower to higher concentration.

C1 SPM C2

C1 >
So, an extra pressure is applied on the
C2 higher concentration side to stop
osmosis.
Pext = 𝚷1 – 𝚷2
 Note

Osmotic pressure of very

dilute solutions is also quite If solute gets associated
signifficant. So, its or dissociated then 𝚷 = i x CRT
measurement in lab is very
easy.
 Reverse Osmosis

If the pressure applied on the solution

side is more than the osmotic pressure
of the solution, then the solvent
Used in particles will move from solution to
desalination solvent side.
of sea-water

Pext 𝚷

>
 Based on the difference
in osmotic pressure

1 Isotonic solution

2 Hypotonic solution

3 Hypertonic solution
 Isotonic Solution

Two solutions having

same osmotic Solution 1 Solution 2
pressure are
considered as
isotonic solution.
C1 SPM C2

𝚷1 = 𝚷2
 Hypotonic & Hypertonic Solutions

Hypotonic

Solution Solution 2
If two solutions 1 Hypertonic
‘1’ and ‘2’ are such
that
C1 SPM C2
𝚷2 > 𝚷1 , then ‘2’
is called
hypertonic
solution and ‘1’ is
called hypotonic 𝚷1 < 𝚷2
solution.
 Hypotonic & Hypertonic Solutions

Pext

Hypotonic

Solution Solution 2
1 Hypertonic

C1 SPM C2

𝚷1 < 𝚷2
Pext
= 𝚷2 - 𝚷1
 Types of Solutions

Hypotonic Isotonic Hypertonic

Solution Solution Solution

Net water gain No net Net water

Cell Swells loss or loss Cell
gain Shrinks
 Plasmolysis

When the cell is placed in a solution

having its osmotic pressure greater
than that of the cell sap, water passes
out of the cell due to osmosis.

Consequently, the cell material shrinks

gradually. The gradual shrinking of
the cell material is called
plasmolysis.
 Application of Osmotic Pressure

a Determination of molecular
. mass of the solute. Widely used to determine molar
masses of proteins and other
biomolecules, as they are
generally not stable at higher
wRT temperatures
Msolute = 𝚷V

● w is mass of solute This method has the advantage

over other methods as pressure
● V is volume of the solution
measurement
● 𝚷 is osmotic pressure of the is around the room temperature.
solution
● T is temperature
● R is universal gas constant
 Note

If solute gets associated or dissociated

then theoretical molar mass of solute will
be different from experimentally
calculated molar mass

Theoretical molar mass of

i = substance

Experimental molar mass of the substance

 Application of Osmotic Pressure

b Desalination of
. water by reverse c.
osmosis Dialysis

Pext
Pext > 𝚷

Artificial kidney removes waste

products from blood through
osmosis.
Sea water Pure water

SPM