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to

Solutions and
colligative properties
 Solutio
n
By
convention

Constituent present
Solven
in the largest
t
amount.
Constituents present
Homogeneous mixture in relatively small Solut
i.e., a single phase amounts. e
containing more than one
component dispersed on
a molecular scale.

+ =

Solut Solven Solutio

e t n
 Not
e

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 3
Ternary
constituen solution
ts

Quaternary
solution
 Liquid
solutions

Liquid in liquid
Gas in liquid e.g., e.g., alcohol Solid in liquid
carbonated and water e.g., salt in
drinks water
 Percentage Concentration
Terms

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

Amount of solute in Volume of a solute (in

Amount of solute in grams
grams dissolved per 100 mL) dissolved per 100
dissolved per 100 g of
mL of solution. mL of solution.
solution.

Weight of solute % V/V = Volume of solute (mL) ×

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

Strength (S)

Molarity
(M)
Molality
(m)
Normality (N)

ppm

Mole fraction ( 𝞆
)
Strength of
Solution

Weight of
solute (in
gram) per litre
(1000 mL) of
solution.
 Molarity Molality
(M) (m)

Number of
Number of
m oles of the
m oles of the
solute per
solute per litre
1000 g or 1 kg
of 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

Normalit = solute Volume of solution (L)
y

Number Mass of the species

of gram = (g)
Gram equivalent
Number of equivalen
mass
gram ts
equivalents of
solute M ass of the species
dissolved per
litre of = (g) Molar mass
solution. n-
factor
 ‘n’ -
factor

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

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

2
5e ‒ + 8H+ + MnO
4 ‒
Mn+ +
H 2O
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
displaced per cations or a
mole of acid/base. total charge
on anions.

Example: H 2SO4 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
of parts of
Weight of solute
solute
present in 1
ppm = (g)
Volume of solution
×
(w/V) 106
million (mL)
parts
of solution.
ppm Moles of
(moles/m ole = soluteof
Moles
×
106
s) solution
 Mole Fraction
(𝓧)

For a binary
solution,

Moles of
Ratio of the
number of
�solut = solute Total moles in =
�e
moles of a solutions n
particular
component to Moles of solvent nN+
𝓧solven = =
the total Total moles in N
n+
number of
t solutions N
m oles of all the
components.

𝓧solute + = 1

𝓧solvent
 Based on the
amount of the
solute dissolved

Unsaturated Saturated Supersaturated

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

It should be prepared in a dust-

free
vessel and at a higher
temperature.

It is m etastable. Mechanical
stress, such as shaking or addition
of solute, causes deposition of
solute.
 Solubility of a Gas in
Liquid
Solubility of one
substance into another
depends on:

Solubility of a substance
1 Nature of solvent &
is its maximum amount
that can be dissolved gas
in a specified amount of
solvent (generally 100 g 2 Temperatu
of solvent) at a specified
temperature re
to form a saturated
solution. 3 Pressur
e
 1. Nature of Solvent &
Gas

Like dissolves When a gas undergoes

like ionisation in a solvent,
then it is highly soluble
in that solvent.
P olar gases dissolve in polar
solvents and non-polar
gases in non-polar solvents.
E.g., HCl is
highly soluble
in water.
 2. Eff ect of
Temperature

Generally Oxygen dissolves only to a small

, extent in water. It is this dissolved
Dissolution of gas oxygen which sustains all aquatic
in liquid is life.
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. Eff ect of Pressure (Henry’s
Law)

𝓧 ∝ P

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

Same unit as that of KH value increases with

a d
pressure: torr or
increase in
bar
temperature.

Different gases have different Higher the value of KH of a

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

P
c KH value of gas is
in different
different
Since, � = KH
�
solvents.
 Graphical Analysis (Henry’s
Isotherm)
Plot of P vs 𝓧 is a straight line passing
through the origin with slope equal to
KH .
T1

Partial pressure
T2
T3
Partial pressure

(P)
Slope = Mole fraction
(𝓧)
KH
(P)

T > T2 > T3
1
Mole fraction
(𝓧)
KH > KH > KH
1 2
3
 Not
e

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 CO 2 in soft At high altitudes, the partial
(a (b pressure of oxygen is less
drinks and soda water,
) the bottle is sealed under ) than that at the ground
level.
high pressure.

Scuba diving tanks

(c are diluted with
) helium.

Low blood oxygen

level causes
anoxia.
 Application of Henry’s
Law

The bubble blocks the capillaries

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

Increased pressure increases solubility of

To avoid bends as well as toxic
atmosphere gases in the blood which are
effects of high concentration of
released when the diver comes towards
nitrogen in blood, tanks used by scuba
the surface. The pressure decreases and divers are filled with air diluted with
results in formation of nitrogen helium.
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
 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
Rate of surface is exactly balanced by the
evaporatio
number rejoining it.
n
At equilibrium,

Rate of Rate of
evaporatio = condensatio
Rate

n n
Rate of
condensation
H 2O (l) ⇌ H 2O
(g)
Kp = Peq (H2O
Time (g))
KP = V.P
.
 Vapour Pressure of
Solution

Vapour pressure of a
Vapour
(a liquid
Pressure ) does not depend on:

Pressure
exerted by the 1 Am ount of liquid
vapour of taken
solvent 'A' and
solute 'B' in 2 Surface area of the
equilibrium liquid
with the liquid
phase.
3 Volume or shape of the
container
 It depends upon
(b the
) nature of the
liquid

Intermolecula Vapour Boilin

r attractive g
forces pressur point
e

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 = 1
atm
pure liquid
 (c Relative
) Humidity
(R.H.)

Relativ Partial pressure of H2 O vapour at given

e = temperature
Vapour pressure of H 2O at same
× 100
%
humidit temperature
y

A gas or gaseous mixture is said to be

saturated with the vapours of a liquid if
the partial pressure of the liquid
vapours is equal to its (saturated)
vapour pressure i.e.
R.H. = 100%
 (d Temperatur
Temperatu
Vapour
) e
re
pressur
e

More molecules V.
from the liquid P.
have enough K.E.
to escape from the
surface of the liquid.
K.E
.
Temperatu K.E. of
re particles
 Temperatur
e

H 2O (l) ⇌ H 2O (g)
Δ > 0
H

According Dependence of
to Le vapour pressure
Chatelier on
principle, temperature is given
increasing the by Clausius-
temperature of a Clapeyron
system in a equation.
dynamic
equilibrium, favours
the endothermic
change.
Clausius-Clapeyron
Equation

ΔH V
ln
P
P2
= R
1
T
1
1
PP 2
1
T
12

Molar enthalpy of
Δ V vapourisation of
H liquid

P2 V.P. of the liquid at

T2

P1 V.P. of the liquid at

T1
 Clausius–Clapeyron equation is important
for
understanding the aNpopteearance of phase
diagrams, particularly the location and shape of
the liquid–vapour and solid–vapour phase
boundaries.

Phase of a substance
is a form of matter that Did you know?
is uniform Diamond and
throughout in graphite are in
chemical diff erent phases.
composition and
physical state.
 Phase
Diagram

Phase diagram of a substance shows

s⇌
the regions of pressure and
temperature at which its various l
phases are therm odynamically Liquid
stable.
Solid
l⇌
P v
The lines separating the regions that
are called phase boundaries, show Vapour
the values of P and T at which two
phases coexist in equilibrium. s⇌
v
T
 Raoult’s
Law

PA ∝ �A PA = 𝓧A P
� o
A
In the solution of
volatile liquids,
the partial
P artial vapour
vapour pressure P
of each pressure of
component is
A component 'A'
directly Mole fraction of
proportional to its �A
� component ‘A’ in
mole fraction. solution
Vapour pressure of pure
component ‘A’ at a
PAo
given temperature
 For Binary Solutions of A
&B
𝓧A PA 𝓧B PB
A B
P P
= o = o

PT = PA + PB

𝓧
o
A
= P A + 𝓧B P B
PT o
A
B
A+ Solutions which obey Raoult’s law
B over the entire range of
𝓧A
concentration are called ideal
B solutions.
𝓧
 Relation between Total Pressure vs Mole
Fraction
𝓧A PAo 𝓧 B P Bo
= 𝓧A
PT
+
+𝓧
B = 1

) 𝓧+
T
P ( Po - P o

o
= Po
A B A
PT PA B
This represents
PB
o
PA ofequation
a straight line ofT P A

vs 𝓧 A is more
PB If P o > P volatile
o
A than B
B

𝓧A = 𝓧A = <
B.P. of B.P. of
A B
0 1
 Composition of Vapour
Phase
Mole fraction of A in
yA AA yAP Dalton’s
vapour phase above the P
solution P= T Law

Mole fraction of B in
AA
𝓧A P Raoult’s
yB P
vapour phase above the
solution
P= o
A Law

Similarly,

= 𝓧B PB
o
PB yBP T

=
 P T in Terms of Composition of Vapour
Phase

𝓧A = 1 yB
+ 𝓧B
1 yA
PT = P Ao
+
P Bo

yAPT yB PT
P o + P o 1 yA 1-
=
A B
=
o o
P
yAA+ PB
+ +
1 yA yB
⇒ = + PAo PBo
PT P Ao P Bo PT = P + (P - P )
o o o

y
A B A
A
P T in Terms of Composition of Vapour
Phase

o
PA

PT
n
itio
o pos
PB r com
ou
Vap

0 Mole fraction of 1
A
 Not
e

Compositions of the liquid and

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

The vapour will be richer in the

m ore volatile component, if the
mole fraction of components in
liquid phase is comparable.
 Pressure Versus Composition Phase
Diagram

Temperature = Let, initially the pressure over

constant the solution is very high so
that no vapour exist above
t ion the liquid.
s i o
m po rve) P
o
u id c i n t cu
A On decreasing the pressure gradually, a
Li q o
bb le p
(Bu point (bubble point) comes when we
n cross the bubble-point curve and first
o s itio
p bubble of vapour starts forming.
o
PB r c om curve)
ou t
Va p w p o i n
e
(D The area between the two
curves is vapour-liquid
equilibrium
0 Mole fraction of 1 region. The vapours cannot exist
A above the bubble point curve and
liquid
can’t exist below the dew point curve.
 Pressure Versus Composition Phase
Diagram

Temperature = On further decreasing

constant the pressure.A point (dew point)
comes when we cross the dew-point
i t io n curve.
p o s o
o m r ve) P
id c t c u
Li q u
po i n A
On crossing the dew-point curve
le
(B ubb almost all the liquid has
n evaporated into vapour i.e. only
o s itio the last drop of liquid (dew)
p
o
PB c om curve)
ou r t remains.
Va p w p o i n
(D e

Beyond this point, no liquid exist in

0 1 the system.
Mole fraction of
A
 Temperature vs Composition Phase
Diagram

The m ole fraction of one component is

plotted on the horizontal axis and the boiling
Va p temperature is plotted on the vertical axis.
our
(De co
w p mpos
t cu ition
oin
o
T rve)
B
If a liquid has a high vapour
Liqu pressure at a particular
id
(c
Boum temperature, it means that its
b leo
curv bp soitinio
p o
TA molecules can escape easily
e) tn
from the surface.

0 Mole fraction of 1
If liquid ‘A’ has higher V.P. than
A ‘B’ at a particular temperature,
then boiling point of ‘A’ is
lower than ‘B’.
 Temperature vs Composition Phase
Diagram

Va p Bubble-point
our Dew-point
(De com curve
w p pos curve
t cu ition
o oin
TB rve)
Boiling Boiling
temperatur temperatur
Liqu e at the e at the
id
(c
Boum
b leo given given
curv bp si
p o
e) otiniot n
TA
pressure, pressure,
as a function of as a function of
the mole fraction the mole fraction
0 Mole fraction of 1 in the vapour in the liquid
phase. phase.
A
 Pressure Composition
Diagram

- P ) 𝓧+
o Temperature =
=
o
PT (P
P o constant
A B A
B
o
PA
i
Liqu
This represents equation d

𝓧A
of a straight line of P T vs
o
PB

0 Mole fraction of 1
A
P T in Terms of Composition of Vapour
Phase
yA yB
1
PT
= o
PA
+ o
PB
+

yA 1-
= yAo + o
PA PB

o
PA P 0
PT = B o
P o + (P - P0)
y
A B A
A
 Ideal
Solution

o
PA P T = PA + B
Solutions that P
obey Raoult's law over the
entire range of o
PB
concentration.
PB PA
If the forces of attraction
between A—A , B—B is
similar to A—B, then A 𝓧A = Mole 𝓧A =
0𝓧 =
𝓧B =
and B will form ideal
1 Fraction
solution. B
0 1
 Ideal
Solution
Characteristi Example
cs s
(i) n-Hexane
Raoult's law is and n-
obeyed. Heptane

Ethyl bromide and

(ii) Ethyl iodide
ΔH mix = 0, i.e., there should not be
an enthalpy change when Benzene and
components Toluene
of ideal solutions are mixed. Chlorobenzene
and
(iii) Bromobenzene
ΔVmi = 0, (1L + 1L = 2L)
there
i.e.,x should not be a
change in volume on
mixing.
 Non-Ideal
Solution

Characteristic
Solutions that do not obey Raoult's s:
law
over the entire range of concentration
1 Raoult's law is not
If the forces of attraction between A— obeyed.
A, ΔH mix ≠
B—B is 2
diff erent from A—B, then A and B 0
will form non-ideal solution. ΔV mix ≠
3
0
 Non-ideal
Solutions

P ositive deviation Negative

from Raoult’s deviation from
Law Raoult’s Law
 Positive deviating Negative deviating
solution solution

If the forces of attraction If the forces of attraction

between between
A—A, B—B is stronger than A—A, B—B are weaker than
A—B A—B

Partial pressure of each Partial pressure of each

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

Hence, the total pressure Hence, the total pressure

over the solution is also over the solution is also
higher than the solutions, if lower than the solutions, if
were ideal. were ideal.
 Positive deviating Negative deviating
solution solution
Vapour
of
Vapour pressure of
pressure
solution o
PA solution
o
PA

o
P
B PA
PB
PA

𝛘A = Mole 𝛘A = 𝛘A = Mole 𝛘A =
fraction fraction
𝛘B =
1
𝛘B = 𝛘B = 𝛘B =
0 1 0

0 V.P B.P 1 0 V.P B.P 1

. . . .
B.P. of both
B.P. of
solution
< A and B B.P. of
solution
> B.P. of both A
and B
Positive deviating Negative deviating
solution solution

Chloroform and Acetone

Water and
Ethanol
Chloroform and Methyl
Chloroform and
Water
acetate H 2O and HCI

Ethanol and CCI4 H 2O and HNO 3

Acetic acid and

Methanol and
Chloroform
P yridine Phenol and
 Comparing Ideal & Non-Ideal
Solutions
Non-ideal solutions
Ideal solutions
Positive deviation Negative deviation

P = 𝓧 P + 𝓧o >o 𝓧 P + 𝓧 < o𝓧 P + 𝓧
o o o
P P
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

Very large deviations from constant temperature and can be
ideality lead to a special class of distilled without any change in the
mixtures known as azeotropes, composition.
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 Azeotropes are of two types:
because the condensate has the
same composition as that of 1. Maximum boiling
the azeotropic liquid. azeotropes
2. Minimum boiling
 Minimum Boiling Minimum Boiling
Azeotropes Azeotropes
Non-ideal solutions showing large Non-ideal solutions showing large
positive deviation from Raoult's law, negative deviation from Raoult's
form minimum boiling azeotropes that law,
boil form maximum boiling azeotropes that
at a temperature lower than the boil at a temperature higher than the
boiling points of its components 'A' boiling points of its components 'A'
and 'B'. and 'B'.

Ethanol - water mixture A mixture of HNO 3 and H 2O containing

containing
≈68% HNO 3 and 32% water by mass
≈ 95% by volume of ethanol

Chloroform - methanol mixture Formic acid - water mixture

containing 87.4% chloroform containing 77.6% formic acid and
and 12.6% methanol by weight 22.4% water by mass.
 Minimum Boiling Maximum Boiling
Azeotropes Azeotropes
Constant Constant
pressure P = Pressure P =
Vapour 101.325 kPa
101.325 kPa composition
Vapour only (Dew point curve)

Temperature
Temperature

C Azeotro
ph oex
Vapour nt
e pe
as ist compositi ist
es en
on (Dew oex ses
t C a
point ph Liquid
Liquid

[K]
composition
[K]

curve)
compositi (Bubble point
on curve)
(Bubble Liquid
point only Azeotro
0 curve) Mole fraction of pe 1 1
Pur Pure 0 Pur Mole fraction of formic Pure
chloroform
methan
e chlorofor wate
e acid formi
ol m r c
acid
 Minimum Boiling Maximum Boiling
Azeotropes Azeotropes
Constant Temperature Azeotrope
Constant
T = 298.15 K Temperature
Liquid Liquid only T = 298.15 K
composition
(Bubble
point Liquid

Pressure
curve)
Pressure

composition
t n
e s te

(Bubble point
a s xis

[kPa]
[kPa]

p h oe

t
curve)

n
C

es ste
a

as xi
Azeotrope

ph oe
p

C
o
u Vapour
r composition
0 Mole fraction of (Dew point curve) 1
o 0 Mole fraction of formic Pur
Pure chloroform Pure
methan n chlorofor
wate acid formic
e
Pure
l r acid
ol m
y
 Immiscible
Liquids

A mixture of two immiscible liquids B.P. of a solution of two

will boil when the total vapour immiscible liquids is less than
pressure the individual B.P. of both the
is equal to the external liquids.
pressure.

The boiling point of the mixture is This concept is

thus, used in steam
lower than that of either distillation.
constituent.
B.P. of
water = 100oC
B.P. of water
(pure) and benzene = 68.9oC
B.P. of mixture
benzene = 80.2oC
(pure)
 Distillatio
n

In a simple distillation, the vapour

over a boiling mixture is Condensate Residue
withdrawn and condensed in a
separate container.
Higher mole Higher mole
fraction of the fraction of the less
The collected liquid is called m ore volatile volatile component
condensate or distillate and component than in than in the initial
the remaining liquid is called the initial liquid liquid mixture.
residue. mixture.

This is the principle of

distillation and is used to
separate a m ore volatile
liquid from a less volatile
liquid.
 Steam
Distillation

A liquid (generally organic)

that is immiscible
with water, and has a higher
B.P. than water
can be boiled (distilled) at a
much lower
temperature by passing
steam through it.

Organic liquid can be

purified from impurities
using steam distillation.
 Dissolution &
Crystallisation

Dissolutio Crystallisati
n on
When a solid solute is added to Some solute particles in the
the solvent, some solute solution collide with the
dissolve and its concentration other solid solute particles
increases in the solution. and get separated out of
the solution.

At
equilibrium

Rate of = Rate of
crystallisation
dissolution
Solute + Solution
Solvent
 Equilibriu
m

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 Aff ecting Solubility of Solid in
Liquid

Nature
of Temperatu Pressur
solvent re e
&
solute
 1. Nature of Solvent &
Solute

Like dissolves like Sodium chloride dissolves readily

in water, whereas naphthalene
and anthracene do not.
Polar solutes dissolve in
polar solvents and non-
polar solute dissolve in
non-polar solvents. Naphthalene and
anthracene dissolve
readily in benzene but
sodium chloride do not.
 2. Eff ect of Temperature on
Solubility

Solute + Solution
Solvent

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

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

T Solubility T Solubility
3. Eff ect of Pressure on
Solubility

Pressure does not have any

significant effect on solubility of
solids in liquids.

Solids and liquids are highly

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

The properties of the solution that Relative lowering

are dependent only on the total of vapour
number of solute particles pressure
relative to solvent/solution
Elevation in boiling
point
Colligativ
e Depression
Propertie in freezing
They are not dependent on
s point
the nature of particle i.e.,
shape, size, charge, etc.
Osmotic
pressure
 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
diff erent from the theoretically predicted the number of particles
value. actually added due to
dissociation or
association of the solute.

NaCl (s) + Na + (aq) + Cl‒

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

The actual extent

Observed colligative
of dissociation/
association can
i = property
Calculated colligative
be expressed with property
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)

Dissociati
on
>1

i = No
1 dissociation/
association

<1

Associatio
n
 i for Dissociation of
Electrolyte
Ax By xAy+ +
(aq)
t= 0 x–
yB
0 C 0

C(1 - 𝜶)
𝜶
t= yC
teq xC𝜶

Net
= C – C𝜶 + xC𝜶
+ yC𝜶

1)𝜶]
concentration = C[1+(x+y-

1)𝜶]
= C[1+(n-
i for Dissociation of
Electrolyte

𝜶]
C[1+(n-1)
i = C

=
1)𝜶
i 1+(n-

“𝜶” is degree of
dissociation

NaCl (100% i = 2
ionised) 1

BaCl2 (100% ionised) i = 3

 i for Association of
Electrolyte
nA An

t= C 0
0 If n= 2 Dimerization

𝜷
C =3 Trimerization
- 𝜷)
t= eq
C(1 =4
t Tetramerization
n
At equilibrium,

𝜷
Net C
concentratio = C – C𝜷
n + n

1
= C 1
+
-
1
�
�
n
 Example
s

C - 𝜷
1 1
i = + 1
C
n

1
i = 1 - �
�
+ 1
n
Dimerisation of CH 3COOH
in benzene (100 %) i = 01
i .5
Dimerisation of C6H 5COOH
in benzene (100 %)
i = 0.
5
 1. Relative lowering
of the vapour
pressure

2. Elevation in
the boiling
Colligativ point
e
Propertie
s 3. Depression in
the 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.

P P2 P P2
1 1

Pure P1 = Pure
Solution P1 <
(non-volatile Pure
solvent
P2 solvent
solute in solvent
P2 solvent
A A A
 Relative Lowering of Vapour Pressure
(RLVP)

Reason of Some of the solute

Lowering of molecules will occupy
V.P. some surface area of the
solution.

Tendency of the solvent

particles to go into the vapour
phase slightly decreases.

Hence, P o > P , where

S olvent S
is V.P.
P o of the pure solvent
Solution and P S is the V.P. of the
solution.
 Relative Lowering of Vapour
Pressure

Lowering in = Po - PS ΔP
V.P.
=
Relative lowering Po - PS
ΔP
in vapour = Po = �solute
�
=
pressure (RLVP) Po
n
=
n+N
n = Number of moles of non-volatile solute Relative lowering
N = Number of moles of solvent in the of the vapour
solution pressure is a
colligative
property, whereas,
lowering in the
vapour pressure is
not.
Relative Lowering of Vapour
Pressure

Raoult’s Law (For

non–volatile
solutes)

The vapour pressure of a solution of a

non-volatile solute is equal to the
vapour pressure of the pure solvent at
that
temperature multiplied by its m ole
fraction.

( 1 - 𝓧solute)
= 𝓧solvent =
PS
Po
Po
 Relative Lowering of Vapour
Pressure

Po n+ N
Po - PS = N = 1 n
n +

N PS
n = Po
P - PS
o
—
1
= Po ‒ P S

Po ‒ PS n M solvent w = Weight of species

PS
= N = wsolute x w
solvent M = Molar mass of
M solute species
 Relative Lowering of Vapour
Pressure
Po - PS wsolute 1000
= x w x Msolvent
PS M solute solvent 1000

Msolvent
P - PS
o
Molality x
PS
= 1000

If solute gets associated or

dissociated

Po - PS
PS
= ixn = i x Molality
Msolvent
1000
N x
 Ostwald-Walker
Method
When dry air is passed through a volatile
liquid, there occurs a loss of weight of
liquid which is directly proportional to its
vapour pressure.

Greater is the volatility of liquid,

greater will be the loss of weight of
liquid
dry
air

Solutio Solve
n nt Anhydrous CaCl2(dehydrating
 Ostwald-Walker
Method
Step 1
Loss of weight of
Initially, note down the ∝ PS
1 solution
weights of the solution set, containers
solvent set Containers & of
dehydrating agent.
Loss of weight of
solvent ∝ Po - PS
Step 2 containers
2 Note down the same weights
after
the experiment is complete. Gain in weight of
∝ P0
dehydrating
agent

Po - PS Loss in weight of
PS
= solvent Loss in weight
of solution
 Elevation in Boiling
Point
Atmospheri Atmospheri
When a non-volatile
c c
solute is added into a
pressure pressure
volatile liquid to form
solution, V.P. decreases.
Lower
vapour
pressure
Solution needs to be
heated to a higher
temperature to boil it, so
that V.P. becomes equal
to external pressure. Pure Solution
solven (with solute)
t
 Elevation in Boiling
Point
Hence, to make the V.P.
T = b.p. of solution
equal b
Tbo(K)
= b.p. of pure solvent
Hence,
wteo ext
hPto
av,e
mwttoaeokha
Paeve
etxht e V.P.
t , (K)
solution by aggrereaateter
equal
tthoehseoaltutho i en
ramount in
1
caommopuanrist oinn atm
n
cto mpupraerissoolnvetnot. pure l ve
So
V.P. of <
solvent.V.P. of pure t
lutio
solution solvent So
n

pressure
= T -T

Vapour
ΔTb o
ΔTb
b
b
ΔTb ∝ m

T bo
Tb
m Temperature
= (K)
 Elevation in Boiling
Point
ΔTb = Kb m

K b = B.P. elevation constant RT o 2

M
b
or, Molal elevation constant Kb = 1000 x ΔH vap
or, Ebullioscopic constant

Kb
● Tb ° is B.P. of pure solvent (K)
It is equal to elevation in ● M is the molar mass of solvent in
boiling point of 1 molal g/mol
solution. ● ΔH vap is the molar enthalpy of
K/m or vapourisation of the solvent (J/mol)
Unit
°C/m or K ● R = 8.314 J/mol-K
s
kg mol–1
 Ebullioscopic Constant
(Kb)

ΔHvap For
Lvap = M water,
● L = 2257.2
vap
J/g
b
● T o = 373 K

o2
RT b 8.314 x
Kb = 1000 x Lvap Kb = (373)2 K kg mol-
1000 x 1

2257.2

● Lvap is the latent heat of vaporisation (J/g) = 0.52 K kg mol-

1
 Not
e
If solute gets
1 associated/dissociated then
ΔTb = i × K b × Molality

2 Kb is the property of
solvent

Elevation in B.P. is proportional

3 to the lowering of vapour
pressure.

ΔT b ∝ Δ
P
 Understanding Elevation of B.P.
Using ΔS

ΔSvap, solvent > ΔSvap, solution Svapou

r ΔS vap,
solution
ΔS vap, solvent
ΔHvap
Since,
ΔSvap = Tb
Ssolution (More randomness
than solvent)

Ssolven
t
ΔHvap,
ΔHvap,
> solution
solvent
Tb, Tb,
solvent solution
As only solvent particles are going into
vapours,

ΔH vap, solvent = ΔH vap, solution ⇒ Tb, solvent < Tb, solution

 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.

V.P. of = V.P. of
solid liquid
 Depression in Freezing
Point

When a non-volatile solute is

dissolved in the solvent, the V.P.
of the solvent in the solution Liquid
decreases.
Solid r e nt
u e

Pressure
1 atm P olv
s
t io
l u
S o
V.P. of solid and liquid solvent
n
will become equal at a
ΔTf Gas
lower
temperature, i.e., F.P. of
solution is Temperature
lower than that of a pure (K)
solvent.
 Depression in Freezing
Point
ΔTf
ΔTf = T -T
f
o

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

ΔTf = Kf m

Kf is equal to the depression m = Molality

freezing
in point of 1 molal
solution.
Kf = F.P. depression constant or
molal depression constant or
cryoscopic constant.
 Cryoscopic Constant
(Kf)

RTf ΔH fus
Kf = o 2M
1000 x fus
Lfus = M
ΔH

K/m or
Unit RTfo 2
°C/m or K
s
kg mol–1
Kf = 1000 x Lfus

o
● Tf is F.P. of pure solvent (K)
● M is the molar mass of solvent in ● Lfus is latent heat of
g/mol fusion (J/g or cal/g)
● ΔH fus is the molar
enthalpy of fusion of the
solvent (J/mol)
●
 Kf of
Water
For
water
● L
fus
= 334.72
J/g
o

● Tf = 273 K

8.314 x
Kf = (273)2
1000 x
K kg mol-
1

334.72

= 1.86 K kg
mol-1
 Not
e

Depression in freezing point

1 is proportional to the
lowering of vapour pressure
i.e. ΔTf ∝ ΔP At freezing point or below it,
3 only solvent molecules
will freeze & not solute
molecules.

2 If solute gets
associated/dissociated then
ΔTf = i × K f × Molality
 Understanding Depression in F.P.
Using ΔS

Ssolution (More
randomness,
Ssolven more entropy)
t
ΔSfus, ΔSfus,
solvent solution

Ssoli
d

ΔSfus, solution > ΔSfus, solvent

ΔH fus
ΔSfus = Tf
Understanding Depression in F.P.
Using ΔS

ΔH fus, solvent
< ΔH fus, solution

Tf, solvent Tf,

solution

As only solvent particles

freeze,

ΔH fus, solvent = ΔH fus, solution

⇒ Tf, solvent > Tf, solution

 Osmosi
s

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-perm eable
m embrane (SPM).

Solutio Solven
n t

SP
M
 Semi-permeable Membrane
(SPM)

Animal/plant cell
Natural
m embrane formed
A membrane just below the outer
that allows only skins.
SP
solvent
M Cu2[Fe(CN)6] & Silicate of
particles to
move across it. Ni, Fe, Co can act as
Artificial
SPM.
 Example of
Osmosis

P eople taking a lot of salt,

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

P ext

The external pressure

that must be applied Solutio Solven
on the n t
solution side
to just stop
the process C1 SP
of osmosis. M

P ext
= �
�
 van’t – Hoff
Formula

� ∝ Concentratio
n (Molarity)
� = CS
� � T

∝ ● 𝚷 = Osmotic pressure
� T
● C = Concentration (mol/L)
�
● S = Ideal solution
constant
● T = Temperature (K)
 van’t – Hoff
Formula

S Ideal
solution � = CRT
constant �

S = 8.314 J mol–1 K–1

n
� =
� V
R (Ideal RT
S = gas
constant)
 Osmotic Pressure
(𝚷)
P ext

If two solutions of concentrations C1 &

C2 are kept separated by SPM, and C 1
> C 2, then the solvent particles
m ovement take place from lower
to higher concentration. Solution Solution
1 2

So, an extra pressure is applied on C1 SP C2

the higher concentration side to M
C1 > 2
stop osmosis. C

= 𝚷1
– 𝚷2
P ext
 Osmotic Pressure
(𝚷)

Osmotic pressure of very

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

If the pressure applied on the

solution side is m ore than the
osmotic pressure of the solution, Used in
then the solvent particles will move desalinatio
from solution to solvent side. n of sea-
water

P ext > �
�
 Based on the
difference in osmotic
pressure, the
solutions can be
classified as:

1 Isotonic
solution

2 Hypotonic
solution

3 Hypertonic
solution
 Isotonic
Solution

Two solutions Solution Solution

having same 1 2
osmotic
pressure are
considered as C1 SP C2
isotonic solution. M

𝚷 = 𝚷
1 2
 Hypotonic & Hypertonic
Solutions

Hypotonic
If two solutions
‘1’ and ‘2’ are such
that
𝚷 2 > 𝚷 1 , then Solution Solution
1 2 Hypertonic
‘2’ is called
hypertonic
solution and ‘1’
is called C1 SP C2
hypotonic M
solution.
Pressure is applied on the
hypertonic solution to
stop the flow of solvent
particles.
 Types of
Solutions

Hypotoni Isotonic Hypertoni

c c
Solution Solution Solution

Net water No net Net water

gain Cell loss or loss Cell
Swells gain Shrinks
 Plasmolys
is

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.
 Applications of Osmotic
pressure

a Determination of
W idely used to determine
m olecular mass of
. m olar masses of proteins and
the solute.
other biomolecules, as they are
generally not stable at higher
wRT temperatures
𝚷
M solute

= V

● w is mass of solute This method has the advantage

𝚷 is osmotic pressure of
● V is volume of the solution over other methods as pressure
● measurement is around the room
the solution temperature.
● T is temperature
● R is universal gas constant
 Not
e

If solute gets associated or dissociated

then theoretical molar mass of solute
will be diff erent from experimentally
calculated molar mass.

Theoretical molar mass of

i = substance
Experimental molar mass of the
substance
b Desalination of
. water by reverse
osmosis

Pex
t

Sea water Pure water

SP
M

P ext > �
�
c Dialysi
. s

Artificial kidney removes

waste products from blood
through osmosis.
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