By Chetan Upadhyay

(19/2277)
 Colligative Properties
In chemistry, colligative properties are those properties of solutions that depend on the
ratio of the number of solute particles to the number of solvent molecules in a solution, and
not on the nature of the chemical species present. The number ratio can be related to the
various units for concentration of solutions, for example, molarity, molality, normality, etc.

Types of Colligative Properties

Colligative Properties are of four types, which are as follows :
1. Relative Lowering of Vapour Pressure
2. Elevation of Boiling Point
3. Depression of Freezing Point
4. Osmosis and Osmotic Pressure
Relative Lowering of Vapour Pressure
When a non-volatile solute is added to a volatile liquid solvent, the vapour pressure of resulting
solution is found to be lower than that of solvent. This decrease in vapour pressure is known as
relative lowering of vapour pressure.

According to Raoult’s law,

p1 ∝ χ 1
p1 = P1°*χ1

where, χ1 = mole fraction of solvent

χ2= mole fraction of solute
p1 = partial vapour pressure of solution or solvent in solution
P1°= vapour pressure of pure solvent
So, psolution = P1°*χ1
psolution/P1° = χ1
1 - psolution/P1° = 1 - χ1
(P1°-psolution)/P1° = X2 = nsolute/(nsolute+nsolvent)

For dilute solutions nsolute+nsolvent ≈ nsolvent

So, (Psolvent°-psolution)/Psolvent° = nsolute/nsolvent
.. . (Psolvent°-psolution)/Psolvent° = (msolute*Msolvent)/(Msolute*msolvent)
 Problem Related to Relative Lowering
of Vapour Pressure
Problem: Calculate the lowering of vapour pressure & vapour pressure of solution containing 50 g
dextrose (mol wt 180) in 1000 g water (mol wt 18). The vapour pressure of water = 17.535
Mm of Hg.
Solution: nA(no. of moles of solvent) = 1000/18 = 55.5 moles
nB(no. Of moles of solute) = 50/180 = 0.278 moles

So, mole fraction of dextrose (χB) = nB/(nA+nB)

= 0.278/(55.5+0.278)
= 0.00498
Hence, vapour pressure lowering,
PA. - pA = χB *PA.
= 0.00498 * 17.535
= 0.0873 mm of Hg
So, vapour pressure of solution,
PA = 17.535 * 0.0873
= 17.448 mm of Hg
Elevation of Boiling Point
When a non-volatile solute is added to a volatile liquid solvent, the boiling point of the resulting
solution is higher than that of the boiling point of pure solvent. This increase in boiling point is
known as elevation of boiling point.

Let Tb° = boiling point of pure solvent

Tb = boiling point of solution
So, elevation of boiling point = Tb-Tb°
Now, for dilute solutions,
ΔTb ∝ m (molality)
ΔTb = Kb*m
Kb = Boiling point elevation constant or molal elevation constant or EBULLIOSCOPIC
constant. The unit of Kb is K kg mol-1. Kb value is for pure solvent, not for solution.
Definition of Kb:- It is defined as elevation of boiling point of one molal solution containing non-volatile solute.

Now, ΔTb = Kb * nsolute/msolvent(in kg)

Tb-Tb° = Kb * [msolute(in g)*1000]/[Msolute(in g mol-1)*msolvent(in
g)]

Also, Kb = (R*Msolvent*Tb.2)/(1000*ΔvapH.)
 Application of Elevation of Boiling Point

1. Antifreeze

2. Cooking

3. Measurement of Molar Mass

4. Sugar Refining
Depression of Freezing Point
Freezing Point :- It is defined as the temperature at which the vapour pressure of the
substance in its liquid phase is equal to its vapour pressure in the solid
phase.

When a non-volatile solute is added to a volatile liquid solvent, the freezing point of the
resulting solution is found to be lower than that of pure solvent. This decrease in freezing
point is known as depression of freezing point.

Let Tf. = freezing point of pure solvent

Tf = freezing point of solution
So, depression of freezing point = Tf.-Tf
Now, for dilute solutions,
ΔTf ∝ m (molality)
ΔTf = Kf*m
Kf = Freezing point depression constant or molal depression constant or CRYOSCOPIC constant. The unit of Kf is
K kg mol-1. Kf value is for pure solvent, not for solution.

Definition of Kf:- It is defined as depression of freezing point of one molal solution containing non-volatile solute.

Now, ΔTf = Kf * nsolute/msolvent(in kg)

Tf.-Tf = Kf * [msolute(in g)*1000]/[Msolute(in g mol -1)*msolvent(in
g)]

Also, Kf = (R*Msolvent*Tf.2)/(1000*ΔfusH.)
Application of Depression of Freezing
Point
Freezing point depression has interesting and useful
applications. When salt is put on an icy road, the salt
mixes with a small amount of liquid water to prevent
melting ice from re-freezing. If we mix salt and ice in a
bowl or bag, the same process makes the ice colder,
which means it can be used for making ice cream.

Freezing point depression also explains why vodka

doesn't freeze in a freezer.
Osmosis and Osmotic Pressure
Semipermeable Membrane:- The membrane which is permeable only to selected liquid
molecules is known as semipermeable membrane.
For example:- Pig’s bladder, cellophane sheet, parchment papers, cupric ferrocyanide etc.

Osmosis:- The flow of solvent molecules from pure solvent to the solution through
semipermeable membrane is known as osmosis.

Osmotic Pressure:- The extra pressure applied on solution side to just stop the flow of solvent is
called osmotic pressure. It is denoted by π.

Now, π ∝ C (molarity)
π ∝ T (kelvin)
So, π ∝ CT
Thus, π = CRT
where, R = Universal Gas Constant
Now, π = (n*R*T)/Vsolution (in L)
π = [msolute(in g)*1000*R*T]/[Msolute(in g mol-1)*Vsolution(in
ml)]
Isotonic Solutions:- Two solutions having same
osmotic pressure at a given temperature are
called isotonic solutions. When isotonic solution
are separated by semipermeable membrane,
then no osmosis occurs.

Hypertonic Solutions:- A hypertonic solution is a

particular type of solution that has a greater
concentration of solutes on the outside of a cell
when compared with the inside of a cell.

Hypotonic Solutions:- A hypotonic solution is a

particular type of solution that has a greater
concentration of solutes on the inside of a cell
when compared with the outside of a cell.
 Application of Osmosis and Osmotic
Pressure
1. A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle.

2. Wilted flowers revive when placed in fresh water.

3. Edema:-People taking a lot of salty food experience water retention in tissue cells and
intercellular spaces because of osmosis. The resulting swelling is called edema.

4. A carrot that has become limp because of water loss into the atmosphere can be placed into the
water making it firm again, water will move into them through osmosis.

5. Water movements from soil into plant roots and subsequently into upper portion of the plant is
partly due to osmosis.

6. The preservation of meat by salting and of fruits by adding sugar protects against bacterial
action, due to osmosis, a bacterium on salted meat or candid fruit loses water, shrivels and dies.
 Abnormal Molar Mass
The accurate value of molar mass can be obtained only if the solution follows two conditions:
1. It should be dilute.
2. The solute must not dissociate or associate in the solution.

In case of electrolytic solutions, the molar mass determined by any of colligative property
method does not agree with the theoretical or expected value of molar mass. Such a molar
mass that is either lower or higher than the expected or normal value is called as abnormal
molar mass.

In case of dissociation of solute molar mass obtained will be less than the true value of molar
mass.
In case of association, it would be higher than the true value.

The abnormality of molar mass can be explained in term of a factor called van’t Hoff factor (i).

i is defined as the ratio of observed value of the colligative property to the calculated value of
colligative property.
So, i = observed colligative property/calculated colligative property
Also, i = normal molar mass/ abnormal molar mass

In case of association of solute, i < 1

In case of dissociation of solute, i > 1
In case of non-electrolyte, i = 1

Thus, modification in colligative property equations:

1. (Psolvent°-psolution)/Psolvent. = i * χsolute

2. ΔTb = i * Kb * m

3. ΔTf = i * Kf * m

4. π = i * C * R

Degree of Dissociation or Ionisation (α):- It is defined as fraction of total substance that undergoes
dissociation.
An → nA
Degree of association:- It is defined as fraction of total substance that undergoes dissociation.
nA ⇌ An
 Relation between i and α
1. Dissociation:- a) For strong electrolytes (like KCl, K2SO4 etc.) An → nA, where n is the no. of
particles after dissociation of one particle.
For example:- KCl → K+ + Cl- , n=2
+ 2-
K2SO4 → 2K + SO4 , n=3
Here, i = n
b) For weak electrolytes (like CH3COOH) An ⇌ nA, where n is the no. of particles after
dissociation.
For example:- CH3COOH ⇌ CH3COO- + H+ , n=2
Here, α = (i - 1)/(n -1)

2. Association:- a) For strong electrolytes nA ⇌ An, where n is the no. of molecules undergoing
association.
For example:- 2CH3COOH ⇌ (CH3COOH)2 , n=2
Here, i = 1/n
b) For weak electrolytes An ⇌ nA, where n is the no. of molecules undergoing association.
Here, α = (i -1)/[(1/n) - 1]

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