COLLIGATIVE PROPERTIES OF SOLUTIONS

The colligative property that we refer here, depends only on the number of
particles in the solution and not in any way on the nature of these particles. The
solutions that are involved here are specified to contain non – volatile solutes.

I. The Vapor Lowering of the Solvent

It is noted that, in a solution, the dissolved solute lowers the vapor pressure
of the liquid solvent in which it is dissolved.
Let N1 = mole fraction of the solvent
N2 = mole fraction of the non-volatile solute
Po = vapor pressure of the pure solvent
P = total vapor pressure above the solution

∆P = vapor pressure lowering = Po – P → (1)

According to Raoult’s Law,
P = Po N1 → (2)
Substitute (2) in (1):
∆P = Po – P = Po - Po N1 = Po (1 - N1) = Po N2 → (3)
In words, the vapor pressure lowering of the solvent is directly proportional to its
vapor pressure and the mol fraction of solute in solution.

To solve for the relative vapor pressure, just get the ratio of
∆P / Po = N2 = n2 / (n1 + n2) = (w2÷M2)/ [(w1÷M1) +(w2÷M2)]

For a very ideal solution, (w2÷M2) is very small compared to (w1÷M1), so

∆P / Po = N2 = (w2÷M2)/ (w1÷M1)
∆P = Po[(w2M1)/(w1M2)]

II. Boiling Point Elevation

 It is noted that the solutions containing non-volatile solutes boil at
temperature higher than the boiling point of the pure solvent
∆Tb = T - To
where: T = boiling point of the solution
To = boiling point of the pure solvent
Using the Clausius Clapeyron Equation
ln (Po/P) = ∆Hv (T - To) ÷ R TTo
But when solution is dilute, T is not much different from TT o
TTo = To2 and ∆Hv = heat of vaporization/mole of the pure solvent
-ln (P/Po) = (∆Hv ∆Tb) ÷ (R To2)
But from Raoult’s Law:
P/Po = N1 = 1 – N2 ln (1 – N2) = -(∆Hv ∆Tb) ÷ (R To2)
if we expand term ln (1 – N2) in series, it will equal to
ln (1 – N2) = - N2 - N22/2 - N23/2 …. = - N2
But for dilute solution, N2 is small, all terms beyond the first can be considered
negligible
- N2 = -(∆Hv ∆Tb) ÷ (R To2)
∆Tb = [(R To2)/ ∆Hv] × N2 but N2 = n2/ (n2 + n1)
Basis: 1 kg of solvent
m = n2 /W1 = moles of solute/kg of solvent = molality
N2 = m/ (m + n1)
where: m = moles of solute
n1 = weight of solvent/ molecular weight of solvent
N2 = m/ (m + n1) = m/[(m) + (1000/18)]
For dilute solution, m is negligible compared to n1
N2 = m/ (m + n1) = m/n1
∆Tb = [(R To2)/ (∆Hv) (n1)] x m
But [(R To2)/ (∆Hv) (n1)] = Kb = molal boiling point elevation constant
or ebullioscopic constant
Since m = (w2÷M2)/ (w1÷ 1000) = (w2÷M2)/ (w1÷ 1000) = (w2 x1000) ÷ (w1 M2)
Therefore: ∆Tb = Kb x m = Kb [(w2 x 1000) ÷ (w1 M2)]
 III. Freezing Point Lowering
When a dilute solution is cooled, a temperature is reached at which solid
solvent begins to separate from solution, the temperature at which this
separation begins is the freezing point lowering of the solution.
Freezing point of the solution is the temperature at which a particular
solution is in equilibrium with a solid solvent. A solution freezes at lower
temperature than the pure solvent.
∆Tf = To – T
where: ∆Tf = freezing point lowering
T = freezing point of the solution
To = freezing point of the pure solvent
A similar derivation using the Clapeyron equation leads to the equation
∆Tf = [(R T o 2)/ ∆Hf] × N2
= [(R T o 2)/ (∆Hf) (n1)] x m
But [(R T o 2)/ (∆Hf) (n1)] = Kf
∆Tf = Kf x m
Where: Kf = molal freezing point elevation constant or cryoscopic constant
∆Hf =heat of fusion / mole of the pure solvent
m = molality
∆Tf = Kf x m = Kf [(w2 x 1000) ÷ (w1 M2),

IV. Osmotic Pressure

Osmosis is a diffusion process which proceeds through a semi-permeable
membrane that permits the passage of water but not of dissolved solute, typically
separating two solutions, or a solvent and a solution and tending to equalize their
concentrations.
Osmotic pressure is a mechanical pressure which must be applied in a
solution to prevent osmosis of the solvent into the solution through a semi –
permeable membrane.
 For dilute solutions obeying Raoult’s Law, the osmotic pressure is derived
using the ideal gas law
PV = nRT, ∏ = (n/V) RT = CRT
where: ∏ = osmotic pressure
C = concentration

Sample Problem 4
An aqueous solution freeze at -1.50℃. Calculate (a) the normal boiling
point, (b) the vapor pressure at 25℃, and (c) the osmotic pressure at 25℃ of the
given solution.

Given: Tf=-1.50℃ (aqueous solution)

For H2O: Tf= 0℃ ; Tbo= 700℃
°
𝑃25° 𝐶 = 23.756mmHg

Required: a) normal boiling point

b) v.p. at 25℃
c) osmotic pressure

Solution:
∆𝑇𝑓 = Kfm; To- Tf = 0 – (-1.5) = 1.5; Kf = 1.86
1.5 𝑚𝑜𝑙𝑒𝑠 𝑠𝑜𝑙𝑢𝑡𝑒
m= = 0.81
1.86 𝑘𝑔.𝑠𝑜𝑙𝑣𝑒𝑛𝑡
a) ∆𝑇𝑏 = Kbm
Tb - Tbo = Tb – 100 = 0.51 (0.81)
Tb = 100.41℃

b) ∆𝑃= Po N2
0.81
Po – P = N2; N2= 1000 = 0.014
0.81+ 18

23.756 – P= 23.756(0.014)
P= 23.42mmHg
 c) ∏= CRT
*for dilute solution, neglect volume of solute
Volume of solution≈ volume of solvent
𝑐𝑚3 𝐿𝑖
=1000g H2O (1 )( )
𝑔 1000𝑐𝑚3
𝑚𝑜𝑙𝑒
∴m = M ( )
𝐿𝑖
∏= 0.81 (0.08205) (298) = 19.81atm

RELATION OF OSMOTIC PRESSURE TO VAPOR PRESSURE

Free energy of the pure solvent = free energy of the solvent in the solution + ∆G
G1o = Ḡ1 + ∆G; Ḡ1 - G1o = -∆G
but Ḡ1 - G1o = RT lna1 = RT ln (P1 / P1o)
When the vapor phase behaves ideally
-∆G = RT ln (P1 / P1o) → (1)
But dḠ1/dP = V1; dḠ1 = V1 dP
where: V1 = partial molal volume of the solvent
in the solution
If we integrate the equation between limits: Ḡ1 = Ḡ1 @ P = 1 atm, and
Ḡ1 = Ḡ1’ @ P = P
Ḡ1’ P P
∫Ḡ1 dḠ1 = [∫1 𝑉1 𝑑𝑃] ; Ḡ1’ - Ḡ1 = [∫1 𝑉1 𝑑𝑃] → (2)

Taking V1 to be independent of pressure, equation (2) becomes

∆G = V1(P – 1) = V1∏ → (3)

where: ∏ = (P – 1) = is the pressure applied to stop osmosis
= osmotic pressure
Substitute (3) in (1)
V1∏= RT ln (P1o / P1); ∏ = [ RT ln (P1o / P1)] ÷ V1 → (4)
Equation (4) shows the relation between osmotic pressure and vapor
pressure lowering.
When the solutions involved are not too concentrated, V1 may be taken to
be identical with V1o, the molar volume of the solvent, equation (4) becomes
 ∏ = [ RT ln (P1o / P1)] ÷ V1o → (5)

NERNST DISTRIBUTION LAW

Walter Nernst (1891) studied the distribution of several solutes between

different appropriate pairs of solvents. He gave a generalization which governs
the distribution of a solute between two non – miscible solvents. This is called
Nernst’s Distribution Law (or Nernst’s Partition Law) or simply Distribution Law or
Partition Law.

This law is applied to determine the distribution of solute between two

immiscible or slightly miscible solvents. To show this, consider a pair of immiscible
solvents in contact A and B, both containing the same substance in solution.

Let ḠA = partial molal free energy of the solute in liquid A

ḠB = partial molal free energy of the solute in liquid B

But ḠA = ḠAo + RT lnaA; ḠB = GBo + RT lnaB

where:
GAo = standard free energy of solute in liquid A
GBo = standard free energy of solute in liquid B
aA = activity of the solute in solvent A
aB = activity of the solute in solvent A
ḠA = ḠB
ḠAo + RT lnaA = ḠBo + RT lnaB
ln (aB / aA) = (ḠAo - ḠBo)/RT

At any given temperature, ḠAo and ḠBo are constants for a given substance
in particular solvents, ln (aB / aA) = k and,
therefore,
aB / aA = k → (1)
 Equation (1) is a mathematical statement of the Nernst Distribution Law
which states that a substance will distribute itself between two solvents until at
equilibrium. The ratio of the activities of the substances in two layers is constant
at any given temperature.

When the solutions are dilute, or when the solute behaves ideally, the activity is
essentially equal to the concentration, C, equation (1) reduces to

CB / CA = k → (2)

where k = distribution or partition coefficient of the solute between two solvents

Example: A solid X is added to a mixture of benzene and water. After shaking well
and allowing to stand, 10 ml of the benzene layer was found to contain 0.13 g of X
and 100 ml of water layer contained 0.22 g of X. Calculate the value of
distribution coefficient.

Solution:
0.13 𝑔
Concentration of X in Benzene (Cb) = = 0.013
10 𝑚𝑙
0.22 𝑔
Concentration of X in Water (Cw) = = 0.002 = 0.002
100 𝑚𝑙
According to the Distribution Law:
k = Cb / Cw = 0.013/0.002 = 5.9

SOLUBILITIES AND DISTRIBUTION LAW

When a solute is shaken with two non – miscible solvents, at equilibrium

both the solvents are saturated with the solute. Since the solubility also
represents concentration, we can write the distribution law as
C1 / C2 = S1 / S2 = kD
where: S1 and S2 are the solubilities of the solute in the two solvents
Hence, knowing the value of the distribution coefficient (k D) and the solubility of
solute in one of the solvents, the solubility in the second solute in the second
solvent can be calculated.
Sample Problem 5:
At 25oC, an aqueous solution of iodine containing 0.0516 g/L is in equilibrium with
a carbon tetrachloride (CCl4) solution containing 4.412 g/L. The solubility of iodine
in water at 25oC is 0.34 g/L. Find the solubility of iodine in carbon tetrachloride.

Solution:
a. To find the value of kD
Concentration of I2 in water (Cw) = 0.0516 g/L
Concentration of I2 in CCl4 (C ct) = 0.0516 g/L
The value of distribution coefficient is k = Cct / Cw = 4.412/0.0516 = 85.5

b. Calculation of solubility
Applying Distribution Law,
𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐼𝑜𝑑𝑖𝑛𝑒 𝑖𝑛 𝐶𝐶𝑙4
= 85.5
𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐼𝑜𝑑𝑖𝑛𝑒 𝑖𝑛 𝐻2 𝑂
𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐼𝑜𝑑𝑖𝑛𝑒 𝑖𝑛 𝐶𝐶𝑙4
= 85.5
0.34
𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝐼𝑜𝑑𝑖𝑛𝑒 𝑖𝑛 𝐶𝐶𝑙4 = 85.5 𝑥 0.34 = 29.07 𝑔/𝐿

LIMITATIONS OF DISTRIBUTION LAW

The conditions to be satisfied for the application of the Nernst’s Distribution law
are
1. Constant Temperature. The temperature is kept constant throughout
the experiment.
2. Same Molecular State. The molecular state of the solute is the same in
the two solvents. The law does not hold if there is association or
dissociation of the solute in one of the solvents.
3. Equilibrium Concentration. The concentrations of the solute are noted
after the equilibrium has been established.
4. Dilute Solutions. The concentration of the solute in the two solvents is
low. The Law does not hold when the concentrations are high.
 5. Non – Miscibility of Solvents. The two solvents are non-miscible or only
slightly soluble in each other. The extent of mutual solubility of the
solvents remains unaltered by the addition of solute to them.

If a solute does dissociate into ions or simpler molecule complex molecules

or if it associates into more complex molecules, then the distribution law does not
apply to the total concentrations in the two phases but only to the concentrations
of the particular species.

When solute A will not dissociate in solvent 1 but is partially dissociated in

solvent 2, then k = C1 / C2, where: C1 = concentration of A in solvent 1 and
C2 = is the concentration of undissociated A in solvent 2.

When a substance distribute itself between 2 solvents without the

complications of association, dissociation or reaction with the solvent, it is
possible to calculate the weight of the substance which can be removed in a
series of extraction.

Suppose we have a solution containing W gram of a substance in a V 1 cc of

solution and suppose this solution is shaken repeatedly with the V 2 cc samples of
pure immiscible 2nd solvent until distribution equilibrium is attained, then, at the
end of n extractions, the weight Wn of solute remaining unextracted

Wn = W [ (kV1) ÷ (kV1+ V2)] n → (3)

where:
W = weight of substance in V1
V1 = volume of the original solution (solvent 1) → from which the
substance is to be extracted
V2 = volume of solvent → use to extract the solute
k = distribution coefficient
n = no. of extractions
Wn = weight of unextracted solution
 W - Wn = W - W [ (kV1) ÷ (kV1+ V2)] n = W {1 - [ (kV1) ÷ (kV1+ V2)] n} → (4)
where:
W = weight in gram of extracted substance originally present
Wn = weight in gram of unextracted substance
W - Wn = weight of extracted solute

Or, this equation can be written in terms of moles, n

n - nn = n - n [ (kV1) ÷ (kV1+ V2)] n = n {1 - [ (kV1) ÷ (kV1+ V2)] n} → (5)

Greater extracting efficiency is obtained by keeping V 2 small and n large. It

is better to extract with several small volumes of solvent than one large volume.