REKHA G R
Lecturer in Chemistry
DISTRIBUTION LAW
Nernst distribution law
Statement:
A solute distributes itself between two immiscible solvents in such a way that the ratio of
the concentrations of the solute in the two solvents is constant at constant temperature,
independent of any other molecular species present, provided that the solute has the same
molecular state in both the solvents.
Thus if a solute X distributes itself between the two immiscible solvents A and B, then we
have
Concentration of X in solvent A C1
= = KD
Concentration of X in solvent B C2
‘X’ remains in the same molecular species in both the solvents. The constant KD is called
distribution coefficient or partition coefficient.
Distribution coefficient
The ratio of the concentration of the solute in the two immiscible solvents is a constant called
distribution coefficient or partition coefficient
C1
= KD
C2
The constant KD is called the distribution coefficient or partition coefficient
C1 and C2 are the concentrations of iodine in water and carbon tetrachloride.
Verification of distribution law taking distribution of iodine in water and carbon
tetrachloride
The law deals with the distribution of a solid between two non-miscible or partially miscible
solvents in contact with each other. Iodine is soluble in both the solvents i.e water and carbon
tetrachloride. When a known volume of a solution to iodine is shaken for a period of time
1|DISTRIBUTION LAW
with carbon tetrachloride, it is found that iodine distributes or divides itself between the water
and carbon tetrachloride layers in such a manner that at equilibrium, the ratio of the
concentrations of iodine in the two layers is constant at a given temperature and is
independent of the actual amount of iodine present. If C1 is the concentration of iodine in
carbon tetrachloride layer and C2 is the concentration of iodine in water layer, then
C1
= KD
C2
The constant KD is known as the distribution coefficient or partition coefficient and equation
is known as the Nernst distribution law. According to this law, a dissolved substance,
irrespective of its amount, distributes itself between two non-miscible solvents in contact
with each other in such a way that at equilibrium, the ratio of the concentrations of the
substance in the two layers is constant at any given temperature. The ratio of distribution of
iodine between carbon tetrachloride and water in contact with each other is 85:01
Concentration of I2 in CCl4 85
Partition coefficient = = at 250C
Concentration of I2 in water 1
The results of the distribution of iodine between water and carbon tetrachloride at 20 0C are
given in table below.
Moles of I2 per litre of Moles of I2 per litre of
KD = C1/C2
CCl4 water (C2)
0.02 2.35×10 ̶ 4 85.1
0.04 4.49×10 ̶ 4 85.2
0.06 7.03×10 ̶ 4 85.4
0.08 9.30×10 ̶ 4 86.0
0.10 11.4×10 ̶ 4 87.5
Limitations of distribution law
i. Applicable only at constant temperature.
ii. Applicable only at lower concentration of solute but not at higher concentration.
iii. The law cannot be applied directly for solutes undergoing association or
dissociation in solvents.
iv. It is not applicable for the solutes which chemically react with the solvents.
2|DISTRIBUTION LAW
Conditions for the validity of distribution law
i. The temperature must remain constant throughout the experiment.
ii. The two liquids (solvents) should be mutually immiscible.
iii. The amount of the solute added should be small i.e the solution should be dilute.
This is essential because in some cases, the solute added affects the mutual
solubility of the solvents.
iv. The solute must have the same molecular state in both the solvents i.e it should
not undergo association or dissociation in any of the solvents. Thus the law is not
valid for the distribution of benzoic acid between water and benzene, because it
has been observed that in benzene, benzoic acid undergoes association to form
dimers i.e it exists as (C6H5COOH)2. Similarly the law is also not valid for the
distribution of an electrolyte between water and non polar solvent, because the
electrolytes undergo dissociation in water.
Association of the solute in one of the solvents
Let ‘X’ represents the molecular formula of the solute. Let it remains as such in the first
phase marked I in which its concentration is C1. Suppose it is largely associated to give the
molecules (X)n in the second phase marked II. The associated molecules will exist in
equilibrium with single molecules as shown. Let C2 be the total concentration of the solute in
this phase.
Applying the law of chemical equilibrium to the equilibrium between the associated and
single molecules (X)n ⇌ nX in the second phase, we have
[ ]n
K = X ⁄[( ) ] ---------------------(i)
X n
n
Or [X] = √K × [(X)n ]
n
[X] =constant × √[(X)n ] -------- (ii)
If the solute exists largely as associated molecules, which is generally true except at large
dilutions, the concentration of the associated molecules [(X) n] may be taken as equal to C2,
the total concentration,
i.e [(X)n] =C2 -----------------------------(iii)
From equations (ii) and (iii)
n
[X] = constant × √C2 -------------(iv)
Since the distribution law is valid only for concentrations of similar molecular species in the
two phases, hence,
C1
= constant -------------------------(v)
[X]
From equations (iv) and (v)
3|DISTRIBUTION LAW
C1
n = constant =KD
√C2
Dissociation of the solute in one of the solvent
Let ‘X’ represent the molecular formula of the solute. It does not dissociate in the solvent
marked I but dissociates into A and B in the solvent marked II. Let C1 be its concentration in
the first solvent and C2 be the total concentration in the second solvent. The distribution law is
valid only for the ratio of concentrations of similar molecular species in the two solvents.
Let ‘α’ is the degree of dissociation of the solute X in phase II. Then the concentrations of the
various species would be as shown below
X ⇌ A + B
C2(1 ̶ α) C2α C2α
Therefore according to the distribution law
C1
[C2 (1−α)]
= KD
Application of distribution law
Solvent extraction process
The most important application of the distribution law is in the process of extraction, in the
laboratory as well as in industry. In the laboratory, for instance, it is frequently used for the
removal of a dissolved organic substance from aqueous solution with solvents such as
benzene, ether, chloroform, carbon tetrachloride etc., The advantage is taken of the fact that
the partition coefficient of most of the organic compounds is very largely in favour of organic
solvents.
4|DISTRIBUTION LAW
Let ‘V’ mL of a solution containing W g of solute be repeatedly extracted with ‘v’ mL of
another solvent which is immiscible with the first. Let w1 be the mass of the solute that
remains unextracted at the end of the first operation.
Then KD will be given by
w1⁄
V
W−w1 =KD
𝑣
or
KD V
w1 = W.
KD V+ 𝑣
Similarly at the end of the second extraction, the amount w2 that remains unextracted is given
by
KD V
w2 = w1 .
KD V+ 𝑣
KD V 2
= W[ ]
KD V+𝑣
In general, the amount that remains unextracted at the end of n operations, wn will be given
by
KD V n
wn= W [ ]
KD V+𝑣
It is evident that in order to make w n as small as possible, for a given value of KD, n should
be as large as possible. But n×v is equal to the total volume of the extracting liquid available
i.e it is constant. Therefore, it is better to keep ‘n’ large and ‘v’ small rather than reverse. In
other words, the efficiency of extraction increases by increasing the number of extractions
using only a small amount of the extracting solvent each time.
******
5|DISTRIBUTION LAW
