HENRY’S LAW & LEGAL DISTRIBUTION NERNST

Henry's Law

Chemical law stating that the amount of a gas that dissolves in a liquid is proportional to
the partial pressure of the gas over the liquid, provided no chemical reaction takes place
between the liquid and the gas. It is named after William Henry (1774–1836), the English
chemist who first reported the relationship.

When a gas is in contact with the surface of a liquid, the amount of the gas which will go
into solution is proportional to the partial pressure of that gas. A simple rationale for Henry's
law is that if the partial pressure of a gas is twice as high, then on the average twice as many
molecules will hit the liquid surface in a given time interval, and on the average twice as
many will be captured and go into solution. For a gas mixture, Henry's law helps to predict
the amount of each gas which will go into solution, but different gases have different
solubilities and this also affects the rate. The constant of proportionality in Henry's law must
take this into account. For example, in the gas exchange processes in respiration, the
solubility of carbon dioxide is about 22 times that of oxygen when they are in contact with
the plasma of the human body.

Henry's Law And The Solubility Of Gases

Concentration of solutions was taken up as part of molar stoichiometry in other sections.

The concentrations used in this section will all be molar concentrations, because in
homogeneous solutions active mass is the ratio of amount of substance to unit volume. Molar
concentration will be indicated by c, with the solute in parenthesis following the symbol, or
by placing the solute molecule or ion symbol in square brackets. Other concentration units,
such as molality, are less commonly usedin aqueous equilibrium calculations.

Gases dissolve in liquids to form solutions. This dissolution is an equilibrium process for
which an equilibrium constant can be written. For example, the equilibrium between oxygen
gas and dissolved oxygen in water is O2(aq) <--> O2(g). The equilibrium constant for this
equilibrium is K = p(O2)/c(O2). The form of the equilibrium constant shows that the
concentration of a solute gas in a solution is directly proportional to the partial pressure
of that gas above the solution. This statement, known as Henry's law, was first proposed in
1800 by J.W. Henry as an empirical law well before the development of our modern ideas of
chemical equilibrium.

Stating the pressure-concentration ratio as an equation and use of the usual modern symbol
for the Henry's law constant on a concentration basis, K'c, gives the following form of Henry's
law:

p = K'c c

In this form p is the partial pressure of the gas, c is its molar concentration, and K'c is the
Henry's law constant on the molar concentration scale. Henry's law is found to be an accurate
description of the behavior of gases dissolving in liquids when concentrations and partial
pressures are reasonably low. As concentrations and partial pressures increase, deviations
from Henry's law become noticeable. This behavior is very similar to the behavior of gases,
which are found to deviate from the ideal gas law as pressures increase and temperatures
decrease. For this reason, solutions which are found to obey Henry's law are sometimes
called ideal dilute solutions.

Limitations of Henry's law

1. Apply only to aqueous solutions
2. There is no chemical reaction between the solvent and the solute, because if there is a
chemical reaction then its solubility can look very large.
.

Statement Of Nernst’s Distribution Law

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.

If a solute X distributes itself between two immiscible solvents A and B at

constant temperature and X is in the same molecular condition in both solvents,
Concentration of X in A = K
Concentration of X in B D

If C1 denotes the concentration of the solute in solvent A and C2 the concentration in

solvent B, Nernst’s Distribution law can be expressed as
C
1
C = KD
2
The constant KD (or simply K) is called the Distribution coefficient or Partition
coefficient or Distribution ratio.
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
C S
1
C = S1 = KD
2 2
where S1 and S2 are the solubilities of the solute in the two solvents.
 Hence knowing the value of the Distribution coefficient (KD) and the solubility of
solute in one of the solvents, the solubility of solute in the second solvent can be
calculated.

Explanation Of Distribution Law

This is an equilibrium law. When the distribution of the solute X has reached
dynamic equilibrium, the rate (R1) at which molecules of X pass from solvent A to B is
proportional to its concentration (C1) in A. The rate (R2) at which molecules of X pass
from solvent B to A is proportional to its concentration (C2) in B. Also, at equilibrium,
the rate of migration of solute from one solvent to the other is equal. Thus we have,

R1 ∝ C1

Where is a
Or R1 = k1 × C1 k1 constant

Again R 2 ∝ C2
where k2 is a
Or R2 = k 2 × C2 contant
Since at
equilibrium R1 = R2

k1 × C1 = k2 × C2

C1 k2
Or = = KD
C k
2 1

This is the Nernst’s Distribution law equation. Since k1 and k2 are constants at the
same temperature, the distribution coefficient KD is also constant if temperature is fixed.

LIMITATIONS OF DISTRIBUTION Law :

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 concentrations. 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.

Oxtoby, Gillis, “Prinsip-prinsip kimia modern edisi 4 jilid 1”