EXPERIMENT NO.

: 2
TITLE: HETEROGENEOUS EQUILIBRIUM

OBJECT: Determination of partition co-efficient of Acetic acid between n-Butanol and Water

THEORY: Thermodynamic Derivation of the Distribution Law:

We Know the Gibbs free energy Equation,

G  H  TS
G  H  TS  ST[T  Const.]
G  U  PV  VP  TS  ST[H  U  PV ][q  TS ][U  PV  q]
dG  VdP  SdT
(G / P)T  V
2 2 P

 dG   VdP
1 1
T  nRT  (dP / P)[Std.Condition]
1

G  G  nRT ln( P /1)

0

G  G 0  nRT ln a[When, ln( P /1)  ln x  ln a, x  molefraction, a  activity, P  pressure]

   0  RT ln a[a  i Ci, , a  activity,i  activityCoefficient, C  Concentraiton]
i

The thermodynamic derivation of the distribution law is based upon the principle that if there are
two phases in equilibrium (i.e. two immiscible solvents containing the same solute dissolved in
them), the chemical potential of a substance present in them must be same in both the phases.

From thermodynamics, we know that the chemical potential of a substance is a solution

given by

where is the standard chemical potential and ‘a’ is the activity of the substance (solute) in the
solution.

Thus for the solute in liquid A, we have

Similarly for the solute in liquid B we have

But as already stated, since the liquids A and B are in equilibrium,

 Further at a given temperature, and are constant for given substance in the
particular solvents. Hence at constant temperature, we have from equation.

And therefore,

This is the exact expression of the distribution law. However, if the solutions are dilute, the
activates are equal to the concentrations so that the expression is modified to

which is the original form of the distribution law.

When a system consists of parts which have different physical properties (perhaps also different chemical
properties) and which are separated by bounding surfaces, the system is said to be a heterogeneous one.

Consider a liquid-liquid system, say water and n-butanol (two immiscible solvents), to which little
quantity of acetic acid is added. Acetic acid will dissolve partly in water and partly in n-butanol. The two
solutions of acetic acid will separate into two layers at equilibrium. The concentrations in the two layers
are different but their ratio is fixed at a constant temperature provided there is neither association nor
dissociation of the solute in solvents and the ratio is independent of the amount of acetic acid added or the
volumes of the two liquids present.

“The concentration of a solute distributed between two phases at equilibrium at a constant

temperature bear a fixed ratio”. This is the Nernst Distribution Law.

This is mathematically expressed as: C1 / C2  K d

Where,
C1 is the concentration of the solute in one solvent and C2 is that in another solvent.
 called the distribution coefficient or partition coefficient.
Kd Is