MLZ 325

SOLUTION
THERMODYNAMICS

THE BEHAVIOUR OF SOLUTIONS

9.1 Introduction
Solution: A phase of variable composition.
Phase: Part of a system that has uniform chemical
composition and physical properties.

Formation of a solution from pure components:

Let the superscript () denote values in the reference
state.
Q
k is the value per mole of the property Q for pure
component k.
The value of Q for the initial unmixed state is the sum
of the values for each of the pure components.

THE BEHAVIOUR OF SOLUTIONS

,P
C1 n1 C2 n2
n1 C1 n2 C2 T

Q M Qsolution
Qunmixed
components

Q M Qsolution
Q
c

Qsolution
nk Q k

Q nk Qk

k 1

k 1

Qsolution
nk Q k nk Qk
k 1

k 1

Qsolution
nk Q k Qk
k 1

THE BEHAVIOUR OF SOLUTIONS

Qsolution
nk Q k
k 1

Q n1 Q1 n2 Q 2
M

Relative integral property of mixing

THE BEHAVIOUR OF SOLUTIONS

Formation of a new solution from the existing one:

C
1

T ,P

C1 n1 1 C2 n2
2 n2
1
n1

Q1 Qsolution final Qsolution initial Q1

M

Q1 Qsolution final Qsolution initial Q1

M

Q1 Q1 Q1
Relative partial molar property of mixing

THE BEHAVIOUR OF SOLUTIONS

Q k measures the change experienced by 1 mole of

component k when it is transferred from its
reference state to the solution with the
composition under consideration.

is the weighted sum of the changes

Thus, Qsolution
experienced in the mixing process by the
individual components.

THE BEHAVIOUR OF SOLUTIONS

The Mixing Process:
T, P, V & S all have absolute values in thermodynamics
In contrast, there is no universally valid state of the
system for which the energy functions U, H, A & G
have a zero value.
Energies of a system are always evaluated with respect
to some reference state.
Problems that involve these functions deal only with
changes in their values for processes.
In the treatment of multicomponent open systems, the
most common process considered in defining the energy
functions is called the mixing process.

THE BEHAVIOUR OF SOLUTIONS

The initial state of any particular component is called the
reference state for the formation of the solution.
It is this state to which values for the energy & other
thermodynamic functions of the solutions are referred.
The mixing process is the change in state experienced by
the system when appropriate amounts of the pure
components are mixed together forming a homogeneous
solution brought to the same T & P as the initial state.

Thus, the mixing process is the formation of a

solution from its pure components at constant
T & P.

THE BEHAVIOUR OF SOLUTIONS

9.2 Raoults Law & Henrys Law
Pure A
If a quantity of pure liquid A is placed in a closed,
initially evacuated vessel at the temperature T, it will
spontaneously evaporate until the pressure in the vessel
reaches the saturated vapour pressure of liquid A,
p A at the temperature T.
.,
In this state a dynamic equilibrium is established in
which the rate of evaporation of liquid A equals the
rate of condensation of A vapour.

re A rc A

THE BEHAVIOUR OF SOLUTIONS

re A f E , T

The rate of evaporation, re A, is determined by the

magnitude of the energy of the bonds between the atoms
of A at the surface of the liquid.
The forces exerted between the atoms are such that each
surface atom is located near the bottom of a potential
energy well, and for an atom to leave the surface of the
liquid and enter the vapour phase, it must acquire an
activation energy, E*.

THE BEHAVIOUR OF SOLUTIONS

Repulsive energy ER

Interatomic separation r

Net energy EN

Attractive energy EA

THE BEHAVIOUR OF SOLUTIONS

The intrinsic rate of evaporation, re A , is determined by
the depth of the potential energy well, i.e., by the
magnitude of E*, and by the T.
On the other hand, the rate of condensation, rc A , is
proportional to the number of A atoms in the vapour
phase which strike the surface of the liquid in unit time.
For a given T, this is proportional to the P of the vapour.

rc A f p
rc A k p A

re A rc A k p A

THE BEHAVIOUR OF SOLUTIONS

Dilute A-B Solution
Raoults law for the solvent
Begin with pure component A & visualize the addition of
a few atoms of component B forming a dilute solution of
the solute, component B, in the solvent, component A.
In this range of compositions the average solvent atom
experiences the same surroundings that it has in the pure
state; only a very small fraction of solvent atoms
neighbour solute atoms.
Thus, the only significant influence that the addition of
solute atoms has upon the properties of the solvent
atoms is to slightly reduce their numbers.
Accordingly, the solvent atoms act as if they were in an
ideal solution.

THE BEHAVIOUR OF SOLUTIONS

This behaviour gives rise to an experimentally observed
limiting law that applies to all solutions, called Raoults
law for the solvent.
If the mole fraction of A in the solution is XA and the
atomic diameters of A and B are similar, then,
assuming that the composition of the surface of the
liquid is the same as that of the bulk liquid, the fraction
of the surface sites occupied by A atoms is XA.
As A can only evaporate from surface sites occupied by A
atoms, the rate of evaporation of A is decreased by the
factor XA, and as, at equilibrium, the rates of evaporation
and condensation are equal to one another, the
equilibrium vapour pressure of A exerted by the A-B
solution is decreased from p A to p A .

THE BEHAVIOUR OF SOLUTIONS

Pure A

Dilute A-B solution

1 re A k p A

X A re A k p A

X A k p A k p A

p A X A p A
p
lim A p A
X A 1 X
A

Raoults law for the solvent A

THE BEHAVIOUR OF SOLUTIONS

Raoults law for the solvent, states that the vapour
pressure exerted by the solvent A in the A-B solution is
equal to the product of the mole fraction of the solvent
A in the solution and the saturated vapour pressure
of pure liquid A at the temperature of the solution.
Raoults law is shown in Fig. 9.1; the components of a
solution which obeys Raoults law are said to exhibit
Raoultian behaviour.

p A

Fig. 9.1

pA

pA

THE BEHAVIOUR OF SOLUTIONS

The Behaviour of Dilute Solutions
Henrys law for the solute
In the same composition range, every solute atom is
completely surrounded by solvent atoms.
That is, until a sufficient number of solute atoms is
added so that their spheres of influence begin to interact,
each solute atom added to the solution makes the same
contribution to the properties of the system.
In this range the average properties of the solute
are proportional to their concentration.

THE BEHAVIOUR OF SOLUTIONS

Case 1:

E A A E B B E A B

The derivation of Raoults law required the assumption

that the intrinsic rates of evaporation of A and B be
independent of the composition of the solution.
This requires that the magnitudes of the A-A, B-B, and
A-B bond energies in the solution be identical, in
which case the depth of the potential energy well of an
atom at the surface is independent of the types of
atoms which it has as nearest neighbours.

THE BEHAVIOUR OF SOLUTIONS

Case 2:

E A B E A A E B B

EA-B is considerably more negative than EA-A and EB-B,

and consider a solution of A & B which is sufficiently
dilue that every B atom on the surface of the liquid is
surrounded only by A atoms.
A A A A A A A A A B A A A A A A
A A B A A A A A A A A A A A A A
A A A A A A A A A A A A A A B A

A A A A A A B A A A A A A A A A

THE BEHAVIOUR OF SOLUTIONS

B atoms at the surface are located in a deeper potential

energy well than are the A atoms of pure A.
In order to leave the surface & enter the vapour
phase, the B atoms have to be lifted from deeper wells.
Intrinsic rate of evaporation of B decreases from re(B)
to re(B).
re(B) < re (B)
Henrys law line lies below Raoults law line.

THE BEHAVIOUR OF SOLUTIONS

Net energy EN
E

A A

Interatomic separation r

Repulsive energy ER

E A B

Net energy EN
Attractive energy EA

Interatomic separation r

THE BEHAVIOUR OF SOLUTIONS

Dilute A-B solution in which
EA-A = EB-B = EA-B

Dilute A-B solution in which

EA-B < EA-A , EB-B

re B X B k pB

reB X B k pB

re B

re B X B pB
pB

Pure B
re B k pB k

re B
pB

r B
pB e
pB X B
re B

pB k B X B

lim

X B 0

k
pB
XB

, B

THE BEHAVIOUR OF SOLUTIONS

Case 3:
Conversely, if EA-B is considerably less negative than
EA-A and EB-B, the solute atom, surrounded only by
solvent atoms, is located in a shallower potential energy
well than that occurs in the pure solute.
re(B) > re (B)
Henrys law line lies above Raoults law line.

THE BEHAVIOUR OF SOLUTIONS

However, this relationship is different for different

solutes added to the same solvent.
This proportionality is thus characterized by a constant
that is specific to the solute-solvent combination in the
system.
This behaviour gives rise to an experiemntally observed
limiting law that also applies to all solutions, called
Henrys law for the solute.
The coefficient B, called Henrys law constant, is the
activity coefficient for the solute and is seen to be
independent of composition in the dilute range.

THE BEHAVIOUR OF SOLUTIONS

The value of this constant depends on both the solute

and the solvent in the system and, for a given solutesolvent combination, varies with T, P.
If the value of the Henrys law constant is
determined as a function of T & P, then all of the
thermodynamic properties of a dilute solution can
be computed!

THE BEHAVIOUR OF SOLUTIONS

Deviation from Henrian Behaviour of the Solute

As the mole fraction of B in the A-B solution is increased, the

probability that all of the B atoms on the surface of the liquid
are surrounded by A atoms decreases.
The occurence of a pair of neighbouring B atoms on the
surface decreases the depth of the potential energy wells in
which they are located and hence increases the value of re(B).
Beyond some critical mole fraction of B, re(B) varies with
composition, and hence Henrys law is obeyed only over an
initial range of concentration of B in A, the extent of which is
dependent on the T of the solution and on the relative
magnitudes of the A-A, B-B, & A-B bond energies.

THE BEHAVIOUR OF SOLUTIONS

A A A A A A A A B B A A A A A A
A A B B A A A A A A A A A A A A
A A A A A A A A A A A A A B B A
A A A A A A B B A A A A A A A A

Net energy EN
E A B

Net energy EN
E B B