Binary Solution

Non-ideal solutions
Non-ideal solutions are those in which solute-solvent interactions are different from solute-
solute and solvent-solvent interactions. So the escaping tendency of any component is
influenced by the presence of others in the solution.

Thermodynamic criteria of non-ideal solutions

1. In a non-ideal solution ∆𝑉𝑚𝑖𝑥 ≠ 0 and ∆𝐻𝑚𝑖𝑥 ≠ 0.
2. The chemical potential 𝜇𝑖 𝑇, 𝑃 of the 𝑖 𝑡ℎ component of the solution will obey the
relation

𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖 0 𝑇, 𝑃 + 𝑅𝑇 𝑙𝑛 𝑎𝑖

Where 𝑎𝑖 = activity = 𝑥𝑖 𝛾𝑖

𝑥𝑖 is its mole fraction in solution and 𝛾𝑖 is the activity coefficient. Therefore –

𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖 0 𝑇, 𝑃 + 𝑅𝑇 𝑙𝑛 𝑥𝑖 𝛾𝑖

= 𝜇𝑖 0 𝑇, 𝑃 + 𝑅𝑇 ln 𝑥𝑖 + 𝑅𝑇 𝑙𝑛 𝛾𝑖

𝜇𝑖 𝑇, 𝑃 = 𝜇𝑖 𝑇, 𝑃 𝑖𝑑 + 𝑅𝑇 𝑙𝑛 𝑥𝑖

3. The components of a non-ideal solution do not obey Raoult’s law.

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Graphical representation of the behaviour of non-ideal solutions

In type I systems, the total pressure as well as the partial pressure of each component show a
small positive deviation from Raoult’s law. At any composition the total vapour pressure will
be intermediate between the vapour pressures of the two pure components.

Type II systems show large positive deviations from Raoult’s law. With change in
composition, vapour pressure gradually rises to a maximum which is above the vapour
pressure of each of the pure components. This means that the escaping tendency from the
solution is more than from pure solvents. This is possible when the solute-solvent interactions
(𝐴 − 𝐵) are weaker than solvent-solvent interactions ( 𝐴 − 𝐴 𝑜𝑟 𝐵 − 𝐵). These systems are
characterised by positive values of ∆𝐻𝑚𝑖𝑥 and ∆𝑉𝑚𝑖𝑥 .

For example let us consider the example of 𝐶2 𝐻5 𝑂𝐻 − 𝐶𝐻3 𝐶𝑂𝐶𝐻3 system. In pure 𝐶2 𝐻5 𝑂𝐻,
the molecules are held together by hydrogen bonds which is drastically reduced when
𝐶𝐻3 𝐶𝑂𝐶𝐻3 is added to the system. Here ∆𝐻𝑚𝑖𝑥 is positive because energy is required to
break the hydrogen bonds.

Type III systems show negative deviations from Raoult’s law. They exhibit a minimum
vapour pressure which is below the vapour pressure of each of the pure components. In this
case the escaping tendency from the solution is less than from pure solvents. Obviously the

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solute-solvent interactions (𝐴 − 𝐵) are stronger than solvent-solvent interactions ( 𝐴 −

𝐴 𝑜𝑟 𝐵 − 𝐵). These systems are characterised by negative values of ∆𝐻𝑚𝑖𝑥 and ∆𝑉𝑚𝑖𝑥 .

Vapour pressure composition diagrams of completely miscible liquids

In the graphical representation of non-ideal solutions, vapour pressures have been plotted
against liquid compositions. Now we plot the vapour pressures simultaneously against liquid
compositions and vapour compositions for all the three types of non-ideal solutions.

In type I, both vapour composition and liquid composition curves are continuous. B is more
volatile than A. Hence at all concentrations of the solution, the vapour will be richer in B than
A. So point 𝑎′ lies closer to the composition of pure B than point 𝑎.

In case of type II solutions, the vapour will be richer in B up to point C. At C liquid and
vapour phases have same composition. Between C and 𝑝𝐵 0 the vapour phase is richer in A.

In type III, the vapour is richer in A up to point D. At D liquid and vapour phases have same
composition. Between D and 𝑝𝐵 0 the vapour phase is richer in B.

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Boiling point composition diagrams

The boiling point of a binary mixture is the temperature at which total vapour pressure
becomes equal to the atmospheric pressure. Therefore a solution having low vapour pressure
will boil at a higher temperature and vice versa. Now in the present case, we assume that B is
more volatile than A. So the vapour pressure of pure A is lower than that of pure B.
Obviously the boiling point of A will be higher than that of B.

For type I solutions, the vapour will be richer in the more volatile component B. For type II
solutions, the vapour pressure becomes maximum at point C. Consequently C will represent
the lowest boiling point of the solution. Similarly for type III solutions, vapour pressure is
minimum at point D. Therefore point D corresponds to the maximum boiling point.

At points C and D, the liquid and vapour phases have same composition and the solution will
boil at a constant temperature. Such a mixture which, like a pure solvent, boils at a constant
temperature, is called constant boiling mixture or azeotropic mixture.

Azeotropic solution
Suppose in a mixture of two liquids, one component has lower vapour (higher boiling point)
than the other. The boiling point composition curves of such liquid mixtures either show a
maximum or a minimum. At these maximum or minimum points, the liquid and vapour
phases have same composition and the solution will boil at a constant temperature. Such a
mixture which, like a pure solvent, boils at a constant temperature, is called constant boiling
mixture or azeotropic mixture.

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EUTECTIC SYSTEMS

Let us consider a general case of

two components A and B which
neither combine to form a
compound nor are soluble in each
other in the solid state. The phase
diagram this system is shown
below. Points A and B represent
the melting points of pure A and

B respectively. It is well known

that the freezing point of a liquid
falls when another substance is
dissolved in it. Therefore, addition of B to A lowers freezing point and AC is the freezing

point curve of component A. The phases in equilibrium along AC are the solid A and the

solution of B in A. Similarly BC is the freezing point curve of component B. The two phases

which are in equilibrium along BC are solid B and the solution of A in B. Thus the number
of phases along curves AC and BC are two.

At constant pressure (1 atm), according to the reduced phase rule equation, the degree of
freedom along curves AC and BC are

𝐹 = 𝐶−𝑃+1=2−2+1= 1

Hence the system is monovariant. The two curves AC and BC meet at point C where solid A,
solid B and the liquid solution of the two components are in equilibrium. Here 𝐹 = 2 − 3 +
1 = 0. So the system is invariant. This means that none of the variables i.e. temperature and
composition can be altered without disturbing the equilibrium. When the temperature is
lowered, melt disappears and the whole mass solidifies. Similarly when the temperature is
increased, the solid melts. At point C, the mixture of A and B have the lowest melting point.

This is the lowest temperature at which the solution of A and B can exist in equilibrium with

both the solids A and B. This is known as the eutectic point (eutectic meaning easy melting).
The corresponding composition and temperature are called eutectic composition and eutectic

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temperature respectively.. The eutectic mixture has a definite composition and a sharp
melting point. In this respect, it resembles a compound. But a careful examination with a
powerful microscope reveals that both the constituents exist as separate crystals. Therefore,
eutectic solid is a mixture and not a compound.

Thus eutectic point is defined as the lowest temperature at which the liquid mixture of
two components can exist and the solution is cooled below this temperature, both the
components separate simultaneously in the solid form having the same composition as
in the solution. The corresponding composition is called eutectic composition.

The KI – Water system:

The KI – Water system is an example of two components systems involving a solid and a
liquid. The temperature versus composition phase diagram this system is shown above. Here
the pressure is assumed to be constant at one atmosphere. So the reduced phase equation
(𝐹 = 𝐶 − 𝑃 + 1) is applicable.

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Curve AC: Point A (00 C) is the freezing point of water at 1 atm. pressure. When KI is added
gradually to water, the freezing point of water is lowered along curve AC. So curve AC is
called the freezing point curve of water. Along this curve the solution of KI in water is in
equilibrium with ice. There are two phases and according to reduced phase equation,
𝐹 = 𝐶−𝑃+1=2−2+1= 1
Thus the system is univariant and there will be a definite composition corresponding to each
temperature. At point C, the solution is saturated with solid KI and freezes at a constant
temperature (-230 C) and a fixed composition (52% KI).

Curve BC: This is known as the solubility curve of KI in water at different temperatures.
The solubility increases with rise in temperature and becomes a maximum at point B which is
the boiling point of the saturated solution. On the other hand, if a saturated solution of KI is
allowed to cool at point B, the solution will freeze along curve BC and solid KI crystallizes
out. This process continues up to point C where the solution freezes a whole with fixed
composition. Along this curve
𝐹 = 𝐶−𝑃+1=2−2+1= 1
Thus the system is univariant.

Point C: It is an eutectic or cryohydric point where ice, solution and solid KI are in
equilibrium. This point corresponds to a definite temperature (-230 C) and definite
composition (52% KI + 48% ice). Here
𝐹 = 𝐶−𝑃+1=2−3+1= 0
Thus it is a non-variant point.

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