What makes Azeotrope?

An azeotrope or a constant boiling point mixture is a mixture of two or more liquids whose proportions cannot be
altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the
same proportions of constituents as the unboiled mixture.

What is liquid?
The liquid is one of the three main states of matter, solid, liquid, and gas. According to the kinetic theory of matter,
all matter is composed of particles that have a certain amount of energy which allows them to move at different
speeds depending on the temperature (energy). There are spaces between the particles. Attractive forces between
particles play their roles when they come close together. In a liquid, the molecules are closer than in a gas. This is
evident from the
Solutions of liquid in liquids
Raoults’ law – Key to distillation

A solution is a homogeneous mixture of two substances. When one liquid dissolves in another, the saturated vapor
pressure of the solution depends on the saturated vapor pressures of the components and on the composition of
the solution. One way of expressing the composition of a mixture of liquids is to express as mole fraction of each
component. By definition, the mole fraction of A in a mixture of A and B = Number of moles of A / Total number of
moles. Using symbol X for mole fraction XA= NA / (NA+NB). NA and NB are moles of A and B. The vapor above a
mixture of liquids A and B will contain both A and B. Raoult’s law says that the saturated vapor pressure of each
component in the mixture is equal to the product of the mole fraction of that component and the saturated vapor
pressure of that component when pure.
This can be expressed as PA =XA(l) x PA (pure), PA is the saturated vapor pressure of A, PA (pure) is the saturated
vapor pressure of pure A, XA(l) is the mole fraction of A in solution. Similarly, for B, PB = XB(l) x PB (pure).
What makes liquids obey Raoult’s law
Raoult’s law is obeyed by a mixture of similar compounds. They are said to form ideal solutions. The substances A
and B would form an ideal solution if intermolecular forces A…. A, A…. B and B……B are all equal. In other words, A
sticks to B with roughly equal energy as A does with A and B does with B. Since the interaction energies between A
and B are almost equal There is neither a volume change nor an enthalpy [heat] change on mixing
The vapor above the mixture of liquids does not have the same composition as the liquid. If XA (v) and XB (v) are the
mole fraction of A and B in the vapor phase, then
XA(v) / XB(v) =PA/PB = XA(l) PA (pure)/ XB(l) PB (pure)

PA and PB are partial pressures of A and B generated by the solution

Total vapor pressure = PA + PB [sum of partial pressures of A and B]
Above is showing the vapor pressure curve for an ideal mixture consisting of liquid A and B. Vapor pressure of this
binary solution obeys Raoult's law. The black line shows the total vapor pressure as a function of the mole fraction
of component B, and the two green lines are the partial pressures of A and B. When the total vapor pressure is v,
the composition of the liquid is represented by point L and the composition of vapor by point V. The line V------- L is
called tie – line. The vapor is richer than the liquid in the more volatile component, A. The difference in composition
between the liquid and vapor is an estimate in the figure.

When the vapor pressure of a liquid reaches atmospheric pressure, the liquid boils. T1 is the boiling temperature of
a liquid with liquid composition l1 in equilibrium vapor composition v1. T2 is the boiling temperature of a liquid that
has liquid composition l2, in equilibrium with a vapor composition v2, figure 3.

To summarize, an ideal solution is one that obeys Rault’s law. Raoult's law states that the vapor pressure of a
solution is dependent on the mole fraction of a solute added to the solution. Raoult’s law is obeyed by a mixture of
similar compounds. Two substances will form an ideal solution when intermolecular forces within each substance
and between two substances are the same. Although there are no ideal gases, ideal solutions may exist If the
molecules are almost identical chemically, e.g., 1-butanol and 2-butanol, then the solution will be almost ideal.
Since the interaction energies between A and B are almost equal, it follows that there is a very small overall energy
(enthalpy) change when the substances are mixed. The more dissimilar the nature of A and B, the more strongly the
solution is expected to deviate from ideality. The highly diluted solution also behaves as ideal solutions due to less
interactions between solute molecules and solute-solvent molecules.

Ideal liquid
It assumes that a mixture of two liquids will obey Rault’s law when they are chemically similar with the mean
strength of the interactions being the same between all the molecules of the solution. The highly diluted solution
also behaves as ideal solutions due to fewer interactions between solute molecules and solute-solvent molecules.

Benzene C6H6 and toluene C7H8 form near-ideal solution and obey Raoult’s law

Typical ideal solutions

Benzene and Toluene

n-hexane and n-heptane
Bromoethane and Chloroethane
CCl4 and SiCl4

Chlorobenzene and Bromobenzene

Nonideal solutions
What pushes a liquid molecule towards Nonideal behavior? At the molecular level what makes ‘Azeotrope’

Deviation from Raoult’s law

Solutions that have vapor pressure greater than that predicted by Rault’s law are said to show positive deviation
from the law. Those with a vapor pressure lower than the calculated value are said to show negative deviation,
figures 5 and 6. Typical of a pair of liquids showing a slight deviation is hexane and ethanol. The molecules are very
different. Molecules of ethanol can more easily escape from a mixture of ethanol and hexane than from pure
ethanol because, in a mixture of ethanol with hexane, hexane interferes with hydrogen bonding between ethanol
molecules. This is against when ethanol is a single liquid where hydrogen bonding holds ethanol molecules
together. A slight negative deviation from Raoult’s law is shown by a mixture of trichloromethane CHCl3 and
ethoxyethane, C2H5OC2H5. Here both molecules are practically non-polar. The intermolecular forces – Vander
walls forces of attraction between these molecules tend to prevent the molecules from escaping into the vapor
phase. This is an important point and needs to be understood to have a good understanding of how Azeotropes
form.

Azeotrope
An azeotrope or a constant boiling point mixture is a mixture of two or more liquids whose proportions cannot be
altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapor has the
same proportions of constituents as the un-boiled mixture.
Azeotropes can form only when a mixture deviates from Rault’s law. There are two types of azeotropes: minimum
boiling azeotrope and maximum boiling azeotrope. A solution that shows a greater positive deviation from Raoult's
law forms a minimum boiling azeotrope at a specific composition. For example, an ethanol-water mixture (obtained
by fermentation of sugars) on fractional distillation yields a solution containing approximately 95% by volume of
ethanol. Once this composition has been achieved, the liquid and vapor have the same composition, and no further
separation occurs. A solution that shows a large negative deviation from Raoult's law forms a maximum boiling
azeotrope at a specific composition. Nitric acid and water are an example of this class of azeotrope. This azeotrope
has an approximate composition of 68% nitric acid and 32% water by mass, with a boiling point of 393.5 K (120.4
°C), figure 6. Each azeotrope has a characteristic boiling point. The boiling point of an azeotrope is either less than
the boiling point temperatures of any of its constituents (positive azeotrope), or greater than the boiling point of
any of its constituents (negative azeotrope).

Nitric acid – Water azeotrope

When the deviation is great enough to cause a maximum or minimum in the vapor pressure versus composition
function, Azeotrope formation is a mathematical consequence.
Credit: Google