Ideal vs non ideal solutions: At molecular level what makes ‘Azeotrope’

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 fact that one volume of water is formed by the condensation of
1300 volumes of steam. The formation of a liquid from gas is due to the attractive forces
between molecules. These must be strong enough to overcome the kinetic energy of the
molecules. When a gas is cooled, the molecules lose kinetic energy until they reach a
temperature at which their kinetic energy will no longer overcome the forces of
intermolecular attraction, and that is the point when the gas liquefies into liquid.

Figure1
The liquid state bears more resemblance to the solid-state than gas. The particles in a liquid
are further apart than in a solid and less ordered. When solids melt, there is usually an
expansion of the order of 10%. The amount of heat required to convert1 mole of a liquid to
vapor at 1 atm is called standard enthalpy of vaporization, ΔH vaporization. The same
amount of heat is released when 1 mole of the vapor condenses at 1 atm pressure. The
amount of heat required to convert 1 mole of a solid into liquid at 1 atm pressure is called
the standard enthalpy of melting ΔHmelting. The same amount of heat is released when 1
mole of liquid solidifies at 1 aim. Standard enthalpies of melting are much smaller than
standard enthalpies of vaporization because the transition from solid to liquid involves
less disruption of intermolecular attractions than the transition from liquid to gas at the
molecular level.

Liquids have a definite volume and are only slightly compressible. The distance between
molecules in a liquid is governed by a balance between forces of attraction between
molecules and forces of repulsion between neighboring electron clouds, figure 1. The forces
of attraction between molecules being less strong than those in solids are not strong
enough to hold the liquid in a definite shape. A liquid flows to fit the shape of its
container.
How liquids evaporate
Since molecules of the liquid are in constant motion, some of them will have enough energy
to escape from a liquid into a vapor state. The term vapor is applied to gas below its critical
temperature. Those that escape will be molecules with energy considerably above average,
sufficient to remove them against the attraction of other molecules of the liquid. The
molecules that remain in the liquid will be of lower energy than those escape, and the
temperature of the liquid will fall. Since the fraction of molecules with high energy increases
with temperature, the rate of evaporation increases with temperature.
Saturated vapor pressure
As the molecules of vapor collide with the walls of the container, they exert pressure. The
maximum vapor pressure at a temperature that can be developed by a liquid is called the
saturated vapor pressure. Since the fraction of molecules with high energy increases with
temperature, evaporation increases as the temperature rises, and saturated vapor
pressure increase with temperature. The magnitude of saturated vapor pressure depends
on the identity of the liquid and the temperature, it does not depend on the amount of
liquid present. Solids have vapor pressure too, but at room temperature, the vapor
pressures of most solids are low.
Solutions of liquid in liquids
Raoult’ 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
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]

Figure 2
Figure 2 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.
The figure below shows the vapor pressure composition curves at two temperatures T1 and
T2. Figure 3

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

Figure 4
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.
To repeat, let us consider a binary solution with liquids A and B. A so-called positive
deviation from Raoult's law results when the constituents have a dis- affinity for each other
– that is A sticks to A and B to B better than A sticks to B. Because this results in the mixture
having less total affinity of the molecules than the pure constituents, they more readily
escape from the stuck-together phase, which is to say the liquid phase, and into the vapor
phase. When A sticks to B more aggressively than A does to A and B does to B, the result is a
negative deviation from Raoult's law. In this case, because the molecules in the mixture are
sticking together more than in the pure constituents, they are more reluctant to escape the
stuck-together liquid phase.
When a pair of liquids show a very large positive deviation from Raoult's law the vapor
pressure composition curve has a maximum. A system with a very large negative deviation
shows a minimum, figure 5.

Figure 5
A maximum in the saturated vapor pressure curve results in a minimum in the boiling point
temperature-composition curve and vice versa
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).
Figure 6
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