IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
On the basis of Raoult's law, liquid–liquid solutions can be classified into ideal
and non–ideal solutions as follows :
(1) Ideal solution
An ideal solution is that solution in which each component obeys Raoult's law
under all conditions of temperatures and concentrations.
An ideal solution will satisfy the following conditions :
(i) There will be no change in volume on mixing the two components, i.e.,
Vmixing = 0
(ii) There will no change in enthalpy (i.e., no heat is evolved or absorbed) when the
two components are mixed, i.e., Hmixing = 0
For example, when we mix 50 cm3 of benzene with 50 cm3 of toluene,
the volume of the solution is found to be exactly 100 cm3, i.e., Vmixing = 0
Further, it is found that Hmixing = 0
Hence, the solution obtained is ideal. Thus,
An ideal solution may be defined as that solution in which no volume change
and no enthalpy change take place on mixing the solute and the solvent in any
proportion.
At the molecular level, an ideal solution may be defined as follows :
An ideal solution of the components A and B is defined as the solution in which
the intermolecular interactions between the components (A–B attractions) are
of the same magnitude as the intermolecular interactions found in the pure
components (A—A attractions and B—B attractions).
A few examples are given below :
(i) Benzene + Toluene
(ii) n–Hexane + n–Heptane
(iii) Ethyl bromide + Ethyl chloride
(iv) Chlorobenzene + Bromobenzene
(2) Non–ideal solution.
A solution which does not obey Raoult's law is called non–ideal solution.
For such solution, Vmixing 0, Hmixing 0. For example, when we mix sulphuric
acid (solute) in water (solvent) the amount of heat generated is very large and a
change in volume is also observed. This is due to formation of a non–ideal solution.
In terms of molecular interactions, a non–ideal solution may be defined as
follows:
A non–ideal solution is that solution in which solute and solvent molecules
interact with one another with a different force than the forces of interaction
between the molecules of the pure components.
Types of Non–ideal solutions. These are divided into two types as explained
below :
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693
IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
(a) Non–ideal solutions showing positive deviations. When a component B
is added to another component A, sometimes the partial pressure of a component A
is found to be more than expected on the basis of Raoult's law. A similar effect is
observed for the other component B in the reversed mixing. The total vapour pressure
for any solution is thus greater than that corresponding to an ideal solution of the same
composition. Such behaviour of solutions is described as a positive deviation from
Raoult's law (Fig. 2.12).
The boiling points of such solutions are relatively lower as compared to those
of the pure components (because higher the vapour pressure, lowering is the boiling
point). For one intermediate composition, the total vapour pressure of such a solution
will be the highest and the boiling point will be the lowest. This solution acquires the
property of boiling at a constant temperature and its composition remains unchanged.
Liquid mixtures which distil without any change in composition are called azeotropes
or azeotropic mixtures. In case of solutions showing positive deviations, we get
minimum boiling (point) azeotropes.
The positive deviations are exhibited by liquid pairs for which the A—B
molecular interaction forces are lower than the A—A or the B—B molecular interaction
forces. For example, mixtures of ethanol and cyclohexane (or acetone) show positive
deviations. In pure ethanol, a very high fraction of the molecules are hydrogen bonded
as shown below :
On adding cyclohexane (or acetone), its molecules get in–between the
molecules of ethanol, thus breaking the hydrogen bonds and reducing ethanol–
ethanol attractions considerably.
Similarly, when carbon sulphide (CS2) is added to acetone [(CH3)2C = O], the
solute–solvent dipolar interactions are weaker than solute–solute and solvent–solvent
interactions. Hence, this solution also shows positive deviation.
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693
IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
In case of solutions showing positive deviations, a slight increase in volume and
absorption of heat takes place on mixing as expected (i.e., V and H both are
positive).
To sum up, for a non–ideal solution showing positive deviation,
(i) PA > xA p°A, PB > xB p°, ptotal > xA p°A + xB p°B
(ii) Hmixing = +ve (iii) Vmixing = +ve
A few more examples of non–ideal solutions showing positive deviations
are given below :
(i) Acetone + Carbon disulphide. (ii) Acetone + Ethyl alcohol.
(iii) Acetone + Benzene. (iv) Methyl alcohol + water
(v) Ethyl alcohol + Water. (vi) Carbon tetrachloride + Chloroform
(vii) Carbon tetrachloride + Benzene (viii) Carbon tetrachloride + Toluene.
(b) Non–ideal solutions showing negative deviations. If for the two
components A and B, the forces of interaction between the A and B molecules are
more than the A — A and B — B forces of interaction, the escaping tendency of A and
B types of molecules from the solution becomes less than from the pure liquids. In
other words, for any composition of the solution, the partial vapour pressure of each
component will be less and the total vapour pressure of the solution will also be less
than that expected from Raoult's law (Fig. 2.13). These solutions are said to show
negative deviations from Raoult's law. Such solutions have relatively higher boiling
points as compared to those of the pure components (because lower the vapour
pressure, higher is the boiling point). For one intermediate composition, the total
vapour pressure of the solution will be the least and the boiling point will be the highest.
Such a solution will also distil without any change in composition and provides an
example of another kind of azeotrope. We call it the maximum boiling (point)
azeotrope.
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693
IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
For example, negative deviation from Raoult's law is exhibited by a mixture of
chloroform (CHCI3) and acetone, (CH3)2CO. When these are mixed, the hydrogen
bonding takes place between the two molecular species as shown below due to which
the escaping tendency of either of the liquid molecules becomes less. Consequently,
the boiling point of solution increases.
In case of solutions showing negative deviations, a slight decrease in volume
and evolution of heat takes place on mixing as expected (i.e., V and H both are
negative).
To sum up, for a non–ideal solution showing negative deviation,
(i) pA < xA p°A, pB < xB p°B, ptotal < xA p°A + xB p°B
(ii) Hmixing = –ve
(iii) Vmixing = –ve
Apart from hydrogen bonding, other weaker intermolecular forces like dipole–
dipole attractions may also be partly responsible for observed deviations from ideal
behaviour.
A few more examples of non–ideal solutions showing negative deviations are
given below :
(i) Chloroform + Benzene. (ii) Chloroform + Diethyl ether.
(iii) Acetone + Aniline. (iv) HCI + Water.
(v) HNO3 + Water. (vi) Acetic acid + Pyridine.
Difference between Ideal and Non–ideal solutions. The various points of
difference may be summed up as follows :
Ideal Solutions Non–Ideal Solutions
1. The interactions between the 1. The interactions between the
components are similar to those in components are different from those
the pure components. of the pure components.
2. There is no volume change and 2. V 0, H 0 on mixing the
enthalpy change on mixing the components.
components (V = 0, H = 0) 3. They do not obey Roult's law. They
3. Each component obeys Raoult's law show positive or negative deviations
at all temperatures and from Raoult's law, i.e., PA xA P°A
concentrations, i.e., PA = xAPA and and PB xB P°B.
PB = xB P°B. 4. Their graphical behaviour is shown in
4. Their graphical behaviour is shown in Figs. 2.12 and 2.13.
Fig. 2.9. 5. They form azeotropes.
5. They do not form azeotropes.
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693
IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
Difference between solutions showing positive deviation and negative
deviation from ideal behaviour. The main points of difference are summed up in the
Table below :
Solutions showing positive deviation Solutions showing negative
deviation
1. The interactions between the 1. The interactions between the
components are less than in the pure components are greater than the
components. pure components
2. Vmixing = +ive. 2. Vmixing = –ive.
3. Hmixing = +ive. 3. Hmixing = –ive
4. PA > xA PA°, PB > xB PB 4. PA < xAPA, PB < xB PB°
5. Form minimum boiling azeotropes 5. Form maximum boiling azeotropes
Azeotropic or Constant Boiling Mixture
Liquid mixture, having a definite composition, and boiling like a pure liquid, is
called a constant boiling mixture or an azeotropic mixture or simply an
azeotrope.
Some Azeotropic mixtures
Components Composition by Weight Boiling Points (K)
A B % OF B A B Azeotrope
SOLUTIONS SHOWING POSITIVE DEVIATIONS (Minimum boiling Azeotropes)
H2O C2H5OH 95.37 373.00 351.3 351.15
H2O C3H7OH 71.69 373.00 370.19 350.72
(CH3)2CO CS2 67 329.25 319.25 312.25
CHCI3 C2H5OH 6.8 334.2 351.3 332.3
SOLUTIONS SHOWING NEGATIVE DEVIATIONS (Maximum boiling Azeotropes)
H2O HCI 20.3 373.0 188 383
H2O HI 57.0 373.0 239 400
H2O HNO3 68.0 373.0 359 393.5
H2O HCIO4 71.6 373.0 383 476
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693
IDEAL AND NON–IDEAL SOLUTIONS Suraj Sir-9883219693
It may be noted from the above table that in case of minimum boiling
azeotropes, the boiling point of the azeotrope is less than the boiling point of either of
the pure components. For example, a mixture of ethanol (b. pt. 351.3 K) and water (b.
pt. 373 K) containing 95.4% of ethanol forms an azeotrope with boiling point 351.15
K. Similarly, in case of maximum boiling azeotropes, the boiling point of the azeotrope
is higher than that of either of the pure components. For example, a mixture of nitric
acid (b. pt. 359 K) and water (b. pt. 373 K) containing 68% nitric acid forms an
azeotrope with boiling point 393.5 K.
Azeotropic mixtures cannot be separated into their constituents by fractional
distillation. For example, if we try to concentrate a dilute solution of alcohol, we can do
so only till it becomes 95.4% because after that it becomes a constant boiling mixture
(azeotrope). The mixture containing 95.4% alcohol and 4.6% water is called rectified
spirit.
SUPPLEMENT YOUR KNOWLEDGE FOR COMPETITIONS
To obtain pure alcohol (100% alcohol) called absolute alcohol from rectified spirit, the
method used is called Azeotropic distillation. For this purpose, rectified spirit is mixed
with a suitable amount of benzene. The mixture is then subjected to fractional
distillation. The folloviring three fractions are obtained at different temperatures.
(i) At 331.8 K, a ternary azeotrope (constant boiling mixture) containing 74.1%
benzene, 18.5% alcohol and 7.4% water by mass is obtained.
(ii) At 341.2 K, a binary azeotrope containing 67.7% benzene and 32.3% alcohol
by mass is obtained.
(iii) At 351 K (last fraction). 100% alcohol is obtained.
CURIOSITY QUESTION
Q. Why pure ethyl alcohol cannot be obtained from rectified spirit (95.4%
alcohol) even by fractional distillation ?
Ans. This is because a mixture of 96.4% alcohol with 4.6% water forms an
azeotrope, i.e., a constant boiling mixture.
NVS Tutorials Girish park / Dunlop Suraj Sir-9883219693