Solutions

Solutionsofofliquids
liquidsininliquids
liquids
 Solutions of liquids in liquids

In a binary system of two liquids, depending upon the nature if the two liquids , the miscibility of one in the other varies.

Accordingly three types of binary liquids mixtures are possible,

 Completely miscible liquid pairs

 Partially miscible pairs
 Completely immiscible pairs

Completely Miscible liquids

In completely miscible liquids, the relative amount of the constituents can be varied to any extent and the constituents
mix freely and only a single phase exist.

Ideal Solutions
A solution is said to be an ideal if it obeys Raoult’s law at all temperature and concentrations .
Raoult’s Law

The partial vapour pressure of a volatile constituents of a solutions at constant temperature is equal to the product if
the vapour pressure of the pure constituents and its mole fraction in the solution.

In a binary solution of A & B, if the number of moles of A and B are n A & nB respectively then the mole fractions of

A(XA) & B(XB) are given as,

nA
XA = and
nA + n B

nB
XB =
nA + n B

In a binary solution, XA + XB = 1
Continued……….
According to Raoult’s law,

PA = XA PA0 and

PB = XB PB0

Where , PA& PB are partial pressure of A & B,

PA0 & PB0 are vapour pressure of A & B

If vapour behaves like an ideal gas, then the total pressure of above mixture is,

P = PA + PB
= XA PA0 + XB PB0
An ideal solution obeys Raoult’s law exactly at all concentrations and temperatures. For any given system, at a given
temperature PA0 & PB0 are constant. Hence a plot of partial pressure of each constituent ‘P’ against its mole fraction ‘X’, in

solution should be a straight line. Also, the total pressure of the ideal solution lie on a straight line joining PA0 and PB0.

PA0
PB0
Vapour pressure

XA=1 Mole fraction XB=1

A more careful statement of an ideal solution, however, includes specifications that no volume change should occur &
that no heat should be evolved OR observed on mixing of the two components.
I,e., ∆ V = 0
∆H = 0
 Most of the systems deviate from Raoult’s law to a greater/lesser degree depending on the nature of the liquids and
the temperature. There are called real or non-ideal solutions

Completely miscible binary solutions can be divided into three categories.

In Figure 1, 2 and 3 behavior of miscible liquid pairs of the three types are shown. The dotted line in all these three
graphs indicate ideal behavior.
Vapour pressure (Kpa)

400

300

200

100

C6H12 CCl4 CH3CHO CS2 CH3COCH3 Mole fraction CHCH3

Mole fraction Mole fraction

TYPE - I TYPE - II TYPE - III

Type - I
Solutions of this type show small ‘+’ve deviation from ideal behavior. The total pressure is at all times intermediate
b/w those of the pure components.
Ex: Cyclohexane - CCl4, CCl4 - C6H6, C6H6 - C6H5CH3, H2O - MeOH, etc.

Type - II
Solutions of this type show large ‘+’ve deviation from Raoult’s law. The total vapour pressure rises to a maximum
which is above the vapour pressure of either of the pure constituents.
Ex: CH3-CHO - CS2, EtOH - CHCl3, H2O - EtOH, etc.

Type - III
In this case, large negative deviations from Raoult’s law are seen & the total vapour pressure curve shows minimum.
i.e., the vapour pressure of certain composition of the solution is below the vapour pressures of either of the pure
compounds.
Ex: Acetone - CHCl3, H2O – H2SO4, H2O - HNO3.
 Vapour - Pressure - Composition curve

The composition of the vapour differs from that of the solution from which it distills over.
These diagrams are important in the study of distillation.

Vapour composition at equilibrium for ideal solution can be easily calculate. But in case of non-ideal solutions it is
calculated from experimentally determined vapour pressure of the two components.

ui d id
Vapour Pressure

Vapour Pressure

Vapour Pressure
L iq Liq iq u
ui L
d Liq
u id
p o ur Va
po
Va ur
O

Vapour
100% 100% 100% 100% 100% 100%
Wt % Wt % Wt %
A B A B A B
Type - I Type - II Type - III
Type - I :
The vapour – pressure – composition curves correspond to conditions of constant temperature. In all the cases, the
vapour – composition curves lie below the liquid – composition curves.

Type - II
The curves show a maximum, the vapour composition and the liquid composition curves are in contact at the point
of maximum vapour pressure.
At this point the compositions of the solution and the vapour are identical. The non-ideality arises due to interaction
between the components

Type - III
The vapour pressure is lower than the predicted value according to Raoult’s law & the interaction could be similar to
acid-base/hydrogen bond formation.
This leads to liberation of heat.
 Temperature - Composition curve

The temperature - composition (or) boiling – point - composition curves can be drawn. The shapes of the curves
depend on the behavior of the system as a function of temperature at constant pressure.

Va
p ou

ur

Temperature
r

Temperature

po
Temperature

D
uid

Va
Liq Li q Liq
ui d

id
ui

u
d

Liq
C
100% 100% 100% 100% 100% 100%
Wt % Wt % Wt %
A B A B A B
Type - I Type - II Type - III
Type - I :
At constant pressure, the boiling point of A will be the highest in the system, that of B the lowest in the system.
Solutions of different compositions of A and B have boing points intermediate between the two.

Type - II
The vapour of the system is maximum for composition C and hence such a solutions will boil at the lowest
temperature leading to a minimum in the boiling point curve.

Type - III
The solutions of composition D has the lowest vapour pressure in the system and the boiling point curve exhibits a
maximum.
 Henry’s Law
Statement:
The solubility of a gas in a liquid is directly proportional to the partial pressure of the gas above the solution at constant
temperature.
Mathematically.
m P
Ȣ
or m = KP
Where, m = Mass of gas dissolved in unit volume of the solvent.
P = Pressure of the gas in equilibrium with solution at constant temperature.
K = Henry’s ;aw constant
Henry’s law constant depends only an temperature.
When several gases are dissolved simultaneously in a solvent, above equation is valid for each gas independently. Thus
the solubility of each gas from a mixture of gases is directly proportional to the partial pressure of the gas in the
mixture.
The value of K is different for different gases.
Henry’s law may also be stated as the volume of a gas that dissolves in a fixed volume of a liquid at constant
temperature is a constant and is independent of the pressure of the gas.

The ideal gas equation, If Henry’s law is valid . Then the graph of solubility of a gas against
equilibrium pressure at constant temperature should be straight line
PV = nRT --------------- (1)
PV = m/M RT ---------- (2)

Solubility of gas in an inert

Where, m = mass
M = Molecular weight of gas

solution
V = m/P RT/M ----------- (3)
m/P is a constant from Henry’s law,
RT/M is a constant for a gas at constant temperature
Therefore equation (3) becomes, V = Constant

Equilibrium Pressure
 Limitations
 In packing of soda cans: Soda water bottles are
always packed under higher pressure to increase the
solubility of CO2​gas.
 In deep-sea diving: Nitrogen is more soluble than
Helium in our blood. In the deep sea, the pressure is
higher than at the surface of the water. When diver
tries to come rapidly towards the surface of the
water, pressure decreases and dissolved nitrogen
comes back from blood and makes bubbles in veins.
Hence, divers use oxygen diluted with helium.
Applications
Henry's law is applicable only when,
 The pressure of the gas is not too high and temperature is
not too low.
 The gas should not undergo any chemical change.
 The gas should not undergo association or dissociation in
the solution.
 The gases reacting with the solvent do not obey Henry’s law
For example, ammonia or HCl reacts with water and
hence does not obey this law.
NH3+ H2O ⇆ NH4+ + OH–
 Azeotropic solutions
The constant boiling mixtures obtained during fractional distillation of non-ideal solutions are called azeotropic
solutions.
The composition of an azeotropic solution is constant at given pressure. On varying the ‘P’ both the composition and
the boiling point changes. This shows that an azeotrope is not a chemical compound but it is only a mixture.
Ex: ethanol (95.5%) + water (4.5%) mixture boils at 351.5 K.
(B.P. of ethanol = 78.1° C, B.P. of water = 100° C)
In order to obtain pure alcohol calculated amount of C6H6 is added to the above mixture.

Ternary mixture (18.5% - OH, 7.4% - H2O and 74.1% C6H6)

∆ , 337.6 K - H2O

Binary mixture (67.6% C6H6 and rest – OH)

∆ , 340.8 K
Pure alcohol (Boiling point = 351.3 K)
 Lever Rule

The composition and amount of material in each phase of a two phase liquid can be determined using the lever rule.
This rule can be explained using the following diagram.

Suppose that the temperature and composition of the mixture is

given by point b in the above diagram. The horizontal line segment
that passes through point b, is terminated at points a and c, which
indicate the compositions of the two liquid phases. Point a
indicates the mole faction of compound B ( ) in Xthe
A
layer that is
B

predominantly A, whereas the point c indicates the composition (

X B that is predominantly compound B. The relative
) of the layer
B
amounts of material in the two layers is then inversely
proportional to the length of the tie-lines a-b and b-c, which are
given by lA and lB respectively. In terms of mole fractions,
 lA = XB −
XA
B
and
lA = X B − XB
B
The number of moles of material in the A layer (nA) and the number of moles in the B layer (nB) are

inversely proportional to the lengths of the two lines lA and lB.

nAlA = nBlB

Or, substituting the above definitions of the lengths lA and lB, the ratio of these two lengths gives the ratio
of moles in the two phases.
XB XA
nA/nB = lB/lA = B - X / XB − B
 Partial miscibility of Liquids

Partially miscible liquids are those that do not mix in all proportions at all temperatures. These are miscible only in a
limited range of concentrations. Phenol-water, aniline-hexane, methanol- carbondisulphide, triethylamine-water are few
examples of liquid pairs that show partial miscibility.

Phenol-water system
A small quantity of phenol when added to water at room temperature dissolves to give a solution but with the additions
of more phenol, at some point phenol does not dissolve any more and two solutions are formed. These, a saturated
solution of phenol in water and a saturated solution of water in phenol, known as conjugate solutions, are in equilibrium
with each other. At a given temperature, the compositions of these two solutions are fixed and are independent of the
relative amounts of the solutions. If the addition of phenol is continued, the added phenol gets dispersed into the
conjugate solution in such a way that the compositions of the two phases remain unaltered, only the relative amounts of
the phases change.

The temperature at which the two liquids become completely miscible is called the mutual solubility temperature (MST)
for that particular composition of the two liquids.
The amount of the phase phenol in water decreases and that of the phase water in phenol increases. When an
extremely small amount of phenol in water is left, addition of phenol results in the system again becoming a single
solution, a saturated solution of water in phenol. Addition of more phenol to this single phase system only makes the
solution more unsaturated in water. Liquid pairs, which show the same behaviour as the phenol-water system, have
been observed to exhibit large positive deviations from Raoult’s law. In these liquid systems there occurs a limited
solubility of one liquid into another and hence two saturated solutions are formed over a certain range of
composition. The liquids are completely miscible beyond this range. Thus, we may say that there exists a miscibility
gap in the system.
339 K
Variation of Mutual Solubility with temperature in Phenol- C
water system

Temperature
At any one temperature in the curve, the composition of
A X B
each layer is fixed by points A & B

The composition of phenol in water is given by A while,

that of water in phenol is given by B at that temperature 100% 95% Water 50% 30% Water 100%
Water 5% Phenol 70% Phenol Phenol
Wt %
The line joining the 2 points A & B is called tie line. With increase of temperature as seen from the curve, the
composition of 2 layers approach each other.
At 339 K, the two layers merge into one homogeneous solution. This temperature is called critical solution
temperature (CST). Above this temperature, if it is seen that the two liquids are miscible with each other in all
proportions and only a single layer of liquid results.
Since temperature is maximum on MST – composition curve, it is critical temperature.
The proportion by weight of the two layers ca be easily calculated using Lever rule.

Wt of aqueous layer XB
=
Wt of phenol layer AB
Any composition at a given temperature represented by points on left of the curve AC (or) the right of the curve CB
consists of only one layer.
All composition between pure water & point A yield a solution of phenol in water. Within the dome shaped area
ACB, the system is heterogeneous & two liquid phases exits, while in area outside the dome only a single layer.
 Upper and lower critical temperature

The upper critical solution temperature is defined as, the temperature above which the two partially miscible liquids
becomes miscible in all proportion.
Ex : For Phenol – Water system the temperature is 339 K
The lower critical solution temperature is defined as, the temperature below which two partially miscible liquids
becomes completely miscible.

Completely immiscible liquid pair

In this case, the addition of one liquid to the other no way affects the properties of either liquids. Each liquid
behaves as if the other is not present.
 Steam Distillation
Distillation of immiscible liquids is utilized industrially and in the laboratory as it involves the lowering of boiling
points of the components.
Purification of organic liquids which either have very high boiling point (or) tend to decompose when heated to their
boiling points can be suitably carried out using the above principle. The other liquid is generally water and the
process is known as steam distillation.

Partition co-efficient (Nernst's Distribution Law)

Statement : “When a solid (or) liquid distribute itself between two immiscible liquids, the ratio of its concentration in
two phases is a constant.
Mathematically,
C1
= K
C2

Where, C1 & C2 are constants of solute in 2 phases.

K = Constant, = Partition Co-efficient
The partition co-efficient holds good when,
1. The two liquids are immiscible & no chemical combination takes place between the solute and solvent.
2. There should not be association/dissociation of the solute molecules.
3. Temperature should be kept constant.
4. (Note) – In case of association (or) dissociation distribution law has to modified & other formula should be used.
If the substance dissolves in a liquid A but dissociates in liquid B, the formula to be used
C1
K =

Ȣ
C2(1- )
Where, C1 = Concentration of solute in Liquid A
=
C2 = Total concentration in liquid B
Ȣ

= Degree of dissociation in B
No change in phase I but associates in phase II, the formula to be used is,
C1
K =
C2(1- )
Ȣ
 Applications of Distribution Law

 Extraction of solvents from solutions using immiscible solvents

 Distribution of Argent ferrous lead.

 Estimation of solubility.

 For studying formation of complex compounds.

 Information about state of molecules.

Thank You