B.
TINA VERNYUY
Course outline
Introduction
Definition of terms
Component systems
Saturated vapour pressure
Raoult’s law
Deviation from raoult’s law
Azeotropic mixtures
Introduction
Phase equilibrium tries to explain
the conditions, usually
temperature, concentration and
pressure at which different
phases of a system exist at
equilibrium.
Definitions
Phase: It is a homogenous part of a system
that is physically distinct from other parts of
the system. They are separated by phase
boundaries.
Phase diagram: it is a graphical summary
of the conditions at which different states of
substances exist in equilibrium.
Component: it is the chemical entity in a
mixture with a definite composition different
from other parts of the mixture.
Types of components
One component system: it contains only
one chemical entity whose phases coexist
in equilibrium. Eg Br2 can exist as Br2 gas
and as Br2 liquid.
Two component system: it contains two
chemical entities whose phases coexist in
equilibrium. They can be completely
miscible, partially miscible or completely
immiscible.
Completely miscible liquids: These are liquids
which completely associate in one another in a
mixture forming homogenous mixtures at all
temperature. Eg H2O/CH3OH.
Partially miscible liquids: They are liquids which
form homogenous mixture at some
temperatures while at some other
temperatures they form two distinct layers. Eg
phenol/H2O etc.
Completely immiscible liquids: they are liquids
which form two distinct layers at all
temperatures and compositions eg,
H2O/kerosene
Saturated vapour pressure
This is the maximum pressure exerted by a
vapour when it is in equilibrium with its
liquid in a closed system at constant
temperature. An increase in temperature
increases the vapour pressure of the
system setting up a new equilibrium.
When saturated vapour pressure equals
atmospheric pressure, the liquid boils.
Raoult’s law
It states that, the partial vapour pressure of a
component in an ideal mixture of two
miscible liquids is equal to the vapour
pressure of the pure component multiplied
by its mole fraction ie the partial vapour
pressue is directly proportional to the mole
fraction.
An ideal or zeotropic mixture is one whose
concentration remains the same even when
only part of the mixture is considered. All
ideal mixtures obey Raoult’s law.
Raoult’s law
From this law, it implies that:
PA = XA.PT
A is a pure component in the mixture.
Ideal mixtures have the following characteristics:
Similar molecular structures
Similar intermolecular forces
No enthalpy change on mixture of the components
No volume change on mixing the components ie
volume is the sum of their volumes
The boiling point of mixture is the weighed mean of
the individual boiling points
The components do not react together or cause any
dissociation
Mostly occurs between successive members of a
homologous series eg methanol and ethanol.
Note
The more volatile components have a
greater tendency to escape into the vapour
stage hence having a higher vapour pressure.
Volatility decreases down each functional
group.
The higher the volatility or pressure, the
smaller the boiling point of the component.
The components of an ideal mixture are
separated by fractional distillation in a
fractionating column based on their boiling
points
Non ideal mixtures
This miscible mixture does not obey
Raoult’s law i.e. the vapour pressure
doesn’t vary linearly with composition.
These mixtures can deviate either
positively or negatively from this law.
Positive deviation
These mixtures exert vapour pressures that are
higher than the ones predicted by the ideal
mixture law. This indicates that there is a higher
tendency for molecules to escape from the
mixture hence the mixture causes dissociation
and weakening of bonds between components.
The bonds or forces usually broken are H-
bonds.
It is usually formed between a component with a
weaker intermolecular force and that with a
stronger intermolecular force.eg ethanol and
benzene, alkanes and oraganic acids, etc
Effects of positive deviation
Increase in the vapour pressure of
mixture
Increase in total volume
Lower boiling point
Decrease in enthalpy as heat is absorbed
to break bonds.
Lower density than expected.
Negative deviation
These mixtures exert a vapour pressure
which is less than that predicted by
Raoult’s law. This is because the
components interact to form stronger
bonds reducing the volatility of the
mixture. Examples: ketones or aldehydes
and alkanes
Effects of negative deviation
Decrease volatility and vapour pressure
Increase in boiling point
Increase in enthalpy change
Decrease in volume
AZEOTROPIC MIXTURES
This is the mixture with a constant boiling
point and whose composition does not
change on boiling at a given temperature.
When boiling, the vapour and liquid have
the same composition and hence cannot
be separated by fractional distillation
Seperation of azeotropic mixtures
Chemical method: here another chemical is
introduced to react with one of the
components of the mixture eg quick lime CaO
to separate water from H2O/ethanol mixture.
Distillation with 3rd component which
counteracts the interaction of the components
eg benzene in ethanol and water.
Absorption: using agents like silica gel and
charcoal. Silica absorbs ethanol/H2O
Solvent extraction: one component may be
extracted by the solvent.
Distribution law
It states that when a solute is added in an
immiscible liquid, the solute distributes
between the two immiscible liquids in a
constant ratio of concentration
irrespective of the amount of solute.
K = conc of solute in solution A
conc of solute in solution B
Where K is the partition coeficient
ANY QUESTIONS
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