CHE 411

ENGR. J. B. ADEOYE
 Vapour Pressure & Boiling

• The vapour pressure of a liquid at a particular temp.is the equilibrium

pressure exerted by molecules learning and entering the liquid surface.
• Note:
• 1. Energy input raises vapour pressure
• 2. Vapour pressure is related to boiling
• 3. A liquid is said to boil when its vapour pressure equals the
surrounding press.
• 4. The ease with which a liquid boils depends on its volatility
• 5. Liquids with high vapour pressures i.e. the volatile liquids, will boil at
lower temperature
• 6. Vapour pressure and hence the boiling point of a liquid mixture
depends on the relativeof the components in the mixture.
• 7. Distillation occurs because of the differences in the volatility of the
components in the liquid mixture.
• Consider a Binary Mixture A – B where
component A is more volatile. The vapour –
liquid equilibrium for each substance of the
mixture is of course with vapour pressure –
temperature relationship shown in figure 1.1
• When the vapour pressures of a liquid are plotted against the corresponding
temperatures, a curve like TBDC results, the curve separates two areas of the plot,
representing respectively, conditions where the substance exists wholly in the
liquid state and wholly in the liquid state and wholly in the vapor state. At point A,
the substance is entirely liquid while at point E, the substance is entirely a vapor. At
all conditions corresponding to points. On the curve TBDC, liquid and vapor co-exist
in any proportion indefinitely. Liquid and vapor represented by pts. On the
vapour,Presscurve are called saturated liquid and saturated vapour respectively.
Vapour or gas at a temperature above that corresponding to saturate is termed
superheated. The vapour pressure curve has two abrupt endpoints at T and C.
point T, from originates curves ST and LT, separating the conditions for the solid
state from those for the liquid and vapour is the triple point at which all three
states of aggregation exist. Point C is the critical point, where distinction between
the liquid and the vapour phases disappear, and all the liquid properties such as
density, viscosity, refractive index, etc. are identical to those of the vapour. The
substance at a temperature above the critical is called a gas which is used to
designate merely a condition relatively far removed from vapour pressure curve.
The temperature corresponding to each pressure on the curve is termed the boiling
point of the liquid at the specific pressure, and that corresponding to one standard
atm. In particular is known as the normal boiling point.
• For isobaric process ADE or isothermal process ABF,
there is a change of phase accompanied by evolution
or absorption of the latent heat of vapourization at
constant temperature. Heat added or given off with
changing temperatures is called sensible heat.
• For binary mixtures, an additional variable,
concentration must likewise be considered. Mole
fractions are the most convenient concentration terms
to use.
• X donates mole fraction of the more volatile
component, A in the liquid and Y*or Y donates the
mole fractions of the more volatile component in the
vapour
 THE BOILING POINT DIAGRAM

• This shows how the equilibrium compositions

of the components in a liquid mixture vary
with temperature at a fixed pressure. The
vapour – liquid equilibrium relations for a
binary mixture A-B are given as a boiling point
diagram shown in Figure 1.2 at a total
pressure of 101.32 kpa.
•  
• The boiling point of A is that at which the mole fraction of A is
1.0 while the b.point of B is that at which the mole fraction of
A is 0. In this example, A is the more volatile component and
therefore has a lower b.point than B.
• Liquid and vapour mixtures at equilibrium are at the same
temperature and pressure throughout so that an infinite
horizontal tie lines can be drawn such as line DF. A mixture at
E is a two-phase mixtures consisting of a liquid phase of
composition at D and the vapour phase of composition at F
such that
• A solution at G is entirely liquid. If it is heated, its conc. remains
unchanged constant and the first bubble of vapour forms at H
and has the composition at J richer in the more volatile
component. Hence the lower curve is called the bubble point
curve. This difference between liquid and vapour compositions
is the basis for distillation operations. As more of the mixture is
vapourised, more of the vapour forms at the expense of the
liquid, giving rise, for example, to liquid L and its equilibrium
vapour K, although the composition of the entire mass is still the
original as at G. The last drop of liquid vapourises at M and has
the composition at N. Superheating the mixture follows the path
MO. Hence the mixture has vapourised over a temperature
range from H to M. so the term b.point for a solution ordinarily
has no physical meaning since vapourisation occurs over a
temperature range i.e. from the bubble point to the dew point.
• If the mixture at O is cooled, all the phenomena discussed above
reappear in reverse order. Condensation starts at M where the
upper curve is termed dew point curve and continues to H.
• The dew point is the temperature at which the saturated vapour
starts to condense while the bubble point is the temperature at
which the liquid starts to boil. The region above the dew point
curve shows the equilibrium composition of the superheated
vapour while the region below the bubble point curve shows the
equilibrium composition of the subcooled liquid.
• The vapour – liquid equilibrium compositions can also be shown
on a distribution diagram (Y*vs X) as in fig. 1.2b. Point P on the
diagram represent the tie line DF, for example, since the vapour
is richer in the more volatile component, the curve lies above
the 45 degree diagonal line.
 RELATIVE VOLATILITY OF VAPOUR – LIQUID SYSTEMS
• This is a measure of the differences in volatillty
between two components, and hence their boiling
points. It indicates how easy or difficult a particular
separation will be. The greater the distance between
the equilibrium curve and the 45 degree line the
greater the difference in liquid and vapour
compositions and the easier the separation by
distillation. A numerical measure of this separation is
called the separation factor or relative volatility, X, in
the case of distillation. This is defined as the ratio of the
concentration ratio of A and B in the vapour phase to
that in the liquid and is given by
• If the relative volatility between two
components is very close to 1, it is an
indication that they have very similarvapour
press characteristcs. This means that they
have very similarb.point and therefore it will
be difficult to separate the two components
via distillation. The larger the value of ( )
above unity, the greater the degree of
separability.
 INCREASE PRESSURE
• At higher temperatures looped curved occur and become
narrower which is readily seen from the distribution
curves of Fig.1.3b. The relative volatilities and hence the
separability therefore usually become less at higher
pressures. As the critical pressure of one component is
exceeded, there is no longer a distinction between
vapour and liquid for that component, and for mixtures
the looped curves are therefore shorter, as at pressures
above (PT3), the critical pressure for A (in the figure).
Distillation separations can be made only in the region
where a looped curve exist
 Constant Temperature Equilibria
•  A solution in a closed container at W is
entirely a liquid, and if the pressure is reduced
at constant temperature, the first bubble of
vapour forms at U, complete vaporization
occurs at S, and further reduction in pressure
results in a superheated vapour as at R.
 PHASE RULE AND EQUILIBRIUM

• The equilibrium in vapour – liquid systems is restricted by the phase rule

F=C–P+2
Where P – number of phases at equilibrium,
C – Total number of components in the two phases when no chemical are occurring
F – number of variants (or degrees of freedom) of the system.

RAOULT’S LAW AND IDEAL SOLUTIONS

• An ideal law, Raoult’s law, can be defined for vapour – liquid phases in equilibrium thus:
=, =
Where Pi- partial pressure of component I in the vapour
Pi – vapour pressure of pure i
Xi – mole fraction of I in the liquid.
• This law holds only for ideal solutions. Many systems that are ideal or non-ideal solutions follow Henry’s law in dilute solution:

= H
Where H is the Henry's constant
• If the vapour is also ideal, Dalton’s law holds
= +

•   =,+ )

Also = =  
• The relative volatility of A with respect to B in the binary system is given by 
• For ideal solutions, it is then possible to compute the entire vapour – liquid equilibrium from the vapour pressure of the pure
substances. For pressures too high to apply the ideal gas law, fugacities are used instead of pressures.