liquid and vapour being present; outside
Liquid–vapour
systems
T he choice of variables under our
control, such as pressure or
temperature, leads to two types of two-
component phase diagram that show the
equilibrium composition of the system under
the selected conditions.
(a) Pressure–composition
diagrams
Figure 1, is a typical pressure–composition
diagram at a fixed temperature. All the points
above the diagonal line in the graph
correspond to a system under such high
pressure that it contains only a liquid phase
(the applied pressure is higher than the vapour
pressure). All points below the lower curve
correspond to a system under such low
pressure that it contains only a vapour phase
(the applied pressure is lower than the vapour
pressure). Points that lie between the two lines
correspond to a system in which there are two
phases present, one a liquid and the other a
vapour. To see this interpretation in more
detail, consider the effect of lowering the
pressure on a liquid mixture of overall
composition a in Fig. 1. The changes to the
system do not affect the overall composition,
so the state of the system moves down the
vertical line that passes through a. This vertical
line is called an isopleth (from the Greek
words for ‘equal abundance’). Until
Figure 1: A typical phase diagram for a
mixture of two volatile liquids. A point
between the two lines corresponds to both
that region there is only one phase present.
the point a 1 is reached (when the pressure has
been reduced to p1), the sample consists of a
single liquid phase. At a 1 the liquid can exist
in equilibrium with its vapour of composition
a '1. A line joining two points representing
phases in equilibrium is called a tie line. The
composition of the liquid is the same as
initially (a 1 lies on the isopleth through a), so
we have to conclude that at this pressure there
is virtually no vapour present; however, the
tiny amount of vapour that is present has the
composition a '1. To use a phase diagram to find
the relative amounts of two phases α and β that
are in equilibrium when the system is in a two-
phase region, we measure the distances lα and
lβ along the horizontal tie line, and then use the
lever rule (Fig. 2) which is derived in the
following Justification:
n a l a=nb l b … … … (lever rule)
Figure 2: The lever rule. The distances lα and
lβ are used to find the proportions of the
amounts of phases α (such as vapour) and β
(for example, liquid) present at equilibrium.
The lever rule is so called because a similar
rule relates the masses at two ends of a
lever to their distances from a pivot (
m a l a=mb l b for balance)
Here n α is the amount of phase α and n β the
amount of phase β. In the case illustrated in
Fig. 2, because lβ ≈lα the two phases are in
equal abundance.
The lever rule:
At p1in Fig. 1, the ratio l vap /l liq is almost
infinite for this tie line, so nliq / nvap is also
almost infinite, and there is only a trace of
vapour present. When the pressure is reduced
to p2, the value of l vap /l vap is about 0.5, so
nliq / nvap ≈ 0.5 and the amount of liquid is about
one-half the amount of vapour. When the
pressure has been reduced to p3, the sample is
almost completely gaseous and because
l vap /l liq≈ 0 we conclude that there is only a
trace of liquid present.
lever rule derivation:
To prove the lever rule, we write
n=nα +n β and the overall amount of A as nx A ,
where n A is the mole fraction of A in the
mixture. The amount of A is also the sum of its
amounts in the two phases:
nx A =( nα +n β ) x A =nα x A + n β x A
where x A , α is the mole fraction of A in phase α
and x A , β is its mole fraction in phase β. Since
also
nx A =nα x A ,α +n β x A , β
by equating these two expressions it follows
that
n α ( x A , α −x A )=nβ ( x A−x A ,β )
which corresponds to eqn 1
(b) Temperature–composition
diagrams
A temperature–composition diagram is a
phase diagram in which the boundaries show
the composition of the phases that are in
equilibrium at various temperatures (and at a
fixed pressure, typically 1 atm). An example is
shown in Fig. 3. Note that the liquid phase
now lies in the lower part of the diagram
because all points below the lower curve
correspond to a system under such low
temperature than it contains only a liquid
phase. The region between the lines in Fig. 3 is
a two-phase region; the regions outside the
phase lines correspond to a single phase.
Consider what happens when a liquid of
composition a 1 is heated. It boils when the
temperature reaches T 1. Then the
Figure 3: The temperature–composition
diagram corresponding to an ideal mixture
(Topic 70) with the component A more
volatile than component B. Successive
boiling and condensations of a liquid
originally of composition a 1 lead to a
condensate that is pure A. The separation
technique is called fractional distillation.
liquid has composition a 2 (the same as a 1) and
the vapour (which is present only as a trace)
has composition a '2. The vapour is richer in the
more volatile component A (the component
with the lower boiling point). From the
location of a '2 , we can state the vapour's
composition at the boiling point, and from the
location of the tie line joining a 2 and a '2 we can
read off the boiling temperature (T 2) of the
original liquid mixture. In a simple distillation,
the vapour is withdrawn and condensed. This
technique is used to separate a volatile liquid
from a non-volatile solute or solid. In
fractional distillation, the boiling and
condensation cycle is repeated successively.
This technique is used to separate volatile
liquids. We can follow the changes that occur
by seeing what happens when the first
condensate of composition a 3 is reheated. The
phase diagram shows that this mixture boils at
T 3 and yields a vapour of composition a '3,
which is even richer in the more volatile
component. That vapour is drawn off, and the
first drop condenses to a liquid of composition
a 4. The cycle can then be repeated until in due
course almost pure A is obtained. Although
many liquids have temperature–composition
phase diagrams resembling the version in Fig.
3, in a number of important cases there are
marked deviations. A maximum in the phase
diagram (Fig. 4) may occur when the favorable
interactions between A and B molecules
reduce the vapour pressure of the mixture
below the ideal value implied by Raoult’s law:
in effect, the A–B interactions stabilize the
liquid. Examples of this behaviour include
trichloro methane/propanone and nitric
acid/water mixtures. Phase diagrams showing
a minimum (Fig. 5) indicate that the mixture is
destabilized relative to the ideal solution, the
A–B interactions then being unfavorable.
Examples include dioxane/water and
ethanol/water mixtures.
Figure 4: A high-boiling azeotrope. When the
liquid of composition a is distilled, the
composition of the remaining liquid changes
towards b but no further.
Figure 5: A low-boiling azeotrope. When the
mixture at a is fractionally distilled, the
vapour in equilibrium in the fractionating
column moves towards b and then remains
unchanged.
Deviations from ideality are not always so
strong as to lead to a maximum or minimum in
the phase diagram, but when they do there are
important consequences for distillation.
Consider a liquid of composition a on
the right of the maximum in Fig. 4. The vapour
(at a '2 ) of the boiling mixture (at a 2) is richer in
A. If that vapour is removed (and condensed
elsewhere), then the remaining liquid will
move to a composition that is richer in B, such
as that represented by a 3, and the vapour in
equilibrium with this mixture will have
composition a '3 . As that vapour is removed, the
composition of the boiling liquid shifts to a
point such as a 4, and the composition of the
vapour shifts to a '4 . Hence, as evaporation
proceeds, the composition of the remaining
liquid shifts towards B as A is drawn off. The
boiling point of the liquid rises, and the vapour
becomes richer in B. When so much A has
been evaporated that the liquid has reached the
composition b, the vapour has the same
composition as the liquid. Evaporation then
occurs without change of composition. The
mixture is said to form an azeotrope (from the
Greek words for ‘boiling without changing’).
When the azeotropic composition has
been reached, distillation cannot separate the
two liquids because the condensate has the
same composition as the azeotropic liquid.
One example of azeotrope formation is
hydrochloric acid/water, which is azeotropic at
80 per cent by mass of water and boils
unchanged at 108.6 °C.

Citation:
 Physical chemistry by Peter Atkin and Julio De Paula
 Physical chemistry by Ira N. Levine
 Physical Chemistry by Robert J Silbey