IPUE 208 C-Single component, two phase systems, Vapour

pressure

Phase diagrams

One can display the properties of compounds via phase

diagrams.
A pure substance can exist simultaneously in more than one
phase for eg. solid, liquid and vapour.
Phase diagrams enable the viewing of properties of two or
more phases as functions of temperature, pressure, specific
volume, concentration and other variables.
Refer to Fig.16.1

A lump of ice was placed in the chamber below the piston,

the chamber was evacuated and the volume of the chamber
was fixed by fixing the position of the piston.
Heating of the ice was started slowly ( so that phases of
water that result would be in equilibrium)
The measured pressures were plotted as a function of
temperature and one would obtain Fig. 16.2 a phase
diagram in which all of the measurements have been fitted
on a continuous smooth curve for clarity.

The initial conditions of p and T in the chamber are at 0 in

Fig 16.2 with the solid in equilibrium with the vapor.
As you raise the temperature the ice starts to melt at point
A, the triple point, the one p,V, T combination at which
solid , liquid and vapour are in equilibrium.
Further increases in the temperature cause pressure to rise
along the curve AB that represents liquid and vapour in
equilibrium.
B is the critical point at which vapour and liquid properties
become the same.

At point A if one had kept the temperature constant and

raised the pressure, the ice would still exist and be in
equilibrium with liquid water along line AC.
C is not the termination of the line just a marker for
convenience.
The line AC is so vertical that you can use the saturated
liquid properties for the compressed liquid.
If the vapour and liquid of a pure component are in
equilibrium then the equilibrium pressure is called the
vapour pressure, which is denoted p*.
At a given temperature there is only one pressure at which
the liquid and vapour phases of a pure substance may exist
in equilibrium.
Either phase alone may exist of course over a wide range of
conditions.

Terminology associated with Fig. 16.3

To conclude:
a) At any given temperature water exerts its vapour
pressure ( at equilibrium)
b) As the temperature increases, the vapour pressure
increases as well
c) It makes no difference whether water vaporizes into
air, into a cylinder closed by a piston or into an
 evacuated cylinder at any temperature it still exerts
the same vapour pressure as long as the liquid water
is in equilibrium with its vapour.

A pure compound can change at constant volume from a

liquid gto a vspour or the reverse via a constant
temperature process as well as a constant pressure process..
A process of vaporization or condensation at constant
temperature is illustrated by lines G-H-I or I-H-G
respectively in Fig 16.3.
Water woulf vaporize or condense at constanty temperature
as the pressure reaches point H on the vapor pressure curve.
The change that occurs at H is the increase or decrease in
the fraction of vapour or liquid respectively at the fixed
temperature. The pressure does not change until all of the
vapour or liquid has completed the phase transition.

Consider an experimental apparatus to collect data to

prepare a graph of values of p and V as a function of
temperature. This time the temperature in the chamber is
held constant and volume is adjusted while measuring
pressure.
Start with compressed liquid water (sub-cooled water)
rather than ice, and raise the piston so that water eventually
vaporizes as the pressure drops. Fig. 16.4 illustrates by
dashed lines the measurements for two different
temperatures T1 and T2.
As the pressure is reduced at constant T1 and V increases
very slightly ( liquids are not very compressible) until the
liquid pressure reaches p*, the vapour pressure at point A.
Then as the piston continues to rise, both the pressure and
temperature remain constant as the liquid vaporizes until all
of the liquid is vaporized ( point B) on the saturated vapour
line.
Subsequently, as the pressure decreases, the value of V can
be calculate via an ideal or real gas equation.
Compression at constant T2 is just a reversal of the process
at T1. The dots in Fig. 16.4 represent just the
measurements made when saturation of liquid and vapour
occurs and are deemed to form the envelope for the two
phase region seen in Fig 16.4 A-B,D-C represents the
conditions under which liquid and vapour can exist at
equilibrium.
Fig . 16.4 shows that a change in the specific volume
occurs in going from a liquid to a solid at the triple point,
i.e water expands when it freezes and this is why ships
trapped in polar ice can be crushed by the force of the
expanding ice.