1.3 Phase Diagrams and Metastable States 9
of temperature, the above equation can be easily integrated and
pvap or=poexp
ff
−
L
kBT
Λ
,
where the constant of integrationpocorresponds to the pressure of an ideal
gas, namelypvap or=po,ifL= 0. From this result, it is clear that for such an
ideal vapor, the vapor pressure remains constant during isothermal conden-
sation, providing a useful physical supplement to the van der Waals isotherm
to delineate the mathematical conjecture in the equation of state (see Section
1.4).
1.3 Phase Diagrams and Metastable States
With the aid of aphase diagram, it is instructive to see how chemical potentials
of two coexisting phases behave in the vicinity of their equilibrium. For a
uniform substance, the Gibbs potentialGcan be used, but for two or more
phases in equilibrium, chemical potentials are more convenient because of
(1.1 µis a continuous function ofpandT,
as shown by a smooth mathematical surface in the three-dimensionalµ-p-T
space of Fig. 1.2. Therefore, for liquid-vapor equilibrium, such surfaces of two
phases should intersect in a curve, along which the two chemical potentials
take an equal value. The two phases can generally coexist, whereas at arbitrary
points other than those on the equilibrium line, only one of these phases with
a lower value ofµcan be stable.
For a simple isotropic substance like water, exhibiting three phases, i.e.
solid, liquid and vapor, these phase surfaces may intersect in pair to give
three equilibrium curves in theµ-p-Tspace. However, if a point lying on all
three surfaces or eqilibrium lines can be found, these three phases can coexist
at such a point called thetriple point(Fig. 1.3). Usually, a phase diagram is
drawn in two dimensions for convenience, e.g. with two variablespandTat
a constantµ, corresponding to the three-dimensionalµ-p-Tsurface projected
on thep-Tplane. Similar projections can also be obtained on theµ-pand
µ-Tplanes, providing useful phase diagrams at constantTand at constantp
conditions, respectively.
Although intersecting curves in phase diagrams represent accessible equi-
librium states, it is important to realize that in practical systems, there are
always so-calledmetastable states, which are represented, for example, by
a pointxon the extention of a constantµ-line in Fig. 1.3. Deviated from
the vapor-liquid equilibrium curve, hence unstable thermodynamically, such
a metastable state can often be observed as if it were stable. For instance,
a vapor can be compressed to a pressure higher than the vapor pressure, if
there are no appreciablenucleifor initiating condensation. Although rather
vaguely defined, the “nuclei” expresses the presence of unavoidable impuri-
ties in practical systems, playing a significant role in condensation. Such a