WEEK 11 - That is, a plot of chemical potential against

temperature slopes down from left to right

Note
- also implies that because Sm(g) > Sm(l), the slope
- thermodynamic criterion for phase equilibrium is is steeper for gases than for liquids
the equality of the chemical potentials of each - Because it is almost always the case that Sm(l) >
substance in each phase Sm(s), the slope is also steeper for a liquid than
- For a one-component system, the chemical the corresponding solid
potential is the same as the molar Gibbs energy
(μ = Gm).
- Combining the First and Second Laws it is
explained how the Gibbs energy varies with
temperature and pressure

Note
- These expressions also apply to the molar Gibbs - The chemical potential of the gas phase plunges
energy, and therefore to the chemical potential. By steeply downwards as the temperature is raised
using the notation of partial derivatives, they can (because the molar entropy of the vapor is so
be expressed as high), and there comes a temperature at which it
lies below that of the liquid
- Then the gas is the stable phase and vaporization is
spontaneous

- By combining the equality of chemical potentials

of a substance in each phase with these
expressions for the variation of µ with temperature
and pressure it is possible to deduce how phase
equilibria respond to changes in the conditions.
Response of Melting to Applied Pressure
Dependence of Stability on the Conditions
- At sufficiently low temperatures the solid phase of
a substance commonly has the lowest chemical
potential and is therefore the most stable phase
- However, the chemical potentials of different
phases depend on temperature to different extents
(because the molar entropy of each phase is
different)
- And above a certain temperature the chemical
potential of another phase (perhaps another solid
phase, a liquid, or a gas) might turn out to be lower
- Then a transition to the second phase becomes
spontaneous and occurs if it is kinetically feasible
Temperature Dependence of Phase Stability
- Because Sm > 0 for all substances above T = 0
- 4B.1a shows that the chemical potential of a pure
substance decreases as the temperature is raised
 by the process of gas solvation, the attachment of
molecules to gas-phase species

Note: where 1 J = 1Pa m3 . It follows that p = 1.0073p*,

an increase of only 0.73 per cent.
Location of Phase Boundaries
Vapor Pressure of Liquid Subjected to Pressure - The precise locations of the phase boundaries—the
- Pressure can be exerted on the condensed phase pressures and temperatures at which two phases
mechanically or by subjecting it to the applied can coexist—can be found by making use once
pressure of an inert gas again of the fact that, when two phases are in
- In the latter case, the partial vapor pressure is the equilibrium, their chemical potentials must be
partial pressure of the vapor in equilibrium with equal.
the condensed phase. - Therefore, when the phases α and β are in
- When pressure is applied to a condensed phase, its equilibrium
vapor pressure rises in effect, molecules are
squeezed out of the phase and escape as a gas.
- The effect can be explored thermodynamically,
and a relation established between the applied
pressure P and the vapor pressure p. - Solution of this equation for p in terms of T gives
an equation for the phase boundary (the
coexistence curve).
Slopes of Phase Boundaries

Note
- One complication that has been ignored is that, if
the condensed phase is a liquid, then the
pressurizing gas might dissolve and change its
properties
- Another complication is that the gasphase
molecules might attract molecules out of the liquid
Liquid Vapor Boundary
- The entropy of vaporization at a temperature T is
equal to ΔvapH/T (as before, all points on the
phase boundary correspond to equilibrium, so T is
a transition temperature, Ttrs), so the Clapeyron
equation for the liquid–vapor boundary can
therefore be written

- The enthalpy of vaporization is positive and

ΔvapV is large and positive, so dp/dT is positive,
but much smaller than for the solid–liquid
boundary. Consequently dT/dp is large, and the
boiling temperature is more responsive to pressure
than the freezing temperature.