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Lecture2 3rdchapter Physicaltransformation

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3 views

Lecture2 3rdchapter Physicaltransformation

Uploaded by

kawsar Akash
Copyright
© © All Rights Reserved
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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4B.

1 Thedependence of stability
on the conditions
At very low temperatures and provided the pressure is not too low, the solid
phase of a substance has the lowest chemical potential and is therefore the most
stable phase. However, the chemical potentials of different phases change with
temperature in different ways, and above a certain temperature the chemical
potential of another phase (perhaps another solid phase, a liquid, or a gas) may
turn out to be the lowest. When that happens, a transition to the second phase is
spontaneous and occurs if it is kinetically feasible to do so.
(a) The temperature dependence of phase
stability
The temperature dependence of the Gibbs energy is
expressed in terms of the entropy of the system by eqn 3D.8

((∂G/∂T)p = −S).
Because the chemical potential of a pure substance is just
another name for its molar Gibbs energy, it follows that

This relation shows that, as the temperature is raised, the


chemical potential of a pure substance decreases: Sm > 0 for
all substances, so the slope of a plot of μ against T is
negative.
Equation 4B.1 implies that because Sm(g) > Sm(l) the slope
of a plot of μ against temperature is steeper for gases than
for liquids. Because Sm(l) > Sm(s) almost always, the slope is
(a) The temperature dependence of
phase stability
The steep negative slope of μ(l) results in it falling
below μ(s) when the temperature is high enough, and
then the liquid becomes the stable phase: the solid
melts. The chemical potential of the gas phase plunges
steeply downwards as the temperature is raised (because
the molar entropy of the vapour is so high), and there
comes a temperature at which it lies lowest. Then the
gas is the stable phase and vaporization is spontaneous.
(b) The response of melting to applied pressure
Most substances melt at a higher temperature when subjected to pressure. It is as
though the pressure is preventing the formation of the less dense liquid phase.
Exceptions to this behavior include water, for which the liquid is denser than the
solid.
Application of pressure to water encourages the formation of the liquid phase.
That is, water freezes and ice melts at a lower temperature when it is under pressure.
We can rationalize the response of melting temperatures to pressure as follows.
The variation of the chemical potential with pressure is expressed [(from the second
of eqns 3D.8)
(∂G/∂p)T = Vm)] by

This equation shows that the slope of a plot of chemical potential against
pressure is equal to the molar volume of the substance.
(b) The response of melting to applied pressure

An increase in pressure raises the chemical potential of


any pure substance (because Vm > 0). In most cases, Vm(l)
> Vm(s) and the equation predicts that an increase in
pressure increases the chemical potential of the liquid
more than that of the solid. As shown in Fig. 4.10a, the
effect of pressure in such a case is to raise the melting
temperature slightly.
For water, however, Vm(l) < Vm(s), and an increase in
pressure increases the chemical potential of the solid more
than that of the liquid. In this case, the melting
temperature is lowered slightly (Fig. 4.10b).
1 pa m3 = 1 J
(c) The effect of applied pressure on vapour pressure
When pressure is applied to a condensed phase, its
vapour pressure rises: in effect, molecules are
squeezed out of the phase and escape as a gas.
Pressure can be exerted on the condensed phases
mechanically or by subjecting it to the applied
pressure of an inert gas (Fig. 4.11);
in the latter case, the vapour pressure is the partial
pressure of the vapour in equilibrium with the
condensed phase, and we speak of the partial
vapour pressure of the substance.
One complication (which we ignore here) is that, if
the condensed phase is a liquid, then the pressurizing
gas might dissolve and change the properties of the
liquid.
Another complication is that the gas phase
molecules might attract molecules out of the liquid by
the process of gas solvation, the attachment of
molecules to gas phase species.
(c) The effect of applied pressure on vapour
pressure
As shown in the following
Justification, the
quantitative relation
between the vapour
pressure, p, when a
pressure DP is applied and
the vapour pressure, p*,
of the liquid in the
absence of an additional
pressure is

This equation shows how


the vapour pressure
increases when the
pressure acting on the
(c) The effect of applied pressure on vapour
pressure
As shown in the following
Justification, the
quantitative relation
between the vapour
pressure, p, when a
pressure DP is applied and
the vapour pressure, p*,
of the liquid in the
absence of an additional
pressure is

This equation shows how


the vapour pressure
increases when the
pressure acting on the
4.6 The location of phase boundaries
We can find the precise locations of the phase boundaries—the
pressures and temperatures at which two phases can coexist—by
making use of the fact that, when two phases are in equilibrium, their
chemical potentials must be equal. Therefore, where the phases a and b
are in equilibrium,

By solving this equation for p in terms of T, we get an equation for the


phase boundary.
4.6 The location of phase
boundaries
a) The slopes of the phase boundaries
It turns out to be simplest to discuss the phase
boundaries in terms of their slopes, dp/dT.
Let p and T be changed infinitesimally, but in
such a way that the two phases a and b remain in
equilibrium. The chemical potentials of the phases
are initially equal (the two phases are in
equilibrium). They remain equal when the conditions
are changed to another point on the phase
boundary, where the two phases continue to be in
equilibrium (Fig. 4.12).
Therefore, the changes in the chemical
potentials of the two phases must be equal and we
can write
4.6 The location of phase boundaries

a) The slopes of the phase boundaries


4.6 The location of phase boundaries

a) The slopes of the phase boundaries

The Clapeyron equation is an exact expression for the


slope of the phase boundary and applies to any phase
equilibrium of any pure substance.
It implies that we can use thermodynamic data to
predict the appearance of phase diagrams and to
understand their form.
A more practical application is to the prediction of the
response of freezing and boiling points to the application
of pressure.

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