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Phase Equilibria

For pure substances with one component, the variance (v) is equal to 3 - the number of phases (p). For a single phase, two variables can be controlled, but in two phases only one variable can be controlled. For binary mixtures with two components, the variance is 4 - p. Additional variables are the compositions of each phase. The general relationship is that variance equals the number of variables minus the number of equations.

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328 views11 pages

Phase Equilibria

For pure substances with one component, the variance (v) is equal to 3 - the number of phases (p). For a single phase, two variables can be controlled, but in two phases only one variable can be controlled. For binary mixtures with two components, the variance is 4 - p. Additional variables are the compositions of each phase. The general relationship is that variance equals the number of variables minus the number of equations.

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Nandhan
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© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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PHASE EQUILIBRIA

JOSHIA WILLIARD GIBB’S


PHASE RULE
In the one−phase regions one can vary either the temperature, or the pressure,
or both (within limits) without crossing a phase line. We say that in these
regions there is a variance of 2. We have indicated in the solid, liquid, and
gas regions that there is one phase and the variance is two. Along a phase
line we have two phases in equilibrium with each other, so on a phase line the
number of phases is 2. However, if we want to stay on a phase line, we can't
change the temperature and pressure arbitrarily. If we change the temperature
− and keep two phases − then the pressure must change also to keep us on the
phase line. Otherwise we go off the line and we no longer have two phases in
equilibrium. So on a phase line the number of phases is 2, but the variance is
1. At the triple point there are three phases in equilibrium, but there is only
one point on the diagram where we can have three phases in equilibrium with
each other. Therefore, at the triple point the variance is zero. Notice that
the variance seems to be related to the number of phases, such as,
v = 3 − p, or (1)

v = 2 + 1 − p. (2)

Let us see next example:


Consider the boiling diagram of a two−component ideal liquid−liquid solution.
In the one−phase regions (liquid or vapor) we have a variance of three because
we can change the temperature, the composition, X, and the pressure (by moving
in and out of the plane of the screen). In the two phase region the variance is
only two because if we change the temperature the compositions of both the
liquid and vapor phases must track as indicated by the tie−lines connecting
the liquid and vapor composition lines. Here it looks like the variance
satisfies,
v = 4 − p, or (3)

v = 2 + 2 − p. (4)
Notice that equations 2 and 4 are the same except for the second term. In
Equation 2 there is one component and the second term is 1. In Equation 4
there are two components and the second term in Equation 4 is a 2. It looks
like the second term may indicate the number of components in the system. We
might guess that the general form for Equations 2 and 4 might be,
v = 2 + c − p.
For pure substances C = 1 so that F =
3 – P. In a single phase (P = 1)
condition of a pure component system,
two variables (F = 2), such as
temperature and pressure, can be
controlled to any selected pair of
values. However, if the temperature and
pressure combination ranges to a point
where the pure component undergoes a
separation into two phases (P = 2), F
decreases from 2 to 1. When the system
enters the two phase region, it
becomes no longer possible to
independently control temperature and
pressure.
For binary mixtures of two chemically
independent components, C = 2 so that
F = 4 – P. In addition to temperature
and pressure, other variables are the
composition of each phase, often
expressed as mole fraction or mass
fraction of one component.
Case 1. There is no equation connecting the variables. Then we can pick the
values of all three variables to be anything we wish, independently of each
other. There are no restrictions on the values of the variables and the
variance is 3.

Case 2. There is one equation connecting the variables,


In this case we can select the values any two of the variables, but when we do,
the value of the third is fixed by the equation. The number of equations is
one and the variance is 2.

Case 3. There are two equations connecting the variables,


n this case we can select the value of any one variable at random, but then
the values of the other two are fixed by the two equations. (Two equations in
two unknowns is a soluble problem.) The number of equations is two and the
variance is 1.

Case 4. There are three equations connecting the variables,

In this case we can not select any of the variables arbitrarily. The values of
the variables are fixed because a system of three unknowns and three (linearly
independent) equations has a unique solution.

The number of equations is three and the variance is zero.


The principle we extract here is that
variance = number of variables − number of equations ≥ 0. (10)
vapor equilibrium system if some vapor
converts to liquid. The system shifts
toward the denser phase.

A molecular interpretation of this


situation can be made with the aid of
Figure 10-14. A liquid is in
equilibrium with vapor at left. The
piston is at position A, and the
external pressure is equal to the
equilibrium vapor pressure of the
system. The piston is then suddenly
moved down to a new position, B. The
instantaneous effect of this stress is
to increase the pressure exerted by
the gas inside the cylinder. The
increase in pressure causes the rate
of condensation, RC, to become greater
than the rate of evaporation, RE, which
depends only on temperature. A net
flow of molecules from vapor to liquid
results -- i.e., the system shifts
toward the denser liquid phase -- to
reduce the internal pressure to the
equilibrium value. Once this value is
reached, RE and RC will again be equal,
and the system will be in equilibrium
again. The difference between the
final and initial equilibrium states
is that there is less vapor and more
Change in temperature. Le Chatelier's
Principle predicts that increasing the
temperature of a system in phase
equilibrium will cause it to shift to
use heat. Conversely, a temperature
decrease will result in a shift that
produces heat. For the equilibrium in
equation 10-6-1, an increase in T will
cause a shift toward the vapor phase
(to the right), since conversion of
liquid to vapor is endothermic and
consumes heat. This will increase the
vapor pressure of the liquid, as we
already know. As a second example,
consider the liquid-solid equilibrium
in equation 10-6-2.
(10-6-2): l <===> s

For the process as written, DH < 0. An


increase in the temperature of the
system causes a shift in the
endothermic direction; i.e., to the
left.

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