5.
25
Drawing the tie line we can determine the amount of each phase using the lever rule,
nl z − xA2 B(s) 0.33 − 0.20
i.e., ! A B(s) = = = 1.626
n 2 xl − z 0.20 − 0.12
Therefore. !n tot = n A2 B(s) + n l = n A2 B(s) + 1.626n A2 B(s) = 10.0 m ol
or !n A2 B(s) = 3.8 m ol and !n l = 6.2 m ol
1. The phase diagram for pure water is shown below. For each point, a to f, give the number of
phases, P, the number of degrees of freedom, F, and the type(s) of phase(s) present.
5.26
(i) Label diagram. Should be able to recognize and draw a one-component phase diagram
(ii) To determine number of degrees of freedom, F, use Gibbs phase rule: F = 2 + C – P
Here we have one-component, C = 1, so F = 3 – P
Point a: one phase, gas, F = 2 (in principle can change p and T)
Point b: two phases, liquid and gas, F = 1 (in principle can change p or T). At this point, the
liquid and gas phases are in equilibrium, so their chemical potentials are equal, μ
! g = μl
Point c: one phase, liquid, F = 2 (p and T)
Point d: Two phase, liquid and solid, F = 2 (p or T). At this point, the liquid and solid phases are
in equilibrium, so their chemical potentials are equal, μ ! l = μs
Point e: one phase, solid, F = 2 (p and T)
Point f: The triple point, three phases, solid, liquid, and gas, F = 0. At this point, the solid, the
liquid, liquid and gas phases are in equilibrium, so their chemical potentials are equal,
!μg = μl = μs
2. The phase diagram for a two-component mixture is shown below. Discuss qualitatively the
changes to the system as the pressure is reduced from that at point a to point a4 through pressures
p1, p2, and p3. Your discussion should focus on the relative amount of liquid vs. vapour phase and
the composition of those phases. NOTE: this vertical line is known as an isopleth.
5.27
At a, only liquid phase (100% liquid) with a composition of a.
At p1, vapour just begins to appear (at the bubble point line). Therefore, the sample is almost
100% liquid (composition a1) with an infinitesimal amount of vapour (composition a1′). i.e,
ng a1 − a1
thinking about the lever rule: ! = ≈0
nl a′1 − a1
At p2, mixture of liquid (composition a2) and vapour (composition a2′). The amount in each
phase can be determine by the lever rule:
ng a′′ − a 2
! = 2 ≈ 3
n l a′2 − a′2′
At p3, almost 100% vapour (at the dew point line). Therefore, the sample is almost 100% vapour
(composition a3′) with an infinitesimal amount of liquid (composition a3)
Things to think about:
Is the solution ideal?
How would deviations from ideality (positive or negative) effect the phase diagram above?
THE END
For the future:
(1) Connect classical thermodynamics with quantum mechanics: statistical thermodynamics,
which connects to kinetic molecular theory via molecular dynamics.
(2) Discuss kinetics (recall many questions in this course focussed on distinguishing kinetics
from thermodynamics). Connect kinetics with quantum mechanics.