PHYS 4050 Assignment 7

Phase Transformations
Due 30 October 2015
1. Calcium carbonate, CaCO3 , has two common crystalline forms, calcite
and aragonite. Thermodynamic data for these phases can be found at
the back of the textbook.
(a) Which is stable at the earths surface, calcite or aragonite?
(b) Calculate the pressure (still at room temperature) at which the
other phase should become stable.
2. Sketch qualitatively accurate graphs of G versus T for the three phases
of H2 O (ice, water, and steam) at atmospheric pressure. Put all three
graphs on the same set of axes, and label the temperatures 0 C and
100 C. How would the graphs differ at a pressure of 0.001 bar?
3. The density of ice is 917 kg m3 .
(a) Use the ClausiusClapeyron relation to explain why the slope of
the phase boundary between water and ice is negative.
(b) How much pressure would you have to put on an ice cube to make
it melt at 1 C?
(c) Approximately how deep under a glacier would you have to be
before the weight of the ice above gives the pressure you found in
part 3b? (Note that the pressure can be greater at some locations,
as where the glacier flows over a protruding rock.)
(d) Make a rough estimate of the pressure under the blade of an ice
skate, and calculate the melting temperature of ice at this pressure. Some authors have claimed that skaters glide with very little
friction because the increased pressure under the blade melts the
ice to create a thin layer of water. What do you think of this
explanation?

Figure 1: Isotherms (lines of constant temperature) for a van der Waals

fluid. From bottom to top, the lines are for 0.8, 0.9, 1.0, 1.1, and 1.2 times
Tc , the temperature at the critical point. The axes are labeled in units of
the pressure and volume at the critical point; in these units the minimum
volume (N b) is 1/3.
4. As you can see from Figure 1, the critical point is the unique point on
the original van der Waals isotherm (before the Maxwell construction)
where both the first and second derivatives of P with respect to V (at
fixed T ) are zero.
(a) Use this fact to show that
Vc = 3N b,

Pc =

1 a
,
27 b2

and kTc =

8 a
.
27 b

(b) When plotting graphs and performing numerical calculations, it

is convenient to work in terms of reduced variables:
t T /Tc ,

p P/Pc ,

v V /Vc .

Rewrite the van der Waals equation in terms of these variables,

and notice that the constants a and b disappear.
5. Plot the van der Waals isotherm for T /Tc = 0.95, working in terms
of reduced variables. Perform the Maxwell construction (either graphically or numerically) to obtain the vapor pressure. Then plot the Gibbs
free energy (in units of N kTc ) as a function of pressure for this same
temperature and check that this graph predicts the same value for the
vapor pressure.