Case study

Phase diagrams
Phase diagram is a graphical representation of the physical states of a substance under different
conditions of temperature and pressure. Phase diagrams plot pressure (typically in atmospheres)
versus temperature (typically in degrees Celsius or Kelvin). The labels on the graph represent
stable states of a system in equilibrium. The lines represent the combinations of pressures and
temperatures at which two phases can exist in equilibrium. In other words, these lines define phase
change points. As we cross the lines or curves on the phase diagram, a phase transition occurs. The
figure below shows an example of H2O (water) phase diagram. The diagram is divided into three
areas, which represent the solid (ice), liquid (water), and gaseous (steam) states of H2O. The line
separating ice and steam represents sublimation (solid to gas) and deposition (gas to solid). The line
separating ice and water represents melting (solid to liquid) and freezing (liquid to solid). The line
separating water and steam represents vaporization (liquid to gas) and condensation (gas to liquid).
There are also two important points on the diagram, the triple point and the critical point. The triple
point represents the combination of pressure and temperature that facilitates all three phases of H2O
at equilibrium. The critical point terminates the water/steam phase boundary and relates to the
critical pressure, the pressure above which a supercritical fluid forms.

The phase diagram is determined by the Gibbs energies of the different phases in the system. The
stable phase at any condition will be the one having the lowest free energy, as illustrated below.
When two phases are in equilibrium, they have the same Gibbs energy, but neither same enthalpy
nor entropy.
Question 1: At 1 atmosphere pressure, ice melts into water at 0 oC. We can also say that the two
phases (ice and water) are in equilibrium at 0 oC and 1 atm. This phase transition can be written as
the following reaction:

H2O (solid, 0 oC and 1 atm) ↔ H2O (liquid, 0 oC and 1 atm)

Judge the sign (positive or negative or zero) for ∆G, ∆H, ∆S of the above reaction:

(a) ∆G > 0, ∆H > 0, ∆S > 0

(b) ∆G > 0, ∆H = 0, ∆S > 0
(c) ∆G > 0, ∆H > 0, ∆S = 0
(d) ∆G = 0, ∆H > 0, ∆S > 0
(e) ∆G = 0, ∆H < 0, ∆S < 0
(f) I do not know

Question 2: At 0 oC and 1 atm, what is the molar ratio of ice to water when these two phases are in
equilibrium?

(a) 50 (ice) to 50 (water)

(b) 1 (ice) to 99 (water)
(c) 99 (ice) to 1 (water)
(d) 99.99 (ice) to 0.01 (water)
(e) (a) – (d) are all possible
(f) I do not know

Question 3: Using thermodynamic data from Appendix 2 of the book, judge whether the following
reaction can happen spontaneously or not.

H2O (gas, 25 oC and 1 atm) → H2O (liquid, 25 oC and 1 atm)

(a) Yes, because ∆H < 0

(b) Yes, because ∆G < 0
(c) No, because ∆S < 0
(d) I do not know

Question 4: Putting 1800 g of ice at -10 oC into a closed container. The container has a moveable
pistol in equilibrium with 1 atm external pressure. Calculate the minimum amount of heat required
to convert all the ice into steam. The heat of fusion for ice is 6 kJ/mol, while the heat of vaporization
for water is 41 kJ/mol, both at 1 atm. The heat capacity for ice, water, and steam is 36, 75, 33 J/mol K,
respectively.
(a) 3500 kJ
(b) 4500 kJ
(c) 5500 kJ
(d) 6500 kJ
(e) I do not know

Question 5: Using thermodynamic data from Appendix 2 of the book, calculate equilibrium
constant for the following reaction.

H2O (liquid, 25 oC and 1 atm) → H2O (gas, 25 oC and 1 atm)

(a) 3
(b) 0.3
(c) 0.03
(d) 0.003
(e) I do not know

Question 6: The boiling temperature and the vaporization heat for water at 1 atm, is 100 oC and 41
kJ
/mol, respectively. Assuming that the vaporization heat does not change with pressure, what is the
approximate boiling temperature for water at 200 atm?

(a) 340 oC
(b) 350 oC
(c) 360 oC
(d) 370 oC
(e) I do not know

Question 7: Mixing 180 g of ice at -10 oC with 1800 g of water at 25 oC. The ice will melt into
water and all the water will reach one temperature eventually. Calculate the final temperature of
water. The experiment is done at 1 atm. The heat of fusion for ice is 6 kJ/mol at 1 atm. The heat
capacity for ice and water is 36 and 75 J/mol K, respectively.

(a) 12.0 oC
(b) 15.0 oC
(c) 18.0 oC
(d) 21.0 oC
(e) I do not know