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CHMY 373 2019 – Problem Set 10
Due: Fri Apr. 12
Reading: Sections 26.1‐26.5
1. Mercurial Phase Transition. The equilibrium between a liquid and its vapor can be
treated analogously to the equilibrium achieved in a chemical reaction, where the
liquid is the sole reactant and the vapor is the sole product.
The Gibbs free energy of formation and enthalpy of formation of mercury vapor at
ambient temperature 298 K and standard pressure 1 bar are 31.8 kJ mol and
61.4 kJ mol , respectively.
a. Determine the Gibbs free energy of formation and enthalpy of formation of
liquid mercury at 298 K and standard pressure.


b. Determine the ∆
and the ∆
of mercury at 298 K and
standard pressure.
c. Write a balanced “chemical reaction” for the vaporization of mercury and
determine the equilibrium constant at 298 K and standard pressure.
d. Determine the equilibrium vapor pressure of liquid mercury at 298 K,
assuming the vapor is an ideal gas. In the presence of gases, assume that any
liquid species have an activity equal to 1.

e. Determine ∆
.
f. Estimate the normal boiling point temperature of mercury using the



and ∆
obtained above.
2. Boranes. Diborane, B2H6, is a toxic, pyrophoric, and unstable gas at ambient
conditions, decomposing into hydrogen and other higher boranes as, for example:
B H
2
→ B H
5
6
H
5
When this reaction is carried out starting with 1 mol of B H
no initial B H
or H
, the degree of dissociation,
, is found to be 0.020 at 25 °C and a fixed

for the decomposition of B H
at 25 °C.
total pressure of 2 bar. Determine ∆
3. Cracking Ammonia, Gromit! The cracking of gaseous ammonia is an industrial
process used to create so‐called “forming gas”, a mixture of hydrogen and nitrogen:
2NH
→N
The equilibrium constant for this reaction is
standard states at 1 bar standard pressure.
3H
4748 at 673 K, using ideal gas
Calculate the final partial pressures of each of the three gaseous species after
pumping pure ammonia into a cracking reactor held at fixed temperature and
pressure of 673 K and 5 bar . You may need to use a calculator or solver program,
and some intuition to deduce the sole physical result.
4. Syngas. “Synthesis gas,” a mixture containing carbon oxides and hydrogen, is a
crucial intermediate for several important chemicals e.g., in the production of
synthetic liquid fuels . Syngas is directly employed to produce methanol, a reaction
that is highly selective when performed over the appropriate catalyst at high
pressures.
2H
→ CH OH
CO
The equilibrium constant for this reaction is
standard states at 1 bar.
0.00627 at 523 K, using ideal gas
If carbon monoxide and hydrogen are initially added in a 1:1 ratio, calculate the
equilibrium partial pressures of the three gaseous species at 523 K and 50 bar. You
may need to use a calculator or solver program, and some intuition to deduce the
sole physical result.

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