Problem 1 (20 pts).

The PVT behavior of a certain gas is described by the equation of state:

P(V − b) = RT

It can be shown that U is a function of T only, γ = CP / CV = constant and C P − CV = R .

a) Show that the entropy of this gas is given by

S = CV ln T + R ln(V − b ) + constant

b) Show that for a reversible adiabatic process, P(V − b) γ = constant

Problem 2 (20 points).

Consider the formation reaction for formaldehyde H2 CO (g) from H2 (g) and CO (g)
at standard conditions of 298 K and a constant pressure of 1 atm

H2 (g) + CO (g) à H2 CO (g)

The standard free energies of formation of H2 CO (g) is ∆Gf0 = -110.0 kJ-mol-1 and that of
CO (g) is –137.3 kJ- mol-1 . (The gas constant R = 8.314 J-deg-1 -mol-1 .)

a) Calculate the standard free energy of reaction for the formation reaction for
formaldehyde described here. (The needed value for H2 should be known to you.)

b) Relate the equilibrium constant in terms of partial pressures KP to the standard

free energy of reaction and thus evaluate the numerical value of KP at 298K.

c) If equimolar amounts of H2 (g) and CO (g) are introduced initially into an empty
chamber at 298K to yield standard conditions, do you expect the reaction at
equilibrium to provide a high yield or negligible yield of H2 CO ?
Problem 3 (20 points).

One mole of an ideal gas expands from P1 = 8 bar and T1 = 600 K to P2 = 1 bar by each
of the following paths:

a. Constant volume; b. Constant temperature; c. Adiabatically.

Assuming mechanical reversibility, calculate W, Q, ∆U and ∆H for each process. Sketch

each path on a single PV diagram.

Fill in your answers in the chart below in units of kJ/mol. Note: For reversible adiabatic
expansion PVγ = constant where γ = Cp /Cv .

Cp = (7/2) R Cv = (5/2) R R = 8.314 J/mol/K

Part W Q ∆U ∆H
a.
b.
c.
Problem 4 (20 points).

Derive analytical expressions for the molar excess entropy s ex (T , ρ ) = s(T , ρ ) − s id (T , ρ )

and the excess chemical potential µ ex (T , ρ ) = µ (T ,ρ ) − µ id (T , ρ ) of the van der Waals
fluid. Here, ρ is molar density, T is temperature, s(T , ρ ) is molar entropy, s id (T , ρ ) is
molar entropy of an ideal gas, µ (T , ρ ) is chemical potential, and µ id (T , ρ ) is chemical
potential of an ideal gas. The van der Waals equation of state is

ρ RT
p= − aρ 2 ,
(1 − ρ b)

where p is pressure, R is the universal gas constant, and both a and b are positive
constant parameters.
Problem 5 (20 points). A vapor-compression refrigeration system operates on the cycle
illustrated in the figure below. The refrigerant is tetrafluoroethane. For the operating
conditions below, determine the following information:

a) the circulation rate of the refrigerant;

b) the power requirement for the compressor;
c) the heat-transfer rate in the condenser;
d) the coefficient of performance of the cycle and the coefficient of performance of a
Carnot refrigeration cycle operating between the same temperature levels.

Operating Conditions
Evaporation t = – 10(°F); condensation t = 90(°F); ?(compressor) = 0.82;
refrigeration rate = 600(Btu)(s)-1 .