Advanced Thermodynamics, Homework Sets 1

Due on Nov. 7, 2024

Q1: (30%) A hot-air balloon can float in the sky by heating up the air in the balloon.
Assume the envelope of the balloon is an adiabatic thin rigid spherical shell with
a fixed volume V0 = 500 m3 and a small opening at the bottom of the shell.
Excluding the air in the envelope, the hot-air balloon has a weight of 250 kg.
The air inside and outside the balloon is treated as an ideal gas with a constant
ratio of specific heats γ = 1.4. The ambient atmosphere is at a temperature
T0 = 20◦ C and a pressure p0 = 101 kPa, with a density ρ0 = 1.2 kg/m3 .
The air inside the balloon is initially at the same state as the ambient atmo-
sphere and is heated by the burner placed at the center of the spherical shell. As
the air near the center is heated, it expands and lift to the top of the shell, while
some of unheated air leaves from the opening at the bottom at the same time.
When the shell is filled with hot air of uniform temperature Tf and uniform
density ρf , the burner is turn off and the balloon starts to float and is ready to
take off (final state). The whole heating process is assumed to be isobaric and
in a short period of time so that the energy exchange between the hot and cold
air in the shell is negligible.

(a) (10%) What are ρf and Tf ?

(b) (10%) Take the space in the spherical shell as a control volume and the
air in the control volume as a system. What is the difference in internal
energy between the initial and final state?
(c) (10%) How much heat does the burner supply?

Q2: (20%) A rigid gas cylinder of 1 m3 contains air at 10 bar and 30◦ C. The air
is vented to the atmosphere via a black box engine that allows the exiting
gas to be maintained at atmospheric conditions of 1 bar and 25◦ C. Assuming
that the process is adiabatic and air behaves as an ideal gas with constant
cp = 30 J/mol · K, calculate the work involved. Numerical answers are required.

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Q3: (25%) Consider a system is filled with a single-component material. Therefore,
the equation combined first and second laws becomes

dU = T dS − p dV + µ dn .

(a) (5%) Show that the expression

du = T ds − p dv .

is equivalent to the above equation in this case.

(b) (5%) If this material is an ideal gas, which satisfies the ideal-gas equation,
pv = RT , then show that
∂ 2s
=0.
∂u∂v
This means the molar entropy of an ideal can be written as

s = f (u) + g(v) .

(c) (5%) Use the expression s = f (u) + g(v), show that the molar internal
energy is a function of temperature only. Also, with the aid of the ideal-gas
equation, show that

g(v) = R ln(v) .

Therefore, by setting a reference state to evaluate the molar entropy, i.e.,

letting s = s0 when u = u0 and v = v0 , then we obtain an expression for
the molar entropy of an ideal gas:
 
v
s = s0 + f (u) − f (u0 ) + R ln .
v0

(d) (5%) If we further consider the ideal gas is calorically perfect, then show
that

f (u) = cv ln(u) .

Therefore, the molar entropy of a calorically perfect gas is

   
u v
s = s0 + cv ln + R ln .
u0 v0

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 (e) (5%) Construct the explicit expression for the molar enthalpy, the molar
Helmholtz free energy, and the molar Gibbs free energy as functions of
their respective characteristic variables, i.e., determine h(s, p), f (T, v) and
g(T, p) for a calorically perfect gas.

Q4: (25%) Rubber is a polymeric material that has properties you are undoubtedly
familiar with from playing with rubber bands. Consider a rubber band of length
L held at a tension f . Note that L and f form a conjugate variable pair. The
rubber band is also characterized by a chemical potential µ and mole number
of n.

(a) (5%) Write out the most general form of the fundamental equation in the
internal energy representation (U ) of a rubber band. Then, derive the
analog of the Gibbs-Duhem equation for a rubber band.
(b) (5%) Using this fundamental equation, express the tension f as a linear
combination of the isothermal derivatives of U and S with respect to L.
(c) (5%) For understanding rubber elasticity, it is important to determine the
relative contributions of internal energy and entropy to f . To achieve this,
we perform the following experiment: Keeping the ends of a stretched
rubber band fixed, we measure the uniaxial tensile stress τ (which is the
tension divided by the cross sectional area of the rubber band) as a function
of temperature T as indicated by Figure 1. Show how the internal energy
and entropy contributions to τ can be separately evaluated on the basis of
these measurements. Give a graphical interpretation on the plot.

Figure 1: A plot of the uniaxial tensile stress (τ ) versus temperature at constant

length.

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(d) (5%) A 1935 experiment by Meyer and Ferri indicated that, for a typical
rubber extended to 4.5 times its original length at temeratures T > 210 K,
the function depicted in the figure is adequately described by the equation
τ = T /200 with τ in units of MPa and T in Kelvins. What conclusion
can you draw about the entropic and internal energy contributions to the
elastic response?
(e) (5%) The equation of state for a particular rubber band is U = θS 2 L/n2 ,
where θ is a constant, L is the length of the rubber band, and the other
symbols have their usual meaning. Determine the chemical potential
µ(T, L/n), and show that the equation of state satisfies the analog of the
Gibbs-Duhem equation in part(a).