2.

Assignment: Basic thermodynamics concepts 2023

Instructions: The solutions to this assignment must be submitted in hard copy, handwritten form.
Typed answers will not be graded! The title page must include your full name, student number, a
statement that this is your own work and your personal signature. Every other page must be
initialled.

Problem 2.1: A real gas has the following equation of state: P(V + b) =
RT . The heat capacity for
the gas at 1 atm is given by C p= A + BT . We wish to use this gas in the Carnot-type cycle:
(i) Tabulate the expressions for q, w and ∆S (as functions of T and P) for each of the steps
A→B, B→C, C→D and D→A.
A → B Isothermal expansion at T2
B → C Adiabatic expansion
C → D Isothermal compression at T1
D → A Adiabatic compression
(ii) For the cyclical process determine the total work obtainable
(iii) Hence determine the Carnot efficiency of the system.

H d  G 
Problem 2.2: The Gibbs-Helmholtz equation for isobaric processes reads: = −T  
RT dT  RT 
(a) Derive, for isochoric processes, an analogous equation that links the Helmholtz free energy A to
the internal energy U.
(b) The molar internal energy of a monoatomic gas, that obeys van der Waals’ equation of state, is
3 a
=
given by U RT − . What are the values that the entropy, the internal energy and the Helmholtz
2 V
free energy assume at T = 0 K?
(c) Calculate the change in the Helmholtz energy for this gas for an isochoric process if the
temperature is raised from T = T1 to T = T2.

Problem 2.3: The enthalpy (Ho), the Gibbs free energy (Go) and the molar volume (Vo) of a
particular compound are known at the reference temperature and pressure (To,Po). You may assume
=
that no phase change occurs. The heat capacity is given by c p A ( B T )2 exp [ − B T ] with A and B
1 ∂V
constants. The isothermal compressibility is defined by κ ≡ −   = m . Note that Vm is a
V
V  ∂P T RT
characteristic molar volume (and a constant!) and R is the gas constant, i.e. κ is a constant at a given
temperature.

(i) State the units for the constants A, B and κ.

1
(ii) Derive an expression for the variation of the molar volume with pressure along an isotherm and
obtain the equation of state for the substance
(iii) Provide a fully annotated sketch to illustrate, in detail, the procedure that you will use to
calculate the changes in the enthalpy and the Gibbs free energy when the temperature and
pressure are increased to new values (T, P).
(iv) Derive analytic expressions for the enthalpy change ∆H = H(T,P) − H(To,Po) and the Gibbs free
energy change ∆G = G(T,P) – G(To,Po). (12)

Problem 2.4: The Helmholtz equation enables us to determine the variation of the internal energy
with volume if the equation of state is known:
∂U  ∂ P
 = T 2  
∂ V T ∂ T  T V
i. Show that the internal energy of an ideal gas does not depend on its volume
ii. Consider a real gas and show that the Helmholtz equation can be integrated to read:
V  ∂ P 
U real (T , V ) = U ideal (T ) +
∞∫ T 2     dV
 ∂ T  T V 
iii. Use this relation to show that the internal energy of a van der Waals gas is given by:
a
U vdWaals (V , T ) = U ideal (T ) −
V
iv. Obtain an expression for the excess enthalpy.
v. Give a physical interpretation for the second term on the right (a/V). What are the units of the
constant a?

Problem 2.5: Show that:

 ∂U   ∂ ln T   ∂H   ∂ ln T 
(a)   = CV   (b)   = CP  
 ∂T  S  ∂ ln P V  ∂T  S  ∂ ln V  P

where U, T, P, H, V, S, CV, CP represent internal energy, temperature, pressure, enthalpy, volume,