Practice Questions

QUESTION 1:

(a) Prove that, for an isothermal ideal gas process that: dS = − R d n P

(b) Show that, for an isobaric ideal gas process that: dS = C p d nT
(c) An important “trick” in deriving the energy and enthalpy equations is to make use of the TdS equations.
The first and second TdS equations are, respectively, given by:
P  V 
TdS = Cv dT + T  dV and TdS = CP dT − T
T  P
dP
T V

Derive the third TdS equation: T dS = CV 

 T  dP + C  T  dV
  
 P V  V  P
P

V   P 
(d) Show that the difference in heat capacities is given by: C p − CV = T  
 T  P  T V
Cp  V   P 
=
(e) Show that for an adiabatic process:   
Cv  P T  V  S

V  T  P 
Hint: You might need to use the identity = −1
T  P P V V T

QUESTION 2. The van der Waals equation of state (EOS) adequately describes the behaviour of the fluid
RTV a
states for a particular compound: PV = −
V −b V
The temperature dependence of the a-parameter is described by the Adachi-Lu expressions:
a(T ) = ac exp  m ( 1 − TR ) 
The value of the constant m is unity for this compound. The critical temperature, pressure and volume for this
compound are known. Furthermore, you may assume that  = C p CV = constant for the ideal gas form of this
compound. The internal energy of the van der Waals EOS is given by:
ac
U real (T ,V ) = U IG (T ) − ( 1 + mTr ) exp  m(1 − Tr )
V
(a) Consider the ideal gas state of your compound. Make use of the information provided and express the
internal energy and the enthalpy of this ideal gas in terms of the absolute temperature and the ratio of
the heat capacities, i.e.  = Cp/Cv.
(b) Derive expressions for the heat capacity (CV) of both the liquid and the vapour phases of the compound
described by the van der Waals EOS.
(c) Show, via a rigorous mathematical derivation, that the enthalpy of vaporisation predicted by the van
der Waals EOS, is given by:
V −b  T a a 
H vap (V , T ) = RT n  V  +m  − 
 VL − b  Tc  VL VV 

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QUESTION 3. The following expression for the activity coefficients is proposed for representing complex
liquid phase behaviour:

ln  A = A + ( B − A) x A − B x A2 and ln  B = A + ( B − A) x B − B x B2

(a) Show that these equations satisfy the Redlich-Kister area test for thermodynamic consistency.

(b) Show that these equations are none-the-less thermodynamically inconsistent.

QUESTION 4. Thermodynamics. The chemical potential of an ideal gas is given by

𝑖,𝐼𝐺 (𝑇, 𝑃) = 𝑖,𝐼𝐺 (𝑇, 𝑝𝑖 ) + 𝑅𝑇 ℓ𝑛(𝑃⁄𝑝𝑖 )

The chemical potential of component i in an ideal gas mixture at temperature T and pressure P is:

𝑖,𝐼𝐺𝑀 (𝑇, 𝑃) = 𝑖,𝐼𝐺 (𝑇, 𝑝𝑖 )

Where pi = yiP is the partial pressure of the ideal gas component in the ideal gas mixture.

(a) Use these equations as starting point and define the fugacity 𝑓̂𝑖 and fugacity coefficient 𝜑̂𝑖 of a
component in a real gas mixture.
(b) Show that 𝑅𝑇 ℓ𝑛 𝜑̂𝑖 is a partial molar quantity and write down an equation that will allow the
determination of ℓ𝑛 𝜑̂𝑖 from ℓn .
(c) Start from the relationship d𝜇(𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑃) = 𝑅𝑇 𝑑ℓ𝑛 𝑓 and show that the fugacity coefficient of
𝑃 𝑑𝑃
a mixture can be evaluated from ℓ𝑛 = ∫0 (𝑧 − 1) 𝑃
𝑑𝑃 𝑑𝑧 𝑑𝑉
(d) Show that along any isotherm = −
𝑃 𝑧 𝑉
 𝑑𝑉
(e) Now show that ℓ𝑛 = ∫𝑉 (𝑧 − 1) + 𝑧 − 1 − ℓ𝑛 𝑧
𝑉

(f) Consider a binary mixture described by this modified van der Waals EOS with a = 0. Let the mixing rule
2
for the b parameter be given by: 𝑏 = (𝑦1 √𝑏1 + 𝑦2 √𝑏2 ) . Use the expressions above to show that the
fugacity coefficient for component 1 can then be expressed as:
𝑅𝑇 ℓ𝑛 𝜑̂1 = 𝑃(𝐶1 + 𝐶2 𝑦22 )
Determine the constants C1 and C2.

QUESTION 5. A way to obtain the expressions for the van der Waals constants is to make
𝜕𝑃 𝜕2 𝑃
(𝜕𝑉) and (𝜕𝑉 2 ) zero at the critical point, nut why do they equal to zero at the critical point? Obtain the
𝑇 𝑇
equation Vc = 3b from this procedure.

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QUESTION 6. Derive the van der Waals Cubic equation of state from
𝑎
(𝑃 + ) (𝑉 − 𝑏) = 𝑅𝑇
𝑉2

QUESTION 7: Morisue et al. proposed the following expression for the excess Gibbs energy of a binary
mixture:

 12  21 
G E = x1 x2  −12 RT + 
 x1e + x2 x1 + x2e − 21 RT


 ij
In effect this model has two adjustable temperature-dependent parameters namely wij =
RT
(a) Derive expressions for the activity coefficients for this mixture.

(b) Express the infinite dilution activity coefficients in terms of the constants w12 and w21.

(c) At atmospheric pressure (760 mm Hg), the system MEK (1) - water (2) forms an azeotrope at 73,5C
containing 89% MEK by mass. You believe that the vapour may be assumed ideal and that the Morisue et al.
activity coefficient model adequately accounts for the nonideal behaviour of the liquid. Can you predict the
full y1-x1 diagram from this single data point? If so how will you go about doing this? What other data do you
need? Use only mathematical equations only and explain in detail!

QUESTION 8. 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   
  T  T V
 dV

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?

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QUESTION 9.