CHE 3161: Chemistry & Chemical Thermodynamics

Solution to Test 3

Date: 09/04/2008 Total Marks: 25

The exam is open book and notes.

1) A pure fluid is described by the canonical Gibbs free energy equation: G = F (T ) +

KP , where F(T) is a substance-specific function of temperature and K is a substance-
specific constant. Determine for such a fluid expressions for V , S, H, U , Cp and CV .
These results are consistent for those for an important model of liquid-phase behaviour.
What is the model?
(10 marks)

Solution: It follows immediately from Eq. (6.10) that:

   
∂G ∂G
V = and S = −
∂P T ∂T P
Differentiation of the given equation of state yields:

dF (T )
V =K and S = −
dT
Once V and S (as well as G) are known, we can apply the equations:

H = G + TS and U = H − P V = H − P K
These become:

dF (T ) dF (T )
H = F (T ) + KP − T and U = F (T ) − T
dT dT
By Eqs. (2.16) and (2.20),
   
∂H ∂U
CP = and CV =
∂T P ∂T V
Because F is a function of temperature only, these become:

d2 F (T ) d2 F (T )
CP = −T and C V = −T = CP
dT 2 dT 2
The equation for V shows it to be constant, independent of both T and P . This is the
definition of an incompressible fluid. H is seen to be a function of both T and P , whereas
U , S, CP , and CV are functions of T only. We also have the result that CP = CV . All of
this is consistent with the model of an incompressible fluid, as discussed in Ex. 6.2.

1
2) Determine the compressibility (Z), residual enthalpy (H R ), residual entropy (S R ),
and the residual Gibbs energy (GR ), of Ethylene at 300 K and 35 bar, using the Redlich/Kwong
equation of state. For ethylene, from Table B.1, ω = 0.087, Tc = 282.3 K, Pc = 50.40
bar.
(15 marks)

Solution:

For the RK EOS, from Table 3.1 we see that σ = 1,  = 0, Ω = 0.08664 and Ψ =
−1/2
0.42748, and α(Tr ) = Tr . Then, β = ΩPr /Tr = 0.05662 and q = Ψα/ΩTr = 4.5038.
The iterative form of the equation for Z is
Z −β
Z = 1 + β − qβ .
Z (Z + β)

Starting with a guess value of Z = 1.0 we can obtain Z = 0.7707 after some iterations.
Since σ 6= , we use Eq. (6.62) for the RK-EOS to get
 
Z +β
I = ln = 0.0709,
Z

and
d ln α Tr dα 1
= =− .
d ln Tr α dTr 2
Using Eq. (6.64),
   
R d ln α
H = RT Z −1+ − 1 qI
d ln Tr
= −1766.4 J/ mol

and Eq. (6.65),

 
R d ln α
S = R ln(Z − β) + qI
d ln Tr
= −4.127 J/ (mol K).

Finally,

GR = H R − T S R = −528.3 J/ mol.