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Test 3 Solution 2008

This document contains the solution to a chemistry exam with two questions. 1) It derives expressions for volume, entropy, enthalpy, internal energy, heat capacity at constant pressure, and heat capacity at constant volume for a pure fluid described by the Gibbs free energy equation. It identifies the model as an incompressible fluid. 2) It calculates the compressibility, residual enthalpy, residual entropy, and residual Gibbs energy of ethylene at 300K and 35 bar using the Redlich-Kwong equation of state.

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Manishaa Varatha Raju
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101 views2 pages

Test 3 Solution 2008

This document contains the solution to a chemistry exam with two questions. 1) It derives expressions for volume, entropy, enthalpy, internal energy, heat capacity at constant pressure, and heat capacity at constant volume for a pure fluid described by the Gibbs free energy equation. It identifies the model as an incompressible fluid. 2) It calculates the compressibility, residual enthalpy, residual entropy, and residual Gibbs energy of ethylene at 300K and 35 bar using the Redlich-Kwong equation of state.

Uploaded by

Manishaa Varatha Raju
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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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.

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