Derek Bischoff

12/9/2016

CHEG 231-080
Chemical Engineering Thermodynamics I
Tetrahydrofuran (THF)
Semester Project
2. Abstract
In this report, we explore various thermodynamic properties and charts of tetrahydrofuran, or
THF for short. The report includes a brief introduction to THF, including its uses, its basic chemistry, its
safety issues, and its environmental impacts. The report also includes an in-depth analysis of
tetrahydrofuran’s thermodynamic properties by focusing on a series of plots that include heat capacity,
enthalpy, multiple phase diagrams, the Joule-Thomson coefficient, and the compressibility factor. These
graphs were created using the Peng-Robinson equation of state, which is based on three pieces of
information: the critical temperature, the critical pressure, and the Acentric factor. The report will also
discuss the strengths of using this model to predict thermodynamic properties.
3. Introduction
a) Basic Chemistry
 Tetrahydrofuran or THF is a polar organic molecule that is commonly used as a
solvent. The structure of the molecule can be seen in Appendix A. It is a heterocyclic
compound that has both carbon and oxygen, thus making it an ether. THF is highly
flammable and can form organic peroxides which can be explosive.3 For this reason,
it is often stored either with a stabilizer or under argon to avoid contact with air.
THF’s triple point has a temperature of 164.76 K.7 It has a critical temperature of
505.1 K and a pressure of 5190000 Pa.7
 I was able to find a zero-pressure heat capacity dependence for THF based on data
from the National Institute of Standards and Technology.7 The equation generated
was: 𝑦 = 2𝐸 − 16𝑇 6 − 1𝐸 − 12𝑇 5 + 3𝐸 − 09𝑇 4 − 3𝐸 − 06𝑇 3 + 0.002𝑇 2 −
0.2591𝑇 + 47.817 The plot and fit can be seen in Appendix B.
 The enthalpy of fusion data was obtained from NIST as well. There were multiple
points present that were in agreement.7 The enthalpy of sublimation had to be
calculated from the enthalpy of fusion and vaporization. I used the lowest
temperature range value for vaporization that was available. There was no data
recorded for the temperature at which these data were taken.
𝑘𝐽
∆𝐻𝑓𝑢𝑠 = 8.540 𝑓𝑜𝑟 𝑇 = 164.76 𝐾
𝑚𝑜𝑙
𝑘𝐽 𝑘𝐽 𝑘𝐽
∆𝐻𝑠𝑢𝑏 = ∆𝐻𝑓𝑢𝑠 + ∆𝐻𝑣𝑎𝑝 = 8.540 + 32.30 = 40.84
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙

 The critical compressibility for THF is .259 and the Acentric factor is .217.2
 For the Peng-Robinson EoS, a[T]= alpha[𝑇] ∗ ((.45723553 ∗ 𝑅^2 ∗ Tc^2)⁄(Pc))
where alpha[T]= (1 + kappa(1 − Sqrt[𝑇⁄Tc]))^2 and kappa=.37464 + 1.54226 ∗
𝜔 − .26992 ∗ 𝜔^2. Also for the PR-EoS, b=(.077796074 ∗ 𝑅 ∗ Tc)⁄Pc=6.245𝐸 − 5.
 The following are the Antoine parameters for THF:

Antoine Equation Parameters (Units: mmHg, °C)

A B C Temperature Range
6.995151 1202.291 226.2541 23-100 °C (296.15 – 373.15 K)
7.427251 1532.811 272.0811 121-265 °C (394.15 – 538.15 K)
7.1053712 1256.68 12
232.62112 -108.5-267 °C (164.65 – 540.15 K)
Antoine Equation Parameters (Units: bar, K)
A B C Temperature Range
4.121187 1202.9427 -46.8187 296.29 – 372.8 K
Both sets of parameters apply for the following Antoine Equation:
𝐵
𝑙𝑜𝑔10 [𝑃𝑣𝑎𝑝 ] = 𝐴 −
𝑇+𝐶
 A triple point pressure could not be found in the literature so I calculated it using the
Antoine equation where the parameters are listed in the table above. With the
temperature and pressure, the molar volume was calculated using the Peng-Robinson
EoS. The molar volume was also calculated for the normal melting point.
 Triple Point Critical Point Normal Melting Point
Temperature 164.76 K 7 501.1 K 7 164.65 K 12
Pressure .1302 Pa 12 5.19 MPa 7 1 atm 12
Molar Volume 4 3
1.052*10 m /mol .225 L/mol 7
6.599*10-5 m3/mol
b) Compound Uses
 THF’s major use is in the creation of polytetramethylene ether glycol, which is then
used to make thermoplastic urethane elastomers, stretch fibers like spandex, and high
performance copolyester elastomers.5 THF is also used in the manufacture of PVC as
a solvent as well as in the synthesis of pharmaceuticals and as a solvent for many
organic reactions.5
c) Safety Issues
 THF is easily absorbed by all routes of exposure such as inhalation, ingestion,
injection, and absorption, but has a low to moderate acute toxicity.4 THF is not
considered a skin irritant, a sensitizer, or mutagenic.4
d) Environmental Issues
 THF has a low bioaccumulation potential and is inherently biodegradable, which
means it does not remain for long times in the environment. There is no ecotoxicity
hazard, or the ability for the chemical to affect an ecosystem, from THF. Exposure to
THF in the workplace was found to be below toxicity thresholds.4
e) Manufacturing Processes
 The two largest producers of tetrahydrofuran are BASF and the Dairen Chemical
Corporation. 5 47% of the world’s THF is produced by these two companies, as of
2015. 5
4. Methods
a) Peng-Robinson EOS description
 Tetrahydrofuran is primarily used when it is in liquid form, for example as a solvent
in a chemical reaction or in the synthesis of polytetramethylene ether glycol, the
major use of THF.11 Therefore, it is important for the equation of state to accurately
predict its liquid properties. Peng-Robinson does this prediction well. Peng-Robinson
was designed for the use with hydrocarbons with less than ten carbons. 10
b) Critical properties
 2 Critical Temperature: 501.1 K
 2 Critical Pressure: 5.19 MPa
 2 Critical Compressibility (zc): .259
c) Overview of numerical procedures used to generate the thermodynamic charts
 To generate the plot of constant pressure heat capacity versus temperature for
𝜕𝑃
different isobars, I first used the standard form of the PR-EoS to take ( ) and
𝜕𝑉
𝑇
𝜕𝑃 𝜕𝑇 𝜕𝑃
(𝜕𝑇 ) . Then I got (𝜕𝑃) by taking the inverse of (𝜕𝑇 ) . Then by the triple product
𝑉 𝑉 𝑉
rule, I found that
𝜕𝑉 1
(𝜕𝑇 )𝑃 = − 𝜕𝑇 𝜕𝑃
. We then want to find CP, which can be viewed as having an
( ) ∗( )
𝜕𝑃 𝑉 𝜕𝑉 𝑇

ideal gas contribution and a real gas correction. The ideal gas contribution was found
as a function of T by using the Excel data fitting option with data from NIST. The
data fit can be seen in Appendix B. The real gas correction for Cp can be found by
 𝜕𝑃 𝜕𝑉
using the equation 𝐶𝑃𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙 = 𝐶𝑣𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙 + 𝑇 ( ) ( )𝑃 − 𝑅 that was obtained
𝜕𝑇 𝑉 𝜕𝑇

from R.M. Pratt and that was also derived in class.9 To find the 𝐶𝑣𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙
𝑇𝑎 ′′ 𝑧+𝐵(1+√2)
contribution, we can use the fact that 𝐶𝑣𝑟𝑒𝑠𝑖𝑑𝑢𝑎𝑙 = 𝑏√8
ln[𝑧+𝐵(1− 2)] which is derived
√
from the expression for internal energy using the Peng-Robinson EoS10. Then to find
the final equation for Cp, I added the ideal gas and residual contributions. This
calculated constant pressure heat capacity for a real gas, tetrahydrofuran, was plotted
in comparison to just the ideal gas to see the deviations from ideality.
 To generate the plot of enthalpy (both specific and molar) versus temperature at
different isobars, I used a departure function using the PR-EoS found by Stanley
Sandler.13 As part of this function, the ideal gas enthalpy needed to be calculated. To
calculate this contribution, we took the integral over Cp from the reference point, the
triple point of THF, to the desired temperature. We then added the real fluid
contribution to the ideal gas contribution for the total enthalpy. Once this plot was
generated in units of J/mol, the specific enthalpy was generated simply by dividing
by the molar mass of THF.
 To generate the plot of z, the compressibility factor, versus pressure, I first used
Mathematica to solve for the roots of the cubic form of the PR-EoS. After noting that
two of the roots were imaginary, the remaining root to the cubic equation was
plotted.
 To generate the plot of the Joule-Thomson coefficient versus temperature at different
1 𝜕𝑣 𝜕𝑣
isobars, the following equation was used9: 𝜇𝐽𝑇 = 𝐶𝑝 [𝑇 (𝜕𝑇 ) − 𝑣] . Since (𝜕𝑇 ) was
𝑃 𝑃
calculated in a previous step for the constant pressure heat capacity, this form of the
coefficient was the most efficient to plot.
 To generate the plot of P versus V at different isotherms using the PR-EoS, the
standard form of the Peng-Robinson equation was used. To generate the spinodal
limits of stability, I plotted 300 isotherms of the PR-EoS. I then took the derivative of
each isotherm and found the critical points (calculus term meaning) by setting each to
zero. I then noted the volume at which each critical point was found. The noted
volumes were then passed into the standard form of the PS-EoS at their respective
isobars to find the pressure. These pressures were then plotted on the P-V diagram as
the spinodal and bimodal limits.
 To generate the plot of P versus T using the PR-EoS, I used the Antoine equation to
plot the liquid-vapor coexistence curve. I used the Clausius-Clapeyron equation to
plot the solid-vapor line. Finally, I used the triple point and the normal melting point
to calculate a linear line to act as the solid-liquid coexistence curve.
5. Results

This is the plot of constant pressure heat capacity as a function of temperature. Overall, there is an upward
𝜕𝐻
trend, which agrees with the enthalpy plot. This makes sense since 𝐶𝑝 ≡ ( 𝜕𝑇 ) and the enthalpy increases
𝑃
with temperature. There appears to be discontinuities in the plot around 500K, which would correspond to
the critical temperature of THF.

This plot is of molar enthalpy and has the same features as the next specific enthalpy plot. The only
difference is that this plot has a different scale due to the units. In both enthalpy plots, there does not
appear to be any significant region over which a linear approximation would be very good.
This is the plot of specific enthalpy versus temperature. As expected, it does increase with higher
temperatures, however, there is a discontinuity on the Pr=.4 isobar as well as around 500 K which is
expected since that is the critical temperature of THF.

This is the plot of the compressibility factor versus reduced pressure. As we get closer to the critical point,
the isotherms begin to dip down. Then finally at the critical isotherm, there is an inflection point at the
critical point.
This plot is the Joule-Thomson coefficient versus temperature. At the critical temperature, there is a
discontinuity, which is to be expected at the critical point.

This is the P-V phase diagram including the spinodal and bimodal limits.
 P-T Phase Diagram for THF
6000000

5000000

4000000
Pressure (Pa)

3000000

2000000

1000000

0
0 100 200 300 400 500 600
Temperature (K)

This is the pressure-temperature phase diagram for tetrahydrofuran on linear scales.

Semi-Log P-T Phase Diagram for THF

10000000
1000000
100000
10000
1000
100
Pressure (Pa)

10
1
0.1 0 100 200 300 400 500 600
0.01
0.001
0.0001
0.00001
0.000001
0.0000001
1E-08
Temperature (K)

This is the same pressure-temperature diagram as before, except now the ordinate is on a log scale to help
emphasize the large range of pressures represented.
6. Discussion
Unfortunately, I was not able to find any plots in the literature that I could compare my graphs to.
Much of the behavior observed in the graphs is explainable. The constant pressure heat capacity curve
shows an increase as temperature increases. It is also important to note the spike at about 500 K, the
critical temperature of THF. This is important since it indicates a phase transition and we know that Cp is
not continuous there. We can also see how that at higher pressures, there is more deviation from ideality.
The molar and specific enthalpy plots have the same shape and characteristics since they differ only by a
scaling factor. There is a general increase in enthalpy with an increase in temperature. In the orange line,
the critical isobar, a nearly vertical segment is again observed at about 500 K, again indicating the critical
point. As for the compressibility factor, z, it is observed that the blue line, the critical isotherm, has an
inflection point unlike the other isotherms, thus indicating the critical point. The Joule-Thomson
coefficient plot shows a decrease in value as temperature increases. I was able to find some plots that
agree with this downward trend as temperature increases. There is again a large spike at around 500 K,
indicating the critical point. In the P-V plot, the regions of the graph can be identified as liquid, vapor,
and a liquid-vapor mixture. The spinodal and bimodal limits are plotted to show stability. The final two
graphs are P-T phase diagrams with different scales.

7. Conclusion
Through the use of low pressure experimental heat capacity data, the critical temperature and
pressure, the Acentric factor, triple point data, and the normal melting point, all of these thermodynamic
properties were able to be predicted through the use of the cubic Peng-Robinson equation of state. The
Peng-Robinson equation of state was designed for use in determining thermodynamic properties of small
organic molecules with less than 10 carbons. Since my molecule matches this description, the PR-EoS
would make good predictions about its thermodynamic properties.
8. References
1. Dortmund Data Bank. Saturated Vapor Pressure
http://ddbonline.ddbst.com/AntoineCalculation/AntoineCalculationCGI.exe (accessed Dec 1,
2016).
2. Lira, C. Peng Robinson Equation of State
http://www.egr.msu.edu/~lira/computer/EXCEL/PREOS.XLS (accessed Nov 26, 2016).
3. Solvent Stabilizer Systems http://www.sigmaaldrich.com/chemistry/solvents/learning-
center/stabilizer-systems.html (accessed Nov 26, 2016).
4. Fowles J, Boatman R, Bootman J, et al. A review of the toxicological and environmental hazards and
risks of tetrahydrofuran. Crit Rev Toxicol. 2013;43(10):811-28.
5. Tetrahydrofuran https://www.ihs.com/products/tetrahydrofuran-chemical-economics-handbook.html
(accessed Nov 27, 2016).
6. Correlation and prediction of the vapor pressures of pure liquids over large pressure ranges Jack
McGarry Industrial & Engineering Chemistry Process Design and Development 1983 22 (2),
313-322
7. .J. Linstrom and W.G. Mallard, Eds., NIST Chemistry WebBook, NIST Standard Reference Database
Number 69, National Institute of Standards and Technology, Gaithersburg MD, 20899,
http://webbook.nist.gov/cgi/cbook.cgi?ID=C109999&Mask=1
8. Pratt, R. M. Thermodynamic Properties Involving Derivatives
http://ufdcimages.uflib.ufl.edu/AA/00/00/03/83/00150/AA00000383_00150_00112.pdf (accessed
Dec 2, 2016).
9. Prediction of the Condensation Behavior of Natural Gas:  A Comparative Study of the
Peng−Robinson and the Simplified-Perturbed-Hard-Chain Theory Equations of State Marianna E.
Voulgaris,Cor J. Peters, and Jakob de Swaan Arons Industrial & Engineering Chemistry
Research 1998 37 (5), 1696-1706
10. P. Rajendran, V. Mahadevan, M. Srinivasan, Synthesis of some low glass transition temperature
polytetrahydrofuran polymers, European Polymer Journal, Volume 25, Issue 5, 1989, Pages 461-
463, ISSN 0014-3057, http://dx.doi.org/10.1016/0014-3057(89)90186-9.
(edirect.com/science/article/pii/0014305789901869)
11. National Center for Biotechnology Information. PubChem Compound Database; CID=8028,
https://pubchem.ncbi.nlm.nih.gov/compound/8028 (accessed Dec 10, 2016).
12. Yaws, Carl L Narasimhan, Prasad, K. Gabbula, Chaitanya. (2009). Yaws' Handbook of Antoine
Coefficients for Vapor Pressure (2nd Electronic Edition). Knovel.
http://app.knovel.com/hotlink/toc/id:kpYHACVPEH/yaws-handbook-antoine/yaws-handbook-
antoineSandler, S. I. Chemical, Biochemical, and Engineering Thermodynamics; John Wiley:
Hoboken, NJ, 2006.
13. Sandler, S. I. (2006) Chemical, biochemical, and engineering thermodynamics. John WileyHoboken,
NJ.
9. Appendix
A. Molecular Structure of THF

B. Zero-Pressure Heat Capacity Data Plot from NIST

C. Mathematica Code
Cp vs. T
The units for the following constants are m^3*Pa/mol*k, Pa, and K respectively for R, Pc, and Tc.

R = 8.314459848;
Pc = 5 190 000;
Tc = 501.1;
ω = .217;
kappa = .37464 + 1.54226 * ω - .26992 * ω ^ 2;
alpha[T_] = 1 + kappa 1 - Sqrt[T / Tc] ^ 2;
a[T_] = alpha[T] * .45723553 * R ^2 * Tc ^ 2  (Pc);
b = .077796074 * R * Tc  Pc;
A[T_, P_] = (a[T] * P)  ((R * T)) ^ 2;
B[T_, P_] = (b * P) / (R * T);

Then I need to find a solution for z in terms of T and P.

RootsZ ^ 3 - 1 - B[T, P] * Z ^2 + A[T, P] - 3 * B[T, P] ^ 2 - 2 * B[T, P] * Z -
A[T, P] * B[T, P] - B[T, P] ^ 2 - B[T, P] ^ 3  0, Z
2.50376 × 10-6 (1. P - 133 133. T)
Z- + 2.36947 × 10-10
T
- 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T - 60 655.3 P T + 1.77244 × 109 T2  

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 T2 T3/2 T

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2  +

1/3
3

2.37319 × 10-14 P3 6.3164 × 10-7 P2

2. + - - -
1 0.0000172186 P2
3 × 21/3 T3 T3 T5/2
5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

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2 wri-fe-6040[2].cdf

2.37319 × 10-14 P3 6.3164 × 10-7 P2

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2  ||

1/3
3

2.50376 × 10-6 (1. P - 133 133. T)

Z- - 1.18474 × 10-10 + 2.05202 × 10-10 
T
- 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T - 60 655.3 P T + 1.77244 × 109 T2  

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 T2 T3/2 T

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2  -

1/3
3

2.37319 × 10-14 P3 6.3164 × 10-7 P2

1 -  3  2. + - - -
1 0.0000172186 P2
6 × 21/3 T3 T3 T5/2
5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 T2 T3/2 T

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2  ||

1/3
3

2.50376 × 10-6 (1. P - 133 133. T)

Z- - 1.18474 × 10-10 - 2.05202 × 10-10 
T
- 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T - 60 655.3 P T + 1.77244 × 109 T2  

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 2. + - - -
0.0000172186 P2
T3 T3 T5/2

+ + - +

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 wri-fe-6040[2].cdf 3

5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 T2 T3/2 T

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2  -

1/3
3

2.37319 × 10-14 P3 6.3164 × 10-7 P2

1 +  3  2. + - - -
1 0.0000172186 P2
6× 21/3 T3 T3 T5/2
5.11567 × 10-9 P2
+ + - +
0.57309 P 0.021023 P 0.000102664 P

2.37319 × 10-14 P3 6.3164 × 10-7 P2

T2 T2 T3/2 T

 2. + - - -
0.0000172186 P2
T3 T3 T5/2
5.11567 × 10-9 P2
+ + - -
2
0.57309 P 0.021023 P 0.000102664 P
T2 T2 T3/2 T

7.1837 × 10-28 - 3.38589 × 108 P + 1. P2 + 1.24206 × 107 P T -

1
T6

60 655.3 P T + 1.77244 × 109 T2 

1/3
3

Z[T_, P_] = - 2.503764462517662`*^-6 1.` P - 133132.86386298086` T +

1

2.3694717132738583`*^-10
T

- 3.3858851854814386`*^8 P + 1.` P2 + 1.2420643212416887`*^7 P T -

60655.30775357311` P T + 1.7724359440358994`*^9 T2  

T2 2.0000000000000004` + -
0.00001721859258629788` P2
T3

- -
2.373188329419524`*^-14 P3 6.316398324769625`*^-7 P2
T3 T5/2

+ +
0.5730901356759318` P 5.115670202414499`*^-9 P2
T2 T2
- +
0.02102300495689787` P 0.00010266431566851241` P
T3/2 T

 2.0000000000000004` + -
0.00001721859258629788` P2
T3

- -
2.373188329419524`*^-14 P3 6.316398324769625`*^-7 P2
T3 T5/2

+ +
0.5730901356759318` P 5.115670202414499`*^-9 P2
T2 T2

- -

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4 wri-fe-6040[2].cdf

- -
2
0.02102300495689787` P 0.00010266431566851241` P
T3/2 T

7.1837026108329495`*^-28 - 3.3858851854814386`*^8 P +
1

1.` P2 + 1.2420643212416887`*^7 P T -
T6

60655.30775357311` P T + 1.7724359440358994`*^9 T2  +
1/3
3

2.0000000000000004` + -
1 0.00001721859258629788` P2
3 × 21/3 T3

- -
2.373188329419524`*^-14 P3 6.316398324769625`*^-7 P2
T3 T5/2

+ +
0.5730901356759318` P 5.115670202414499`*^-9 P2
T2 T2
- +
0.02102300495689787` P 0.00010266431566851241` P
T3/2 T

 2.0000000000000004` + -
0.00001721859258629788` P2
T3

- -
2.373188329419524`*^-14 P3 6.316398324769625`*^-7 P2
T3 T5/2

+ +
0.5730901356759318` P 5.115670202414499`*^-9 P2
T2 T2

- -
2
0.02102300495689787` P 0.00010266431566851241` P
T3/2 T

7.1837026108329495`*^-28 - 3.3858851854814386`*^8 P +
1

1.` P2 + 1.2420643212416887`*^7 P T -
T6

60655.30775357311` P T + 1.7724359440358994`*^9 T2 
1/3
3
;

We can then find the molar volume in terms of z.

V[T_, P_] = (R * T * Z[T, P]) / (P);

Finding dPdTatV :
dPdTatV[T_, P_] =
(R / (V[T, P] - b)) - ((a '[T]) / (V[T, P] * (V[T, P] + b) + b * ((V[T, P] - b))));

Finding dTdPatV :
dTdPatV[T_, P_] = 1  dPdTatV[T, P];

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 5

Finding dPdVatT :
dPdVatT[T_, P_] = (- R * T)  (V[T, P] - b) ^ 2 +
2 * a[T] * (V[T, P] + b)  ((V[T, P] * (V[T, P] + b) + b * ((V[T, P] - b)))) ^ 2;

We can then use the triple product rule to find dVdTatP

dPdVatT*dTdPatV*dVdTatP = -1;
dVdTatP = -1/(dPdVatT*dTdPatV);

dVdTatP[T_, P_] = - 1  (dPdVatT[T, P] * (dTdPatV[T, P]));

Just verifying that it works :

dPdVatT[T, P] * dVdTatP[T, P] * dTdPatV[T, P]
-1

Then combining equations 18 and 14 from source 10 :

CvResidual[T_, P_] = (a ''[T] * T)  b * Sqrt[8] *
LogZ[T, P] + B[T, P] * 1 + Sqrt[2]  Z[T, P] + B[T, P] * 1 - Sqrt[2];

CpResidual[T_, P_] = CvResidual[T, P] + (T * dPdTatV[T, P] * dVdTatP[T, P] - R);

Then we can add Cp residual and Cp ideal gas to find the true Cp. The Cp ideal gas data was fit using
the Excel data fitting options.

CpIG[T_] =
2*^-16 * T ^ 6 - 1*^-12 * T ^5 + 3*^-9 * T ^4 - 3*^-6 * T ^ 3 + 0.002 * T ^2 - 0.2591 * T + 47.817;

Therefore, our final equation for Cp is :

Cp[T_, P_] = CpResidual[T, P] + CpIG[T];

Printed by Wolfram Mathematica Student Edition

6 wri-fe-6040[2].cdf

Combined Plot of Cp vs. T for Each Isobar

Plot[{Cp[T, Pc * .05], Cp[T, Pc * .4], Cp[T, Pc * 1], Cp[T, Pc * 1.75], CpIG[T]},
{T, 164.76, 1.2 * Tc},
PlotLegends  {"Pr=.05", "Pr=.4", "Pr=1", "Pr=1.75", "Ideal Gas"},
AxesLabel  {"Temperature (K)", "Cp (J/mol*K)"}]
Cp (J/mol*K)

500

400 Pr=.05
Pr=.4
300 Pr=1
Pr=1.75
200
Ideal Gas
100

Temperature (K)
300 400 500 600

Enthalpy vs. T
To find the enthalpy vs. temperature graph, I will use departure functions. For each isobar, I will use the
departure function for Peng-Robinson evaluated at my reference state (triple point temperature {164.76
K} and triple point pressure {0.0835109 Pa }.

General Departure Function Using Peng - Robinson from pg. 218

Tref = 164.76;

HidealGas[T_] = Integrate[CpIG[T], {T, Tref, T}];

HdepartureTotal[T_, P_] = R * T * Z[T, P] - 1 +

(T * a '[T] - a[T])  2 * Sqrt[2] * b * LogZ[T, P] + 1 + Sqrt[2] * B[T, P] 
Z[T, P] + 1 - Sqrt[2] * B[T, P] + HidealGas[T];

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 7

Combined Plot of Molar Enthalpy vs. Temperature

Plot[{HdepartureTotal[T, Pc * 1.75], HdepartureTotal[T, Pc * 1],
HdepartureTotal[T, Pc * .4], HdepartureTotal[T, Pc * .05]},
{T, 164.76, 1.2 * Tc}, PlotLegends  {"Pr=1.75", "Pr=1", "Pr=.4", "Pr=.05"},
AxesLabel  {"Temperature (K)", "Molar Enthalpy (J/mol)"}]
Molar Enthalpy (J/mol)

60 000

40 000 Pr=1.75
Pr=1
20 000
Pr=.4
Temperature (K) Pr=.05
300 400 500 600

-20 000

Combined Plot of Molar Enthalpy vs. Temperature

PlotHdepartureTotal[T, Pc * 1.75]  72.11, HdepartureTotal[T, Pc * 1]  72.11,
HdepartureTotal[T, Pc * .4]  72.11, HdepartureTotal[T, Pc * .05]  72.11,
{T, 164.76, 1.2 * Tc}, PlotLegends  {"Pr=1.75", "Pr=1", "Pr=.4", "Pr=.05"},
AxesLabel  {"Temperature (K)", "Specific Enthalpy (kJ/kg)"}
Specific Enthalpy (kJ/kg)

800

600 Pr=1.75
400 Pr=1
200 Pr=.4
Temperature (K) Pr=.05
300 400 500 600
-200

-400

Z vs. P
Critical Temperature =501.1 K
Pitzer Acentric Factor (ω) = .217
Critical Compressibility (zc) = .259
These two values in addition to Tc and Pc were obtained from: http://www.egr.msu.edu/~lira/comput-
er/EXCEL/PREOS.XLS

Printed by Wolfram Mathematica Student Edition

8 wri-fe-6040[2].cdf

Finding Kappa (k)

ω = .217;
k = .37464 + 1.54226 * ω - .26992 * ω ^ 2;

Then Finding α (T)

Tc = 501.1;

All temperatures are in units of K.

α[T_] := 1 + k 1 - Sqrt[T / Tc] ^ 2

Then Finding a (T)

R = .083145;
Pc = 51.9;

The gas constant has units of L*bar/mol*K and P has units of bar.

a[T_] := .45724 * R ^2 * Tc ^ 2  (Pc) * (α[T])

Then Finding b
b = .07780 * R * Tc  Pc
0.0624558

Units are L/mol.

Then finding A and B in General Terms of T and Pr

A[T_, Pr_] := ((a[T]) * (α[T]) * (Pr * Pc))  R ^ 2 * T ^ 2
B[T_, Pr_] := (b * Pr * Pc) / (R * T)

A and B at Tr = 1
If Tr = 1, then T = Tc*1 = Tc.

T1 = Tc;

A1[Pr_] := a[T1] * α[T1] * (Pr * Pc)  R ^ 2 * T1 ^ 2

B1[Pr_] := (b * Pr * Pc)  R * T1

A and B at Tr = 1.2
If Tr = 1.2, then T = Tc*1.2.

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 9

T2 = Tc * 1.2;

A2[Pr_] := a[T2] * α[T2] * (Pr * Pc)  R ^ 2 * T2 ^ 2

B2[Pr_] := (b * Pr * Pc)  R * T2

A and B at Tr = 1.5
If Tr = 1.5, then T = Tc*1.5.

T3 = Tc * 1.5;

A3[Pr_] := a[T3 * 1.5] * α[T3] * (Pr * Pc)  R ^2 * T3 ^ 2
B3[Pr_] := (b * Pr * Pc)  R * T3

A and B at Tr = 2
If Tr = 2, then T = Tc*2 .

T4 = Tc * 2;

A4[Pr_] := ((a[T4]) * (α[T4]) * (Pr * Pc))  R ^ 2 * T4 ^ 2

B4[Pr_] := (b * Pr * Pc) / (R * T4)

Printed by Wolfram Mathematica Student Edition

10 wri-fe-6040[2].cdf

Equation for Z Predicted by PR EoS at Tr=1

Solvez ^ 3 - 1 - B1[Pr] * z ^2 + A1[Pr] - 2 * B1[Pr] - 3 * B1[Pr] ^ 2 * z -
A1[Pr] * B1[Pr] - B1[Pr] ^ 2 - B1[Pr] ^ 3  0, z

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

z  0.0000666667 (5000. - 389. Pr) +

3.7195 × 109 - 6.44236 × 109  - 1. + 1.06052 Pr - 0.0605284 Pr2  
1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030 Pr2 - 1.46556 × 1029 Pr3 +
0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 -
7.46815 × 10-12 + 1.29352 × 10-11  1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030
Pr2 - 1.46556 × 1029 Pr3 + 0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 ,
z  0.0000666667 (5000. - 389. Pr) + 3.7195 × 109 + 6.44236 × 109 
- 1. + 1.06052 Pr - 0.0605284 Pr2  
1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030 Pr2 - 1.46556 × 1029 Pr3 +
0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 -
7.46815 × 10-12 - 1.29352 × 10-11  1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030
Pr2 - 1.46556 × 1029 Pr3 + 0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 ,
z  0.0000666667 (5000. - 389. Pr) - 7.439 × 109 - 1. + 1.06052 Pr - 0.0605284 Pr2  
1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030 Pr2 - 1.46556 × 1029 Pr3 +
0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 +
1.49363 × 10-11 1.11149 × 1031 - 1.76814 × 1031 Pr + 6.71345 × 1030 Pr2 -
1.46556 × 1029 Pr3 + 0.00729479 √ 4.24603 × 1065 Pr2 - 8.59274 × 1065 Pr3 +
4.447 × 1065 Pr4 - 9.91768 × 1063 Pr5 - 1.11204 × 1062 Pr6 1/3 

z1[Pr_] := 0.00006666666666666667` 5000.` - 389.` Pr -

7.4389996728855715`*^9 - 1.` + 1.06052` Pr - 0.06052840000000001` Pr2  
1.1114946662743443`*^31 - 1.7681434852159013`*^31 Pr +
6.713448413638046`*^30 Pr2 - 1.465562032026887`*^29 Pr3 +
0.007294791053386977` √ 4.246025480682195`*^65 Pr2 -
8.59273893484482`*^65 Pr3 + 4.447002340981526`*^65 Pr4 -
9.917681620448268`*^63 Pr5 - 1.1120399396004995`*^62 Pr6  +
1/3

1.49362973513899`*^-11 1.1114946662743443`*^31 - 1.7681434852159013`*^31 Pr +

6.713448413638046`*^30 Pr2 - 1.465562032026887`*^29 Pr3 +
0.007294791053386977` √ 4.246025480682195`*^65 Pr2 -
8.59273893484482`*^65 Pr3 + 4.447002340981526`*^65 Pr4 -
9.917681620448268`*^63 Pr5 - 1.1120399396004995`*^62 Pr6 
1/3

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 11

Equation for Z Predicted by PR EoS at Tr = 1.2

Solvez ^ 3 - 1 - B2[Pr] * z ^2 + A2[Pr] - 2 * B2[Pr] - 3 * B2[Pr] ^ 2 * z -
A2[Pr] * B2[Pr] - B2[Pr] ^ 2 - B2[Pr] ^ 3  0, z

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

z  0.0000555556 (6000. - 389. Pr) +

3.0485 × 1010 - 5.28016 × 1010  - 1. + 0.464076 Pr - 0.0420336 Pr2  
6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033 Pr2 - 4.66944 × 1031 Pr3 +
0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 -
9.11195 × 10-13 + 1.57824 × 10-12  6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033
Pr2 - 4.66944 × 1031 Pr3 + 0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 ,
z  0.0000555556 (6000. - 389. Pr) + 3.0485 × 1010 + 5.28016 × 1010 
- 1. + 0.464076 Pr - 0.0420336 Pr2  
6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033 Pr2 - 4.66944 × 1031 Pr3 +
0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 -
9.11195 × 10-13 - 1.57824 × 10-12  6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033
Pr2 - 4.66944 × 1031 Pr3 + 0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 ,
z  0.0000555556 (6000. - 389. Pr) - 6.097 × 1010 - 1. + 0.464076 Pr - 0.0420336 Pr2  
6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033 Pr2 - 4.66944 × 1031 Pr3 +
0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 +
1.82239 × 10-12 6.11944 × 1033 - 4.25983 × 1033 Pr + 1.56772 × 1033 Pr2 -
4.66944 × 1031 Pr3 + 0.00298843 √ 9.42387 × 1071 Pr2 - 6.49695 × 1071 Pr3 +
1.83643 × 1071 Pr4 - 6.07932 × 1069 Pr5 - 6.72637 × 1067 Pr6 1/3 

z2[Pr_] := 0.00005555555555555556` 6000.` - 389.` Pr - 6.096998171737942`*^10

- 1.` + 0.46407633195264664` Pr - 0.04203361111111111` Pr2  
6.119443911191258`*^33 - 4.259833625843394`*^33 Pr + 1.567717039678073`*^33 Pr2 -
4.669442617015683`*^31 Pr3 + 0.0029884335150971385` √ 9.423874760099713`*^71
Pr2 - 6.496952940779882`*^71 Pr3 + 1.836431491735722`*^71 Pr4 -
6.079320087188218`*^69 Pr5 - 6.726367276312535`*^67 Pr6  +
1/3

1.822390428558043`*^-12 6.119443911191258`*^33 - 4.259833625843394`*^33 Pr +

1.567717039678073`*^33 Pr2 - 4.669442617015683`*^31 Pr3 +
0.0029884335150971385` √ 9.423874760099713`*^71 Pr2 -
6.496952940779882`*^71 Pr3 + 1.836431491735722`*^71 Pr4 -
6.079320087188218`*^69 Pr5 - 6.726367276312535`*^67 Pr6 
1/3

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12 wri-fe-6040[2].cdf

Equation for Z Predicted by PR EoS at Tr = 1.5

Solvez ^ 3 - 1 - B3[Pr] * z ^2 + A3[Pr] - 2 * B3[Pr] - 3 * B3[Pr] ^ 2 * z -
A3[Pr] * B3[Pr] - B3[Pr] ^ 2 - B3[Pr] ^ 3  0, z

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

z  0.0000444444 (7500. - 389. Pr) +

1.51563 × 1015 - 2.62514 × 1015  - 1. - 0.0232667 Pr - 0.0269015 Pr2  
7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046 Pr2 -
2.93802 × 1045 Pr3 + 0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 -
1.83276 × 10-17 + 3.17443 × 10-17  7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046
Pr2 - 2.93802 × 1045 Pr3 + 0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 ,
z  0.0000444444 (7500. - 389. Pr) + 1.51563 × 1015 + 2.62514 × 1015 
- 1. - 0.0232667 Pr - 0.0269015 Pr2  
7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046 Pr2 - 2.93802 × 1045 Pr3 +
0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 -
1.83276 × 10-17 - 3.17443 × 10-17  7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046
Pr2 - 2.93802 × 1045 Pr3 + 0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 , z 
0.0000444444 (7500. - 389. Pr) - 3.03126 × 1015 - 1. - 0.0232667 Pr - 0.0269015 Pr2  
7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046 Pr2 -
2.93802 × 1045 Pr3 + 0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 +
3.66551 × 10-17 7.52024 × 1047 + 2.62457 × 1046 Pr + 3.09699 × 1046 Pr2 -
2.93802 × 1045 Pr3 + 0.00413388 √ 4.1489 × 1097 Pr2 - 2.88153 × 1098 Pr3 -
2.61935 × 1097 Pr4 - 1.23207 × 1097 Pr5 - 1.39165 × 1095 Pr6 1/3 

z3[Pr_] := 0.000044444444444444447` 7500.` - 389.` Pr - 3.0312555462086465`*^15

- 1.` - 0.02326674363402491` Pr - 0.026901511111111106` Pr2  
7.520235065275227`*^47 + 2.6245707199704497`*^46 Pr + 3.096991430296838`*^46 Pr2 -
2.9380180594924765`*^45 Pr3 + 0.004133883157820275` √ 4.148899644195943`*^97
Pr2 - 2.8815325738295385`*^98 Pr3 - 2.6193504971281664`*^97 Pr4 -
1.2320674807026808`*^97 Pr5 - 1.391650614707753`*^95 Pr6  +
1/3

3.6655144845865515`*^-17 7.520235065275227`*^47 + 2.6245707199704497`*^46 Pr +

3.096991430296838`*^46 Pr2 - 2.9380180594924765`*^45 Pr3 +
0.004133883157820275` √ 4.148899644195943`*^97 Pr2 -
2.8815325738295385`*^98 Pr3 - 2.6193504971281664`*^97 Pr4 -
1.2320674807026808`*^97 Pr5 - 1.391650614707753`*^95 Pr6 
1/3

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 wri-fe-6040[2].cdf 13

Equation for Z Predicted by PR EoS at Tr = 2

Rootsz ^ 3 - 1 - B4[Pr] * z ^2 + A4[Pr] - 2 * B4[Pr] - 3 * B4[Pr] ^ 2 * z -
A4[Pr] * B4[Pr] - B4[Pr] ^ 2 - B4[Pr] ^ 3  0, z

z (1 - 0.0389 Pr) -
1
3
21/3 - 1 - 0.0677373 Pr - 0.0151321 Pr2   3 2 + 0.203212 Pr + 0.0228558 Pr2 -

0.00329638 Pr3 + 0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr

7.20975 + 1. Pr 98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1. Pr2  +
1/3

2 + 0.203212 Pr + 0.0228558 Pr2 - 0.00329638 Pr3 +

1
3 × 21/3
0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr 7.20975 + 1. Pr
98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1. Pr2  ||
1/3

z (1 - 0.0389 Pr) + 1 +  3  - 1 - 0.0677373 Pr - 0.0151321 Pr2  

1
3
3 × 22/3 2 + 0.203212 Pr + 0.0228558 Pr2 - 0.00329638 Pr3 +

0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr 7.20975 + 1. Pr

98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1. Pr2  -
1/3

1 -  3  2 + 0.203212 Pr + 0.0228558 Pr2 - 0.00329638 Pr3 +

1
6 × 21/3
0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr 7.20975 + 1. Pr
98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1. Pr2  ||
1/3

z (1 - 0.0389 Pr) + 1 -  3  - 1 - 0.0677373 Pr - 0.0151321 Pr2  

1
3
3 × 22/3 2 + 0.203212 Pr + 0.0228558 Pr2 - 0.00329638 Pr3 +

0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr 7.20975 + 1. Pr

98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1.  -
1/3
Pr2

1 +  3  2 + 0.203212 Pr + 0.0228558 Pr2 - 0.00329638 Pr3 +

1
6 × 21/3
0. + 0.00173024  Pr - 3.20481 × 10-15 + 1. Pr 7.20975 + 1. Pr
98.5889 + 1. Pr 48.8393 + 6.7064 Pr + 1. Pr2 
1/3

Printed by Wolfram Mathematica Student Edition

14 wri-fe-6040[2].cdf

1 - 0.038898036999999996` Pr -
1
z4[Pr_] :=
3
21/3 - 1 - 0.06772947289851705` Pr - 0.015130572824533686` Pr2  

3 2 + 0.2031884186955512` Pr +

0.022855539654757107` Pr2 - 0.003295877656735473` Pr3 +

0.` + 0.0017299753957803843`  Pr - 2.1369642629949893`*^-15 + 1.` Pr
7.20936468310982` + 1.` Pr 98.59550740200514` + 1.` Pr
√ 48.84374913290441` + 6.70635214794859` Pr + 1.` Pr2 1/3  +

2 + 0.2031884186955512` Pr + 0.022855539654757107` Pr2 -

1
3 × 21/3
0.003295877656735473` Pr3 +
0.` + 0.0017299753957803843`  Pr - 2.1369642629949893`*^-15 + 1.` Pr
7.20936468310982` + 1.` Pr 98.59550740200514` + 1.` Pr
√ 48.84374913290441` + 6.70635214794859` Pr + 1.` Pr2 1/3 ;

Combined Plot of Tr=1, Tr=1.2, Tr=1.5, and Tr=2

Isotherms
Plot[{z1[Pr], z2[Pr], z3[Pr], z4[Pr]}, {Pr, 0, 7},
PlotLegends  {"Tr=1", "Tr=1.2", "Tr=1.5", "Tr=2"},
AxesLabel  {"Reduced Pressure", "Z"}, PlotRange  {0, 1.4}]
Z
1.4

1.2

1.0 Tr=1
0.8 Tr=1.2
0.6 Tr=1.5

0.4
Tr=2

0.2

Reduced Pressure
0 1 2 3 4 5 6 7

Joule-Thomson Coefficient vs. T

Using equation 19 from source 10:

Joule[T_, P_] = 1  Cp[T, P] * (T * dVdTatP[T, P] - V[T, P]);

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 15

Cp[400, Pc * 1]
139.556 + 0. 

Combined Plot of The Joule - Thomson Coefficient

Plot[{Joule[T, Pc * .05], Joule[T, Pc * .4], Joule[T, Pc * 1], Joule[T, Pc * 1.75]},
{T, 164.76, 1.2 * Tc}, PlotLegends  {"Pr=.05", "Pr=.4", "Pr=1", "Pr=1.75"},
AxesLabel  {"Temperature (K)", "Joule-Thomson Coefficient (K/Pa)"}]
Joule-Thomson Coefficient (K/Pa)

0.00002
Pr=.05
0.000015 Pr=.4

0.00001
Pr=1
Pr=1.75
5. × 10-6

Temperature (K)
300 400 500 600

P-V Phase Diagram

Peng - Robinson P-V Diagram
PengRobinson[T_, V_] = ((R * T) / (V - b)) - ((a[T]) / (V * (V + b) + b * (V - b)));

Plot[{PengRobinson[1.75 * Tc, V], PengRobinson[Tc, V],

PengRobinson[.75 * Tc, V], PengRobinson[.4 * Tc, V]}, {V, .0001, .004},
PlotRange  {0, Pc * 1.5}, PlotLegends  {"Tr=1.75", "Tr=1", "Tr=.75", "Tr=.4"}]

7 × 106

6 × 106

5 × 106 Tr=1.75
4 × 106 Tr=1

3 × 106
Tr=.75
Tr=.4
2 × 106

1 × 106

0.000 0.001 0.002 0.003 0.004

DPengRobinson[T_, V_] = D[PengRobinson[T, V], V];

Printed by Wolfram Mathematica Student Edition

16 wri-fe-6040[2].cdf

To calculate the envolope, we will use 100 isotherms.

isotherms = 300;

Create a row of isotherms with Tr from .75 to .99.

TrEnvelope = Tablex, x, 0.75, 1, 1 - .75  isotherms;

Converting from function of reduced temperature. Note that TEnvelope is in a

Table.
TEnvelope = TrEnvelope * Tc;

VListInitial = {};

V /. Solve[DPengRobinson[Part[TEnvelope, i], V]  0]], {i, isotherms}];

Do[AppendTo[VListInitial,

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

Solve::ratnz : Solve was unable to solve the system with inexact coefficients.
The answer was obtained by solving a corresponding exact system and numericizing the result. 

General::stop : Further output of Solve::ratnz will be suppressed during this calculation. 

VListInitial;

NewVList = {};

AppendTo[NewVList, VListInitial[[u, 4]]], {u, isotherms}]

Do[AppendTo[NewVList, VListInitial[[u, 3]]];

NewVList;

We can make a new list ignoring those first two values. The first two, refer to one specific isotherm, as
do the 3rd and 4th values, etc. in NewVList.

PList = {};

AppendTo[PList, PengRobinson[TEnvelope[[i]], NewVList[[i + 1]]]], {i, isotherms}]

Do[AppendTo[PList, PengRobinson[TEnvelope[[i]], NewVList[[i]]]];

PList;

Length[PList]
Length[NewVList]
600

600

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 17

tt = ListPlot[Thread[{NewVList, PList}], PlotRange  {0, 3*^7}];

rr = Plot[{PengRobinson[Tc * 1.75, V], PengRobinson[Tc * 1, V],

PengRobinson[Tc * .75, V], PengRobinson[Tc * .4, V]}, {V, .0001, .001},
PlotRange  {0, 3*^7}, PlotLegends  {"Tr=1.75", "Tr=1", "Tr=.75", "Tr=.4"},
AxesLabel  {"Molar Volume (m^3/mol)", "Pressure (Pa)"}];

Show[rr, tt]

Pressure (Pa)
3.0 × 107

2.5 × 107

2.0 × 107

1.5 × 107

1.0 × 107
Spinodal

5.0 × 106

Bimodal

Molar Volume
0.0000 0.0002 0.0004 0.0006 0.0008 0.0010

P-T Phase Diagram (Exported to

Excel)
For the P - T phase diagram plot, I will use the Clausius - Clapeyron equation to plot the solid - vapor
line. I will then use the Antoine equation to plot the liquid - vapor line. I will then find two points on the
fusion line (normal melting point and triple point) and then draw a straight line between them since on
most phase diagrams this line is approximately linear.

Clausius - Clapeyron (S-V)

Ttrip in units of Pa and Ttrip in units of K.

Printed by Wolfram Mathematica Student Edition

18 wri-fe-6040[2].cdf

Ttrip = 164.76;
Ptrip = .1302;

Using the equation of pg. 319 with T1 set to the triple point temperature. Then we need to find the
enthalpy of sublimation. We can use the data from NIST to find delHvap and delHfus. It is important to
note that the lower bound on the range for delHvap was 235 K. delHfus units are J/mol.

delHfus = 8540;
delHvap = 32 300;
delHsub = delHvap + delHfus;

PresClCl[T_] = ExpPtrip * - delHsub / R 1  T - 1  Ttrip;

Straight Line (S-L)

I will find a straight line through the following two points (164.65, 101325) and (164.76, .1302) which are
the triple point and the normal melting point.
m=y2-y1/x2-x1=101325-.1302/164.65-164.76
y-y1=m(x-x1)

VapPresSL[T_] = 101 325 - .1302  164.65 - 164.76 * T - 164.76 + .1302;

Antoine (L-V)
Aant = 7.10537;
Bant = 1256.68;
Cant = 232.621;

Using the units of the Antoine parameters, the pressure output is in mmHg and the temperature input is
in Celsius.

PvapAntoine[T_] = 10 ^ Aant - Bant  T - 273.15 + Cant * 133.322365;

After plotting, it was observed that the Clasusius-Clapeyron equation did not intersect the other two
graphs at the triple point. Thus, I will force the two to intersect by applying a correction to the Clausius -
Clapeyron equation.

Printed by Wolfram Mathematica Student Edition

 wri-fe-6040[2].cdf 19

Combined Plot and the Final Phase Diagram

Cartesian Coordinates

{T, 0, 540.15}, PlotLegends  {"Antoine (L-V)", "Straight Line (S-L)",

Plot[{PvapAntoine[T], VapPresSL[T], PresClCl[T]},

"Clausius-Clapeyron (S-V)"}, PlotRange  {0, 1.2 * Pc}]

60

50

Antoine (L-V)
40

Straight Line (S-L)

Clausius-Clapeyron (S-V)
30

20

10

0 100 200 300 400 500

Semi - Log

{T, 0, 540.15}, PlotLegends  {"Antoine (L-V)", "Straight Line (S-L)",

LogPlot[{PvapAntoine[T], VapPresSL[T], PresClCl[T]},

"Clausius-Clapeyron (S-V)"}, PlotRange  {10, 1.2 * Tc}]

500

200

Antoine (L-V)
Straight Line (S-L)
100

50 Clausius-Clapeyron (S-V)

20

0 100 200 300 400 500

Due to limitations in Mathematica plotting, I made tables of values using the mathematica functions,
which were then graphed in Excel.

Printed by Wolfram Mathematica Student Edition

20 wri-fe-6040[2].cdf

Table from Clausius - Clapeyron

CLCL = Table[PresClCl[T], {T, 10, 540.15, 10}]
8.151 × 10-27 , 6.28759 × 10-13 , 2.67655 × 10-8 , 5.52231 × 10-6 , 0.00013516, 0.00113938,
0.00522355, 0.0163659, 0.039783, 0.0809661, 0.14481, 0.235078, 0.354205,
0.50334, 0.682529, 0.890941, 1.1271, 1.38908, 1.67471, 1.98167, 2.3076,
2.6502, 3.00725, 3.37664, 3.75644, 4.14482, 4.54016, 4.94094, 5.34583,
5.7536, 6.16318, 6.5736, 6.98401, 7.39366, 7.80188, 8.2081, 8.61181, 9.01257,
9.41001, 9.8038, 10.1937, 10.5794, 10.9607, 11.3375, 11.7097, 12.0771,
12.4397, 12.7974, 13.1501, 13.4979, 13.8407, 14.1786, 14.5114, 14.8393

Export["CLCL.xls", CLCL]
CLCL.xls

SystemOpen["CLCL.xls"]

Table from Straight Line

SL2 = Table[VapPresSL[T], {T, 159, 167, .02}]
5.30574 × 106 , 5.28732 × 106 , 5.26889 × 106 , 5.25047 × 106 , 5.23205 × 106 , 5.21363 × 106 ,
5.1952 × 106 , 5.17678 × 106 , 5.15836 × 106 , 5.13993 × 106 , 5.12151 × 106 , 5.10309 × 106 ,
5.08467 × 106 , 5.06624 × 106 , 5.04782 × 106 , 5.0294 × 106 , 5.01098 × 106 , 4.99255 × 106 ,
4.97413 × 106 , 4.95571 × 106 , 4.93728 × 106 , 4.91886 × 106 , 4.90044 × 106 , 4.88202 × 106 ,
4.86359 × 106 , 4.84517 × 106 , 4.82675 × 106 , 4.80833 × 106 , 4.7899 × 106 , 4.77148 × 106 ,
4.75306 × 106 , 4.73463 × 106 , 4.71621 × 106 , 4.69779 × 106 , 4.67937 × 106 , 4.66094 × 106 ,
4.64252 × 106 , 4.6241 × 106 , 4.60568 × 106 , 4.58725 × 106 , 4.56883 × 106 , 4.55041 × 106 ,
4.53199 × 106 , 4.51356 × 106 , 4.49514 × 106 , 4.47672 × 106 , 4.45829 × 106 , 4.43987 × 106 ,
4.42145 × 106 , 4.40303 × 106 , 4.3846 × 106 , 4.36618 × 106 , 4.34776 × 106 , 4.32934 × 106 ,
4.31091 × 106 , 4.29249 × 106 , 4.27407 × 106 , 4.25564 × 106 , 4.23722 × 106 , 4.2188 × 106 ,
4.20038 × 106 , 4.18195 × 106 , 4.16353 × 106 , 4.14511 × 106 , 4.12669 × 106 , 4.10826 × 106 ,
4.08984 × 106 , 4.07142 × 106 , 4.05299 × 106 , 4.03457 × 106 , 4.01615 × 106 , 3.99773 × 106 ,
3.9793 × 106 , 3.96088 × 106 , 3.94246 × 106 , 3.92404 × 106 , 3.90561 × 106 , 3.88719 × 106 ,
3.86877 × 106 , 3.85035 × 106 , 3.83192 × 106 , 3.8135 × 106 , 3.79508 × 106 , 3.77665 × 106 ,
3.75823 × 106 , 3.73981 × 106 , 3.72139 × 106 , 3.70296 × 106 , 3.68454 × 106 , 3.66612 × 106 ,
3.6477 × 106 , 3.62927 × 106 , 3.61085 × 106 , 3.59243 × 106 , 3.574 × 106 , 3.55558 × 106 ,
3.53716 × 106 , 3.51874 × 106 , 3.50031 × 106 , 3.48189 × 106 , 3.46347 × 106 , 3.44505 × 106 ,
3.42662 × 106 , 3.4082 × 106 , 3.38978 × 106 , 3.37135 × 106 , 3.35293 × 106 , 3.33451 × 106 ,
3.31609 × 106 , 3.29766 × 106 , 3.27924 × 106 , 3.26082 × 106 , 3.2424 × 106 , 3.22397 × 106 ,
3.20555 × 106 , 3.18713 × 106 , 3.16871 × 106 , 3.15028 × 106 , 3.13186 × 106 , 3.11344 × 106 ,
3.09501 × 106 , 3.07659 × 106 , 3.05817 × 106 , 3.03975 × 106 , 3.02132 × 106 , 3.0029 × 106 ,
2.98448 × 106 , 2.96606 × 106 , 2.94763 × 106 , 2.92921 × 106 , 2.91079 × 106 , 2.89236 × 106 ,
2.87394 × 106 , 2.85552 × 106 , 2.8371 × 106 , 2.81867 × 106 , 2.80025 × 106 , 2.78183 × 106 ,

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 wri-fe-6040[2].cdf 21

2.76341 × 106 , 2.74498 × 106 , 2.72656 × 106 , 2.70814 × 106 , 2.68971 × 106 , 2.67129 × 106 ,
2.65287 × 106 , 2.63445 × 106 , 2.61602 × 106 , 2.5976 × 106 , 2.57918 × 106 , 2.56076 × 106 ,
2.54233 × 106 , 2.52391 × 106 , 2.50549 × 106 , 2.48707 × 106 , 2.46864 × 106 , 2.45022 × 106 ,
2.4318 × 106 , 2.41337 × 106 , 2.39495 × 106 , 2.37653 × 106 , 2.35811 × 106 , 2.33968 × 106 ,
2.32126 × 106 , 2.30284 × 106 , 2.28442 × 106 , 2.26599 × 106 , 2.24757 × 106 , 2.22915 × 106 ,
2.21072 × 106 , 2.1923 × 106 , 2.17388 × 106 , 2.15546 × 106 , 2.13703 × 106 , 2.11861 × 106 ,
2.10019 × 106 , 2.08177 × 106 , 2.06334 × 106 , 2.04492 × 106 , 2.0265 × 106 , 2.00807 × 106 ,
1.98965 × 106 , 1.97123 × 106 , 1.95281 × 106 , 1.93438 × 106 , 1.91596 × 106 , 1.89754 × 106 ,
1.87912 × 106 , 1.86069 × 106 , 1.84227 × 106 , 1.82385 × 106 , 1.80543 × 106 , 1.787 × 106 ,
1.76858 × 106 , 1.75016 × 106 , 1.73173 × 106 , 1.71331 × 106 , 1.69489 × 106 , 1.67647 × 106 ,
1.65804 × 106 , 1.63962 × 106 , 1.6212 × 106 , 1.60278 × 106 , 1.58435 × 106 , 1.56593 × 106 ,
1.54751 × 106 , 1.52908 × 106 , 1.51066 × 106 , 1.49224 × 106 , 1.47382 × 106 , 1.45539 × 106 ,
1.43697 × 106 , 1.41855 × 106 , 1.40013 × 106 , 1.3817 × 106 , 1.36328 × 106 , 1.34486 × 106 ,
1.32643 × 106 , 1.30801 × 106 , 1.28959 × 106 , 1.27117 × 106 , 1.25274 × 106 , 1.23432 × 106 ,
1.2159 × 106 , 1.19748 × 106 , 1.17905 × 106 , 1.16063 × 106 , 1.14221 × 106 , 1.12379 × 106 ,
1.10536 × 106 , 1.08694 × 106 , 1.06852 × 106 , 1.05009 × 106 , 1.03167 × 106 , 1.01325 × 106 ,
994 826., 976 403., 957 981., 939 558., 921 135., 902 713., 884 290., 865 867.,
847 444., 829 022., 810 599., 792 176., 773 754., 755 331., 736 908., 718 486.,
700 063., 681 640., 663 217., 644 795., 626 372., 607 949., 589 527., 571 104.,
552 681., 534 259., 515 836., 497 413., 478 990., 460 568., 442 145., 423 722.,
405 300., 386 877., 368 454., 350 031., 331 609., 313 186., 294 763., 276 341.,

110 536., 92 113.6, 73 690.9, 55 268.2, 36 845.5, 18 422.8, 0.1302, - 18 422.6,

257 918., 239 495., 221 073., 202 650., 184 227., 165 804., 147 382., 128 959.,

- 36 845.3, - 55 268., - 73 690.7, - 92 113.4, - 110 536., - 128 959., - 147 381., - 165 804.,
- 184 227., - 202 650., - 221 072., - 239 495., - 257 918., - 276 340., - 294 763.,
- 313 186., - 331 609., - 350 031., - 368 454., - 386 877., - 405 299., - 423 722.,
- 442 145., - 460 567., - 478 990., - 497 413., - 515 836., - 534 258., - 552 681.,
- 571 104., - 589 526., - 607 949., - 626 372., - 644 794., - 663 217., - 681 640.,
- 700 063., - 718 485., - 736 908., - 755 331., - 773 753., - 792 176., - 810 599.,
- 829 022., - 847 444., - 865 867., - 884 290., - 902 712., - 921 135., - 939 558.,
- 957 980., - 976 403., - 994 826., - 1.01325 × 106 , - 1.03167 × 106 , - 1.05009 × 106 ,
- 1.06852 × 106 , - 1.08694 × 106 , - 1.10536 × 106 , - 1.12378 × 106 , - 1.14221 × 106 ,
- 1.16063 × 106 , - 1.17905 × 106 , - 1.19748 × 106 , - 1.2159 × 106 , - 1.23432 × 106 ,
- 1.25274 × 106 , - 1.27117 × 106 , - 1.28959 × 106 , - 1.30801 × 106 , - 1.32643 × 106 ,
- 1.34486 × 106 , - 1.36328 × 106 , - 1.3817 × 106 , - 1.40013 × 106 , - 1.41855 × 106 ,
- 1.43697 × 106 , - 1.45539 × 106 , - 1.47382 × 106 , - 1.49224 × 106 , - 1.51066 × 106 ,
- 1.52908 × 106 , - 1.54751 × 106 , - 1.56593 × 106 , - 1.58435 × 106 , - 1.60278 × 106 ,
- 1.6212 × 106 , - 1.63962 × 106 , - 1.65804 × 106 , - 1.67647 × 106 , - 1.69489 × 106 ,
- 1.71331 × 106 , - 1.73173 × 106 , - 1.75016 × 106 , - 1.76858 × 106 , - 1.787 × 106 ,
- 1.80542 × 106 , - 1.82385 × 106 , - 1.84227 × 106 , - 1.86069 × 106 , - 1.87912 × 106 ,
- 1.89754 × 106 , - 1.91596 × 106 , - 1.93438 × 106 , - 1.95281 × 106 , - 1.97123 × 106 ,
- 1.98965 × 106 , - 2.00807 × 106 , - 2.0265 × 106 , - 2.04492 × 106 , - 2.06334 × 106 

Printed by Wolfram Mathematica Student Edition

22 wri-fe-6040[2].cdf

Export["SL2.xls", SL2]
SL2.xls

SystemOpen["SL2.xls"]

Table from Antoine

ANT = Table[PvapAntoine[T], {T, 10, 540.15, 10}]
2.47604 × 1050 , 2.78702 × 1070 , 3.84094 × 10128 , 6.409624024680068 × 102384 ,
3.49239 × 10-124 , 4.88833 × 10-56 , 3.88179 × 10-34 , 2.46726 × 10-23 , 6.72847 × 10-17 ,
1.2569 × 10-12 , 1.38356 × 10-9 , 2.61342 × 10-7 , 0.0000152969, 0.00039504,
0.00563252, 0.0514718, 0.3342, 1.65936, 6.64899, 22.3856, 65.3075,
169.098, 396.006, 851.548, 1702.04, 3193.91, 5673.5, 9605.93, 15 591.7,

337 595., 430 848., 542 448., 674 493., 829 106., 1.00842 × 106 , 1.21454 × 106 ,
24 380., 36 877.9, 54 154.5, 77 441.6, 108 128., 147 753., 197 991., 260 638.,

1.44957 × 106 , 1.71555 × 106 , 2.01447 × 106 , 2.34825 × 106 , 2.71872 × 106 ,
3.12762 × 106 , 3.57662 × 106 , 4.06725 × 106 , 4.60096 × 106 , 5.17906 × 106 

Export["ANT.xls", ANT]
ANT.xls

SystemOpen["ANT.xls"]

Printed by Wolfram Mathematica Student Edition