Chemical Data Collections 27 (2020) 100371

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Chemical Data Collections

journal homepage: www.elsevier.com/locate/cdc

Consistency of thermodynamic properties from CHEMCAD

process simulations
C. James, M. Armstrong, G. Washington, A. Biaglow∗
Department of Chemistry and Life Science, United States Military Academy, West Point, 10996 New York, United States

a r t i c l e i n f o a b s t r a c t

Article history: Accurate calculations of properties such as enthalpy, entropy, and fugacity are crucial for
Received 24 September 2019 chemical process design. These properties are calculated from equations of state in com-
Revised 20 December 2019
monly used process design software such as CHEMCAD [1], and software-based calcula-
Accepted 12 March 2020
tions of properties have been routine for decades. It is important to be able to rely on
Available online 21 April 2020
the accuracy of these calculations. Furthermore, students of thermodynamics and process
Keywords: engineers must be able to easily reproduce the calculations from the process simulator.
Lee-kesler In this study, we attempted to validate the compressibility factors, enthalpy, entropy, and
Enthalpy fugacity coefficients from CHEMCAD by comparing the results of the process simulator to
Entropy results from a published solution algorithm [2]. Our results show good consistency for
Fugacity most molecules. However, we observe large deviations for nitric oxide, water and hydro-
Compressibility gen, and somewhat smaller deviation for a few other molecules. This report presents a
Process detailed comparison of the thermodynamic properties of 48 molecules at two different
CHEMCAD
states to demonstrate that our calculation is correct and that the deviations for hydrogen
and water are real.
Published by Elsevier B.V.

Specifications Table

Subject area Chemical Engineering

Compounds Methane, ethane, propane, n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane, ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, acetaldehyde, acetylene, benzene,
1,3-butadiene, cyclohexane, ethanol, ethylbenzene, ethylene oxide, formaldehyde, methanol, styrene,
toluene, air, ammonia, bromine, carbon monoxide, carbon dioxide, carbon disulfide, chlorine, hydrogen,
hydrogen sulfide, hydrogen chloride, hydrogen cyanide, nitrogen, nitrous oxide, nitric oxide, nitrogen
dioxide, dinitrogen tetroxide, oxygen, sulfur dioxide, sulfur trioxide, water
Data category Computational simulations
Data acquisition format Tabular
Data type Simulated
Procedure Calculation of change in property values from State 1 to State 2 using an equation of state, followed by
modeling of the same change in state using a process simulator.
Data accessibility Data is included with this article.

∗
Corresponding author.
E-mail address: [email protected] (A. Biaglow).

https://doi.org/10.1016/j.cdc.2020.100371
2405-8300/Published by Elsevier B.V.
2 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371

1. Rationale

Accurate calculation of properties such as enthalpy, entropy, and fugacity are crucial for chemical process design. These
properties can be calculated from equations of state in process design software such as CHEMCAD [1], and software-based
calculations of properties have been routine for decades. Because of the importance of thermodynamic properties in process
design, engineers and students must be able to easily reproduce the data from the process simulator. In this study, we
attempted to confirm the compressibility, enthalpy, entropy, and fugacity coefficients calculated by CHEMCAD by comparing
the results of the process simulator to results from a published solution algorithm [2].
Our procedure was to first calculate the properties at two defined states as well as changes between two states using
the Lee-Kesler method [2]. State 1 in our study is defined in terms of reduced temperature and pressure as Tr =0.90 Pr =0.10,
and state 2 is defined as Tr =2.2 and Pr =0.8, where Tr =T/Tc and Pr =P/Pc . We selected these two states carefully so as to
give relatively large property changes while at the same time staying well away from any phase transitions. All of our
calculations were conducted using the algorithm published in Reference 1 and implemented by us in Mathematica [3].
We then implemented the same method in CHEMCAD. Property data were then arranged in a tabular format for direct
comparison. We analyzed the same corresponding states and state changes for all 48 molecules in Table C.1 of Introduction
to Chemical Engineering Thermodynamics [4], a commonly used text.
Our results show consistency for most molecules in our study, with large deviations for nitric oxide, water and hydro-
gen, and smaller but still significant deviations for a few other molecules, namely dinitrogen tetroxide, nitrogen dioxide,
and sulfur dioxide. We repeated the calculations for 48 molecules to demonstrate that the observed deviations are real
and reproducible. These results are important because of the ubiquitous nature of water and hydrogen in process design
simulations, so it is important to understand how they arise.

2. Procedure

The procedure used here is published in Reference 1 and briefly outlined here. Eqs. (1.1) to (1.5) appear in Reference 1
and are repeated here. We first briefly describe our algorithm and then we discuss how the simulation is implemented in
CHEMCAD.
Equation of State – Modified Benedict-Webb-Rubin
P V     
B C D c4 γ γ
Z=
r r
=1+ + 2 + 5 + 3 2 β+ exp − (1.1)
Tr Vr Vr Vr Tr Vr Vr2 Vr2
ω  
Z = Zsimple + · Zre f erence − Zsimple (1.2)
ωre f erence
Fugacity Coefficient
 
f B C D
ln = Z − 1 − ln (Z ) + + + +E (1.3)
P Vr 2Vr2 5Vr5
Residual Enthalpy and Entropy

R H − H ig b2 + 2 b3 /Tr + 3 b4 Tr2 c2 − 3 c3 /Tr2 d2
H = = Tr Z − 1 − − 2
+ + 3E
RTC TrVr 2TrVr 5TrVr5
S − Sig P
  b1 + b3 /Tr2 + 2 b4 Tr3 c1 − 2 c3 /Tr3 d1
SR = + ln = ln (Z ) − + − + 2E (1.4)
TC P ig Vr 2Vr2 5Vr5
    
b2 b b c c d c4 γ γ
where B = b1 − − 32 − 43 , C = c1 − 2 + 33 , D = d1 + 2 , and E = β + 1 − β + 1 + 2 exp − 2
Tr Tr Tr Tr Tr Tr 2Tr3 γ Vr Vr
Enthalpy and Entropy

T
 2  2
c/T e/T
H= H of + 0.001 · a+ b· + d· dT + H R
298.15 Sinh[c/T ] Cosh[e/T ]
 2  2  P  (1.5)
T 1 c/T e/T
S = Sof + 0.001 · 298.15 a+ b· + d· dT − ln + SR
T Sinh[c/T ] Cosh[e/T ] 1.0

Constants for Simple Fluid: Constants for Reference Fluid:

b1 = 0.1181193 c1 = 0.0236744 d1 = 0.155488 × 10−4 b1 = 0.2026579 c1 = 0.0313385 d1 = 0.48736 × 10−4
b2 = 0.265728 c2 = 0.0186984 d2 = 0.623689 × 10−4 b2 = 0.331511 c2 = 0.0503618 d2 = 0.0740336 × 10−4
b3 = 0.15479 c3 = 0.0 β = 0.65392 b3 = 0.027655 c3 = 0.016901 β = 1.226
b4 = 0.030323 c4 = 0.042724 γ = 0.060167 b4 = 0.203488 c4 = 0.041577 γ = 0.03754
 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371 3

In Eq. (1.5), the standard enthalpy and entropy of formation and the constants a-e for ideal gas heat capacity calculations
are specific to the molecule being studied. For consistency, all of these constants were taken from CHEMCAD, which uses
the DIPPr data set [5], as described below and shown in Fig. 1.
The first step in the procedure is to solve the equation of state (1.1) for reduced volume (Vr ) given reduced temperature,
pressure, and acentric factor (Tr , Pr , and ω). This is done once for the simple fluid (defined as ω=0), and once for the ref-
erence fluid (ωreference =0.3978). Calculation of Vr then allows calculation of Z for the simple and reference fluids. Second,
using Eq. (1.2), the compressibility factors (Z) for the simple and reference fluid results are combined in a Pitzer-type corre-
lation (1.2) using the acentric factors for the reference compound and the compound being analyzed (methane, ethane, etc.)
Third, the resulting Z values are used to calculate the fugacity coefficient (f/P), residual enthalpy (HR ) and residual entropy
(SR ) from Eqs. (1.3) and (1.4) for the simple and reference fluids and again combined with corresponding Pitzer-type cor-
relations similar to Eq. (1.2). Finally, absolute enthalpy and entropy are calculated from the residuals, the ideal gas values,
and the standard enthalpy and entropy of formation using Eqs. (1.5). “Absolute” in this context refers to gas-phase forma-
tion properties at 298.15 K and 1 bar, and is analogous to CHEMCAD stream properties, as opposed to differences between
streams.
The Lee-Kesler computations were also performed in CHEMCAD. The first step is to draw the process in the simulator.
Referring to Fig. 1, a simple process using a compressor (A) and heat exchanger (B) converts the fluid from T1 and P1 to
T2 and P2 . CHEMCAD requires specification of actual temperatures and pressures as opposed to the reduced values. The
stream box to the left of the process flow diagram is set to display the relevant properties from the streams. Next, we set
the desired thermodynamic model. The enthalpy model is chosen in “Thermodynamic settings (C),” and was set to Lee-
Kesler with ideal gas heat capacity constants from DIPPr. These settings are each indicated with red arrows in the figure.
The critical temperature, pressure, standard enthalpy of formation, and standard Gibbs energy of formation used in our
Mathematica algorithm are found under “Basic Data” (D). Enthalpy of formation and Gibbs energy of formation are used to
calculate the entropy of formation used in Eq. (1.5). The heat capacity coefficients are found in “Library Heat Capacity Data”
(E). All relevant settings and constants are indicated with red arrows in the figure.

3. Data, value and validation

Our results are summarized in Tables 1 through 5. Tables 1 to 4 are comparisons of absolute enthalpies, absolute en-
tropies, fugacity coefficients, and compressibility factors, respectively. Table 5 is a comparison of the change in enthalpy
and entropy from State 1 to State 2. The tables also show a comparison of our calculations with the results obtained from
CHEMCAD. All comparisons are at State 1 and State 2, where State 1 is at a reduced temperature and reduced pressure of
Tr1 = 0.9 and Pr1 = 0.10 and State 2 is at Tr2 = 2.2, Pr2 = 0.8.
Significant differences in the results are highlighted in bold red font in the tables. We used a comparison of percentage
errors to determine these outliers. The values highlighted in red show more than ten standard deviations difference between
the percentage error for that data point and the average percentage error of the non-outliers. For example, for the H1
values for nitric oxide in Table 1, the calculated enthalpy from Mathematica is 85,419 J/mol and the CHEMCAD value is
85,813 J/mol, giving a difference of 394 J/mol and an average of the two values of 85,616 J/mol. The difference expressed as
a percent deviation from the average is 100(394/85,616), or 0.46%. The average of all deviations in H1 over the entire table,
not including highlighted outliers, is 0.0159% with a standard deviation of 0.0351%, and 0.46% is greater than 10 standard
deviations from the average. That is to say, in this example, 0.46 > 0.0159+10 × 0.0351, or 0.46>0.37), which justifies the
indication of this point as an outlier. All other bold red values in Tables 1-5 were similarly analyzed.
Using the criterion described above, discrepancies in the data occur for nitric oxide, nitrogen dioxide, dinitrogen tetroxide,
and water in Table 1. In Table 2, we see discrepancies for ethylbenzene, formaldehyde, hydrogen, hydrogen chloride, nitric
oxide, sulfur dioxide, and water. Of these, the most significant deviation appears to be for water. In Table 5, for enthalpy
and entropy differences, we see discrepancies for hydrogen, nitric oxide, dinitrogen tetroxide, and water. The discrepancies
for water and hydrogen are explained below.
From the thermodynamics documentation in the help menu, “Steam tables are used to determine the enthalpy of water
(if water is the only component and SRK enthalpy is selected).” It appears CHEMCAD also makes this choice when Lee-Kesler
was selected for enthalpy. We also repeated the calculation using the steam table equations cited by CHEMCAD [7] and ob-
tained the same result. Interestingly, when water is “cloned” in CHEMCAD and the cloned water is used in the simulation,
the values are much closer to the Mathematica calculation. For H1 for cloned water, we observe −232,913 J/mol in CHEM-
CAD, versus −232,898 J/mol in Mathematica, while H2 becomes −198,044 J/mol in CHEMCAD versus −198,036 J/mol in
Mathematica. For entropy values S1 and S2 , the values for cloned water values are −47.84 and −28.53 J/mol•K, respec-
tively, while we calculate −48.15 and −28.69 J/mol•K. The ability to use the cloning feature to circumvent the use of
steam tables does not appear to be documented in the software and was made apparent to us during the review of this
manuscript.
Hydrogen is also noteworthy with a large deviation in entropy, as shown in Table 2. This deviation is due to the way
CHEMCAD handles the ideal gas heat capacity integral (eq. (1.5)). The software uses upper and lower bounds on the func-
tion to prevent the return of unreasonably high values from the integral. This is a very reasonable and prudent programming
approach but also causes the large discrepancy seen for this molecule. It would be useful if the company provided documen-
4 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371

Fig. 1. Screenshots of the implementation of the simulation methods in CHEMCAD. Methane data published with permission of the American Institute
of Chemical Engineering (AIChE®) and its thermo-physical property research consortium, the Design Institute for Physical Properties (DIPPR®) using the
DIPPR Evaluated Database ©.
 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371 5

Table 1
Comparison of calculated Lee-Kesler enthalpies with CHEMCAD Lee-Kesler enthalpies at reduced temperatures and
pressures of (Tr1 = 0.9, Pr1 = 0.10) and (Tr2 = 2.2, Pr2 = 0.8). The subscripts MMA and CC designate Mathematica
and CHEMCAD, respectively. Enthalpy units are J/mol.

Species H1,MMA H1CC |H1 | H2,MMA H2,CC |H2 |

methane −79,372 −79,372 0 −70,468 −70,468 0

ethane −85,406 −85,407 1 −56,124 −56,124 0
propane −102,426 −102,428 2 −43,818 −43,818 1
n-butane −116,931 −116,931 0 −19,293 −19,294 2
isobutane −127,324 −127,326 2 −35,589 −35,590 1
n-pentane −129,858 −129,863 5 11,870 11,867 3
n-hexane −140,184 −140,192 8 49,214 49,210 5
n-heptane −149,430 −149,442 12 91,562 91,555 7
n-octane −157,872 −157,875 3 137,227 137,217 10
ethylene 50,160 50,159 1 70,764 70,763 0
propylene 21,296 21,294 2 69,391 69,390 1
1-butene 6447 6444 3 89,291 89,289 2
1-pentene −6381 −6388 7 117,438 117,434 4
1-hexene −17,659 −17,669 10 152,285 152,281 4
1-heptene −27,405 −27,415 11 192,575 192,569 6
1-octene −35,843 −35,857 15 237,635 237,627 8
acetaldehyde −159,335 −159,342 7 −102,280 −102,283 3
acetylene 225,463 225,461 2 246,530 246,529 1
benzene 105,644 105,639 5 247,543 247,541 2
1,3-butadiene 117,284 117,281 3 195,109 195,108 1
cyclohexane −94,388 −94,392 5 108,268 108,266 3
ethanol −223,007 −223,051 44 −138,921 −138,940 19
ethylbenzene 75,222 75,211 10 317,057 317,051 6
ethylene oxide −46,167 −46,170 3 11,977 11,975 2
formaldehyde −113,940 −113,946 6 −87,843 −87,847 3
methanol −193,635 −193,667 32 −141,237 −141,253 16
styrene 195,335 195,329 6 429,999 429,996 4
toluene 83,293 83,286 8 272,328 272,324 4
air −5320 −5320 0 −397 −397 0
ammonia −43,999 −44,004 5 −19,767 −19,769 3
bromine 38,559 38,557 2 66,982 66,981 1
carbon monoxide −115,881 −115,881 0 −110,887 −110,887 0
carbon dioxide −394,815 −394,818 3 −377,658 −377,659 1
carbon disulfide 126,224 126,223 1 167,414 167,413 1
chlorine 2199 2199 1 21,889 21,889 0
hydrogen −7526 −7528 2 −6361 −6361 0
hydrogen sulfide −19,757 −19,757 1 −1076 −1076 0
hydrogen chloride −92,868 −92,869 1 −80,525 −80,526 1
hydrogen cyanide 138,709 138,695 14 165,866 165,858 8
nitrogen −5512 −5512 0 −784 −784 0
nitrous oxide 80,924 80,923 1 98,889 98,888 1
nitric oxide 85,419 85,813 394 93,310 92,990 320
nitrogen dioxide 35,738 35,665 73 63,452 63,438 14
dinitrogen tetroxide 15,787 15,673 113 75,925 75,895 30
oxygen −4803 −4803 0 1004 1004 0
sulfur dioxide −293,710 −293,715 5 −265,829 −265,832 3
sulfur trioxide −388,493 −388,509 16 −343,150 −343,159 9
water −232,898 54,775 287,673 −198,036 89,842 287,878

tation of this feature. Furthermore, the library heat capacity data shown in Fig. 1(E) shows that CHEMCAD indicates a lower
bound for the ideal gas heat capacity polynomial, and the lower bound for hydrogen is 250 K. The absolute temperature
at which we report the discrepancy is 29.94 K, which is well below 250 K and seems at first to be extreme. However, the
reduced temperature of 0.9 at 29.94 K is not unreasonable as a process condition, and corresponding states theory indicates
that thermodynamic properties should be consistent with the other molecules in this study at the same reduced conditions.
At the time of writing of this paper, CHEMCAD was in the process of revising the software to mitigate this issue.
We took the following additional steps to validate our work. First, each author independently repeated the calculations
for the highlighted molecules. Second, we and repeated the entire study using the Peng-Robinson equation of state [6] in
Mathematica and CHEMCAD, with similar discrepancies. Third, we applied exactly the same algorithm to all 48 molecules
to minimize the chance of data entry error. This also demonstrates that our algorithm is in good agreement with CHEMCAD
6 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371

Table 2
Comparison of calculated Lee-Kesler entropies with CHEMCAD Lee-Kesler entropies at reduced temperatures and
pressures of (Tr1 = 0.9, Pr1 = 0.10) and (Tr2 = 2.2, Pr2 = 0.8). The subscripts MMA and CC designate Mathematica
and CHEMCAD, respectively. Entropy units are J/mol•K.

Species S1,MMA S1,CC |S1 | S2,MMA S2,CC |S2 |

Methane −112.88 −112.70 0.18 −98.08 −98.04 0.04

Ethane −192.33 −192.10 0.23 −146.25 −146.20 0.05
Propane −273.66 −273.40 0.26 −186.51 −186.40 0.11
n-butane −350.75 −350.50 0.25 −216.27 −216.20 0.07
Isobutane −370.00 −369.80 0.20 −238.93 −238.80 0.13
n-pentane −425.24 −425.00 0.24 −242.96 −242.80 0.16
n-hexane −496.93 −496.60 0.32 −266.68 −266.50 0.18
n-heptane −566.50 −566.20 0.30 −287.42 −287.30 0.12
n-octane −634.37 −634.00 0.37 −306.37 −306.20 0.17
ethylene −74.00 −73.97 0.02 −42.91 −42.88 0.03
propylene −149.48 −149.20 0.28 −79.60 −79.53 0.07
1-butene −227.68 −227.40 0.28 −114.38 −114.30 0.08
1-pentene −305.36 −305.10 0.26 −146.14 −146.00 0.13
1-hexene −378.24 −378.00 0.24 −171.78 −171.60 0.18
1-heptene −449.23 −448.90 0.33 −194.50 −194.30 0.20
1-octene −518.21 −517.90 0.31 −214.44 −214.30 0.13
acetaldehyde −119.38 −119.10 0.28 −55.08 −54.94 0.14
acetylene 39.67 39.92 0.25 68.70 68.78 0.08
benzene −112.50 −112.20 0.30 38.38 38.48 0.10
1,3-butadiene −126.52 −126.30 0.22 −22.26 −22.17 0.09
cyclohexane −458.32 −458.10 0.22 −233.95 −233.80 0.15
ethanol −207.70 −207.30 0.40 −116.15 −115.80 0.35
ethylbenzene −241.41 −241.40 0.01 2.67 2.82 0.14
ethylene oxide −129.93 −129.70 0.23 −64.94 −64.85 0.09
formaldehyde −29.30 −29.01 0.29 −3.61 −3.48 0.13
methanol −126.66 −126.30 0.36 −75.86 −75.56 0.30
styrene −123.90 −124.60 0.70 101.57 101.30 0.27
toluene −172.56 −172.30 0.26 22.93 23.06 0.13
air −38.35 −38.17 0.18 −29.58 −29.54 0.04
ammonia −112.76 −112.50 0.26 −89.60 −89.48 0.12
bromine 93.59 93.82 0.23 110.19 110.30 0.11
carbon monoxide 51.44 51.66 0.22 60.46 60.52 0.06
carbon dioxide −17.80 −17.64 0.16 3.30 3.32 0.01
carbon disulfide 175.22 175.50 0.28 209.17 209.30 0.13
chlorine −9.88 −9.67 0.21 5.63 5.68 0.05
hydrogen −66.58 244.70 311.28 −59.17 −59.14 0.03
hydrogen sulfide 27.93 28.15 0.22 44.96 45.01 0.05
hydrogen chloride −9.06 −8.83 0.23 0.21 0.28 0.07
hydrogen cyanide 31.94 32.28 0.34 55.23 55.43 0.20
nitrogen −39.07 −38.87 0.20 −30.11 −30.07 0.04
nitrous oxide −94.19 −93.97 0.22 −71.93 −71.86 0.07
nitric oxide −24.87 −22.67 2.20 −11.71 −12.30 0.59
nitrogen dioxide −71.54 −71.03 0.51 −45.31 −44.75 0.56
dinitrogen tetroxide −296.04 −295.50 0.54 −218.97 −218.30 0.67
oxygen −36.53 −36.34 0.19 −27.50 −27.47 0.03
sulfur dioxide 3.77 4.05 0.28 30.68 30.79 0.11
sulfur trioxide −80.10 −79.76 0.34 −34.59 −34.38 0.21
water −48.15 121.60 169.75 −28.69 141.40 170.09

for the vast majority of the molecules in this study, providing evidence that the algorithm is most probably correct. Fourth,
further validation was obtained using a third-party online Lee-Kesler calculator [8]. In all 48 cases, the online calculator was
in perfect agreement with our results but differed from CHEMCAD in the molecules discussed above.
In summary, CHEMCAD is a state-of-the-art process simulator and is widely used in the engineering community. Engi-
neers should understand what the simulator is doing and how different selections affect the underlying math and results.
As engineers, we are also challenged to understand why an outlier may still be a valid result. To explore how the simulator
works and understand the outliers, it is interesting and informative to check the simulation calculations, and this paper
provides a performance report for users of the software who might rightfully want such an assessment.
 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371 7

Table 3
Comparison of calculated Lee-Kesler fugacity coefficients (f/P) with CHEMCAD Lee-Kesler fugacity coefficients at
reduced temperatures and pressures of (Tr1 = 0.9, Pr1 = 0.10) and (Tr2 = 2.2, Pr2 = 0.8). The subscripts MMA and
CC designate Mathematica and CHEMCAD, respectively.

Species φ 1,MMA φ 1,CC |φ 1 | φ 2,MMA φ 2,CC |φ 2 |

methane 0.955 0.954 0.0001 0.988 0.992 0.0037

ethane 0.953 0.954 0.0008 0.993 0.999 0.0052
propane 0.952 0.953 0.0014 0.997 1.002 0.0058
n-butane 0.951 0.953 0.0019 0.999 1.005 0.0061
isobutane 0.951 0.953 0.0016 0.998 1.004 0.0059
n-pentane 0.950 0.952 0.0024 1.002 1.008 0.0061
n-hexane 0.949 0.952 0.0029 1.005 1.011 0.0054
n-heptane 0.948 0.952 0.0035 1.008 1.014 0.0057
n-octane 0.947 0.951 0.0040 1.011 1.016 0.0052
ethylene 0.953 0.954 0.0007 0.993 0.998 0.0050
propylene 0.952 0.953 0.0013 0.996 1.002 0.0057
1-butene 0.951 0.953 0.0018 0.999 1.005 0.0060
1-pentene 0.949 0.952 0.0029 1.005 1.011 0.0061
1-hexene 0.949 0.952 0.0029 1.005 1.011 0.0061
1-heptene 0.948 0.952 0.0033 1.007 1.013 0.0059
1-octene 0.947 0.951 0.0043 1.009 1.015 0.0055
acetaldehyde 0.949 0.952 0.0028 1.005 1.011 0.0061
acetylene 0.951 0.953 0.0017 0.999 1.005 0.0060
benzene 0.951 0.953 0.0020 1.000 1.006 0.0061
1,3-butadiene 0.951 0.953 0.0018 0.999 1.005 0.0060
cyclohexane 0.951 0.953 0.0020 1.000 1.006 0.0061
ethanol 0.942 0.949 0.0067 1.025 1.025 0.0001
ethylbenzene 0.949 0.952 0.0030 1.005 1.011 0.0060
ethylene oxide 0.951 0.953 0.0019 0.999 1.005 0.0061
formaldehyde 0.949 0.952 0.0027 1.004 1.010 0.0061
methanol 0.944 0.950 0.0058 1.021 1.023 0.0021
styrene 0.950 0.953 0.0022 1.001 1.007 0.0061
toluene 0.950 0.952 0.0026 1.003 1.009 0.0061
air 0.955 0.955 0.0003 0.987 0.990 0.0032
ammonia 0.950 0.952 0.0024 1.002 1.008 0.0061
bromine 0.952 0.953 0.0010 0.995 1.000 0.0054
carbon monoxide 0.953 0.954 0.0008 0.993 0.998 0.0051
carbon dioxide 0.950 0.953 0.0022 1.001 1.007 0.0061
carbon disulfide 0.953 0.954 0.0009 0.994 0.999 0.0053
chlorine 0.953 0.954 0.0005 0.992 0.996 0.0048
hydrogen 0.959 0.956 0.0024 0.975 0.971 0.0040
hydrogen sulfide 0.953 0.954 0.0008 0.993 0.999 0.0052
hydrogen chloride 0.952 0.953 0.0012 0.995 1.001 0.0056
hydrogen cyanide 0.947 0.951 0.0041 1.012 1.017 0.0050
nitrogen 0.954 0.954 0.0003 0.990 0.995 0.0043
nitrous oxide 0.952 0.953 0.0013 0.996 1.002 0.0057
nitric oxide 0.944 0.950 0.0060 1.022 1.023 0.0016
nitrogen dioxide 0.939 0.948 0.0090 1.037 1.030 0.0076
dinitrogen tetroxide 0.936 0.946 0.0108 1.047 1.031 0.0151
oxygen 0.954 0.954 0.0000 0.989 0.993 0.0038
sulfur dioxide 0.950 0.952 0.0025 1.003 1.009 0.0061
sulfur trioxide 0.947 0.951 0.0042 1.012 1.017 0.0049
water 0.948 0.952 0.0034 1.008 1.014 0.0057
8 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371

Table 4
Comparison of calculated Lee-Kesler compressibility factors with CHEMCAD Lee-Kesler compressibility factors at
reduced temperatures and pressures of (Tr1 = 0.9, Pr1 = 0.10) and (Tr2 = 2.2, Pr2 = 0.8). The subscripts MMA and
CC designate Mathematica and CHEMCAD, respectively.

Species Z1,MMA Z1,CC |Z1 | Z2,MMA Z2,CC |Z2 |

methane 0.9526 0.9525 0.0001 0.9892 0.9929 0.0037

ethane 0.9508 0.9517 0.0009 0.9944 0.9996 0.0052
propane 0.9496 0.9512 0.0016 0.9975 1.0032 0.0057
n-butane 0.9486 0.9507 0.0021 1.0003 1.0063 0.0060
isobutane 0.9491 0.9509 0.0018 0.9989 1.0048 0.0059
n-pentane 0.9476 0.9503 0.0027 1.0032 1.0092 0.0060
n-hexane 0.9467 0.9499 0.0032 1.0061 1.0115 0.0054
n-heptane 0.9456 0.9494 0.0038 1.0089 1.0143 0.0054
n-octane 0.9445 0.9489 0.0044 1.0117 1.0165 0.0048
ethylene 0.9510 0.9518 0.0008 0.9937 0.9987 0.0050
propylene 0.9499 0.9513 0.0014 0.9969 1.0026 0.0057
1-butene 0.9488 0.9508 0.0020 0.9997 1.0057 0.0060
1-pentene 0.9467 0.9498 0.0031 1.0057 1.0115 0.0058
1-hexene 0.9470 0.9499 0.0029 1.0058 1.0116 0.0058
1-heptene 0.9460 0.9495 0.0035 1.0078 1.0134 0.0056
1-octene 0.9451 0.9491 0.0040 1.0103 1.0155 0.0052
acetaldehyde 0.9468 0.9499 0.0031 1.0055 1.0113 0.0058
acetylene 0.9489 0.9509 0.0020 0.9995 1.0054 0.0059
benzene 0.9484 0.9506 0.0022 1.0008 1.0068 0.0060
1,3-butadiene 0.9487 0.9507 0.0020 1.0000 1.0060 0.0060
cyclohexane 0.9485 0.9507 0.0022 1.0008 1.0068 0.0060
ethanol 0.9395 0.9467 0.0072 1.0260 1.0252 0.0008
ethylbenzene 0.9465 0.9498 0.0033 1.0062 1.0120 0.0058
ethylene oxide 0.9487 0.9508 0.0021 1.0001 1.0060 0.0059
formaldehyde 0.9470 0.9500 0.0030 1.0049 1.0109 0.0060
methanol 0.9412 0.9474 0.0062 1.0213 1.0228 0.0015
styrene 0.9481 0.9505 0.0024 1.0020 1.0080 0.0061
toluene 0.9473 0.9501 0.0028 1.0039 1.0099 0.0060
air 0.9530 0.9528 0.0002 0.9882 0.9914 0.0032
ammonia 0.9476 0.9503 0.0027 1.0032 1.0092 0.0060
bromine 0.9503 0.9515 0.0012 0.9955 1.0010 0.0055
carbon monoxide 0.9508 0.9517 0.0009 0.9940 0.9992 0.0052
carbon dioxide 0.9480 0.9505 0.0025 1.0020 1.0080 0.0060
carbon disulfide 0.9506 0.9516 0.0010 0.9949 1.0002 0.0053
chlorine 0.9514 0.9520 0.0006 0.9926 0.9974 0.0048
hydrogen 0.9571 0.9546 0.0025 0.9759 0.9713 0.0046
hydrogen sulfide 0.9507 0.9517 0.0010 0.9944 0.9996 0.0052
hydrogen chloride 0.9501 0.9514 0.0014 0.9963 1.0019 0.0056
hydrogen cyanide 0.9444 0.9488 0.0044 1.0124 1.0171 0.0047
nitrogen 0.9519 0.9523 0.0004 0.9912 0.9956 0.0044
nitrous oxide 0.9499 0.9513 0.0014 0.9968 1.0025 0.0057
nitric oxide 0.9408 0.9473 0.0065 1.0225 1.0234 0.0009
nitrogen dioxide 0.9354 0.9450 0.0096 1.0378 1.0293 0.0085
dinitrogen tetroxide 0.9321 0.9437 0.0116 1.0470 1.0310 0.0160
oxygen 0.9523 0.9524 0.0001 0.9897 0.9936 0.0039
sulfur dioxide 0.9475 0.9502 0.0027 1.0036 1.0096 0.0060
sulfur trioxide 0.9441 0.9487 0.0046 1.0130 1.0175 0.0045
water 0.9456 0.9474 0.0018 1.0088 0.9963 0.0125
 C. James, M. Armstrong and G. Washington et al. / Chemical Data Collections 27 (2020) 100371 9

Table 5
Comparison of differences in Lee-Kesler enthalpy and entropy for change from reduced temperatures and pressures
of (Tr1 = 0.9, Pr1 = 0.10) to (Tr2 = 2.2, Pr2 = 0.8), calculated versus CHEMCAD, in J/mol and J/mol•K, respectively.
The subscripts MMA and CC designate Mathematica and CHEMCAD, respectively.

Species HMMA HCC H SMMA SCC S

methane 8899 8904 4.7 14.8 14.7 −0.1
ethane 29,282 29,283 1.3 46.1 45.9 −0.2
propane 58,608 58,612 3.7 87.2 87.0 −0.2
n-butane 97,635 97,636 0.6 134.5 134.3 −0.2
isobutane 91,735 91,740 5.2 131.1 131.0 −0.1
n-pentane 141,728 141,727 −1.0 182.3 182.2 −0.1
n-hexane 189,398 189,400 2.0 230.2 230.1 −0.1
n-heptane 240,991 240,995 4.0 279.1 278.9 −0.2
n-octane 295,092 295,100 7.6 328.0 327.8 −0.2
ethylene 20,604 20,604 0.4 31.1 30.9 −0.2
propylene 48,095 48,096 0.8 69.9 69.7 −0.2
1-butene 82,843 82,845 1.4 113.3 113.1 −0.2
1-pentene 123,819 123,818 −1.0 159.2 159.1 −0.1
1-hexene 169,944 169,950 6.0 206.5 206.4 −0.1
1-heptene 219,980 219,984 4.0 254.7 254.6 −0.1
1-octene 273,478 273,484 6.0 303.8 303.6 −0.2
acetaldehyde 57,056 57,059 3.1 64.3 64.2 −0.1
acetylene 21,067 21,068 1.0 29.0 28.9 −0.2
benzene 141,900 141,900 0.0 150.9 150.7 −0.2
1,3-butadiene 77,826 77,827 1.4 104.3 104.1 −0.1
cyclohexane 202,656 202,658 2.0 224.4 224.3 −0.1
ethanol 84,086 84,111 25.3 91.6 91.5 −0.1
ethylbenzene 241,835 241,840 5.0 244.1 243.9 −0.2
ethylene oxide 58,144 58,146 1.6 65.0 64.9 −0.1
formaldehyde 26,097 26,103 6.1 25.7 25.5 −0.2
methanol 52,398 52,415 17.1 50.8 50.7 −0.1
styrene 234,663 234,670 7.0 225.5 225.9 0.4
toluene 189,035 189,039 4.0 195.5 195.4 −0.1
air 4924 4924 0.0 8.8 8.6 −0.1
ammonia 24,233 24,235 2.1 23.2 23.0 −0.1
bromine 28,423 28,424 1.1 16.6 16.5 −0.1
carbon monoxide 4994 4994 0.3 9.0 8.9 −0.2
carbon dioxide 17,157 17,159 1.8 21.1 21.0 −0.1
carbon disulfide 41,189 41,190 0.9 34.0 33.8 −0.2
chlorine 19,690 19,691 0.5 15.5 15.3 −0.2
hydrogen 1165 1167 −0.3 7.4 −303.8 −311.2
hydrogen sulfide 18,681 18,681 0.5 17.0 16.9 −0.2
hydrogen chloride 12,342 12,343 0.6 9.3 9.1 −0.2
hydrogen cyanide 27,156 27,163 6.6 23.3 23.2 −0.1
nitrogen 4728 4728 0.1 9.0 8.8 −0.2
nitrous oxide 17,964 17,965 0.7 22.3 22.1 −0.2
nitric oxide 7892 7177 −714.6 13.2 10.4 −2.8
nitrogen dioxide 27,724 27,773 48.4 26.2 26.3 0.0
dinitrogen tetroxide 60,138 60,222 83.2 77.1 77.0 −0.1
oxygen 5807 5807 0.1 9.0 8.9 −0.2
sulfur dioxide 27,881 27,883 2.2 26.9 26.7 −0.2
sulfur trioxide 45,343 45,350 7.1 45.5 45.4 −0.1
water 34,862 35,067 204.4 19.5 19.7 0.2

Declarations of Interest

None.

References

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