Jean Richard Limas

and Richard Freze Computer Estimation of Thermodynamic

Centre Universitaire de St. Jerome

Properties of Real Gases

rue Henri Poincare
13397 Marseille Cedex 4, FRANCE

A large number of papers dealing with the computer esti- ft2T 7

a4 =
(0.042m) (9)
mation of thermodynamic properties of real fluids have ap-
peared recently (1-5). Generally, the predicting methods 0.0982 (10)
which yield accurate results over a wide range of conditions
are quite complex to use and need Lengthy calculations on c =
CjT-1/2+C2T-2 (11)
large core memory computers. They are often limited to J?3T 3.s
the prediction of the departure functions. Our purpose was Cl= p cr 0.059904 (1 -M) (12)
to provide the students and the research staff of our school R3T 5

with a simple and efficient means to evaluate some proper- C2 = + 0.091944m) (13)
-p-f-(0.018126
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ties of real gases for computer calculations in applied ther- critical temperature (°K), Pc critical pressure
Tc = =
Downloaded via UNIV OF ILLINOIS CHICAGO on September 12, 2020 at 04:12:59 (UTC).

modynamics and chemical engineering. We set up on a acentric factor, and ft! gas constant (82.05606
small computer, a package of FUNCTION subroutines (atm), ai = =

cm3 atm mole-1 K-1). To obtain the specific volume, the

written in Fortran IV, which were able to calculate sepa-
compressibility factor (Z PV/RT) is computed for each =

rately specific volumes, heat capacities, enthalpy and en- value of P and T by solving the cubic eqn. (14) derived
tropy of a large number of compounds for a given pressure from eqn. (4). In all cases the largest real root was retained.
and temperature. The characteristic properties of these
compounds, used in these functions, are stored in a perma- Z3 -
Z2 -

Z[P2b2/R2T2 + Pb/RT -

aP/R21^\ +
nent file on disc memory. (ab -
c) P2/R3T3 = 0 (14)
Principle of Computation The basic expressions (15)—(19) for the departure functions
The method we used involved, first the estimation of the (6) have been developed from the equation of state (4). The
value of the thermodynamic function for the compound in resulting equations (see Appendix) allow us to calculate the
the ideal gas state, and second, the associated isothermal isothermal variations of the thermodynamic properties
function departure which was derived from a generalized studied.
equation of state.
Several types of correlations have been used (6-9, 24) to
obtain analytical expressions for the ideal gas heat capacity
(Cp°), enthalpy (ff°), and entropy (S°). <»
Passut and Danner (8) and Huang and Daubert (9) used
a set of thermodynamically consistent equations ((l)-(3)),
based on a polynomial development of the fifth degree for
In
(p)-r[v-^Ldv+z-i-i"z «i7>

Cp Cp'
(£)/ -'
—

the enthalpy (\ R Jr \ /t R\dT/v \dV/r

R
«•
H° = A + BT + CT2 + DT3 + ET* + FT5 (1) (Cv-ca°\ /E-E°\ fH-H° „1 _
a 3 ,
(19)
\—R—)T-Fr\—R-)v-yr[—R—+T(Z~ 1JJv
_

Cp° = B + 2CT + 3 DT2 + 4ET3 + 5 FT4 (2)

Program Description
S° = BlnT + 2 CT + 3/2 DT2 + 4/3 ET3 + 5/4 FT4 + G (3)
Four FUNCTION subroutines have been written in For-
(H° =
0 kJ kg-1 at 0°K, S° = 0 kJ kg-1K-1 at 0°K and 1 atm) tran IV on a Hewlett Packard HP 2100 computer with 16k
of core memory.1 Each one evaluates a particular property
These equations produce values which fit well with the
values calculated by statistical mechanical procedures for VOLU (NOM.P.TK.IL'NIT) ; Specific Volume
146 gases. CP (NOM.P.TK.IUNTT) : Heatcapacitv
ENTHA (NOM.P.TK.HJNIT) Enthalpy
generalized equations of state
:
Among the numerous ENTRO (NOM,P,TK,IUNIT) : Entropy
(10-17) which we have tested, we selected the three param-
eters model of Lee and Edmister (16). This equation (4) NOM is a chain of 20 characters which represent the name
was initially intended for the calculation of fugacity coeffi- of the gas. This name allows the program to identify the
cients and enthalpy departure of gases. This model gives a compound in the permanent data file which contains for
good representation of PVT data in a wide pressure and every gas, the following information: name, molecular
temperature range. It is very simple to use and can readily weight, critical properties Pc, Tc, Zc,2 the acentric factor,3
be extended to gas mixtures. and the numerical constants of the expressions (1), (2), (3),
RT a c
with their temperature range of validity. P is the pressure
_

(4) in atm. TK is the temperature in K. IUNIT is an integer

V-b V(V-b) V(V-b)(V+b)
variable which allows the user to select the desired unit
where
system (Table 1). These functions may be easily included
o =
oi —

o*TT 4- o3T 1
4- 04T ^
(5) in a Fortran IV program. Their core requirement does not
exceed 2100 words. They can be readily modified for gas
R2TC2 ,
a 1 (0.25913 -

0.031314m) (6)
P,
R2TC
a 2 =
(0.0249 4- 0.15369m) (7)
P< The listing of the functions is available upon request.
1

2
R2TC3
(0.2015 + 0.21642m)
The values used are from ref (17), (18).
a3 = -

(8) 3 The values used are from ref

(19), (20).

288 / Journal of Chemical Education

 Table 1. Different Unit Systems Used in the Functions

Specific Heat
IUNIT Volume Capacity Enthalpy Entropy

1 fr lb
1
Btu lb 1
Btu lb”1 Btu lb 1

°R"l_ °R"‘ _

2 m3 kg-1 kcal kg
1
kcal kg" kcal kg 1

K"1 K""1
3 m3 kg-1 kJ kg 1 K kJ kg-1 kJ kg 1 K_
4 cm3 mole" kcal mole“ kcal mole" kcal mole“
K_l K"i

1.216

TEMPERATURE
-

00

Figure 2. Isobaric enthalpy change of (1) oxygen, (2) hydrogen sulfide, and
(3) propane, at P = 10 atm. The asterisks mark the data from {23), while the
continuous graphs represent the calculated values.

Table 3. Comparison Between Experimental and Predicted

Values of Cp for Ten Gases
i
CL
(_3
Abso-
lute
Aver-
Pressure Num- age
Temperatu re I nterval ber of Devi-
. 900
160. WO 1606.000 Compound Interval ( K) (Bar) Points ation Reference

TEMPERATURE-00 150—1000 1—70 30 0.2 {23)

% 150—1000 1—70 30 0.2 {23)
Figure Heat Capacity of oxygen at (1) P = 1 atm, (2) P = 40 atm, and (3) P
1. 250—1 000 1 70 24 2.5 {23)
= 70 atm. The asterisks mark the experimental data while the continuous 373—1073 1—40 42 2,8 {36)
cA4 156—356 1—50 75 1.4 {23, 31)
graphs represent the calculated values. 310—500 1—50 30
c2h6 0.9 {23)
c3hb 293—377 0.5—34 38 0.9 {37, 35)
mixtures. Actually, the data file contains the physical prop- 293-35 3 0.5—5 15 0.7 137)
;-c4h„
erties of 46 gases commonly used (diatomic, triatomic, and c2h4 273—423 1—50 25 1.4 {23)
hydrocarbons). c,h„ 298—47 3 1—59 52 1.4 {34)

Analysis of Results
We checked the subroutines on ten different compounds
in a wide range of temperatures and pressures. The results Applications
are illustrated by Figures 1 and 2, and the mean errors in
Case 1. Adiabatic Compression of a Pure Gas4
percent are given in Tables 2 and 3. The errors observed
are generally <2%; however, greater errors may occur in the A methane stream available at 298°K (Ti) and 14 bars
region of saturated vapor, reaching even 10-20% for highly (Pi), is to be compressed to 340 bars (P2) in an adiabatic
polar compounds. This phenomenon has also been ob- operation, (a) reversibly and (b) irreversibly with an effi-
served in the neighborhood of the critical point. These lim- ciency of 0.75.
itations are inherent to the equation of state we chose; A program will calculate in each case the outlet tempera-
however, with the overall accuracy obtained in the temper- ture of the gas and the work of compression.
ature and pressure range most frequently used, let us be- In the first part of this problem, we need to determine by
lieve that our choice was an acceptable compromise. So if an iterative procedure, the outlet temperature T% for which
one takes some care when using it in the region of dense expression (20) is minimum.
gases, this package is an attractive tool for the teaching of ENTRO (NOM,
|ENTRO (NOM, Px, Tx, 3) -
P2, T2,3)| (20)
applied thermodynamics, chemical engineering, and for re-
search applications. The compression work is equal to

Table 2. Comparison Between Experimental and Predicted Values of V, H. and S for Ten Gases

Absolute average % deviation

Temperatu re Pressure No. of No. Of No. of

Compound Interval ( K) Interval (Bar) Points Points Sa

120- 1000 0.4—100 65 0.1 65 0.2 65 0.2 {23)

°2 62 1.0 149 0.8 50 2.0 {23, 25, 26)
N2 220- 700 1—2000
400- 1400 1—100 63 0.4 63 1.2 63 1.4 C3)
COj 2.6 36 3.0
H 2° 373- 1273 1—98 49 0.3 36 (27)
310- 810 1—60 67 1.0 61 1.5 64 1.8 {28)
H2S 0.1
133- 623 3—217 119 2-2 147 1.9 90 {29, 30, 31)
ch4 2.0 81 1.2
c2h6 260- 510 1—500 140 1.4 75 {23, 32)
C ,H? 360- 600 1—25 30 0.2 93 1.0 30 0.5 (35)
298- 423 1—49 18 0.1 18 1.1 18 1.0 (23)
C jH6 300- 523 1—99 49 0.8 46 3.1 59 0.4 (33, 34)

These values are based on isobaric properties change.

Volume 53, Number 5, May 1976 / 289

Wrev =
AHrev =
ENTHA (NOM, P2, T2, 3)
-

ENTHA (NOM, Pi, Ti, 3) (21) (^)r=f-« + M2^+M-

In the second part, the outlet temperature T% is calculated, C(3V2-62)(V,+ 6)-2]V-2|(I/-6)-2 (26)

by the same iterative procedure, by minimization of ex-

pression (22) IT (!Lr)v -11" (‘ -

y)<-^r-*-30c,T~;
+

In
(l (0.375 CiT-1 5 3C2T-3)6-2 +
v(^) J ff-1 (27)
- -

| (ENTHA (NOM, P2, T% 3)

-

ENTHA (NOM, Pi, T,, 3)) -

AHrev/0,75| (22)
H H° (a, + 2a3T-1 + 6a47’-5) In
=
(l fe-1
- - -

A)
***** ADIABATIC COMPRESSION OF CH4
(0.75CiT-0-5 + -
b~2 + PV -

RT (28)
* DATA: 1.5C2r-2)ln(l
INLET TEMPERATURE 298.00 K In = Z -
1 —
In Z —

INLET PRESSURE 14.00 BARS

OUTLET PRESSURE 340.00 BARS 1291
*** REVERSIBLY S -S° _

R
* OUTLET TEMPERATURE 579.13 K
* INLET ENTROPY 10.21 KJ/KB/K
[sk<“‘ + 2«r'1 + +1
v)
- " -

*
OUTLET ENTROPY 10.21 "
m ]
* INLET ENTHALPY 610.61 K.J/KG
*
*
OUTLET ENTHALPY
COMPRESSION WORK
1327.63 "
717.02 "
^5 [C + 1.5 CjT-0-5 + 3C2T-2] In (l
-
+

In Z —
In P (30)
***
IRREVERSIRLY-(EFF1CIENCY 75%)
Literature Cited
* OUTLET TEMPERATURE 646.46 K
* INLET ENTROPY 10.21 (1) Yen, L. C., and Alexander, R. E., A.I.C.H.E. (Amer. Inst. Chem. Eng.)J., 11 (2), 334
K-J/KG/K (1965).
* OUTLET ENTROPY 10.60 "

KJ/KG (2) Johnson, D. W., and Colver, C. P., Hydrocarbon Proces., 48 (1), 127 (1969).
* INLET ENTHALPY 610.61
(3) Henley, E. J., and Beirute, R. M., Chem. Eng. J., I, 291 (1970).
*
OUTLET ENTHALPY 1566.64 "
(4) Jelinek, R., “Computer Programs for Chemical Engineering Education,” Vol. 5,
* COMPRESSION WORK 956.03 "
“Thermodynamics,” Aztec Publishing Co, Austin, 1972.
(5) Starling, K. E., “Fluid Thermodynamic Properties for Light Petroleum Systems,"
Gulf Publishing Company, Houston, 1973.
Case 2. Adiabatic Flame Temperature During the Combustion (6) “Technical Data Book Petroleum Refining,” American Petroleum Institute, 2nd
of H2S with a 100% Excess Air Ed., Washington D.C., 1971, Chap. 7.
(7) Thinh, T. P., Duran, J. L., Ramalho, R. S., and Kaliaguine, S., Hydrocarbon Proces.,
50(1), 98 (1971).
H2S(g) + 3/202(g) S02(jj) + H20{g) (23)
-*
(8) Passut, C. A., Danner, R. P.t Ind. Eng Chem. Process Des. Develop., II (4), 543

AHc =
288°K). The reactants
124.0 kcal mole-1 (at T = are (1972) .

(9) Huang, P. K., Daubert, T. E., Ind. Eng. Chem. Process Des. Develop., 13 (2) 193
initially at 288° K. The energy balance state is (1974).
(10) Hirschfelder, J. O., Buehler, R. J., Me Gee, H. A., Sutton, J. R., Ind. Eng. Chem.,
50(3), 375 (1953).
£ n, [Hi (T) -

Ht (288)J =
Affc (24)
(11) Edmister, W. C., Vairogs, J., Klekers, A. J., A.I.C.H.E. (Amer. Inst. Chem. Eng.) J.r
14 (3), 479 (1968).
where Hi(T) is the enthalpy of the product of combustion (12) Tsonopoulos, C., Prausnitz, J. M., Cryogenics, 9, 315 (1969).
i. Using an iterative method a program determines the (13) Sugie, H., anc| Lu, BC. Y., Ind. Eng. Chem. Fundam., 9 (3){ 428 (1970).
(14) Starling, K. E., Han, M. S., Hydrocarbon Proces., 51, 129 (1972).
temperature at which the energy balance is verified. (15) Yamada T., A I.C H.E. (Amer. Inst. Chem. Eng.) J., 19 (2). 286 (1973).
(16) Lee, B., Edmister, W. C., Ind. Eng. Chem. Fundam., 10 (1), 32 (1971).
(17) Sugie H, Lu, BC. Y, A.I.C.H.E. (Amer. Inst. Chem. Eng.) J., 17 (5), 1068 (1971).
(18) Kudchadler, A. P., Alani, G. H., Zwolinski B. J., Chem. Rev., 68,659 (1968).
********** ADIABATIC FLAME TEMPERATURE (19) Mathews J. F., Chem. Rev., 72 (1), 71 (1972).
(20) Reid R. C., Sherwood T. K., "The Properties of Gases and Liquids,” 2nd Ed., Me
SH2 + 3/2 02 = S02 + H20 Graw-Hill, New York, 1966.
(21) Passut C. A., Danner R. P., Ind. Eng. Chem. Process. Des. Develop., 12 (3), 365
REACTION ENTHALPY : -124.0 KCAL/MOL AT T (1973) .

288°K (22) Canjar L. N., Manning F. S., “Thermodynamic Properties and Reduced Correla-
tions for Gases,” Gulf Publishing Co., Houston, 1967.
EXCESS AIR 100 X AT P = 1 ATM (23) “Landolt-Bornstein zahlenwerte und funktianen," Band IV, Teil 4, Bandteil a, 6th
MOLES OF S02 1.
ed., Springer-Verlag, Berlin, 1967.
MOLES OF H20 2. (24) Glushko, V. P., (Editor), “Thermodynamic and Thermophysicai Properties of
MOLES OF 02 I. 5 Combustion Products," Vol. 1,1.P.S.T., Jerusalem, 1974.
MOLES OF N2 II. 28 (25) Dawe, R. A., and Snowdon P. N., J. Chem. Therm., 6,293 (1974).
(26) Mage, D. T., et ah, Chem. Eng. Progr. Symp. Ser., 59 (44), 61 (1963).
********** flam TEMPERATURE : 1334.2°K (27) Keenan, J. H., Keyes, F. G., Hill, P. G., Moore, J. G., “Steam Tables: Thermody-
namic Properties of Water Including Vapor, Liquid and Solid Phases,” John
Wiley & Sons, New York, 1969.
(28) West, J. R., Chem Eng. Progr., 44(4), 287, (1948).
Appendix (29) Vennix, A. J., Leland T. W., Kobayashi P., J. Chem. Eng. Data, 15(2), 238 (1970).
(30) Harrison R. H., Moore R. T,, DousJin D, R.( J. Chem. Eng. Data, 13(2), 131, (1973).
Equations derived from the generalized equation of state (31) Jones M. L., et ah, Chem. Eng. Progr. Symp. Ser., 59 (44), 52 (1963).
(4) are (32) Reamer H. H., et ah, Ind. Eng. Chem., 36 (10), 956 (1944).
(33) Farrington P. S., Sage H. B., Ind. Eng. Chem., 41(8), 1734 (1949).
(34) Bier K., et ah, J. Chem. Therm., 6, 1039 (1974).
y
=
\R + [(a2 + a3T-2 + 5a 4 T-6) -

(35) Yeaavage V. F., Katz D. L., Powers J. E., J. Chem. Eng. Data, 14(2), 197 (1969).
(36) Raznjevic K., "Tables et Diagrammes Thermodynamiques," Eyrolles, Paris, 1970.
(0.5C,r-1-5+ 2C3T-3) (V + 6)-1]V-1j(V- 6)-1 (25) (37) Ernst G., Busser J., J. Chem. Therm., 2, 787 (1970).

+ +

290 / Journal of Chemical Education