Correlation of Ideal Gas Enthalpy,

Heat Capacity, and Entropy

Charles A. Passut and Ronald P. Dannerl
Department of Chemical Engineering, The Pennsylvania State University, University Park, Pa, 16802
The accepted values of the ideal gas enthalpy, heat capacity, and entropy of 89 compounds, mostly hydro-
carbons, have been represented by a set of three thermodynamically consistent polynomials. The constants
for these equations, derived by minimizing the deviations in all three properties simultaneously, are tabu-
lated together with the average and maximum percent deviation for each compound. The overall error
analysis indicates that thermodynamic consistency can be maintained while yielding excellent predictions
for the three properties.
I deal gas properties are frequently required in correlations
of enthalpy, heat capacity, and entropy. In general, these
properties are correlated in terms of their deviations from
ideality and, thus to obtain reliable absolute values, accurate
predictions of the ideal gas values are required.
The American Petroleum I nstit'ute, Research Project 44
publishes ideal gas enthalpy, heat capacity, and entropy
values in tabular form. These values were corrected for the
molecular weight change to the carbon-12 basis. Frequently
it is more convenient t'o have these values represented by
analytical equations for comput,er applications.
Several methods have been used to obtain analytical ex-
pressions. I n the M I "Technical Dat'a Book-Petroleum
Refining" (1971), a set of three independent polynomial
equations for ideal gas enthalpy, heat capacity, and entropy
are given. Xn independent set of constants is provided for
each polynomial and thus one cannot go from one equation
to the other by the standard t'hermodynamic formula-Le.,
AH* =JCp*dT and AS* =J ( Cp * / T) d T. This method pro-
vides greater accuracy in fitting of the individual properties
at the expense of being thermodynamically inconsistent.
I n a recent publication, Thinh et' al. (19i1) reviewed the
published equations for predicting ideal gas heat capacity and
presented a listing of constants for the ideal gas heat capacity
of numerous hydrocarbons and relat'ed compounds in t'he
form:
Cp* =a +bT +cT2 +dT3
(1)
Values for the entropy and ent'halpy can be predicted from
this equat.ion by the appropriate thermodynamic relations.
However, some loss in accuracy for enthalpy and entropy
values is inevitable by t'his procedure, since t'he actual heat
capacit,y behavior is not theoretically constrained to follow
any particular polynomial. The method described below
yields thermodynamically consistent equations with good
accuracy for all three properties.
The forms of the equations used were as follows. For the
enthalpy:
H* =A +BT +CT2 +DT3 -+ET4 +FT5
(2)
where 9, B, C, D! E, and F are derived coefficient's, with the
enthalpy in Btu/lb and the temperature in "R.
To whom correspondence should be addressed.
For the heat. capacit'y, ( Cp* =dH*/dT):
Cp* =B +2 CT +3 CT2 +4 ET3 +5 F T 4
( 3)
and for the entropy, [S* =J( Cp*/ T) dT]:
S* =B In - +2 C(T - TB) +"2 D( T2 - TB2) +
T
TB
"3 E( T3 - T B ~ ) +'/4 F(T' - TB') +G'
(4)
where TB is t'he base temperat'ure for the ent'ropy equation
(l "R), and G' is the constant of int'egration. Equation 4 may
be further simplified by combining the constant base tem-
perature terms with the consbant G' t'o give Equation 5 :
S* =B 111T +2 CT +' 1 2 DT2 +
4/ 3ET3 +5/4FT4 +G
( 5)
where t'he constant G now contains the base correction.
The data bases used were 0 Utu/lb at 0"R for the enthalpy
and 0 I3tu/lb "R at 0"R and 1 atm pressure for the entropy-
the same as those used for tmhe XPI Research Project 44 tables.
(I t should be noted that these bases cannot be used for a
system in which a chemical react,ion has occurred.) The en-
thalpy, heat capacity, and entropy data used in these corre-
lations were taken from API Research Project 44 rvith the
exception of SO2, H2S, and XI-1; which were obtained
from AIcBride et al. (1963). The entire temperature range
available from t'he API -RP-44 data was included. The degree
of the polynomial in Equation 2 was chosen by balancing
t'he improved accuracy obtained with additional terms against
the increased complexity of the equations.
Cor r el at i onal Met hod
Since the constants in the equation are linear, a linear
method of solution xas indicated. The three different data
t'ypes (enthalpy, heat capacity, and entropy) were arranged
in one matrix [VI . The seven coefficients t'o the three equa-
t'ions rvere arranged in the coefficient matrix [A]. A tempera-
ture matrix was prepared to sat.isfy Equation 6:
[ T I nx7[ ~15X l =[VI nYJ (6)
The subscripts denote rows and columns, respectively.
To solve for the values in the [ A] matrix, the [TI matrix is
first transformed into a square matrix by multiplying Equa-
tion 6 by the t'ranspose of the [TI matrix,
Ind. Eng. Chem. Process Des. Devel op., Vol. 1 1 , No. 4, 1972 543
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Ind. Eng. Chem. Process Des. Develop., Vol. 1 1 , No. 4, 1972
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Ind. Eng. Chem. Process Des. Develop., Vol. 11, No. 4, 1972 545
The result of this operation is:
( 7)
where [SI and [C] are the resultant matrices.
The [A] matrix may be evaluated by inverting the [SI
matri x The matrix [SI is equivalent to a simultaneous least-
squares analysis for the three sets of ideal equations. A proof
of this procedure is given by Zeleznik and Gordon (1961).
The [SI matrix in Equation 8 can be inverted by standard
reduction techniques to find the values in the coefficient ma-
trix [A]. However, this matrix possesses certain special prop-
erties which can simplify the inversion. The [SI matrix is
positive, symmetric, and nonsingular. Therefore, the method
of Cholesky can be used to invert the matrix (Lapidus, 1962).
This method minimizes round-off errors in the inversion.
The Cholesky method will not be described here, but vas
built into the computer program developed to solve for the
ideal gas property coefficients.
I nitial work with the equations showed that forcing the
enthalpy equation through 0 at 0R was an unnecessary and
undesirable restriction even though the base for the values is
0 at 0R. Since none of the data are in the range of 0R and
since no empirical equation for the enthalpy can be ex-
trapolated outside the range of the available data, there is
no apparent loss from the addition of a constant, temper-
ature-independent term, to the enthalpy equation. I n the
same way the heat capacity equation has a constant term
when the enthalpy equation is differentiated. Again the heat
capacity is not predicted to be zero at absolute zero but the
equation for Cp* is not applicable in this range. The constant
term in Equation 4 (G) is the predicted entropy of the ideal
gas at the chosen base temperature of 1R and unit pressure.
This value comes out of the regression analysis, and once
again, since there is no data in this region, the predicted
value has no real significance. The temperature limitations
of the data are shown in Table I.
Resul ts
The constants obtained for the enthalpy, heat capacity, and
entropy equations of the 89 compounds are given in Table I.
The overall average percent error and maximum error ob-
tained in predicting the absolute values of the enthalpy,
heat capacity, and entropy are also given.
A comparison of the results of this work, those of the API
Technical Data Book (1971) and Thinh et al. (1971) are
shown in Table 11. The equations of Thinh have been com-
pared only for the 7 5 hydrocarbons common to both studies.
Furthermore since Thinhs equations have been developed
only for the temperature range of 298-1500K for the com-
parison given in Table 11, the equations of this work were
evaluated in this same temperature range. The values of
enthalpy and entropy for comparison with the correlations
of Thinh et al. had to be calculated as the property change
Table II. Comparison of Results wi t h Previous Work
Av % er r or a
capaci t y Ent hal py Entropy
Heat
Complete temperature range,
89 compounds
This work 0 436 0 064 0 040
XPI TechnicalDataBook 0 877 0 388 0 036
This work 0 249 0 14gb 0 721b
Thinh et al. (1971) 0 194 0 2746 0 721b
a ( l OO/ S ) L: [(predicted value - tabulated value)/tabulated
These values are based on predicted property change
298-1500K, 75 compounds
value].
from 298K.
from 298K since Thinhs equations cannot be used to obtain
absolute values.
The results given in Table I1 show marked improvement
over the independent set of three equations reported in the
API Technical Data Book. I n comparison to the correlations
of Thinh et al. for the 75 common hydrocarbons, there is a
loss in accuracy in the prediction of heat capacity, but a
decided improvement was obtained in the enthalpy predic-
tions. Since the enthalpy differences are, in general, the most
useful quantities, this improvement is significant. Further-
more the equations presented in this work have the advantage
of extending the temperature range. On the other hand, the
newly developed equations have the disadvantage of being
one degree higher in their powers of T compared to the equa-
tions of Thinh et al., but this added complexity is a necessity
when the equations are applied over the larger temperature
range available for many compounds.
In conclusion, Equations 2, 3, and 5, together with the
coefficients in Table I, are recommended for predicting the
ideal gas properties of the compound listed. They represent a
thermodynamically consistent set of equations with minimum
overall predictive errors.
l i t er at ur e Cited
American Petroleum Institute, Technical Data Book-Petro-
leuin Refining, 2nd ed., Chap. 7, Washington, D.C., 1971.
American Petroleum Institute Research Project 44, Selected
Values of Physical and Thermodynamic Properties of Hydro-
carbons and Related Compounds, Thermodynamics Research
Center, Texas -4&M University, College Station, Tex. (loose-
leaf data sheets extant 1972).
Lapidus, L., Digital Computation for Chemical Engineers, pp
NcBride, B. J ., Heimel, S., Ehlers, J . G., Gordon, S., SASA
Thinh, T. P., Duran, J . L., Ramalho, R. S. , Kaliaguine, S. ,
Zeleznik. F. J .. Gordon. S. . NASA Tech. Kote D-767, Washing-
240-57, McGraw-Hill, Kew York, N.Y., 1962.
Report hTo. SP-3001, 1963.
Hydrocarbon Proems., 50 (l ), 98-104 (1971).
ton, D.C , 1961.
-
RECEI VED for review J anuary 27, 1972
ACCEPTED J une 1, 1972
This work was sponsored by the American Petroleum Institute,
Division of Refining.
546 Ind. Eng. Chem. Process Des. Develop., Vol. 11, No. 4, 1972