Correlation of Constants in the
Benedict-Webb-RubinEquation of State
n-PARAFFINS, 1-BUTENE, AND Z72-D1METHYLPROPANE
L. N. CANJAR, R. F. SMITH', ELIAS VOLIANITIS,
J. F. CALLUZZO2, AND MANUEL CABARCOS
Carnegie I n s t i t u t e of Technology, P i t t s b u r g h 13, Pa.
HE prediction of thermodynamic properties of mixtures of
T iight hydrocarbon vapors has long been a troublesome prob-
lem in the petroleum and associated industries. The ability to
calculate the enthalpy of various grades of gasoline, for instance,
would be of great value in petroleum processing. With the in-
formation available a t present, however, such a calculation is not
possible. If reasonably precise calculations of this type are to
be made possible, fundamental data in this area are needed.
n-PARAFFINS
The prediction of properties of mixtures is invariably attacked
by attempting some combination of properties of pure compo-
nents. Many of the pure hydrocarbons up to about Cs have been
investigated experimentally; P-V-T data are thus available for
these compounds. As thermodynamic properties can be cal-
culated from P-TI-T data, it is possible to estimate the properties
of mixtures containing these compounds. However, many gas
mixtures of industrial importance contain compounds above Cs,
for which practically no data are available a t present. It is not
likely that experimental data will ever be available for these
compounds, as they tend t o decompose under temperatures a t
which the data are needed.
I n view of this lack of data and the difficulties involved in
obtaining them, attempts have been made to estimate P-V-T
behavior for these compounds. The most widely used method
of estimating P-V-T behavior is the compressibility factor chart.
However, this generalized correlation becomes increasingly in-
accurate for compounds heavier than butane and therefore cannot
be applied to the Cg and heavier compounds. Before a reduce3
correlation can be used, i t is necessary to estimate the critical
properties, which introduces an additional error.
The present work represents an attempt to correlate the eight
constants of the Benedict-Webb-Rubin equation ( 8 ) with some
property or properties of the compound, with a view towards
extrapolating this correlation to compounds that cannot be
measured experimentally.
B,RT - A , - ")
T2 d 2 +
(bRT - a)da + aade +
cd
[(I + yd*)]e-ydz
This equation was chosen because of the extensive applica-
tion i t has recently received in petroleum processes and because
i t covers a more extensive region of measured P-V-T data than
other equations of state.
T h a t such a correlation exists cannot be proved theoretically,
as the equation itself is empirical. However, in view of the flex-
ibility inherent in an equation containing as many as eight
arbitrary constants ( 7 ) ,i t does not seem unreasonable to assume
that some correlation can be found within a homologous series
such as the paraffins.
1 Present address, E. I. du Pont de Nemours & Go., Inc., Wilmington, Del.
2 Present address, Shell Oil Co., Wood River, Ill.
I n order to establish the most likely form of such a correlation,
the original constants as recorded by Beneciict, Webb, Rubin,
and Friend ( 8 ) were plotted against critical temperature, critical
pressure, molecular weight, and normal boiling point. Several
combinations of these, such as the ratio of the critical temperature
to critical pressure, were also considered. Critical temperature
was the parameter that apparently offered the greatest hope for
correlation and futilre extrapolation. Two of the constants,
A , and Bo, appeared to be linear with T,, although there was con-
siderable scattering from the straight lines. The other six con-
stants appeared to be smooth functions of T,, but as they were
not linear they offered little hope for extrapolation. However,
when the logarithms of these constants were plotted against T,,
the lines were straight, again with appreciable scattering,
Methane, ethane, and possibly propane could not be included in
this type of correlation. This was not an unexpected develop-
ment, as the same was found to be true in other correlations of
hydrocarbon properties. The correlation of normal boiling point
with molecular weight for paraffins, for example, begins with
butane.
These findings are not unreasonable when the shapes of the
molecules involved are considered. The difference between the
shapes of the ethane and methane molecules is obviously much
greater than that between n-pentane and n-hexane, for instance.
Thus i t appears that a correlation which does not contain some
shape factor can exist only over the range where the addition of
methyl groups does not seriously alter the shape of the molecule.
The first attempt to eliminate this scattering consisted in drawing
what appeared to be the best straighi line through the points, and
simply moving the points onto the lines. These adjusted con-
stants were then used to calculate pressures, which were checked
against experimental data. This method proved unsatisfactory,
as calculated pressures varied from the experimental value by
as much as 5 to 10%. While such agreement was not acceptsble
as a final result, i t gave hope that a more judicious adjusting
procedure might arrive at a set of constants which would correlate
smoothly and still satisfactorilyrepresent the original data.
I n examining the procedure used for determining constants
for the Benedict-Webb-Rubin equation (8)it was found t'lat there
(1) is a considerable flexibility in the determination of the first two
constants, Bo and b. Thus for any of the compounds B, and b
can be varied appreciably. With this in mind calculations were
begun to evaluate new constants for the paraffins for which data
were available. The data used in these calculations were as
follows: propane (S),n-butane ( 6 ) , n-pentane ( 4 , IO), n hexane
( 9 ) , and n-heptane ( 1 1 ) . Data from methane and ethane were
also available, but they could not be included in the correlation.
As the calculations were continued, i t was found impossible to
correlate propane in this way.
As each of the constants was evaluated for all the compounds,
i t was plotted against T,. If the constants scattered from the
straight line, the previous calculations were evamined for places
where flexibility existed. Adjustments were made in this way
1028
May 1955 INDUSTRIAL AND ENGINEERING CHEMISTRY 1029

Table I. Deviations from Observed Pressures for Butane Table 11. Deviations from Observed Pressures for Pentane
Pobsd., Deviation Temp., Pobsd., Deviation
Temp.,
0 c. Atm. Atm. % c. Atm. Atm. %
d = 1.0 Gram-Mole per Liter d = 1.0Gram-Mole per Liter
150 24.68 -0.15 0.61 200 25.70 -0.26 1.01
175 27.50 -0.15 0.55 225 28.74 -0.21 0.73
200 30.24 -0.16 0.53 250 31.67 -0.20 0.63
225 32.92 -0.16 0.49 275 34.55 -0.18 0.52
250 36.55 -0.17 0.48 300 37.37 -0.18 0.48
275 38.18 -0.14 0.37
300 40.76 -0.10 0.25 d = 1.5Gram-Moles per Liter
d = 1.5 Gram-Moles per Liter 200 31.13 -0.29 0.93
225 36.27 -0.18 0.50
150 30.94 -0.22 0.71 250 41.22 -0.13 0.32
175 35.68 -0.18 0.45 275 46.04 -0.09 0.20
200 40.22 -0.18 0.45 300 50 76I -0.07 0.14
225 44.67 -0.16 0.36
250 49.01 -0.18 0.37 d = 2.0 Gram-Moles per Liter
275 53.33 -0.18 0.30 200 33.66 -.0.24 0.71
300 57.58 -0.16 0.28 225 41.13 0.04 0.10
d = 2.0Gram-Moles per Liter 250 48.32 0.12 0.25
275 55.32 0.10 0.18
150 34.39 -0.32 0.93 300 62.25 0.08 0.13
175 41.31 -0.12 0.29
200 47.88 -0.08 0.17 d = 2.6 Grams-Moles per Liter
225 54.29 -0.12 0.22 200 34.63 0.13 0.37
250 60.62 -0.08 0.13 225 44.47 0.40 0.89
275 66.82 -0.16 0.24 250 54.06 0.44 0.81
300 72.97 -0.15 0.22 63.53 0.48 0.78
275
d = 2.5 Gram-Moles per Liter 300 72.93 0.38 0.52
150 35.93 -0.38 1.06 d = 3.0 Gram-Moles per Liter
175 45.15 ... 200 34.97 0.44 1.29
200 53.92 0.08 o:i2 225 47.16 0.54 1.15
225 62.50 0.08 0.09 250 59.40 0.63 1.06
250 70.93 -0.06 0.05 71.66 0.54 0.75
275 79.34 -0.04 0.14 275
300 87.63 -0.13 300 83.96 0.36 0.43
d = 3.0Gram-Moles per Liter d = 3.5Gram-Moles per Liter

175 0.19 200 35.20 0.86 2.44

200 0.31 225 50,03 0.74 1.48
225 0.13 250 65.38 0.61 0.93
250 0.03 275 80.98 0.56 0.69
275 300 96.72 0.49 0.51
300 0:09 d = 4.0Gram-Moles per Liter
d = 3.5 Gram-Moles per Liter 200 35.76 0.75 2.09
175 50.08 0.25 0.50 225 54.08 0.61 1.13
200 63.65 0.10 0.19 250 73.32 0.63 0.86
225 77.21 0.41 0.16 275 93.09 0.77 0.83
250 90.67 -0.12 0.13 300 113.05 0.45 0.40
275 104.25 -0.25 0.24 d = 4.5Gram-Moles per Liter
300 117.70 -0.50 0.42
200 37.77 0.54 1.42
d = 4.0Gram-Moles per Liter 225 61.01 0.56 0.92
175 52.20 0.16 0.31 250 85.55 0.97 1.13
200 68.61 275 110.47 0.77 0.70
225 85.20 -6165 0:OG 300 135.93 0.79 0.60
250 101.84 -0.16 0.16 Av. deviation = 0.42atm.
275 118.57 -0.48 0.40 Av. deviation = 0.78%
300 135.27 -0.80 0.59 Critical Dressure (obsd.) = 33.31atm.
d = 5.0Gram-Moles per Liter Critical pressure (calcd.) = 36.70atm.
175 58.30 0.02 0.04
200 81.96 -0.25 0.31
225 106.23 -0.20 0.19
250 130.80 -0.50 0.38 seven constants-Bo, b, C,, c, y, a,and A,-all of which resulted
275 155.59 -1.05 0.66
300 180.56 2.00 1.11 in straight lines when plotted against T,. As before, the log-
d = 6.0 Gram-Moles per Liter arithms of these constants were plotted in each case, except for
175 74.32 0.62 0.86 A , and Bo. However, when the final constant, a, was calculated
200 109.23 0.72 0.66 and plotted against T,, the points did not fall on a straight
225 145.02 0.75 0.52
250 181.11 0.35 0.19 line. I n fact, there was a definite curvature whether the con-
275 217.50 -1.08 0.50
300 253.96 -2.52 0.99 stant or its logarithm was used. This curvature, unlike the
Av. deviation = 0.30atm. scattering encountered with the previous constant, could not
Av. yo deviation = 0.35% be eliminated b y simply adjusting the constants. Because the
Critical pressure (obsd.) = 37.48atm.
Critical pressure (calcd.) = 37.78atm. uncertainties of extrapolation are much greater for curves than
for straight lines, a correlation other than log a us. T , was sought.
It seemed likely that some other characteristic of the com-
until the constant or its logarithm plotted smoothly against To. pound, probably molecular weight, might be required to complete
I n some cases i t was necessary to adjust not only the particular the correlation. After some experimentation i t was found that
constants t h a t scattered, b u t also some of the previous ones that log a / N , plotted against T , resulted in a straight line. N , here
had already been smoothed. This was true in cases where there represents the number of carbon atoms in the molecules, which
was no flexibility in the particular calculation involved-for in- for the homologous series is obviously equivalent to molecular
stance, virtually no flexibility existed in the determination of weight as a correlating variable.
C,, c, and y . Therefore, if any of these constants scattered, i t With the successful correlation of a, a complete set of smoothly
was necessary to go back to the calculation of Bo and b in order correlated constants was now available for n-butane, n-pentane,
to make the adjustment. I n this way the constants were n-hexane, and n-heptane. Experimental data were checked
adjusted to correlate smoothly, while still representing the ex- using these constants to determine whether they were still a
perimental data. This procedure was successful for the first valid representation of that data. The results of these calcula-
1030 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 47, No. 5

Using these constants in the Benedict-Webb-Rubin equation

Table 111. Deviations from Observed Pressures for Heptane and Young's value for the critical temperature and density, a
Temp., Pobsd., Deviation critical pressure of 24.78 atm. is calculated, which is 0.14 atm.
c. Atm. Atm. % less than the observed value.
d = 1.0 Gram-Mole per Liter To estimate the P-V-T properties of the heavier n-paraffins,
275 25.19 -0.37 1.47 the following procedure is required.
300 28.68 -0.28 0.98
325 32.03 -0.25 0.78 1. Estimate roughly the critical temperature.
350 35.34 -0.20 0.57

275
d - 1.5 Gram-Moles per Liter
28.55 -0.11 0.38
2. Calculate the B-W-R constants using Equations 2 to 9.
3. Calculate pressures as a function of density along the esti-
mated critical isotherm.
300 34.43 0.02 0.06 4. If the slope of the isotherm is zero a t the point of inflection,
325 40.12 0.04 0.10 the value of T,estimated in step 1 is correct. If the slope is not
350 45.74 0.14 0.31
zero, a new estimated critical temperature must be tried and
d = 2.0 Gram-Moles per Liter steps 1 t o 4 repeated.
275 29.72 0.24 0.81
300 38.08 0.32 0.84 To demonstrate this, estimated critical temperatures of 615",
325 46.38 0.28 0.60
350 54.63 0.20 0.37 619", and 620' K. for n-decane were tested using the above
d = 2.5 Gram-Moles per Liter
procedure (Table V). American Petroleum Institute Research
0.37 1.22
Project No. 44 (I), has estimated the critical properties of n-
275 30.38
300 41.29 0.06 0.15 decane t o be:
325 52.89 0 . I9 0.36
350 64.58 0.26 0.39 To = 619" K.
P, = 20.8 atm.
d = 3.0 Gram-Moles per Liter d, = 1.66 moles per liter
31.70 -0.36 1.14
46.65 -0.36 0.77 The agreement is excellent in the light of the fact that the
62.30 -0.27 . 0.43
0.23 critical point listed by API Project No. 44 is an estimated value.
-
78.53 -0.18
d 3.5 Gram-Moles per Liter An attempt was made t o develop a similar correlation for the
36.62 -G.73 1.99 isomeric forms of n-paraffins, b u t i t was concluded that too few
57.67 -0.49 0.85 data are available for a reliable correlation.
79.57 -0.25 0.31
102.18 -0.12 0.11
d = 4.0 Gram-Moles per Liter
53.17 -0.18 0.34 Table IV. Pressure Deviations for n-Hexane
83.40 0.32 0.38 Density, Pobsd., Deviation
114.24 0.29 0.25
146.88 0.05 0.03 G.-MoIes/Liter Atm. Atm. %
Av. deviation = 0 . 2 5 atm. T = 250' C.
Av. % deviation = 0.5807,
Critical pressure (obsd.) = 2 7 . 0 0 atm. 2.5 36.63 -0.35 0.96
Critical pressure (calcd.) = 2 7 . 2 3 atm. 3.0 38.17 0 13 0.34
3.5 40.85 -0.51 0.80
4.0 47.04 -0.18 0.38
T = 275' C.
2.5 47.06 -0.41 0 87
tions, listed in Tables I t o IV, show an over-all average deviation 3.0 51.62 0 09 0.17
of 0.32 atm. or 0.57y0 for the four compounds, over the range for 3.5 58.29 -0.48 0.83
4.0 70.35 -0.48 0.57
which the Benedict-Webb-Rubin equation can be expected to Av. deviation = 0 . 3 2 atm.
hold. The eight constants are thus successfully correlated with Av. % deviation = 0.61%
Critical pressure (obsd.) = 2 9 . 9 2 atm.
T,and No. The equations of the correlation are as follows: Critical pressure (calcd.) = 2 9 . 8 6 atm.

A , = 0.0487 T , - 13.01 (2)

Bo = (4.337 X 10-4)T, - 0.0951 (3) The uncertainty of the correlation increases with increasing
log,, C o = 0.005497 T , 3.728 + (4) carbon number of normal paraffins. However, the correlation
log10 a: = 0.004691 T, - 5.030 (5) does enable the estimation of properties a t conditions where they
loglo y = 0.003303 To - 2.900 (6) will probably never be measured because of chemical instability.

log,, (a,) = 0.004141 T , - 1.941 (7)

Because of the limited procedure used in arriving a t the correla-
tion and the lack of experimental data for high molecular weight
compounds which could be used t o test the correlation further:
lOg,o ( b ) 0.005187 Tc - 3.498 (8) the equations presented here should be used with caution.
loglo c = 0.007521 Tc 2.373 + (9)
R = 0.0820544 1-BUTENE AND 2,2-DIMETHY LPROPANE

The correlation was checked by calculating the critical pressure In the course of this investigation, in which an attempt was
for n-octane. The critical point for n-octane as reported by made to correlate the constants of the Benedict-Webb-Rubin
Young (1%')is given as: equation of state for hydrocarbons, some work was done in fitting
the P-V-T data 1-butene and 2,2-dimethylpropane (neopentane)
T , = 569.4' K. to this analytical expression.
d, = 2.0576 gram-moles per liter Although the constants eventually were not used in the above-
P, = 24.64 atm.
mentioned correlation, they are undoubtedly useful for other
The values of the Benedict-Webb-Rubin constants as calculated applications.
from Equations 2 to 9 using Young's value of the critical tempera- The method used in fitting the experimental data to the
ture are: Benedict-Webb-Rubin equation was essentially that described
by Benedict, Webb, and Rubin (7), except that no attempt
A , = 14.719 b = 0.2854 was made to fit the vapor pressure data. Since the Benedict-
Bo = 0.1518 c = 4.523 X lo6
C , = 7.211 X lo6 CY = 0.004376 Webb-Rubin equation can be expected t o hold from zero density
a = 20.89 y = 0.09566 to about 1.8 times the critical density, only the experimental data
May 1955 INDUSTRIAL AND ENGINEERING CHEMISTRY 1031

for this range of densities were considered. The virial form of the
equation is: Table V. Critical Isotherm for n-Decane
Density Assumed TC
P = RTd + (BoRT - A , - 6 ”> d 2 + cd G.-Moles/Iher 615’ K. 619’ K. 620’ K.
P , Atmospheres.
(bRT - a ) d 3 + aada + 3
[(l + yd2)e-yd2] 0.5 16.04 16.03 16.03
1.0 19.15 19.46 19.55
1.5 17.20 19.04 19.64
1-Butene. The experimental data reported by Beattie and 2.0 15 55 20.60 21.98
3.0 30.09 48.60 53.49
Marple (6) were used in this work. Table VI indicates the agree-
ment between the pressures observed by Beattie and Marple and
those calculated by the Benedict-Webb-Rubin equation using the
following constants: LITERATURE CITED

A, = 9.060 c = 0.274920 X loe (1) American Petroleum Institute Research Project No. 44, Car-
Bo = 0.116025 a = 0.910889 X negie Institute of Technology, “Selected Values of Properties
C , = 0.927280 X lo6 y = 0.0295945 of Hydrocarbons.”
a = 1.682 R = 0.0820544 (2) Beattie, J. A., Douslin, D. R., and Levine, S. W., J. Chem.
h = 0.0348156 Phys., 20, 1619 (1952).
(3) Beattie, J. A , , and Kay, W. C., J . Am. Chem. SOC.,59, 1586
2,2-Dimethylpropane. The experimental data reported by
(1937).
Beattie, Douslin, and Levine ( 8 ) were used in fitting the P-V-T (4) Beattie, J. A., Levine, S. W., and Douslin, D. R., Ibid.. 74, 4778
data for 2,2-dimethylpropane t o the Benedict-Webb-Rubin (1952).
equation. Table VI1 shows the agreement between experimen- (5) Beattie, J. A., and Marple, S. J., I b i d . , 72, 4143 (1950).
tally observed and calculated pressures using the following con- (6) Beattie, J. A., Simard, G. L., and Su, G. L.. I b i d . , 61, 26 (1939).
stants in the Benedict-Webb-Rubin equation: (7) Benedict, M., Webb, G. B., and Rubin, L. C., J . Chem. Phys.,
8, 334 (1940).
A, = 12.9635 c = 0.546 X IO6 (8) Benedict, M., Webb, G. B., Rubin, L. C., and Friend, L.,
Bo = 0.170530 a = 0.002 Chem. Eng. Progr., 47, 419, 571 (1951).
C, = 1.273 X lo6 y = 0.05 (9) Kelso, E. A., and Felsing, W. A., IND. ENG.CHEM.,34, 161
a = 3.4905 R = 0.0820544 (1942).
6 = 0.0668120
(10) Li, K., and Canjar, L. M., Chem. Eng. Progr. Symposium Ser.,
All the equation of state constants presented here are based on No. 7, 49, 147 (1953).
(11) Smith, L. B., Beattie, J. A., and Kay, W. C., J . Am. Chem.
the c.g.s. units.
Soc., 59, 1587 (1937).

P
T = t o C.+273.160
= atmospheres
(12) Young, S., Sci. PTOC. Roy. D u b l i n SOC.,12, 374 (1910).

d = gram-moles per liter RECEIVED

for review August 9, 1954. ACCEPTED
December 7, 1954.

Table VI. Comparison of Calculated with Observed Data for 1-Butene

Density, Moles per Liter
1 .o 1.5 2.0 2.5 3.0 3.5 4.0 5.0 6.0 7.0 8.0
Temp.,
0 c. (Int.) Pressure, Normal Atmosphere
150.0
Obsd. 25.60 32.76 37.21 39.74 41.02 41.63 41.95 52.66 46.22 63.13 117.33
Obsd. - calcd. -0,0170 -0,0452 -0,0709 -0,1135 -0.14136 -0,1821 -0,1937 -0.0809 -0.0073 f0.4033 +8.g383
175.0
Obsd. 28.35 37.34 43.86 48,60 52.16 55.04 57.69 64,04 76.69 108.07 183.55
Obsd. - calcd. -0.0106 -0,0680 -0,2923 -0,2923 -0.3675 -0,3216 -0,1400 +0.4387 +0.4532 +0.6908 f9.7620
200.0
Obsd. 31.03 41.76 50.24 57.11 62.94 68.23 73.51 86.32 108.30 153.70 248.94
Obsd. - calcd. +0.0049 -0.0392 -0.1428 -0.2673 -0,3353 -0.2581 -0,0438 +0.5581 +0.6037 +1.1061 f11.5977
225.0
Obsd. 33.65 46.08 56.47 65.42 73.51 81.29 89.32 108.98 140.68 199.98 .....
Obsd. - calcd. +0.0313 +0.0023 -0.0795 -0,1600 -0.1790 -0,0783 +0.1610 t-0.6996 +0.6519 f1.5293 ... , ,
250.0
Obsd. 36.20 50.27 62.48 73.50 83.84 94.11 103.93 131.47 172.72 245.26 .. .. .. .. ..
Obsd. - calcd. +0.0878 i-0.1029 +0.1106 +0.0817 f0.1473 +0.3303 +0.6459 +1.3376 f1.5832 +3.4878

Table VII. Comparison of Calculated with Observed Data for 2,2-Dimethylpropane

Density, Moles per Liter
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 6.0
Temp.,
C. (Int.) Pressure, Normal Atmosphere
160.6
Obsd. 23.73 28.73 30,84 31.48 31.56 31.58 31.73 33.12 38,56 85.36
Obsd. - calcd. +0.0032 -0.0014 +0.0812 +0.0179 -0.1881 -0.4121 -0,2413 +0.4631 f1.8709 f12.1302
175.0
Obsd. 85,46 31.62 35.13 37.12 38.46 39.70 41.77 46.03 55:45 114.62
Obsd. - calcd. -0.0199 -0.0518 -0.1383 -0.2535 -0.3272 -0,1765 +0.6710 +0.5852 f1.7079 f11.3286
200.0
Obsd. 28.35 36.51 42.2.5 46,59 50,43 54.63 60,36 69.68 85.78 165.35
Obsd. - calcd. +0.0015 -0.0855 -0.2486 -0.3862 -0,4048 -0.2540 -0,0045 +0.3161 f1.2843 +10.6288
225.0
Obsd. 31.21 41.29 49.18 55.92 62.44 69.85 79.60 94.10 117.24 217.08 -
Obsd.
250.0
- calcd. -0.0017 -0.0868 -0.2290 -0.3613 -0,3590 -0,2558 -0.0965 +0.0717 f0.6456 + 9.5872
Obsd. 33.96 45.90 55.95 65,ll 74.43 85.15 99.10 118.74 149.00
Obsd.
275.0
- Calcd. f0.0605 +0.0168 -0.0984 -0.1819 -0,1605 -0.0401 f0.0141 +0.1564 +0.4512 +268,83
9.0612
Obsd. 36.71 50.49 62.65 74.25 86.41 100.58 118.85 144.02 181.OS 320.93
Obsd. - calcd. +0.0862 +0.0925 +0.0620 +0.0594 +0.1573 +0.2901 f0.2716 +0.3339 fO.5483 +8.6252