The PVT-Behavior of Ethane in the Gaseous and

Liquid States
EDWARD M. PHILlIPS* NORTHWESTERN U.
GEORGE THODOS EVANSTON, ILL.

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ABSTRACT
A reduced density correlation for the gaseous
and liquid regions of ethane has been developed from
all the experimental PVT data available in the
literature for this substance. Saturated vapor and
liquid densities reported for methane, propane and
n-butane were utilized to establish the rectilinear-
diameter line for ethane. This line was then used
with the saturated-vapor data for ethane to produce
the saturated envelope for this substance. Most of
the saturated liquid data reported for ethane were
found to be inconsistent with the saturated-liquid
curve resulting from this study.
The correlation covers the regions 0.65 < TR < 6.0
and 0 < PR < 15. For regions for which no experi-
mental data have been reported, the isobars of
the correlation were extended by the use of the
theorem of corresponding states. This correlation
is presented both on rectilinear and log-log co-
ordinates.
INTRODUCTION
At the present time, there is considerable interest
thlOugh the critical point. This law, although
empirical, has been well established by continued
verification since its conception in 1886. This
rule has been applied to the saturated density data
of methane,6 propane 17 and n-butane8 to produce
,the straight lines presented in Fig. 1 w!Iich pass
through the critical point T R = 1.00, PR = 2.00.
The rectilinear-diameter relationship for ethane
was established from the lines for the other sub-
stances in Fig. 1 by plotting the quantity PR +
PR against Zc for different reduced temperaturei. A
crit'lcal analysis of the saturated vapor and l'quid
densities reported for ethane by Kuenen,10 Maass
and McIntosh,ll and Sage, Webster and Lacey18
revealed that the values of PR + PR resulting
from these studies were incoJsistent with the
rectilinear-diameter line obtained from the reliable
density data of the other substances, as shown in
Fig. 1. In the analysis of these data, reduced
quantities were calculated using the critical con-
2 .8
~\j
~
2,7
~

in the exact PVT behavior of pure hydrocarbons. 2 .6

Matschke and Thodos 12 recently have developed a
comprehensive compilation of experimental vapor
~~
"c! '1i 2 ,5
and liquid density data for methane. Similar studies
have been conducted for other pure substances.4 , 7
"...\.q..
t;,~
In the present study the density data available in ~~ 2,4
I ~\~
ETHANE {z.·0,2851 ~~
the literature for gaseous and liquid ethane have
been critically reviewed and utilized to develop
r-Tc=305,4 oK Pc=4820atm
~ 2.3
Y6
a reduced density correlation for this substance.
pc=0,203 g/cm'
1\.,
,
6
6
SA TURATED LIQUID AND VAPOR DENSITIES - 6
~
Kuenen
Maass and Mc Intash
2,2

The rectilinear-diameter rule proposed by Cailletet

and Mathias S states that the sum of the saturated
I> Sooe, Webster, and Lacey
~~~ 2.1
liquid and vapor densities of a pure substance is
a linear function of temperature which passes
u,:> e.6 0 08 U~ ~

Original manuscript received in Society of Petroleum Engineers Reduced Temperature, TR• f.c
office Nov. 6, 1960. Revised manuscript received Dec. 20,
1961. FIG. 1 - APPLICATION OF THE
*Now associated with the Research and Development Dept. RECTILINEAR-DIAMETER RULE TO THE
of The Atlantic Refining Co., in Philadelphia, Pa.
SATURATED DENSITY DATA OF METHANE,
12References given at end of paper. ETHANE, PROPANE AND N-BUTANE.
SPE 1632-G
JUNE, 1962 83
stants of ethane. Tc == 305.4'K, Pc == 48.20 atm
and Pc == 0.203 gm/cc. which were measured by
Beattie. Su and Simard,2 and are recommended by
Kobe and Lynn.9 The deviations of the experimental
densities from the expected rectilinear-law line
exhibited in Fig. 1 are most likely the result pf
experimental inaccuracies in the data, much of
which were obtained more than 30 years ago. The
critical densities resulting from the studies of
Kuenen,10 Maass and McIntosh,ll and Sage, Webster
and Lacey 18 are considerably different from the
value of Pc == 0.203 gm/cc. which was used to
reduce their saturated densities presented in Fig.
1. If the critical density resulting from each of
their studies were used to reduce the corresponding
experimental saturated densities, these points
would fall close to the ethane line obtained from
the interpolation of the data of the other substances.
liquid densities reported by the other investigators.
Further experimental work is required to verify the
saturated liquid curve for ethane chosen in this
study.
Density data for the superheated region of ethane
are reported by Beattie, et ai,l,3 Michels, et ai, 13
Sage, et ai,l8 Yee 20 and Reamer, et ai. 16 In 1944,
Reamer, Olds, Sage and Lacey l6 reported that the
work of some of the previous investigators appeared
to be questionable. Therefore, these investigators
conducted experimental PVT measurements for the
superheated region of ethane, and claim that their
data are accurate to within 0.5 per cent. All of the
available density data for ethane are presented in
Figs. 2 and 3. In Table 1, reduced densities obtained
from enlarged plots of Figs. 2 and 3 are given for a
number of temperatures and pressures, including
saturated vapor and liquid values.

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REDUCED DENSITY CORRELATION
In Figs. 2 and 3 a reduced density correlation is
presented which was developed from all of the
experimental data available in the literature. In
many cases, the data were not available in a form
suitable for direct use in the correlation. Therefore,
it was necessary to construct intermediate cross-
plots from which the information necessary to
produce the isobars included in this study could
be obtained. The saturated vapor data of Porter lS
were found to be consistent both internally and
with the trends exhibited by the saturated vaFor
data of methane, propane and n-butane. Consequently,
the saturated liquid curve was calculated from the
rectilinear-d iameter line for ethane and the corre-
sponding saturated vapor points. The data of Sage,
Webster and Lacey,18 which comprise the most
recent saturated liquid densities reported for ethane,
fall closest to this curve. As before, the use of a
critical density of Pc == 0.203 gm/ cc is the cause
of the deviations from this curve of the saturated
In Figs. 2 and 3, the isobars below PR == 1.00
were extended to interset:'t the saturat~d vapor
curve by the use of vapor pressure data for etha~ 19
For the regions of the compressed liquid phase and
the dense gaseous phase for which no data are
available, the isobars in Figs. 2 and 3 are presented
as dotted lines. The extension of the isobars into
the compressed liquid region above TR == 0.65 was
accomplished by the use of a reduced density plot
for nitrogen 4 and the following relationship.
• • • • • . • • • • • . • (1)
Such an extension is considered reliable since both
of the substances are nonpolar and have similar
critical compressibility factors.
For the extension of the density data of Figs.
2 and 3 into the dense gaseous-phase region, use
4
ETHANE (1,,0.285)
3
T,·3()5.4·K p,.4820 aIm
, ",.0..20.3 g/cm'
2 ~

~ :.--,
\
\

',,~,

1.0 - • Beattie, Hadlock, and

It~ ~, ",I,'.~4'
- PoffenberQer ,
~l~
0..8 -
_
0 Beattie, Su,ond Simard
+ Beattie, Su. and Simard
t~
1;\'
.\
,' ' ,,, ,
, ,'
o!. 0.6
0. 5 -
= : ="Ond Mcintosh
+ Michels. van Strooten, ,
,
"., , ·iIii - and Dawson ,'Ie V , ,
. ."- ",,, ,, , ,
0.4 -
o.....l~ -
• Porter
• Reamer. Old'. Sage. ~"
,
o
"- 0. 3 -

-,
'C and Locey

f 15 i -
.a. 5aQe. Webster. and
Locey \
,\\
'" , , ,
~ £ o. 2 - v Y.. ,
\\ ~"
\~ , , , ,
J ,
r.0~ r..
~\,j, \ ... \. \. \.
, ,
~' , ' ,
, ,,
0..10
, ,
0..0 8 , ,, ,

".
,'10
0..0.6 v.e" , , , ,
0..0 5 " ,
,,
, ,
0.0.4 ,
" ,,\, ,, ,

16 11 18
0'
19 20
0.0.3
0.6 0.8 1.0

Reduced Temperature, T" =

'" 2
f.c
3 4 5 6

FIG. 3 - REDUCED-STATE DENSITY

FIG. 2 - REDUCED-STATE DENSITY CORRELATION CORRELA TION FOR ETHANE (LOG-
FOR ETHANE (RECTILINEAR CO-ORDINATES). LOG CO-ORDINATES).

84 ~OCIETY Ot' PETROLEUM ENGI:'i'EERS JOURNAL

has been made of the compressibility-factor correla- z c = critical compressibility factor
tions of Nelson and Obert 14 and the theorem of
P = density, gm/ cc
corresponding states with the following relationship.
Pc = critical density, gm/ cc
PR = reduced density, p/Pc
(2) PR[ = reduced density of saturated liquid, Ps,lPc
PR v "" reduced density of saturated vapor, Ps v Ipc
Ps = saturated density, gm/cc
where for each isobar P R is the density at the
highest temperature for which an experimental PR B . . reduced density at saturated conditions,
value was available. The log-log plot presented Ps/Pc
in Fig. 3 e,pables densities to be obtained for
reduced temperatures as high as TR "" 6.0 and low REFERENCES
reduced pressures.
1. Beattie, J. A., Hadlock, Cawfield and Poffenberger,
NOMENCLATURE Noland: Jour. Chem. Phys. (1935) Vol. 3, 93.
2. Beattie, J. A., Su, G. J. and Simard, G. L.: Jour.
P = pressure, atm ACS (1939) Vol. 61, 924.

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Pc = critical pressure, atm 3. Beattie, J. A., Su, G. J. and Simard, G. L.: Jour.
ACS (1939) Vol. 61, 926.
P R = reduced pressure, PIPe
4. Byrne, Robert and Thodos, George: AIChB Jour.
T = temperature, oK (1961) Vol. 7, 185.
T c = critical temperature, oK 5. Cailletet, L. P. and Mathias, E. O. J.: Compt. rend.
(1886) Vol. 102, 1202.
T R = reduced temperature, TIT c
6. Cardoso, Ettore: Jour. Chem. Phys. (1915) Vol. 13,
z = compressibility factor 312.

TABLE 1 - REDUCED DENSITY VALUES FOR ETHANE

Sat'd. Sat'd. PR = PR = PR = PR = ~= PR = ~= PR =
TR Liquid Vapor 0.10 0.15 0.20 0.60 0.80 1.00 1.20 1.80

0.50 2.791
0.60 2.626 0.012
0.70 2.442 0.036 2.469
0.80 2.220 0.100 0.0379 0.0599 0.0860 2.258
0.85 2.086 0.155 0.0350 0.0550 0.0770 2.132
0.90 1.923 0.236 0.0330 0.0510 0.0700 0.160 1.989
0.95 1.701 0.364 0.0310 0.0479 0.0663 0.143 0.262 1.800 1.890
1.00 1.000 1.000 0.0294 0.0448 0.0610 0.133 0.227 0.361 1.000 1.700
1.05 0.0280 0.0424 0.0579 0.124 0.200 0.302 0.442 0.700 1.200 1.400 1.500
1.10 0.0266 0.0402 0.0547 0.117 0.185 0.268 0.370 0.500 0.700 0.940 1.165
1.20 0.0369 0.0494 0.103 0.163 0.222 0.294 0.380 0.476 0.572 0.689
1.30 0.0337 0.0450 0.0936 0.145 0.197 0.255 0.318 0.388 0.459 0.536
1.40 0.0311 0.0417 0.0850 0.131 0.179 0.228 0.280 0.333 0.393 0.451
1.50 0.0290 0.0388 0.0792 0.121 0.162 0.207 0.252 0.300 0.350 0.396
1.60 0.0269 0.0362 0.0726 0.112 0.149 0.190 0.230 0.273 0.314 0.357
1.70 0.0254 0.0339 0.0680 0.103 0.139 0.176 0.212 0.251 0.290 0.327
1.80 0.0320 0.0640 0.0965 0.130 0.164 0.199 0.234 0.270 0.303
1.90 0.0301 0.0600 0.0910 0.122 0.153 0.190 0.220 0.252 0.282
2.00 0.0286 0.0570 0.0860 0.115 0.144 0.183 0.208 0.235 0.263

PR = 10.0 PR = 12.0 PR = 14.0

0.70 2.501 2.536
0.80 2.308 2.358 2.433 2.473 2.531 2.574 2.617 2.651
0.90 2.090 2.159 2.215 2.261 2.307 2.378 2.433 2.485 2.527
1.00 1.800 1.925 2.012 2.077 2.135 2.221 2.293 2.358 2.402
1.10 1.300 1.635 1.780 1.879 1.957 2.068 2.159 2.230 2.282
1.20 0.812 1.288 1.528 1.674 1.773 1.918 2.023 2.106 2.170
1.30 0.621 1.005 1.280 1.466 1.594 1.770 1.897 1.988 2.059
1.40 0.515 0.827 1.080 1.280 1.428 1.626 1.771 1.871 1.951
1.50 0.449 0.702 0.930 1.124 1.280 1.500 1.651 1.764 1.852
1.60 0.401 0.618 0.821 1.000 1.159 1.383 1.544 1.667 1.759
1.70 0.363 0.555 0.740 0.904 1.059 1.289 1.451 1.574 1.669
1.80 0.339 0.509 0.678 0.830 0.978 1.203 1.369 1.491 1.588
1.90 0.317 0.471 0.628 0.770 0.910 1.130 1.299 1.419 1.513
2.00 0.295 0.440 0.583 0.720 0.850 1.065 1.229 1.360 1.452
JUNE, 1962 85
 7. Hamrin, C. E., Jr., and Thodos, George: AIChB Jour.
(1958) Vol. 4, 480.
8. Kay, W. B.: Ind. and Bngr. Chem. (1940) Vol. 32,
358.
9. Kobe, K. A. and Lynn, R. E., Jr.: Chem. Rev. (1953)
Vol. 52, 117.
10. Kuenen, J. P.: Phil. Mag. (1895) Vol. 40, 173.
11. Maass, O. and Mcintosh, D.: JOI#'. ACS (1914) Vol.
36, 737.
12. Matschke, D. E. and Thodos, George: Trans., AlME
(1960) Vol. 219, 396.
13. Michels, A., van Straaten, W. and Dawson, J.: Physica
(1954) Vol. 20, 17.
86
14. Nelson, L. C. and Obert, E. F.: Trans., ASME (1954)
Vol. 76, 1057.
15. Porter, Frank: Jour. ACS (1926) Vol. 48, 2055.
16. Reamer, H. H., Olds, R. H., Sage, B. H. and Lacey,
W. N.: Ind. and Bngr. Chem. (1944) Vol. 36, 956.
17. Reamer, H. H., Sage, B. H. and Lacey, W. N.: Ind.
and Bngr. Chem. (1949) Vol. 41; 482.
18. Sage, B. H., Webster, D. C. and Lacey, W. N.: Ind.
and Bngr. Chem. (1937) Vol. 29, 658.
19. Sondak, N. E. and Thodos, George: AIChB Jour.
(1956) Vol. 2, 347.
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Arbor, Mich. (1936).
***
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SOCIETY OF PETROLEUM ENGI:'I'EERS JOURNAL