W5 5tL6

Non-Ideal Behavior of Gases and Their Mixtures

ABDUS SATTER*
JUNIOR ME&ER AlME
JOHN M. CAMPBELL
MEMBER AIME I U. OF OKLAMOMA
NORMAN, OKLA,

ABSTRACT obtained by the use of a mukiple number of

empirical constants. This has lead to multiple-

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

Reported herein are-the results ofa careful and constant equations such as Benedict-Webb-Rubin,
detailed study of the non-idea! behauior of pure Beattie-Bridgman, Keyes, etc., which are ,capable
gases andtbeir mixtures. hrcluded are: (l] new data of yielding very precise results for pure gases in a
on five ternary systems composed o f me thane, ethane range for which data to get the constants are
and H2S; (2) a simple compressibility {aCtOr corre- available. As a’ mstter of practicality, though, the
lation that is’ inherently superior to present use of such equstions for gas mixtures is limited.
correlations, particularly for gases containing H2S Because of the infinite riumber of gas analyses
and C02; and(3) a detailed study o/combination rides available, any attempt to compile the constants
and the e{iect of system composition on the cbcice needed requires a prohibitive amount of experimental
thereof. data. This could be overcome by the use of a
This study makes use o) the rather large mass oj combination rule, but there is no real advantage in
data already available in the literature. A complete doing so because the end result offers no practical
re- examination of t be data and ideas presented in irnpove ment over the Z factor correlation.
the last 25 years. was considered desirable as a The most widely used method of predicting the
prelude to our basic concern — the effect of volumetric properties of pure gases is based ‘upon
diluents on gas bebauior. A consideration of both the “theorem of corresponding states”. According
tbe macroscopic and microscopic properties of to this theorem, “all pure substances have
gases provides a better. insight which, in turn, corresponding molal volume at corresponding
gives a.iirmer basis for improved correlation tech- temperature
. and .Dressure if the reference .~oint of
niques, Such a study has shown that expressing correspondence is the critical point”. Generalized
the compressibility factor Z as a function 0/ ! compressibility charts for gases were prepared
acentric /actor w, as well as reduced temperature first by Cope and associates~ in 1931 and later by
and pressure, yields a correlation that is broader Brown and co-workers2 in 1932. However, the most
in scope. commonly used charts are those of Dodge, 3 Nelson
Tbe study of various comb&ation rules has and 0bert,4 Hougen and Watson; and Standing and
shown that better results are obtained by “tailoring” Katz.6
the rule used to the system composition, To do so The work of Katz and co-workers has ptovided
improves the basic reality of results by overcoming us with basic data for the hydrocarbons most
some of the anomalies often found when using Kay$s widely used today. Their original chart 6 was
rule a[one. Tentative recornmendat ions are made compared with a relatively Iargg. amount of mglti-
regarditrg the most reliable corribination rule for component data for gases consisting almost entirely
use with a gi,ven class 01 gas. The data presented of normal paraffin hydrocarbons. A deviation of
are useful for estimating the direction and magnitude only t 1.2 per cent was obtained.39 In the 20 years
of the expected deviatio~ when using a given rule. following publication of this work it has been
Although more work is needed, particularly around found that rhe behavior of most mixtures of paraffin
the critical region arid with C02 mixtures, the hydrocarbons could be predicted by this correlation
advantage o{ the classification scheme proposed is within at least 5 per cent. Where difficulty has
apptient, been encountered it has largely involved one or
more of the foI1owing circumstances: pressures above
INTRODUCTION 4,000 psig, mixttires containing large amounts of
heavv, ends and/or aromatics. ., svstems in the
When one attempts to write a PVT equation to fit critic aI region and mixtures containing polar
the data for actual gases, greater precision is compounds and/or C02.
The abnormal error sometimes found with such
Orisinal manuscript received Ju1 y 12, 1963. Revised manu. gases, not too unexpected for this method, is
script received Nov. S, 1963. Paper presented at SPE Fall
Meeting, Oct. 6-9, 1963, in New Orleans.
*Now with Pan American Petroleum Corp. in Tulsa, Okla. lRefere*ces given at end of paper.

DECEMBER, 1968

. . . . . . . . . .,. .
:. ,.
 — —..

predicated on the presence of only a homologous
series of compounds. Therefore, even .though the
above approach continues to be completely satis-
factory for most gases containing only normal
paraffins, there is real value in increasing the
certainty of the results in the areas shown.
In recent years, increased efforts have been made
to refine the approximate two-parameter theorem of
corresponding states. The fundamental differences
in behavior between molecules of unlike pure
substances depending upon their sphericity, polarity
and quantum effects have been of interest for the
purpose of generalizing rheir volumetric behavior.
Varioua inve stigators,7- 14 have suggested a third-
or even a fmtrrh-parameter theorem of corresponding
states.
correlation. The latter involves classifying gas
mixtures in some manner and then finding the best
combination rule for each classification. The
zesults presented herein confirm the basic soundness
of that idea.
DEVELOPMENT OF A BASIC TIiREE-
PARAMETER CORRELATION FOR PURE GAS
Several investigators have used a third parameter,
in addition to P, and Tr, as a means of predicting
the compres~ibility factor Z. Z=, the compressibility
factor at critical conditions, is one logical parameter.
Lydersen, et al, 8 for example, have, s-howu that
inclusion of this third term yields excellent results
for a large range of materials tested. In spite of

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

Unlike pure ~ases, any method of predicting the this, there is some doubt that this factor alone
volumetric properties of gaseous rnixt ures has to wou Id be sufficient. inasmuch as several materia 1s
cleat with the interactions berween dissimilar that have substantially the same Z c seem to behave
molecules in the system. Unfortunately, the present differently in gas mixtures. Also, there seems to
knowledge about the interactions in comp Iex be no way in which this factor could account for
systems are limited; therefore familiar methods polarity, one of several factors affect: .$ gas
lack an accuracy comparable to d-ret obtained with behavior.
pure gases. Another approach has been presented by PitzerJ
Because of the .moblems encountered with some et al, 10,20 The molecular conditions for strict
gas mixtures, combination rules other than Kay’s conformity with this theorem have been fairly weIl
have been reposed. Joffe 16 and recenily Leland, 17 established. 21122 Pitzer has defined a character.
Prausnitz,& and Stewart 19 have presenred differ- is tic parameter in the following manner:
ent combination rules for predicting the pseudo-
critical properties - of mixtures. The latter three c)= -Iog Pr -l . . . . . . . . . . . . (1)
authors have also made use of some type of a
with Pr being the reduced vapor pressure (P/Pc )
three-parameter correlation for predicting the when the reduced temperature T, (T/Tc ) = 0.7,
compressibility factor of mixtures. Pitzer called this correlation”. parameter the
If one examines the many factors affecting gas “acentric factor”. For a simple fluid (e.g., A, Kr,
behavior, it becomes readily apparent that there is Xe, CH4) which foHows the corresponding states
little hope of finding a simple correlation rhat
behavior, rLIis almost precisely zero. The acentric
would apply for aU the infinite combinations of
factor of any other fluid may be considered as a
moIecules to be encountered. Continuing efforts to
measure of its deviation from the behavior of the
do so have resulted in increasingly complex
simple fluid or its nonconformity from the corre-
correlations that are too cumbersome for routine
sponding states principle.
use. This probably accounrs in part for the fact
On the basis of Pitzer’s modified theorem of
~,n8~neers ~ general have continued to use the corresponding states it follows’ that:
proven” Z “chart approach even in areas where its
applicability is Iirnited,
In reaIity, one can never be certain whether the z=g=/(P,, ~,d . . . . . . . . ..(a
error in the correlation is due to the combination ;-q? KL
rule used or in the chart itself. If one uses a given This theoiy then requires that any group of sub-
combination rule such as Kay’s and then draws his stances with equal values of acentric factor should
Z chart to fit actual data, the rule and the chart conform among themselves to the principle, of
become inseparable from the standpoint of future corresponding states. Pitzer found that for most
use. Some recent investigators have apparently substances (excluding highly polar compounds) Eq.
overlooked this when they used Z charts based on 2 could be re-expressed as a power series in the
Kay’s rule to formulate different combination rules. acentric factor as follows:
For example, the Standing and Katz chart is
inherent Iy more accurate when used wirh Kay’s rule, Z-zo+fmz’ . . . . . . . . . . ..(3)
regardless of what you think of that rule, because
that was rhe basis of the chart in the first place. where ZO and Z‘ are each functions of Pr and T,.
.Although there am s~veral pbvious alternatives, Charts for the two fwctions Z“ and Z‘ were
it is the authors’ belief that the most practical prepared by analyzing compressibility factor data
soJution to our problems lies in developing a Z on severaI pure fhtids in the region T, = 0.8 to 4
factor correlation that best fits a wide ‘ra~ge ‘of and P, = O to 9. Agreement waa obtained up to 0.5
@re gases and then use varying combination rules per cent over most regions with a maximum deviation
for “fitting’.’ a wide range of gas mixtures to this of about 2 per cent. >.

SS4 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

. . . . . .. . . . . .. . . .
 The above are only two of the many approaches

()
p:/3
that have been proposed. Riedel,g for example, has
proposed the slope A of the vapor pressure curve at F= 5.665 * (9)
T5/s Ml/2 ””.”....
the critical temperature as the third parameter. A c
more detailed discussion of these approaches is
found in Ref. 32. “ The compressibility factors of the systems under
h study were interpolated and in some instances
PROPOSED FOUR-PARAMETER THEOREM extrapolated to even values of Pr and Tr. At higher
OF CORRESPONDING STATES values of P, and Tr the experimental data $vere

relatively sparse. The region representing Pr from

Significant contributions have beerr made in the O to 14 and T,, from 1 to 2 was selected for
field of statistical mechsnics for describing the detailed study. For the sake of “simplicity and
PVT behtivior of pure fluids from the standpoint of convenience’? the parameters 2= and F were com-
molecular properties. 12~2s-2s Unfortunately, the ,bined as F/Zc (Table 1). The compressibility
application of the molecular theory is presently factors were then plotted as a function of this new
limited to simple gases. Any improved simple variable for a given Pr and Tr. It should be

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

equation of state, however, should recognize the emphasized that definition of the new variable
insight it provides into gas behavior. Consequently, F/Zc does not change the supposition of the
an empirical equation of state based upon molecular four-parameter theorem of corresponding states as
parameters was developed. It was assumed that expressed by Eq. 8.
Two typical sets of Z vs F/Zc curves are shown
P = i(~/fl, kT, b,rn, Pc ,~c/i?, kT . . . . . (4)
c in Figs. 1 and 2 which are for P, = 1 and 5,
respectively, and the various values of Tr indicated.
In Eq. 4 :he variables m, p=, .!&/lT, and kTc are Most bf the points fall on straight lines. Among the
considered to be characteristics of molecular two non-hydrocarbon components H2S shows better
species. In statistical mechanics, molecular prop- agreement than C02. For example, an error of -2.5
erties such as intermolecular force constants are per cent can be noted for C02 at Pr = 5 and T, = 1.9.
empirically correlated with _Vc, Tc, and indirectly For a given P, and Tr the compressibility factors
Pc. If these quantities are chosen to be primary, were also plotted as a function of the acentric
Eq. 4 may be reduced by the application of the Pi factors of the substances under study. Table 1 lists
Theorem of dimensionless snaly sis as follows: the acentric factors of these substances as given
t-w Pitzer.10 Several other authors 29-31 have also
Pr = /’(vr, ~, F)............(5) reported slightly different but essentially the same
acentric factors. Figs. 3 and 4 show two typical
Where the parameter F is given by Z vs u curves for the same values of f, and Tr
~ pc 1/3 that were used in the case of Figs. 1 and 2. The
F=- (6) agreemen of this correlation with the experimental
(~Tc)?/6(?n)1fl” “ .’ “ ‘ . “ . ‘ “ . data is somewhat better than the proposed four-
parameter correlation, especially in the case of
F may be considered - specific for a given C02 and H2S.
substance. The reduced volume Y, may be expressed The values of F/z= for the various components
as follows: were then compared with the acentric factors of
these substances. Fig. 5 shows a curve relating
Z T,
J=+= —........
ZCP,
... (7) F/Zc with OJ. Except for C02, an excellent corre-
spondence can be noted between these quantities.
-c
The failure of C02 to conform with this correlation
Combining Eqs. 5 and 7, a four-parameter reduced may be due to the significant quadruple moment
equation of state is obtained
possessed by C02 or the way in which F and Z.
Z=/’’(Pr, Tr, Zc, F) . . . . . . . . . (8) have been combined in the proposed four-parameter
reduced equation of state.’-
Eq. 8 i~ an example of the various modifications It is likely that the proposed four- parameter
which can be made of the common two-parameter theorem may be valid for a group of substances
theorem of corresponding states. In factt this belonging to the same homologous series. Further
equation is alao an extension’ “of the modified work beyond the scope of this investigation would
theorem proposed by Meis sner and Saferisn.7 be’ required to substantiate this. The exact func-
EVALUATION OF THE PROPOSED THEOREM tional relationship of Eq. 8 should be established.
The validity of the proposed theorem was investi- The exceIlent correlation found in Figs. 1 through
gated by correlating the experimental compressibility 5 ~ffers ~ insight inro the fundamental differ~nces
factors of several gases obtained from the literature. between characteristics of different substances.
Critical constants P=, T= and Z=, molecular weight Moreover, it provide~~ a real clue to the relative
M, calculated parameters F and PVT data references advantage of introducing additional parameters.
for these systems are listed in Table 1. The The findings illustrated in Figs. 1 through 5 and
parameter F was comptited by the following equation: &e work of Hooper and JoffesO led us to believe
DECEMBEIt, 1968 ass

. .
“.

I I
that use of an acentric factor offered the most
I I 1 promise of any third parameter in terms of ita
ability to characterize differences in molecular
species and because of its inherent simplicity.
Except for C02, it provided an accurate representa-
tion of the variables in Eq. 6 and Zc. For these
reasons, a basic decision was made to express Z
as a function of P,, Tf and a.

PREPARATION OF COMPRESSIBILITY
CHARTS FOR Z* AND Z ‘

The compressibility factor tables presented by

Pitzer and co-workers are limited to the region of
Tf = 0.8 to 4, and Pr up to 9. Although this range
covers the area of the greatest practical utility,
NJ data beyond P, = 9 are required in engineering

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

analysis to meet the demand for high pressure work.
Also, in the process, an opportunity would be
presented for further checking of the acentric factor
concept.
The experimental compressibility factors of a
number of pure substances (methane, ethane,
propane, isobutane, normal butane, normal pentane,
carbon dioxide and hydrogen sulfide) were inter-

0 0.1 0.2 0.3

F/ifc

FIG. 1—COMPRESSIBILITY FACTOR AS A FUNCTION

OF F/Z= AT P, = 1 AND THE VALUES OF T, AS

1,1

I .0

0.9

I ,. I
0,6 /@I
—
Iu 0.8

I !3 ++.%l+’O 0,3
I
0;

0.2
04

O o
● me
1 J“ 3
0 0.1 0.2 0.3 w
F/i!c
FIG. 3—COMPRESSIBILITY FACTOR AS A FUNCTION
FIG, 2—COMPRESSIBILITY FACTOR AS A FUNCTION OF ACENTRIC FACTOR AT P, = 1 AND THE VALUES
OF F/Z= AT P, 5 ANDTHE VALUESOF ~ INDICATED.
❑
OF T, AS INDICATED.

sOCIETY OF PETROLEUM ENGINEERS JOURNAL

8S6
,. -.
. . ,.. ...’.’
 .-

.—. .

‘“~
I p, s’S,()
I Tf

0.3 ‘
1.0r

*
●O
0.9 0.2 “
HgS
- %% 0 cog
&i*
2 b\
0,1 ‘ c ~HeR
-%
EC4Hl~

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

lt”C5H12

&——_L_—
0 0.1 ( )
——

al

FIG. 5 — ACENTRIC FACTOR AS A FUNCTION OF

i=(zc.

0
I 0.1
I
0.2
Fortunately, the vslues of 2° were not affected by
the scarcity of data. The acentric factor of methane
w is so close to being zero that, regardless of the
FIG. 4 —COMPRESSIBILITY FACTOR AS A FUNCTION slope, the value of Z* remains within a reasonable
OF ACENTRIC FACTOR AT P, = S AND THE VALUES “range of accuracy. Since Z‘ is a corrective term,
OF T, INDICATED. the final result may still be reasonably accurate,
polated and/or extrapolated to even values of especially for gases having small acentric factors,.
reduced temperatures Tr = I to 2 and pressures p, The final values of Z“ and Z‘ in the extended
O to 14.26-28 The compressibility factor for each region of P, = 10 to 14, and T, = 1 to ~ are listed
~oi?t in this region was plotted as a function of in Tables 2 and 3, respectively. The original
the acentric factor of each subscsnce. These points compressibility tables were extrapolated to P, =
were then fitted with the best straight lines for 14 at T, = 0.8, 0.85, 0.9, 0.95, 2.5, 3, 3.5 and 4 by
evahrating 2°, the value of Z at aI = 0, ~d Z’ the ,using the curves of T, = 1 and 2 as guidelines.
slope of the straight line. These extrapolated values are also Iiated in Tables
The values of Z“ and Z‘ for Pr = O to 9, and T, = 2 and 3. Thus it waa possible to extend the original
1 to 2 were found to be in good agreement with tables to P, = 14 over the fuH original temperature
those reported by the original authors. The values range. The data up to Pr = 9, which can be found
of ZO beyond this region up to P? = 14 fell in line in Ref. 10, have not been reported in this paper.
with the previously established range. This was Graphical representation of the extended tables are
evidenced by plotting on a large graph the values shown in Figs. 6 and 7 for T, = 1 to 2, and up to
of Z* as a function of Pr for various Tr. A simi Iar Pr = 14. These figures are recommended for pre-
plot of Z‘ ahowed’ some disagreement with the dicting the compressibility factors of pure gases
original table. This discrepancy was probably due and their mixtures.
to fewer points available ai higher pressures for To estimate the. accuracy of the extende,i region
precisely defining the slope of tke straight line. of Pitzer’s tables, 85 predicted values of ccmpres-
. ——
TABLE 1 —. INFORMATION USED FOR GENERALIZED CORRELATIONS OF COMpRESSIBILITY FACT@S
Source
of PVT Molecular ‘c (a xW5)

Cempeund Date Weight (pSi.J) ZC F FIZC ~ (de!ey) . ~’ (cm’) ~’

_—QI L_____ ..— —
CH4 (26,27) 16.042 343.26 673,08 0,290 0.0956.0.330 0,013 26 0,05
Cz He (26) 30,069 549.72 708.35 0.28S 0.0480 0,168 0.105 44*7 06057
Ca H* (26) 44,095 665.82 617.23 0.277 0,0322 0,116 0.152 I’

I-CA H ,Q (26) 580}21 734,58 529,06 0.283 0.0246 0.087 0, la4

n. C4H10 (26) 58.121 765,31 550.66 0.274 0,0241 0;088 0,201 104 0,063
n-C5H1z (26) 72.147 a45.64 489.38 0.269 0.0191 0.071 0,252
C02 (28) 44,01 S47.56 1071,34 0,275 0,0456 0.166 0.225
H.# (2?) 34.076 672,48 1306.47 0.284 0,0467 0.164 O; 100 1002 0,698

DECEMBER, 196$ 897

... ,,
:. —..

sibility factors of several gases used in extendkg
the original charts have been compared with the
experimental values. The root mean square deviation
of the predicted values about 1.2 per cent. Errors
generally increase with increasing pressures. At a
later date, about 1,100 compressibili~ factors of
several mixtures were predicted by using the
exte’nded Pitiier’s tables. Many of these data points
fell in the extenderl region. The errors encountered
definitely superior to ihat obtained with the con-
ventional compressibility factor charts.
Figs. 6 and 7 are used in the same manner as a
conventional Z chart except that two steps are
involved. Eqs. 1 md 3 specify the perrinent rela-
tionship. The values of Z“ and Z‘ are calculated
from Figs. 6 “and 7, respectively. The value of
acentric factor in’ case of a pufe substance may be
found from the literature as cited earlier or calculated
!

from Eq. 1 by using vapor pressure data. The

in this region agree with those of the original
values of, Z: Z‘ and o are then substituted in Eq.
region. This substantiates fuiher the ‘reasonable
3 to establish the value of Z, for use in the
accuracy of the extended region. In all systems
conventional compressibility factor equation
tested with these charts the basic accuracy was

1.2

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

1.1 ‘

Lo & REDUCED TEMPERATURE Tr --

0.7

0.6

0,5 ‘. II 11

[ ‘J\~{
0.3
1.1

0.20. 12,0 13.0 14.0

I.0 2.0 3.0 9.0 10.0
REDUCED PRESSURE ‘.?r ‘ ,
FIG. 6 — GENERALIZED COMPRESSIBILITY FACTORS ZOA’I’ REDUCED TEMPERATURES AND PRESSURES.

L
SOCIETY OF PtlTKOLEUM ENGINEERS JQURNA
SW
. ,.’
 TABLE 2— VALUES OF 2(0) FOR COMPRESSIBILITY TABLE 3- VALUES OF Z(’) FOR COMPRESSIBILITY
FACTOR CALCULATION (EXTENSION OF FACTOR CALCULATION (EXTENSION O-F
PITZER% CORRELATION) PITZER% CORRELATION)
-( 1)
I
~(o)
~ Tr ~
— 10
—— 11 12
—,— 13 J&
.
0,80 1,417 10551 1,686 10819 1,952 0080 -00400 -0,430 -0.460 -0,490 -0,520
0,85 1,367 1,493 1,619 1.745 10s71 0,85 -0,390 -0,420 -0.450 -0,480 -0,510
o#90 10330 1,45 I 1.573 1,694 10815 0.90 -0,380 -0,410 -0,440 -0,470 -0.500
“0.93 10303 1.421 1.539 1.657 1*775 0.95 -0,370 -0,400 -0,430 -0,460 -0,490
1.00 1.281 1,398 1*514 1.631 1.748 1.00 -0.360 -0,390 -0,418 -0,445 -00470
1,05 1,249 1,358 1,467 1,576 1*686 1.05 -0.336 -0,361 -0,304 -0.404 -0,424
1.10 1.224 1.327 1.430 1.533 1.636 1.10 -0,307 -0,330 -0,352 -0.371 -0,391
1015 1,201 1,299 1*395 1.492 1.589 1.15 -0.262 -0,290 -0.318 -0,343 -0,368
1.20 1,183 1.275 1.365 1,458 t.549 1.2Q -0.220 -0,248 -0.274 -0,298 -0.320

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

1,25 1.172 1,261 1.348 1,435 1,524 1,25 -0.164 -0,190 -0,215 -0,240 -0.26 I
T*3O 1,162 1.248 1.332 1.418 1.504 1*3O -0.108 -0,125 -0.140 -O* 157 -0.175
1,40 10150 1.230 1.311 1.390 1.471 1.40 -0,030 -0,049 -0,065 -0,081 -0,095
1.50 1.141 1.212 ;.2$3 1.354 1.425 1.50 +fLo54 +0.036 +0,019 +0.00 1 +00017
1,60 1.137 1,200 1,262 1.325 1.388 1.60 +t’,125 +0.109 +0,094 +0, 080 +0,064
1,70 1* 137 1,194 1,251 1,307 1.364 1.70 +0.201 +0. 183 +0, 163 , +0. 145 +0,125 : ,
1,80 10141 1.181 1,244 1.293 1.345 1.80 +0.290 +0,270 +0,247 +0,223 +0, 199 –.
1,Qo 1.144 1.190 ‘1.238 L284 1,330 1.90 +0,3B5 +0,368 +0,346 +0.321 +0.295
2,00 1.149 1.191 1.234 ,1.276 1,318 2,00 +0.454 +0,448 +0.435 +0,416 +0.395
2,50 1.167 1,198 1,230 1,261 1,291 2.50 +0.530 +0,537 +0.527 +0.510 +0,487
3,00 1.173 1.198 1.222 1.247 1,271 3.00 +0.545 +0.590 +0.601 +0,596 +0, 580
3*5O 1.168 1.189 I.21O 1,230 1.250 3.50 +0.545 +0.590 +0,630 +0.670 +0,665
4,00 1,160 1,179 L 197 1,216 1,235 4.00 +0.545 +00590 +0,630 +0,670 +0,709

- “’l I
I I I I
~[~ I I I t-t-H
1
REDUCED TEMPERATURE
20&&
Tr
- -
-- .
!0 - +-
0.4 .
+. .+
I

I 0.3

0.2
50 iv-w-.]
-.-L I
0.1

~
lno
. -. -
-LmtH53 .

I -0.1
\

-0.2

I
0

REOUCEO PRESSURE Pr

FIG, 7 — GENERALIZED C0MpRE8sIBmITY FAcTORs z *m REDUCED TEMPERATuREs AND PRESSURES,

DECEMBER, 196S : . I 899 ,.

>
... - . . . ., “.. ... . .,
 Py=zw’. . . . . . . . . . . . . .. (10) apparatus,ss but it is faater and more convenient
to use, when it has been calibrated, than either
EXPERIMENTAL METHOD AND RESULTS the Burnett or the original Bean unit. s’$ The new
apparatus also has the unique advantage of ob-
The experimental work of this investigation
taining data faster than either of the standard
consisted in measuring the compressibility factors
units, It overcomes another disadvantage of the
of five selected gaseous mixtures of methane,
Burnett equipment, which gives a wide spread of
ethane and hydrogen sulfide. Table 4 shows the
points at high pressures and close spacing at low
chromatography ic composition analysis of these
pressures. .
mixtures. The compressibility data at the nominal
temperatures of 100, 130 and 160 F up to a maximum COMBINATION RULES FOR PREDICTION
pressure of “7,026 psia are tabulated in Table 5. OF PSEUDO-CRITICAL PROPERTIES
The apparatus used consisted primarily of a
carefully calibrated variable-volume cell in which Any method of predicting the vohtmetric properties
volumetric data on a sample at various temperatures of mixtures should deal not only with the non-
and any increment of desired pressures could be ideality of pure components but also with the
obtained .32 After the determination of the PVT non-ideality of mixing. While the former problem

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

data, the sample was expanded through what might can be treated successfully, the latter is not fully
be called a modified F3ean apparatus for determining understood. In order to study the non-ideality of
the mass of the sample. mixing of substances of diversified characteristics,
,To determine the reliability of the experimental one is faced with the probIem of understanding the
equipment and procedure, compressibility data were interactions between the disaimiIar, molecules in
obtained on several samples of pure methane at the the system. Although a large amount of work has
three experimental temperatures of the mixtures, been reported in statistical mechanics to account
and compared with the published values.26 The root for the mo~ecular interactions}z~ SSFSG the approach
mean square deviation of the experimental values is limited ‘to simple cases. Nevertheless, the basic
from those of the literature was found to be 0.005. concepts concerning the molecular interactions can
Admittedly, the accuracy of the modified Bean unit be applied to the macroscopic properties.
is not as precise as that of the widely used Burnett Due to the complexity of the problem, , it is
logical to assume that a single combination rule
cannot account accurately for molecular interactions
TABLE 4—CHROMATOGRAPHIC ANALYSIS OF
EXPERIMENTAL MIXTURES (EXPRESSED AS in alI systems. As a practical matter, mixtures are
MOLE FRACTION) therefore classified in this work as consisting of
,- Mixture Mix;re ‘Mix~re Mixture MlgJro only non-polar components, and polar and non-polar
Components A D substances. Witbin this broad classification, a
—— .— .
CH4 0.871 00831 0,836 0,800 00713 series of combination rules have been proposed” for
C2H6 0.064 0.071 0.117 0.107 0,090 predicting the pseudo-critical properties of a
H2S 0,065 0,098 0,047 0,093 00197
mixture. To find the compressibility factor, Eq. 2

TABLE 5.-THE EXPERIMENTAL COMPRESSIBILITY FACTORS OF THE METHANE. ETHANE.H~O@OGEN SULFIDE SYSTEM
Mixture A Mixturo B Mlsture C Mixture D
z
Pressure
psia 101,5” F 130.9° F 160.0” F 101,8” F 131,7° F J61.1e F 10l,l° F 129.74F 160.2° F !01.7° F 130.6e F 160.3° F

1026 0,886 0.907 0,920 0,872 0,897 0.915 0,865 0.887’ 0,911* 0.851 0,874 0.896

2026 0,811 0,852 0,883 0,790 0,833 0.863 0,785 0,825 0,861 0.761 0.804 0.840

‘ 3026 0.813 0,8S1 0.880 0*791 0.827 0,860 0,789 0,825 0,859 0.766 0,803 0.837

4026 0,869 0,898 0,918 O*85 I 0.874 0,898 0,853 0.876 0.900 0,833 0.855 0.880

5026 0,951 0,969 0.982 0,937 0.947 0.961 0.942 0,954 0.967 ‘ 0.923 0,934 0,948

6026 10044 1.053 1.056 1,032 1,032 1.037 1.039 1.042 1.047 10022 1.023 1,029

7026 1.141 1.141 1.138 1.130 1,122 1.120 1*141 1.134 1,131 1,124 1.116 1*113

*At this point P = 1036 psia..

Mixture E

Pressure
z
psia 101.8DF
.— 13005” F .161,0” F
1026 0,830 0.856 0,880
2026 0.714 0.762 0.807
3026 0?717 0,754 0.794
4026 0.786 0,808 0,835
5026 0.882 0,889 0,905

6026 0.982 0,979 0.985

7026 1.085 1.072 1,071

840 SOCIETY OF PETROLEUM ENGINEERS. JOURNAL

. .,
. .
. ...
 .1

has been extended to gas mixtures as follows:

u~ ) .’ .,...... . (11) K.--= sx;l+l+l . . . . . ..(19)
‘= f(~r#TprJ

The above relationship may be expressed also

therefore, I
in a manner following Pitzer:
.
=% (20)
z =zO+rllpz’. . . ...*.... .. (12) T. . . . .. . . . .0 *.. . . .
pc
1’
where 2° and Z‘ are each functions of ppr and TPr,
Among the set of eight combination rules presented
in this investigation for prediction of the pseudo-
P
pc
=—‘pc . . . . . . . . . . . . . . .(21)
,
J
I
crit{c al press ure and temperature of a mixture,
Methods 1, 3 and 4 are due to Kay,fi Stews;; Method 4.
Burkhardt and Voo>g and Leland and Mueller, Statistical Mechanical Approach
respectively. The development of Methods 2 and 5 Suggested by Leland and Mueller
through .8 may be found in Ref. 32. Method 4, as A slightly different form of the mixing rules

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

reported in this paper, is a slightly different vess ion originally proposed by Leland and Mueller is given
of the original approach. The pseudo - critical

I ff
below:
properties as given by the different methods can I
I be predicted from data on the pure componerits. A
simple algebraic rul, has been adopted for the ‘i ‘jJ~Tc)ii
(Tc)jj“2
acentric factor, as fOllOws:
, T@= =
j=lj=l
T-1 \,,* /–

n
a~=i~~xiai......... . . . . (13)
i=l $2“xi+(%1”+
/=1 (?)33
MIXTURES CONTAINING NON-POLAR COMPONENTS

H%)x%131T”
Metbori L
According to the method proposed by Kay, the
following simple algebraic relationship exists for , . .
L\ \ rat A
predicting the pseudo-critical pressure and cemper-
awre:

P
pc
‘i$~Zf(PC)i.
-
. . . . . . . . . . (14)
1
................ .(22)

,TPC =i~l~i(Tc)i . . . . . . . . .’. (15) ‘Pc {=1

3 ii(zc)~
Ppc=
I r 1- \,, * /- -\l.T13
Method 2.
Empirical Statistical Mechanical Approach
This metnod, although empirical in nature, is
based on the nature of interactions between unlike . . . . . . . . . . . . . . . . : (.2>)

molecules in a system:
where the exponent y is given by an empirical rela-
tionship as follows: I
.

rf
P X. (T.j, 1
Y=/1 ‘:-l ““”””””””(24)

. . . . . . . . . . . . . . . . . . (17)
Method 3.
Leland and co-workersa7 later reported th~ followkg
Virial Approach Suggested by
relationship: ‘n
Stewart, Burk.bardt and Voo

Y“=- 0.75 I ~~ I + 2.44 . . . . (25).,

is
. ...*. . . ...” ““””
. .(18) L
T Xi (Pc)i
J

I DECEMBER, 1963
S41 1

.. .
----- . .. . . .,. . .. . .. . .
 ,.

dissimilar non-polar species, the coefficient reflects

For values of P i$l Xi (Tc \/T ~~1 xi (Pc )f >2, y the interactions between two different non-polar
molecules. In either instance ~ ia still zero and.
was set = 1, and for values ~0.4, y was set = 2.2.
the coefficient is computed by using the parameters
MIXTURES CONTAINING BOTH POLAR AND of the two different species. Finally, there is the
NON-POLAR COMPONENTS case where i &j and i is a non-polar and j is a polar
The primary concern in predicting the volumetric component. In this inatsnce the coefficient en-
properties of gasecus m:xtures containing polar and counters the interactions between non-polar and
non-polar substances has been to account for the polar molecules. The quantity $ is greater than
interactions between polar andnon-plar molecules. zeroi and calculated from the properties of the two
One method of doing this is to use a potential spe ties.
function which describes the intermolecular forces Method 6.
between one non-polar but polsrizable molecule i and Modification of Method 4
one polar molecule i. Based on this concept,
Methods 2 and 4 may then be modified.
Method 5.

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

Modification of Method 2

T
pc = i=l ~=1
“; $ ‘ix; Pc)i’(Tc)~l%P+g’Y
. . . . . . . . . . . . . . . . . (26)

‘pc=jl;lxi,~($$;)~j[,+,iJ.
I (1 + cipz

......,.%,
...,...,
.. . (27)
-1

where

. . . . . . . . . . . . 0 .,... . ‘(32)
,
Method 7.
The reduced dipole moment, p* of the polar Another Modification of Method 2
molecule and polarizibility of the non-polar molecule It his been noted by Blanks and Prausnitz38
may be given by the following empirical relation- that the modified force constants of the intermolec-
ships: . ular potential functions, such as used for the
Pc ~ development of Methods 5 and 6, tend to under-
p3.7705xlo 18+ ~ . . ! . . (29) estimate the second virial coefficient of the
()()c c polar-non-polar mixtures. Since the second virial
coefficient and compressibility factor are closely
where p is in e.s.u.
related, similar results may be expected in predicting’
Pc is in psi
the compressibility factor. In the present study, the
TC is in ‘K. expression (1 + ~ii) in Eqs. 26 and 27 is changed
and to (1 - &i.). The net result of this treatment is to
aP=
a* = 2.826 X 10-21 — decrease ~pc and Ppc which, in turn, increases Tpr
zc7’c””. ”””. J30) and E’pr. Thus the predicted compressibility factor
()
would be higher than those given by Method 5.
where a is in cc/molecule
P= is in psi Method 8.
‘f= is in ‘R. Another Modification of Method 4

For mixtures containing one polar compound, By the same token, as discussed for Method 7,
three cases are encountered in the operation of the the expression (1 + &ij) irr Eqs. 31 and 32 is changed
tO(l-~ij). “
dQuble summation term..~ the Case where i = j, ths
coefficient refers to the interactions between the
molecules of the same species. The coefficient is ANALYSIS OF DATA
then evaluated from th~ properties of the pure The validity of {he proposed ~ethods of prediction
component with ~ = O. In the case where i and j are , has. been determined irr the present study. In

S42 SOCIETY OF PETROLEUM EN CINDERS JOURNAL

 .- -.

addition to the data for the five experhnental ternary components, have been shown in Fig. 8. It is
mixtures, data obtained on nine binary systems evident from this figure that Method 3 is the most
from the literature have been examined also. The accurate prediction tool for these mixtures. The
references, compositions, the temperature and trei-rd which is observed in the case of these
pressure ranges, and the number of experimental equimolal mixtures also applies for other mixtures
points for these systems studied are listed in of these systems studied. Table 7 lists the standard
I Table 6. Table 1 shows the essential parameters deviations of the values predicted by each method
1. for the pure components. A total r of 1.096 from 359 “-experimental compressibility factors.
1.
compressibility-factor data were analyzed with a Method 3 yields a standard deviation of 2.03 per
computer. The method of calculation of the com- cent which is better than 3.26 per cent reported by
pressibility factor of a mixture at a given pressure Stewart, .et al, in their correlation with the Lyderson-
and temperature was similar to that described in Greenhorn-Hougen compressibility chart, At only
case of a pure gas, except that the pseudo-critical one our of 359 experimental points was a maximum
pressure and temperature and pseudo-acentric factor deviation of - 24,18 per cent noted for 0.2 molal
were computed according to the combination rule methane-ethane mixture in the critical region. If
,.

used. A two - dimensional 4- point Lagrangian this point is excluded, a revised deviation of 1~58 ?’1
interpolation was performed in a 27 x 40 (reduc~’d per cent can be obtained for this method.

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

temperature x reduced pressure) table of values of Method 1, which is based upon Kay’s mole
Z“ and Z‘, Am error analysis was also made. For average rule, shows standard deviations of 3.14
each mixture the absolute and standard deviations and 2.93 per cent for 359 and 358 experimental
from the experimental data of the values predicted points, respectively. In case of mixtures of the
same homologous series, the modified Kay’s rule
by any method were calculated. The maxirtwm..
deviation and the reduced pressure and temperature seems to be sufficiently accurate for predicting I
at which it occurred were also noted. The detailed interaction between unlike molecules of different
analysis ef errors has not been reported in this sizes such as in the merhane-n-pentane system. A
paper but may be found in Ref. 32. good agreement may be thus obtained between the
Four systems of hydrocarbons consisting of experimental data and values predicted by this
methane as the common component, and ethane, method. Method 4 gives nearly equal accuracy as
propane, n-butane and n-pentane as the other that of Method 3, whereas Method 2 is the least

TABLE 6-REFERENCES AND EXPERIMENTAL DATA EMPLOYED

Source Mole. Frac. Mole Free. Moln Free. Temp. Pressure No, of
of I St 2nd 3rd R:;ge Rrmmm
..-. .w- state s

I
System PVT Dato Component Component Component psia Observed
——
0,800 0.200 70-250 4@o-3ooo 28
CH4-CzHe (27) 0,500 0,500 70-250 400-3000 27
0,200 0~800 70-250 400-3000 28
0,800 , 0.200 100-280 400-8000 44
CH4.C3HB (27) 0.500 0.500 100-280 400-8000 42
0,200 0,800 100-280 800-8000 42
0,800 0.200 1OO-2BO 400-7000 32
CH4.nCAH,0 (27) 0.500 0,500 1OO-2BO 1500-7000 25

I
0.200 0,800 100-280 800-7000 32
0.800 0,200 100-280 400-5000 22
CHe-nC8H la (27) 0.500 0,500 100-280 400-5000 17
0,200 0,800 160-280 800-5000 19
00800 0,200 100-280 400-9000 48
C2He.C02 (28) 0,500 0,500 100-280 400-9000 48
0,200 0.800 100-280 400-9000 48
0,800 0.200 100-280 400-7000 39
C3HWC02 (28) 0,500 0,500 100-280 400-7000 40
0.200 0,800 1OO-2BO 400-8000 44
0.800 0,200 160-340 .400 -6000 34
n. C4Hto.COz (28) 0,500 0,500 160-340 400-7000 36
0,200 0,800 160-340 400-8000 44
0,800 0.200 100-280 400-10000 52
CH4.H2 S (28) 0.500 0.500 100-280 400-10000 51
06200 0,800 100-280 400-10000 48
0,800 0.200 2B-340 .800 -7000 28
(2*) 0,500 0,500 160-340 400-7000 36
I 0,200 0,800 160-340 400-7000 36 I
0,871 0,064 0,065 ‘1OO- 160 1026-7026 21
0,831 0,071 0,098 100-160 1026-7026 21
CH4.CZ H@.HzS (32) 0,83s 0.117 0.047 100-160 1026-7026 21
0,800 , 0,107 00093 .100- 160 1026-7026 21
0.713 0,090 o* 197 100-160 1026-7026 21

DECEMBER, 1963 943

-. !-. -.

.,, .
,. ..,. ‘. . .. . .. . ..
 -16,0 f I I t I
I I I I T’-wi’ P’ I
1 I I 1 1 I I J
H
I 1“ ., I 1
[2.0
$ CH4-ktHc CHS*SHC CliI-N-CJi,O Ct4 -N-COHN

12.0.

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

S.o

ACENTRIC-FACTOR w
1 I 1 1 1 1 [
FIG, 8 — COMPRESSIBILITY FACTOR DEVIATION OF O.OL
0.15 0.16 0.17 O.le 0.[9 0:20 0!21 “ O,ee
EQUIMOLAL HYDROCARBON MIXTURES.
ACENTRIC FACIOR w .
accurate of all. FIG, 9 — COMPRESSIBILITY FACTOR DEVIATION OF
Three. binary systems of carbon dioxide and EQUIMOLAL HYDROCARBON-CARBON DIOXIDE MIX-
ethane, proparie and n-butane have been investigated TURES.
in the present study.” Although these systems are discarded and new values of standard deviations .
non-polar in nature, Methods 1 through 4 were found were calculated. Table 7 also shows the result of
to be less accurate for predicting the compressibility this investigation. An elimination of about 7 per
factors of this class of gases. Fig. 9 shows that cent of the original 381 experimental points has
Method 2 is the best of the four prediction methods. increased considerably the accuracy of the different
Table 7 shows a standard deviation of 7.27 per methods. Method 2 was still found to be the most
cent for Method 2, for 381 observed points. The accurate of all? with a standard deviation of 4.68
reason for this higher discreparicy was ~bvious per cent for 353 experimental points. The compres-
because etrors as high as 50 per cent were noted sibility factors of the mixtures of this class, under
for some points. The maximum deviations occurred all temperature and pressure conditions, were
in the critical area. In order to determine the underestimated by the four methods used. Stewart,
accuracy of the different methods in the area other et al, have also observed higher errors for systems
than the critical range, all data in the region of hydrocttrbons and carbon dioxide than hydrocarbon
bounded by 0.9 L ~ ~ 1.15 and 0.8 ~ ~ ~ 2 were mixtures, ●

TABLE 7-COMPARISON OF STANDARD DEVIATIONS OF PREDICTED COh\PRESSkilLITY

FACTORS OF DIFFERENT SYSTEMS FROM THE EXPERIMENTAL VALUES
Standard Deviatkr, Por Cent
Number of PREDICTION METHOD
Points Roc~:tmo:ded
Systems Observed No. 1 No, 2 No. 3 No, 4 .. No, S No, 6 Na, 7 No. 8
—— —— —— —. —
Blnory Mixtures 3s9 3.14 5.41 2,03 2,29
H ydrocarbwrs
(358)* 2,93 5.34 I*58 1*81 No, 3 .
Binary Mixtures of 381 9*39 7.27 8.11 9,78 No, 2**
Hydtacarbons and 7,97 4,68 5050 6,83 No, 3***
@arbm Dioxide (355)* (353)* (350)’ (347)*
Blnory Mixtures of
Hydrocarbons and 251 11,13 3.00 2s88 4*74 3.58 5*37 2.50 4.24 No, 7
Hydrogen Sulfide No, 3***
Ternary Mixtures of
Hydrocarbons and 105 2,00 0,92 1019 1,28 1.17 1,59 0,76 0.93 No, 7
Hydragan Sulffde No, 3***

Tofol Number of”PeIrrts Observed 1096. ,

*The number in the porenthesls Is used to calculate revised standard devlat km
**MoY be ~sed *xeludlnQ the ~eeien 0.9 ~~ <1.15 and 0,8 ~~ <2. o far the besf”result.
rF**qmpler ~ethad ~lYIng n~rIy Oquol accuracy, This msthod moy be u~~d [or routine cqlculotlo~)

344 SOCIETY OF” tiETROLEUM ENGINEERS JOURNAL’

 ,..

,’ :.. .
The compressibility factors of two binary systems and non-polar molecules of n-pentarm
having the common component hydrhgen sulfide, For the ternary mixtures of the methane, ethane
and the second components methane and n-pentane, and hydrogen sulfide system, aIl methods offered
as we 11 as our experimental ternary system, were excellent ag&Ement between the predicted and
compared with the predicted values given by eight experimental data. The accuracy which was observed
different methods. As with”the non-polar mixtures of for the different methods could be attributed to the
carbon dioxide and hydroca;,bons, the predicted low content of ethsne and hydrogen sulfide in the
results of the non-polar and polar mixtures were, ternary mixtures. ,,
in most instances, lower than the experimental As shown in ‘Table 7, Method 7 is the best for
values, Fig. 10 and Table 7 show that the most predicting the compressibility factors of ternary
accurate method for the binary systems is ,Method mixtures, with a standard dhiation of 0.76 per
7 which results in a standard deviation of 2.5 per cent. Our analysis shows that the maximum error
cent for 251 experimental data, including those also involved is -1.88 per cent, in the case of a mixture
in the criticaI region. Methods 2 and 3 show nearly containing as high as 10 per cent ethane and 20
equal agreement with deviations of 3 and 2.88 per per cent hydrogen sulfide. Fi~ 11 has been prepared
cent, respectively. The maximum error for Method 7 to show the excellent agreement between the
was noted to be -12.13 per cent in the critical range experimental points of this mixture at the various

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

compared to -15.41 per cent and -15.65 per cent.,for, temperatures and presmrres and the predicted com-
Methods 2 and 3, respectively. pressibility factor curves by Method 7.
Method 1 was found to be the least accurate
with the highest standard deviation of 11.13 per PREDICTION OF NON-IDEAL BEHAVIOR
cent. A maximum deviation of -33.3* per cent was
The foregoing discussion shows that no universal
also noted for the equipolal mixture of the n-
merhod was found in this investigation @ accu-
pentane —hydrogen sulfide system, Like all other
rately predicting the compressibility factors of all
methods, this one resuhs in lower standard devia-
widely varying gaseous mixtures. However, it does
tions in the case of methane-hydrogen sulfide than
clearly show that greater accuracy can result by ‘
n-pentane-hydrogen sulfide s ystem; however, in
tailoring the calculation method to the gas
the Iatter case, the erzars in Method I were characterist its. The following methods are
increased to more than five times those of the
tentatively recommended to improve the reliability
former system. It is apparent that the mole-average
of calculations for gaa mixtures:
rule of Method 1 is entire Iy unsatisfactory to account
for the interaction between nearly spherical but 1. Non-Polar Gas Mixtures:
polar molecules of hydrogen sulfide and long-chain a. Paraffin hydrocarbons with negligible diluent
contamination. Method 3 for all ranges of pressures
and temperatures.

‘FlzJ3
1.0

>1 +
&aI
,,
In

g
-.. — .
● ~ 0.9
M!ZTHOO *P +.&$ \ Q
20.0 v .
8
/ ~, E
i N-C5-H2S ~\
r?
* CH4- H2S g
4
z“ I 5.0
0 MtiLE
P % H2S ) r T 0.8 —-- ..—
s
g ,0,0
(20) (50) (m
. r
/(80)
—
(50)
_l.m-
z I
00
1 .
0.1,
0.7
9 1000 2090 3000 4000. .: 10 6QQ0 ? 10
PRESSURE, PSIA
AcENTRIC FAC~ u ‘ FIG, 11-COMPARISON OF PREDICTED AND EXPERI-
FIG, 1O—COMPRESSIBILITY FACTOR DEVIATION OF MENTAL COMPRESSIBILITY FACTORS FOR MIXTURE
HYDROCARBON-RYDROGEN SULFIDE MIXTURES. E.,

.DECEMBER, 19tiS S4S

,“ . .
. . ..
.’. . - !“
.. . .. -.
. ... . .,.-
 b. Hydrocarbons and Carbon Dioxide. Method 2, P = pseudo-reduced pressure of a mixture = P/~c
pr
excluding the region bounded by 0.9 <Tr <1.15 R =’ universal gas constant
and 0.8 ~Pr < 2. Simpler Method 3 may be used
T = absolute temperature
with slightly less accuracy than Method 2 under
the same conditions as above. TC = critical temperature of a pure fluid
2. Non-Polar and Polar Gas Mixtures: “ Tpc = pseudo-critical temperature of a mixture
a. Hydrocarbon and Hydrogen Sulfide. Method 7. Tr = reduced temperature of a ,pure fluid = T/Tc
Less accuracy may occur in the criticaI region. Tpf = pseudo-reduced temperature .-f a mixture =
Method 3 may be used for slightly Iess accuracy Tqpc
than Method 7. y=- specific molal volume of a pure fluid
&. critical volume of a pure fluid
SUMMARY
G“ reduced volume of a pure fluid = ~/~c
The use of more
parameters than reduced
x= mole fraction of a component in a mixture
temperature and pressure for defining Z results in
z= compressibility factor = P_V/R T
a correlation having a broader applicability. Although

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

several reasonable alternative approaches are Zc = critical compressibility factor of a pure fluid
evident, the use of acentric factor OJ appears to be Z“ = compressibility factor of a simple fluid with
the best, because it seems to more nearly represent zero acentric factor
the net effect af different molecular species. Its z’= slope of the compressibility factor vs acentric
primary weakness would be its inability to accu- factor curve at a given ~ and ~
rately predict C02 behavior. a. polarizibility of a non-polar molecule
The detailed analysis of data on pure gaaes has ~* = reduced polarizibility of a non-polar molecule
enabled the authors to extend the original Pitzer
1’= exponent in virial expansion
charts to a point where they are applicable in the
very high pressure range where existing charts are v= dipole momenr of a polar molecule
weakest. P“ = reduced dipole moment of a polar molecule
By using both the new data reported herein and u = acentric factor of a pure fluid
multi-component data from the literature, it hss = pseudo-acentric factor of a mixture
been shown that classifying gas mixtures and ‘P “
~ = correction factor given by Eq. 28
tailoring a given combination for each such classi-
fication is philosophically sound. Although much
further work remains in this area, the results
ACKNOWLEDGMENT
reported serve, as a firm basis for improving present
calculation accuracy. Even though the results with The authors gratefully acknowledge the assist-
mixtures containing C02 definitely need improvement ance of the Continental Oil Co. for providing access
the deviation is consistent in one direczion. to their computer. The assistance of John Lohrenz
Consequently, merely shifting the curves gives an and Bruce Bray of that organization is particularly
accuracy hi~erto unobtainable. appreciated. The support of the Socon y Mobil Oil
Most important, a further insight, which serves Co. for a portion of this work is also gratefully
as a springboard for further clarification of the acknowledged.
problem, is provided into gas behavior.
REFERENCES

1, Cope, J. W., et ah ltd. Eng, Cbem. (1931) Vol. 23,

NOMENCLATURE 887.
2, Brown, G. G., et al: lt.d Etrg. Cbetn. (1932) Vol. 24,
F= dimensionless molecular parameter 513.
3. Dodge, B. F.: Chemical Engineering Thermodynamics,
b . Planck’s 6.623 x l&27 erg-see
constant, McGraw-Hill Book Co., Inc., N. Y. (1944).
i,j = subsc~” . = denoting molecular species 4, Nelson, L. and Obert, E. F.: Trans., ASME (1954)
Vol. 76, 10!YI.
5, Hougen, O. A., et ah Chemical Process Principles,
k . Boltzmann’s constant, 1.3803 x 10=15 erg/ John Wiley and Sons, Inc., N. Y. (19S9).
molecule 6, Standing, M, and Katz, D. L.: Trans., AIME (1942)
M= molecular weight Vol. 146, 140.
. mass’ of a molecule 7. Meissner, H, P. and Saferian, R.: Cbem. Engr. Pro~
(1951) vol. 47, 579.
‘:= Avogadro’s number, 6,0235 x 1023 molecules/
8, Lyderaon, A, L., et al: Generalized Thermodynamic
gram-mol
Properties o/Pure Fluids, U, of Wisconsin Eng, 13XPL
n= number of molecular species in “a system Ststion, Repo:t No. 4, Madison, Wis. (19S5).
P. absolute pressure 9, I?iedel, L,: Chmaie Ir.zg.Tecbn. (1954) Vol. 26, 83. ”
Pc = critical pressure of a pure fluid 10, Pitzer, K. S,, et al: Jour. ACS (1955) Vol. 77.3433.
11. Hall, N. A. and lbele, W. E,: Trans., ASME (195S)
PV = ps eudo-cricical pressuri of a mixture
vol. 77, 1003.
t = reduced pressure of a pure fluid = P/$c
12. Him3felder, J. O., et al: Molecular Theory of Gases
s.S6 SOCIETY OF PRTROLEUM ENGIREERS JoURNAL
 and Liquids, John WiIey and SOSIS, Inc., N. Y. (19W. Njjrogen, API, N.Y. (19S0).
13. Eubank, P, T. and SmLth, J. M.: AICbE jow. (1962) 27. Kualnes, I-L N, and Gaddy,
. V. L,: Jour. Acs (1931)
. .
Vol. 8, 117. vol. 53, 394,
14. Hirachfelder, J. O., et al: lnal Engi Cberm (1958) 28. Sage, B. H. and Lacey, W, N,: Some Properties oj
vol. 50, 375, 386, the Lighter Hydrocarbons, Hydrogen Sulfide, and
150 Kay, W, B,: Irad. Eng. Cherm (1936) Vol. 28, 1014. Carbon Diozide, New York (i95S).
AP1,

16. Joffe, J.: Chern. 13ngr. Prog\ (1949) VOL 4S, 1’60. 29. fhfell, J. B.. et ah Ind. Enz, Chem. (1956)
.-–, Vol.
--.-—48.,
2069, - “
17, Leland, T. W., Jr. and Mueller, W. H.: Inal En~ Chern,
(1959) vol. 51, !597, 30. Hooper, E, D, and Joffee, J.: Jour. Chem, Eng, Data
(1960) VOL 5, 1S5.
184 Prasanitz, J. M. and Gunn, R. D.: AICbE jour. (195S)
vol. 4, 430, 494. 31. Chao, K. C. and Seader, J., D.: AIChE .Jour, (1961)
Voti 7, 598,
19, Stewart, W. F., et al: Prediction oj Pse&do-Critic@l 32. Satter, A.: Ph.D. Thesis, U. of Oklahoma, Norman,
Constants ~or Mixtwes, preeented et the AIChE meet- Qkla. (1963).
ing, Kansas City, Mo. (1959).
33. Burnett, E. S.: J. Appl. Mech, (1936) V01. S8, A136,
20, Pitser, K. S.: jour. ACS (19S5) Vol. 77, 3427.
34. Bean, H. A,: ]. l?es., Nst’1, Bur, Standarde (1930)
2 L Pitzer, K S.: J. Cbern. Pbya. (1939) Vol. 1, 583. Vol. 4, 645,
22. Guggenheim, E. A.: J. Cherm Phys. (1945) Vol. 13,

Downloaded from http://onepetro.org/spejournal/article-pdf/3/04/333/2157481/spe-566-pa.pdf by guest on 07 January 2023

35, Bird, R, B,, etal:Trarze., ASME (1954) Vol, 76, 1011,
253,
36, Guggenheim, E, A,: Mixtures, Clerendon Preaa,
23. Hirachfelder, J. O., et al: Trars, ASME (1949) VO1. London (1952).
71, 92L
37, LeIand. T, W., Jr.. et alt AIChE .low, (1961>
. . . . .. VOL
---. 7.,
24, Guggenheim, E. A, and McGlashsn, M. L.: PVOC*Roy. 535. “-”
Sot.. London (1951) VO1. A206, 44S.
38, 131anke, R. F. and Prausnitz, J, M.: AIChE ]ozr.
25, Nelson, L. and Obert, E, F.: AfC)Jf7Jour. (1955) Vol.
(l962)voL 8, 86.
1, 76,
39. Mathewa, T. A., Roland, C. H. and Katz, D, L.:
26, 8age, B. H. and Lacey, Vi. N.: Thermodynamic
Pmt. NGAA (1942) 41, Aiso Petr. Reh.-. (1942) VOL
Properties of the Lighter Paraffin Hydrocarbons and .
21, 58. * *“*

,. ,’ ..

DECEMBER, 1968