--
PETROLEC M TRANSACTIONS
Recent Correlations of Hydrocarbon
Properties With Composition
H. T. KENNEDY
C. H. 60WMAN
MEMBERS AIME
A. N. CROWNOVER
E. P. Ml ESCH
JUNIOR MEMBERS AlME
AB!3TRA~
The paper presents correlations of (I) molar volume oj
gaseous hydrocarbon mixtures with pressure, temperature,
composition and properties of the C,-plus fracfion; (2)
shrinkage of oils during fiash and differential liberation of
gas, including the calculation of formation volume factor
under various conditions; and (3) bubble-point pressure
with temperature, composition and characteristics of C,-
plus.
The data on which the correlations are based comprise
1,615 measurements on 900 hydrocarbon systeins, includ-
ing numerous systems containing nitrogen, hydrogen SUL
fide and carbon dioxide. In each correlation, tire ttumbcr
of data points covered and the accuracy is substantially
greater than in previously available work, Thus, tire equa-
tion yielding molar volumes of ~ases has an average dev/-
ation of 2.04 per cenf, applied to mixtures having fem-
peratures up to 513F and presrures up io 9,800 psia, com-
, pared to 2.37 per cent for the Benedict- Webl>-Rubin equa-
tion applieti to the same data, and, 4.53 per cent (or. ~fle
method based on the law of corresponding states.
Tlw equations presented are ali explicit in the depend-
ent vwiuble, and require no iteration on the digital cent-.
puter,
, ..
: INTRODUCTION
The ease and accuracy of determining the composition
of hydrocarbon mixtures, compared to the difficulty of
measuring their properties under reservoir conditions,
makes it desirable to utilize composition as the key to
physical behavior to the greatest possible extent. As a re-
sult, there are available correlations between composition,
or easily measured characteristics dependent on composi-
tion, and practically every important engineering property
of reservoir fluids. The task confronting us is one of find-
ing More exact relationships between important variables
rather than extending correlations, to new properties, -
This paper describes new, correlations of molar volumes
of gases, formation volume ,factors, and bubble-point, pres-
sures with composition, temperature and where possible,
Original manwscrhst received in Societ of Petrolmns %dnssrs
Aus. s,. 1964.. Revised manuscript of S 4 E 916 l=eiVe~JUnets. 1965.
~~~
-,
Y&%ntedsat-SPIS Annmd -FsS Mvethu? held In wonton. Oct.
?.
*Presently rmoeiated with Mene C4rande 0S Co.,$km Tome, VenehueIa.
Discussio~ of this and sdi followinx teahnicnf papers in invited. .Dis-
cusdon in writing ( thrsv copies)
Jmmd of Petrolsutss Technotwv.
msy be
Any dkc us%%
1966, should be In the form of E new papa.
%fe%s%%D%.
No discussion should ex-
csed 10 r.ser cent of the mamascript being dieew?$e&
.+.
TEXAS A&M U.
COLLEGE STATION,TEX.
GULF RESEARCH h DEVELOPMENT CO.
PITTSBURGH, PA.
HUMBLE OIL & REFINING CO.
PLEASANTON, TEX.
CONTINENTAL OIL CO.
PONCA CITY, OKLA.
pressure. Each correlation is obtained by emplaying a suf-
ficiently large amount of data so the calculated properties
are probably as least as accurate as the measurement on
,which they are based.
MOLAR VOLUME OF GASES
Although many equations Jf slate have been proposed
for pure gases, only a few methods are applicable to hy - +
drocarbons at conditions comparable to those in petroleum
reservoirs. Still fewer are useful in describing the behavior
of mixtures, with which the petroleum engineer is largely
concerned.
The correlation presented here involves procedures sim-
ilar to those of Alani fmd Kennedy, The van dcr Wassls
equation
T=(p++(v)-[)
~ ~ ~ ~~
is mod itied to make a and b funct ions of tcmpcraturc in-
(1)
stead of being constttnts fox: each material. This is a cubic,
equation, which may have either one or three red roots.
The lowest root corresponds to liquid volume, while the
highest applies to gas. When the procedure was applie .I
to 703. pressure-temperature points of 164 gases of known
composition and volume, the average deviation was 12.0S
per cent, and the standard deviation 8,15. The above cal-
culations were made using the constants derived for liquids.
by Alaqi and Kennedy and the mixture equtition devel@ed
by them.
A closer approximation to, measured molar volumes is
obtained by employing different sets of constants for dif~
ferent areas on the pressure-temperature chart, and by
changing the relationship between .a,y find b,,, for mixtures
and the a, and b, for individual hydrocarbons, The various
sets are shown in Table 1, and the areas for which they
are. recommended are. plotted, in Figs. 1 through 7. In
these figures; the area designated by zero is in the criticai
region for pure materials, and the values obtained for
them may be unreliable. For normal mixtures, however,
the area may be added to any of the bounding areas with.
out substantial error. The new relationships employed are
---z)
office
aa=l~xati~xc+ac~+
%
be+~o~ 3)
b~=[$x;%l+y+
lRefermwes glvek at end of haper.
,
;110!3
 ,,
i,

rABIE l-CONSTANTS FOR INDIVIDUAL PURE HYDRDCARSONS TABLE 2-VAUJES OF CONSTANTS IN EQS. 6 AND 7

HYDROCARBD# -N -K_ & JkKJ ~ Am = 20700S.27 So = 34, 140S92

METHANE 4531, 7679 235, 17851. o, 029360; ;7 n. 565,?60.%
AI J - 1917..3642 B! = 0.1S80S616
ETHANC A lu?9. O!l 108.$6147 0, 18925$40 0. 6967.?704 As = -3S3,37924 S: = -0.15014S66
16137.566 .tO $)8893 0.15933369 o. 56i1q459
: 43790. 49Z .507, 84t80 t, 2650444 .0. 43595750 Aa = 4333792,4 BJ = 0.000239s1 357
rl 11489,810 375, 4F736 .0, 7z8 13S?8 1. 548a5M
E r775e.. 61 t .56, 748+24 0, 4t0497w 0. S31M932 Ad = S,1 746995 Ba = -39,619146

P RCPA NE A ZOB12,509 450,87102 .0,42664591 1.9948474

B 319,?2. 647 .70, ?58281 0, a6475213 0. 5Z011743
c
D
2,?149. 429
57B1O, 555
129,96$93
.560, 666+7
O, ZW8N06
1. 586S15S
0,86346678
.0765504)9
The values of a.,+ and b~,+ are given by W. 6 and 7
E* 20Z47, 757 190, ZMZO 0. z 1586+58 o, 9oe32519

& 59473,45$ -118! 51442 2, 9244690 .0. 38097650

w I
1-BUTANE
4+286. )38 -15. 499+06 1.351$644 0, 470?6 139 a~,+ = A, + A,W + A,+ A, A, W1 , , (6)
: 2994*, 9s8 17?. 5714s 0. 36?62318 1.0824i95 d T
D. 3,Z204,420 1%1,bsl?l 0.35862284 1.1013834

N. BU1A!4E ,4 69.?.?3.037 .206,90583 5, 4926bt 5 .2.6131894

13zi25. 70 -943.55042 Z, 8019055 .0.84973553 ha,+ = -B,, + B, W+- B,: + B,T + B,d . . (7)
: 33917.554 111,47493 0. 4Z0b5Z6Z 1.0103595
w 33016. ZIZ 1*6. 85445 0, 29021257 1. 11*8144

PEXTANES A 123941. Z5 -41?., 19725 7.14 L47L9 -4. 483U5? The values of the coefficients A,, through A,, and B,,
4401s. U40 159. r.7161 0.57161821 1, )448161
: 37046. z 34 .?99.6M30 0, 21954185 1,4364289
through B, are shown in Table 2,
11ZXAXE5 537,?3.633 21A 8N47 0 ~71a9187 ! .400280. In E+. 6 and 7, d and W are, respectively, the density
:. v(v3. m.. <W. 510,. ? 0. 3ml&3b 1, 59.?,40.
in gram/ml and the molecular weight of the heptanes-
;;rlhomx: i 3::. bm3 -P, @@b278704, 0, 5198783.
plus fraction, and T is the absolute temp~rature in R.
7}4$, r.cllr 30?. .033, 0, 1/5512.+, 0, 500b5h*
CARDOX DIOXIDE h
B 8,?,. . 7,0) 11,1.4,,73b 0, 16524593 0, 387317:1, Eq. 1 can be arranged in decreasing powers of V to
HYD1<OGE: 13-W. 7.1I
yield
S1,LFIDE

,ND1cATE5 .4LAX1 1.luU!D COX51AX[S

+=fw+~v-+=o()
The solution of Eq. 8 is a simple operation on the digital ,
The values of a, and b, are calculated from the relations computer, involving no iterative procedures. It is import-
ant to note that over part of the pressure-temperature
+
range, multiple roots may be present, and that the highest
a~=Ke r,,,... . . . . ...(4)
root must be selected as representing the gas volume.
fl, =ltrr+c. .,. .. c... .(5) The average deviation of 2.04 per cent obtai,ned when
Eq. 8 is solved for 703 data points on which the correla-
The values of N, K, M and C are read from the correct tion is based, compares with an average devitttion of over
set in Table 1 according to the pressure-tempera[ ure chart.

I II
A $
c
.A

B
* (.--) I
o

I k!
G
m
o
I
I

~...
Q(-J
fi~
1)
1-
I I
0 ii
~
0 5:0 1000 1500 I 5
250 750 1250
PRESSURE, @D
PRESSURE, psia
FIG. 3BUTAXE.
FIG. IF,TNAXE,

B .

c A
D

D.
-1. .- ]. . .: --- ...
l-l
250 750 1250 1750 2175 500 1000 1500 It 5
PRESSURE, psia PRESSURE, psia
.
FIC. 2PRCML4NE, FIC. IP+G,IhITANIt..

$OURNAL OF PETR41LEUM TECUNO.LOGY.

. . .
, .. . . . .
!. .,.. -.
-
 .-.

TABLE 3GROUPS AND DEVIATIONS FOR EQ, 9, TABLE 4-eGNSrANTS FOR EQ, 9, DI FFSRENTIA1 LIBERATION
DIFFERENVA1 SEPARATION <mow I I; RQIJP z
. ~. mow 4
- Composition Umlis, MoW. Average Al . o, 50),,, ~1 a *.hV~ll0:
A, . 0, ILi,,x,ol
%
. 0. 9?486.101
He~t&I~ Dato
Pohlts
Davlotlon AZ - 0,41I,*, IJ-I AL 0.)1~~61{ AL. 0.?21,1,
!01
~z
..0. ,6,0?
[%]
3 . 0, Z11J9
Grow , Mdham A, ..0. 5m00 (1, .0. 19)90x 101
- - +3 .O. Jol$tfo;
..0,,6905 h, . 0,46625 A, ,.0, 1?59?.101
1 0-30 50.100 65 ,83 44 A4 = 0. !4289. !0
1,16 . 0.?2503 A5 . 0. ZO1O8 A5 . 0, ?068$.101
2 I 0.40 20.30 104 ~% A, . 0.2975%101
4! 1.56 . 0.71872 Ak .-0.43151 x10. J Ak = 0,.44669
3 40.50 15.50 % .66 . 0. noe]d
37 1.66 . 0,20048 A, . 0.16004 A, =.0. 98022 ..0, ,02,,,.,02
4 50.100 0.50 ._ % %
247 Average 1,21 = 0,94467 .10-1 A8 ..0. t0435xtok s 0.50136.101 .4B . 0. 36021%101
% %
. 0,99!91 . 0.22009,101 .0, ,11,g,x, ol .A9 .0. 5s138%101
% % %
..0.10,,8 ..& 503, $ . 0.79352101
A 10 %0 %0 % 0.59688
..0.21556 , 0. 17371,101
4.53 by the method of corresponding states and 2.37 per AI1
.1
All -0,31157
*.0,64, B
%1 ~11 0.1537~Jo2
* 0.27648
~lz 07zxL0 +u % 0, $~zo~q
cent for the Benedict-Webb-Rubin equation. ~13
..0,,*8,SX,0.1
Al 1
. 0. Z7405.10. I
~13 .O 3492210
Atz
..0. ZZ,ga,(ll
413
. 0, 1989ZX1O
1 ..IL,*9U,,J.I . 0.35001
Al+ %4 % .0 1B$33 %
..0. ,o,~,x,o~
OIL VOLUME FACTORS 415 0z+78
. 0. 165?+
h5 =QZ52961O;
. 0. 150,9.,0
A15 %5 0 1898*1Q:
~,h % )6 = t45410X]0:i % Q.7705*1D,
. 0, lo8$%10~ ..0, JOJ3,%,0 ..0. ,$5$,.,0
The shrinkage of oil as gas is evaporated is frequently 317
..0.,,c],,c.~.
AIT=-0.11U55 17 %7
A18 = 9,1113wo2 . 0.427 ?9. ,0-4 . 0,76630x 10-4
calculated by K-values. However, if only volumetric data 418
s 0.+4475.107 A19 ..0. s71?9.,0.5
*18
-6 18
= 0.aa371 ,10-~
:19 h9 04993010 19
are required, it is a somewhat simpler operation, on the ~zo ..0. W377.101* = 0. 39401x10.1\ = 0, JO,.OZX,O-lJ ,.~.tis.,~,o-ls
&lo % %0
digittd computer, and one which is at least as accurate, if .
we use a direct correlation of shrinkage with composition,
pressure and temperature. The residual volume is also af- squares computations, the average absoiutc deviation was
fected by the process by which separation is accomplished. 3,0 per cent. However, the deviation varied with the
i.e., by differential or flash method, amounts of methane and heptanes-phls present; and vfsr-
The correlations of volume fidctors for differential sep- ious groupings, based on composition, were tried. The final
uristion were based on 247 data points on the same number choice is shown in Table 3, which also shows the number
of oiis. The differential volume factor, defined as the ratio of data points included in each group and [heir average
,. ctf the volume of the bubble-point oil at temperature T absolute deviations from the mean.
to that of the stock-tank oil obtained bv differentially The constants in Eq. 9 for [he different groups w-e giv-
separating gas from oil at T to 14$7 psia, ~nd cooling th; en in Tabie 4.
residual oil to 60F is given by Eq. 9. Eq. 9 can also be used to calculate the formation VOl:
ume factors of oils from which gas is separated in two
v,,.,..
. stages, the temperature and pressure of the first stage be-
A, + A,x,,,s + A,,x,.<,:
v, ing variable. and the second stage being 2sstock tank at
+ A JX: + A :.u., +- A ~.Y,.,
+ A ,X,.:, + ~ ,.t,o,, + .A,.Y,,,.,,
+ A -.x,(.J+ A,,x.,.i + A Gx,.,,
,----
A
+ A,., In.r,., -t- A,, inPt,,, +A,,
520
T
/ o ,

/TTl :1
w
-f- A,,, *
[-1 A,+-
x,..+ w
+
2
+ A,. ~--
[1
~ ,1
)!,<,.
+ A,,, -
11
[ ,1
+A,,..-
d
. . . 8
.[
x(.;, w 1 0 500 loco 1500 1875 I
When the equation was isppiied to the 247 data points. PRESSURE, psia

using a single set of constants A, . . . A,, obtained by least- Pk. 6HF.x:\\}:s 1

., r

6(B
f

A
c .
.* . -. I
B
J 1750 2175
,=:s

50G 1000 1500 [875 250 750 1250

PRESSL$E, psio
.,
Fit. 5-PI:NTANI.s
? sEPrEM EsE!5t,
1,965 1107 ..
.,
=. _.
.,. ., . . . . . . .. .,, .,.,
. . .. . . . . . . . .. .. . . . :..:. .. =... .-, _ . ... .. .. ~.,.,
.:;.,.:: .- -
 , -

,,
60F and 14,7 psia. The factor so calculated is defined as percentage for the different groups are shown in Table 9,
the volume of oil saturated at reservoir temperature. and along with the number of data points included in each
pressure, whatever these conditions may be, per volume group.
of stock-tank oil. The symbols T arid P, for this applica- In addition to the 489 natural oil systems, six binary
tion, refer to the temperature and pressure of the separa- systems representing a bubble-point pressure range from
tor rather than of the reservoir. Eq. 9 representing a total 167 to 5,198 psiaj and a temperature range from 100 to
of 114 data points obtained from 30 different oil compo- 220F were investigated. A single relationship represents the
sitions was applied to separator pressures of 15, 65, 115 data with reasonable accuracy, after the data are segregat-
and 215 psia, with the average and maximum deviations ed in regard to the methane content.
shown in Table S.
Different sets of constants were used for each separator
pressure, as shown in Table 6, The constants do not show =+
0.3+(=%)2 9
a regular variation, and interpolation of the coefficients for X,>t
application to intermediate pressures is not recommended.
The formation volume factors calculated by Eq. 9, on the
+-4,
()
1 - X.i
The data for the binary systems used to develop the
++ ,, (11)

other hand, are suitable for interpolation and to a reason-

able extent, extrapolation. ,
~It is difficult to compare the accuracy of the present TABLE 6-CONSTANTS FOR EQ. 9, FLASH llBtRATION
method with that of methods previously de.4cribed because G!{UUP 15 ,s!. G1<OU1,
65,,,. $xov1> 115,.,. GRO1,P t 1L t,.>,,-
data are not available to calculate volumes by the sever- 2 t
Al -o. 1391Q; Al -O ~$byi ,~1 0. IQN$lQ, 1 O. s~lot
al methods on the same systems, If we rearrange the data Az = o. 10835*IO
A2
= 0.29708, 10
Al o.~~1$go, Al 0.457]0
and calculations cited by Katzz to put them on the same .\3 . 0. 1(,.41.101 /\, i 0. 1.487.101 ,\l 0.2021 !.10 ,,, . 0. ,7,,,

basis as those in Tables 3 and 5, we obtain average devi- - ,,4 ,.0. zw,sx, ol ,,4 ..0. ,,.77, ,01 ,,4 ..0. /12,,4.,0
A.1 . ~?zn;
A, . 0. 705,1 ,>5 . 0. I,, u.lol .A5 = (7. !491. A5 . 0. 1.870. !0
ations of 7.44 per cent for systems in which crude gravity, = o, ;f, ,#,? z 0,1143 ZX10 ,\t .. O. W65X1O1
A,, A,,
soh.sbility, pressure and temperature are taken into account, 6
A,
= .4187K
= 0.68135.101 A? = 0. 50812x1O! A, = 0.4(.46$.80 ,\7 - O.IMWdO1
and 3.15 per cent for systems in which gas gravity, in ad- %
. 0. 51730x101 A8 - 0.5 Z7?5X101 A8 = O.3I355X1O AH = IL471,?%101
dition to these four variables, is accounted for, The forma- ,,? LO. 1 ,04%!02 ,,9 ,.0, ,0+2*X,02 Aq :.0, , , ,,l!. ,o~ ,,,. . 0, M,ocx,oz

tion volume. factors of 14 systems measured by Weinaug: A lo = 0. a~s~~lo: 110 = , 571 +10 0, ~~+:v~: .~m Q.~JS$J=J

and calculated with the aid of K-values and special cor- 111 o~~o;lo,
. 0, 269$.2.10
111 = 0, ~~71t: \ll 0, ~~@l~, All -.4 3*
12 A 14 0298 o h z 02080$10 Alz 0.1535
rection coefficients, show an average deviation of 6.12 per A 13 o. 17577 ~13 o 567 ~l>, o Al% -O. )s~xj
cent when placed on the same basis as the present corre- 14 0. !18: \l.l = 0 5719 \14 o~1; 14 = .ZU5

lations, 315 o.79~oz!ol A15 o.~~tilc: A15 .O 7<512 ~15 0. l~l~sq

,,, , ,.0. !5,0,,0
AM =-O.61W1O. , M 0 los~~lo. , 11,, 0, ~l. ,
..8

XJEBLE por~s o~ cohfipLEx MIXTURES 17 =O(414310.3

= 0, 74616X1O
A17 0, ~5z~lo., ~17=0,7713~19., 117 0. ~@71~1~.,

18 18 = 0502 Q., AM = 0, 825~fi0., .18 0.02+0.,,

A knowledge of bubble-points is important in studying
:; :;G::::: ;: :-; ;%;: 5 $ :::4;::::: 5 $:.: :%
r%servoir performance and in entering correlations such as
those on shrinkage just presented.
Cmrelation of bubble-points with temperature and corn- TASLE 7-DEFINITION OF Y-TERMS IN EQ. 10
position is based on 665 measurements on 489 different
oils, The data on composition include the rnol fraction of Yz == h (xoi + XO, + W, + xO, + x21,8 + xS2 + xcN12t

hydrocarbons methane through heptanes-plus, alongt with Ys = In [ (16.042 .o, + 30.06S no= + 44.o94 w, + 58.12 W, t
34.076 X112S + 28.016 XN: +. 44.01 XOO,) / (w, + XO, +
the molecular weight and density of the heptanes-plus and q + A04 + XI%$J + yN2 I X002) 1..
the mol fraction of nitrogen, hydrogen sulfide and carbon
Ya = XoaJ- Xo
dioxide. : , [72.146XIJD + S6.172KUO)
sThe relationship between the above variables is very r4 =
[Kok + w)
$omplex, and the best equation, in which .a single set of rs = Xo,+ Yla = W* + XOLJ3+ X118,Y
constants was employed for all compositions, had an aver- Ye= lnT YI+ = In MO,
age deviati~n of 7.96 IX.r cent, This accuracy was substan- Yz=T Y155 XNV
tially improved, however, by segregating the data into Ys=lnd (.(+ + AN,)
groups, based on the mol per cent of methane, and em- Yu=d * a (1 - q - XN2)
ploying a different set of constants foc each group. Segre- Y14= Inxo,+ Y17 - r%
gation. into groups according to temperature gave little YJI = In W rla = w!,
improvement. The equation is ,-
ylz .>
In (P~P) = A,}-t A,Y, +A,Y, + . . . A,,Y,, . . (10) %+

The Y terms are defined in Table 7.

The coefficients A, through .4,, employed in Eq. 10 for TASLE 8COEFFICIENTS FOR EQ. 10

the various ranges in mol per cent methane are shown in P.,csl
Meth...
.
0-10 10-.?0 20.30 30.49 40. s0 _
Table 8, The average absolute deviations in .psia and in 18401. s96 , M. 2?8215 .126.76,57 569,91594 199. b8959 .147.8? 522
..0930979s -,34329579 1. 149B409 .,48835190 4;0705383 , 7s573010
..90ZIS33Z 2.6168172 . 1.0806382 .1.3148809 .1.1546327 1.8917532
3. ZM67Z6 1, 1M8800 s , 5547b317 .3. MM3+6 5,6727104 .54758445
..m9a5597 . . al nt576 ..01631 $46 ..00548988 ..01247*93 ,00708215
.13576740 12, 617259 .613209b> .10. b13104 2.#5519WJ 8, 5376253
TABLE 5DEvIA?jONS FOR EQ. 9 APPLIED TO FLASH SEPARATIONS .32, 968370
.551L 16s6 -2.491527$ 44.524920 -158.98655 .40.09516Z
.9. $1263?$ .01998795 0717.7S8 -. zhQ5z738 ..06655179 .05115629
Avwwae - Maximum .2Z0. 32611 24.300856 14. 4s4bb7 20. 491*Z* 18.M4300 -19.379871
Prs5sur8 Dwlatlw Deviation @9.9B9b> .Z5, 5L1097 .1+ 125555 -21,.360666 .17, 2,?721Z 27.310809
-... _@!J).. . (wr*nf) . .Lawwnt] . . 629904+6 -6,4896463 .,44614279 . +, 0251404 i. M414*3 .:1. f44S484.
- ..3755809D -. .?8831079 . . 5656$+66 ..57517331
15 1.67 3.63
;2. 497463$
.19,0%150
,.93832637
.3,2218020 -.+2541531 1. .?905?00 .32911992 ,-,36451723 .
>,8259897 >.2522468 .1. 3z89(.22 -. 0B709576 ..91146400 4.0161813
65 1 !37 3,05 -. 3210,?573 -.478>8040. -.98907051 .5.5182050 I 5.18<030 .1. 5Z7J3.H
115 p.. 1 ,3? 3.41 268.64220 3Z. 448996. .6.81641Z7 18. 38?+15 . 1$,964156 5. 6* E7440
-214.67470 .12. {4109Z 6.4 IZ9690 -6.3301139 4. 430260+ ..alolz677
213 -;: 1,00 2.57 W6. 70849 . . 665J9181 -?.0107085 .?5.84981+ b, 6062762 -5.1693<20
., -47.951565 13.050627
?93. r163~ al. 261293 .9, 1?10=32 .?8.6651.?5
. 1 Av&aee 1.35 3.16

I \ JOURNAL OF PETROLEUM TECHNOLOGY

1108
 TABLE 9 TABLE 1 lCOMPARt$ON OF CORRELATIONS

~wC~t No. of Avarage Av. Dw. Av. DOV.

Data Points Error (P311 fw?;::;eh) Rwc.lod Re&ted
soy t44r& N:fmo~
0.10 39 27.7 8.95 Author Elam
10-20 94 77,5 8.26 Equatlen 01[s P0tnt2 Systems
(%} (%)
20-30 132 59.4 4.08 StOndlns!a CmlffOrnla t 05 22 5.0 17.1
30-40 I 67 82.7 2.71 Swd@n and Gulf Coast and
40-50 124 lt3 3.73 Rzazm~* Rocky M.auntaln Area 1S8 188 9.3 14.s
50,70 109 159 3.S2 Elnm~ TeKu2 231 231 13,6 13,6
lazaterl . 1s8 I 37 3,8*
%, 10 M02t all malor 011
Praduclng reslen2 66s 489 4.71
iquation were taken from the work of Sage and co-work- Eq, 11 Six mtt of binary
hydrocarbon data 720 25 I ,48
ers and 3~hoch and co-workers.xx me systems investi-
*For samples essentially free of HzS, COZ and Nz only.
gated, constants employed for each group, the number of
data points (some of which were interpolated from iso-
therms) and the average absolute deviation for each group
u,, a,., a%+ = functions of temperature in equations of
are shown in Table 10. Eq. 11, notwithstanding its sim- state for component i, for the mixture and for C?+ re-
plicity, gives a satisfactorily low average deviati~n. spectively.
The major interest of petroleum engineers in these sim-
pter systems lies in the possibility of using their behavio~ b,, b,,, bg,+ = functions of temperature in equations of
as modek! for the more complex natural ~ystems. It <seems state for component f, for the mixture and for C,. re-
that Eq. 11, following as it does a generalization Of Ra- spectively.
oults law, may be moditled to serve this ptirpose. Unfor- cl, c, . . . C,+ = methane, ethane up through heptanes-plus
tunately, all modifications based on Eq. 11 showed sub-
stantially higher deviations than ~. 10 when applied to d = density, gram/ml of heptanes-plus
the 489 hydrocarbon systems.
K, N, M, C = constants in Alani and Kennedy equation
A comparison of the average deviations obtained by the of state, also in present gas equation
bubble-point correlations presented here and those found
in the literature is shown in Table 11. The deviations ob- P = pressure, psia, P,,, bubble-point pressure, psitt
tained when the first two literature references are applied
to present data are substantially higher thap when applied P. = separator pressure, psig
to the data oh which the correlations are based: , R = grt.. constant = 10,73147
The work presented here is a condensation of two dis-
sertationsSand atheais submitted to the Petroleum En- T= absolute temperature, R
gineering Dept. of Texas A&M U, Forafuller account of v ~P, = volume of reservoir fluid at bubble-point and
the equations tested and for further identification of the temperature, 7
systems involved, the reader is referred to the original
document or a microfilm copy thereof. V,n = molar volume; cu ft/lb-nlol
v,= stock-tank wolume, 60F and 14.7 psia
NOMENCLATURE w= molecular weight of heptanes-phts
A., A,., . A., B., ,B, . . .. B, = coefficients in, correlation
x(, xc, + = rcsl fraction of component i and heptanes-
equations
phss, rbwpcctively,
n,.? = COnStantSof material in van der Wtudls equation Y= composite wtriuble in bubble-point correht-
tion.
TA16LE 1O-COEFFICIENIS FOR EQ. 11 . .
% Fr.m.r. ma .: ACKNOWLEDGMENT ,
MM... Rams Pk.5r.t*
.
A~ -% ~?. ~3 &
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T- 54 1471. 3wb - .~39 .3601 .1422 -817423.46 3,83
xl-m 570.1157 .39 19fi6. 75Z7 .1800. *825 12063.481 .1 S290, 472 -787326.83 .93 It is a pleasure to acknowledge the generosity of the
30-50
50.74
856-1632
1471-1917
69.
46
1634. 3Z1O
139s. 7256
1419.0423
14S9. 5572
317.68496
i562. 234.?9
.S36. 06163 ..731593.96
74,599175
1,40
-46W48. 53 .85
Cities Research and Development Co. and the Gulf Re-
mrd ,. s..,.! search and .Developmertt Co., on whose. fellowships the
Meti.n..n i+nd=-itiai. 220 F)
10-20 394-745 13 661, 2)296 6S78, ?736 . 19549.S92 30192.368 -505842.96 L 47
major part of the results presented here were obtstined. Da-
20-30
30.50
64 S-1.?08 19 26?4. 7519
-300.98984
- 156!5. 323
8455.8494
60234.816
.9936 .5376
.67066 .197 -46>098.46 Z. 4b ta supplied by the Carter Div. of the Humble Oil and Re-
1045-1845 28 U79. 9279 .a92518. 71 2.02
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, M,16,..
Bma,y S,tm
Ee%ane [100 F -220 F)
Core Laboratories, Inc., Gulf Oil Corp., Houston Labora-
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30.50 1255-2065 28 1412.07.?2 207518040 219.75618 -537.40216 .6930Z1. 72 .84 Petroleum Corp., the Houston Research Center of the
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Bm.a..swell!
Humble Oil and Refining: Co. and the Research Labora-
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.18
.14 .. . . REFERENCES
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3.1.*. .-. D.<*II.3 (100 F -220 F) drocmkons at High Tempemlnrcs mzd 1%..wms, Twin.,
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5. Sage, B. H., Lavender, H. M. and Lacey, w, N,: phase Ertui- 13. Standing, M. B,: A Pressure-VoIume-Temperature Correl~tion
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Phase Equilibria in Hydrocarbon Systems (Volumetric and neering Dept., rexas A&M U. ( 1961 J.
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H. and Mayiield, F. D.: Solnhility of Methane in Benzene., Pressures., MS Thesis. Petroleum Engineering =f2ept,, TeXW
lnd. Eng. Chern. (1940) 32,788. A&M U. ( 1962), ***

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1110 JvtlRNALzOF PETt;OLEUM TECHNOLOGY ;
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