. .

L5L5

Correlation of Interracial Tension of Hydrocarbons

E. W. HOUGII*
MISSISSIPPI STATE U.
H. G. WARREN*”
STATE COLLEGE, MISS.
MEMBERS AIME
I

ABSTRACT mole fractions and molal volumes of the liquid and

gaseous phases are known. One method of corrdatitig
Correlation of interracial tension 0/ tbe metbane -
IFT was proposed by Weinaug acid Katz 2 and
n-pentane ard methane-rz-decane systems was made
modified by Hough and Stegemeier.s The tr,odified
by Hougb and Stegemeier by the use of the Weinaug
formula is: ,
and Katz equation, The methane-n-heptane and
ethylene-n-heptane systems were investigated by
the authors. Additional systems taken from the
literature were the methane-propane system by
Weinaug. and Katz, the methane-n-butane system by
Penrrington and Hough, and the n-butane -carbon . . . ..$ . . . . (1)
dioxide system by Brauer and ,Hougb.
These systems were analyzed by the Weinaug-
Katz equation and the Sugden equation on the IBM where Y= interracial tension, dynes/cm
1620 1/ computer using a regression amlysis Pi = parachor of tb e first component
program, Parachor and exponent values for each
P2 = parachor of the second component
component and sys tern were determined. Tbe
expen-mental work was close to the critical point xl, %2 = mole fractions in the liquid phase
of the tight component in the n-butane-carbon YID Y2 = mole fractions in t!le vapor phase
dioxide and etbylene+heptane systems, between vL,vv = molal volumes (cti ft/lb mole)
the critical points oj the light and hea.]y components 1/62.43 = conversion factor, Ib/cu ft to gm/
in the methane. n.pentane, methane-n.heptane and cc
rrietbane-n-decane sys terns, and close to the critical
K= exponent of die parachor relation
point o/ the heavy component in the methane-pmpane
and methane-n- butane systems. and subscripts
An em>irical formula was developed to find a L= liquid
value of the constant B in the Sugden equation for v= vapor
binary hydrocarbon systems from the parachor 1= component 1
values of the two components. inter/acial tension 2 . component 2.
[or binary hydrocarbon systems was found to be a
In a binary system, there are two degrees of
direct function of liquid-vapor phase density
difference in the same manner as a single-component
freedom; that is, the values of xl, xz yl, Y2,
VL and Vv are determined at any particular tem-
system.
perature and pressure. Therefore, for each
DISCUSSION temperature and pressure at which an experimental
value of IFT was measured, the values of xl, yl,
Incerfacial tension may be defined as the measu~e VL and Vv were found, and the following values
of the specific free surface energy between two were calculated:
phases having different compositions.l ‘Ihe inter-
racial tension (IFT) for a binary system may be
predicted for any temperature and pressure if the

Original manuscriptreceived in Societ y of Petroleum Engineers

office July 8, 1966. Revised manuscript received Nov. 1’?,
1966. P@cr (SPE 1S6S) was presented ●t SPE 4 lat Atmual
Fstl Meeting held in Dallas, Tex., Oct. 2-5, 1966. @ Copyright
1 (1 - %1) (1 - y~)
X2. — —-- . (3)
1966 Aneri==an hrstitute of Mining, Metallurgical, and Petroleum 62.43 V’
Engineers, tnc.
Vv. .
*Preoently ●tSchool of Technology, Southern Illinois U.,
[ J
Cu-borldde, nl.
* q+,=ntl ~ at Mo~t*n.q College of Mined science ~d This further simplified I?einaug and Katz’s formula
Tecfmohrgy, Butte, Mont. to:
preference. giVW et eml of paper.

DECEISBER, 1966 54
 Tsmpwaturo M@hed to
Y=plx2+ P2x2]K . . . . . . . . . (4) System Invostlgatars
—.
Rang. Find IFT

m.thans-praparm W.lnaug.Katx2 5 te 149F Capillary rho

For each experimental value of IFT, the unknown msthans.n.butan. P.nninuten.Haugh6 100 to 190F Pmdwrt drap
values were P 1, P2 and K. , To obtain better and m.than~wp.ntane Stcgsmci.r.HauSh 7100 *C 200 F Pendant drep
faster results, the IBM 1620 H compter was used m.thuns.n-d.cam Heugh.Stsgtm.ims 100 to 190F Pcndont drap
to calculate PI and P2. To solve for the unknown n.butans-carbon Brauor.He~h8 100 to 160F Pendant drop
d}axidc
values, varioua values of K were selected, l/K
was cslculated~ experimental IFT values were The experimental determination of IFT near the
raised to the l/K power and PI and P2 were critical loci of the systems was close to the critical
obtained by the method of least squares. By varying point of the lightcomponent in the n-butane-csrbon
K, the best values of PI and P2 were found for dioxide and ethylene-a-heptane systems, between
each system for which IFT experimental data the critical points of the light and heavy components
were available. in the methane-n-pentane, methane-n-heptane and
If IFT data raised to the l/K power is called methane-n-decane systems and close to the critical
Y, Eq. 4 then becomes: point of the heavy component in the methane-
propsne and methane-n=butsne systems.
Y= P1X1+P2X2 ., . . . . . ...(5) Another method of correlation of these seven
systems was the Sugden equation. g y = B[Ap]E
The least square equations are: where y = interracial tension; B = constarst; Ap =
density difference between a system’s liquid and
vapor phases (gm/cu cc); E = exponent.
The advantage of the Sugden equation for binary
systems is its simplicity. One curve may be drawn
for aH temperatures a-d pressures. Two deter-
minations of IFT at different density differences
Eqs. 6 and 7 can be solved
simultaneously for could be used to establish a curve from which
PI and P2 . The sum of the squares of regression IFT values could be estimated at any densi~
(SSR) for a binary system is given by Tramel:4 difference between the system’s liquid and vapor
phases. The General Foods Corp. multiple regression
program for “up to 18 variables was used to find B
and E values for each system.
R 2 is a measure of the portion of variation in Y
explained by the regression: RESULTS
The parachor and K values of each component
R2 = SSR as found by Weinaug-Katz equation by the method
. (9)
~y2-m ””””””””” previously discussed are given .in Table 1. The
, n parachor values given by Weinaug and Katz, z
When an R2 value is calculated, a new value of K Hough and Stegemeier,s Pennington and Houghr5
is assigned and a new set of Y values is calculated. and Brauer and Hough 8 are also given in TabIe 1.
Eqs. 6 through 9 are recalculated. This process is
repeated until R2 is a maximum value. The best TABLE 1- PARACHOR AND EXPONENT VALUES

values of PI, P2 and K are obtained from the data Perachers

when R 2 is a maximum value because the maximum Hydracarban First Second
System Data Source Cempcment Cempanont K
R 2 value corresponds to the minimum value of — .
z[Y-P~x~ - P2 X21? m.thano.prapano Weinaug.Katz 77.0 150,3 4.000
Hough.Stegemeie~ 77.9 158,0 3.667
It is realized that minimizing dre error in 1’
Preson~ work 77.9 154,0 3.667
(which was done) is not the same as minimizing methane.n.butmm WelnOug.Katz 77.0 189,9 4,000
the error in y. However, the former is more accurate Ponnlngtan.Hough 77.9 200,0 3,667
since the actual experimental errors in y increase Prasont work 77.9 198,0 %667
with the magnitude of y. Printouts of each value of methane.n.pentarm W~inaug.Katz 77.0 231,5 4.000
interracial tension correlated were compared to the Haugh.Stegemmlar 77*9 246,0 3.667
Prosant work 77.9 243,0 3.667
experimental values.
mcthans-n.heptane Weinaug.Katz 77.0 31285 4.000
The methane-n-heptane and ethylene-n-heptane Haugh.Stsgsmoiw 77.9 - 3.667
systems were investigated in the present work, S Prosont work 77.9 33%0 3.667
and values of IFT were calculated using the m.thana-n.d.cano Woinaug.Katz
maximum to minimum pendant drop diameter ratio Haugh.stagcmmi.r 77.9 463,0 3.;67
Pr.s.nt wark 77.9 476,0 3.667
R as a function of I/H. In addition, the following
.thylonc.n.hmptana Wofnaug.Katz 100.1 31205 4000
binary systems available in the literature were Haugh.Stagcmoiw
analyzed. Prosmt work Y&o -
332,0 3.667
n.butarm.carban Wainaug-Katz
dioxld. Brausr-Haush 300.0 83.6 3.667
Prasont wok 198.0 78,0 3,667

S40 sOCIETY OF PETROLEUM ENGINEERS JOURNAL

l%e parschor and K vahtea found in the present component increases. The following empirical
work were determined directly from the IFT values formula was developed so that a B value for the
of the binary systems. The psrachor and K values binary mixtures could be ca.!culated from the
of the other investigators were determined from psrachors of the individual components: B = 1,270/
pure component IFT values by the Sugden equation. (P~3tl 1 x P23/11) Whete B = cal~]ated B value;
The actual best parachora and K values for each 1,270 = empirically determined constant; PI _
system did not give consistent values of K or parachor of component ~ and P2 = parachor of
parachors for a component used in more than one component 2.
system. Methane parachor values varied from 16.44 The calculated B values fmm this formula are
in the methane-propane system to 247.3 in the given in Table 3. The methane-propane system has
methane-n-pentane system, but it was found that a difference of 3.7 per cent. There is remarkable
the value of 77.9 given by Hough and St :gtsneier agreement between the remaining four of the five
for methane was a reasonable average value and binary systems containing methane with a maximum
gave calculated values of IFT cIose to experimental difference of 0.7 per cent in the methane-n-pentane
values when” used with *e other component para chor system. The ethylene-n-heptane system has a
and a K value of 3.667. The K values varid from difference of 4.6 .oer cent.
3,250 in the methane-n-propane system to 3.720 in Sugden used comparison methods to assign
the methane-n-butane system and the value of 3.667 parachor values to various compounds by breaking
given by Hough and Stegemeier was found to be a the compounds into units. This same method was
reasonable, average value and one that gave tefined in the present work so that the para chors
calculated value of IFT close to experimental found by this method wouId agree with the parachors
values when used with the parach~. s as previously calculated from the experimental data by the
discussed. The parachor va!ues of the present Weinaug-Katz equation. The units for hydrocarbons
work agreed well- with those given by the other and the values assigned to each unit are given
investigators. below.
The B and E vahres of each system found by the Hydrocarbon Present
Unit Sugden Work
Sugden equation are given in Table 2. The E value ——
was not constant, and it varied from 3.287 in the CH2 39.0 45.0
methane-n-pentane system to 3.941 in the methane- c 4,8 27.0
H 17.1 9,0
n-burane system. The B value also was not constant,
but it seemed to indicate a wend from a high value Table 4 shows a comparison between parachor
for light component systems to a low value for values of Weinaug and Katz, Hough and Sregemeier,
heavy component systems. present work (modified Weinaug and Katz equation),
The B, values of the Sugden equation were Sugden and present work (hydrocarbon- units).
calculated with an E value of 3,667. The B values Except for the methane parachor, the present work
calculated from experimental values of IFT and (modified Weinaug-Katz equation) and present work
density difference are given in Table 3 as experi- (hydrocarbon units) agree within 0,5 per cent for
mental values of B. It is apparent that the binary the normal hydrocarbons.
systems containing methane have a B vaIue that If any effect due to the double bond is not
decreases as the moIecular weight of the heavy
considered for ethyIene, the erhylene parachor
TABLE 2 — B AND E VALUES FOR BINARY SYSTEMS
will be 90. Using this parachor with rhe n-heptane
parachor, the B value for the ethylene-n-heptane
Number of
system is 76.5 or a difference of onIy 0.66 per
Syst*m IFT Raodings B E
cent from experim encall y determined value of B.
motharw.propanm 41 122.14 3,074 The greatest percentage error in calculating IFT
methano.n-butant 37 122.58 3.941
methan+n.pmtane
values using the Sugden equation with an empiri-
36 60.03 3.287
msthans-n.heptane 75
cally calculated B value will .be in the small values
70.00 3.s04
methwm.n.docane 27 62064 3,538
of IFT; i.e., those IFT values less than 0.5
.th ylano.n.haptane 52 72.06 3.604 dynes/cm. However, the absolute IFT error wi!l be
n.butane.carbon dioxide :5 41,33 3,551 ao smaIl at these low values that the big percentage
difference is not significant.
TABLE 3 - B VALUES FOR BINARY SYSTEMS
WHEN E ❑ 3.667 SUMMARY

N#mber of
B The IFT values of binary systems maybe estimated
System IFT Readings Experimonial” Calculated with Ae modified Weinaug-Katz equation if the
mothmm.prapane 41 102 ?8.2
parachor, mole fractions and molal volumes are
methans-n.butane 37 92 91.5 known, or the IFT values may be estimated by the
mathane.n.pentano 36 87 86.4 Sugdcn equation if the dennity difference of the
msthans-n.heptane 75 79 79.s liquid and vapor phases is known. The present
m.tharm.n.decana 27 72 72s4 work indicates that experimental data. may be
.thyl.n..n.hsptan. ’52 76 ?9.5 analyzed quickly and accurately by the use of
digital computers.

OECEXBER. 1966
 TABLE 4- CORRELATION OF PARACHOR VALUES
Hydrocerben
Perachw 60WC0 mmharw n.propano n.butonc n.pontrwm n.hsptane n.docarw
—— .— —.
Wolnaug.Katx 77.0 1s0.3 189.9 231.5 3125 -
Houph, Steg.mci.r, 77.9 1*.O 200.0 246.0 - 463.0
Brewr, P.nnlngton
Pr.sent work ● 77*9 154.0 19800 24%0 33200 476,0
(modiflnd Wtinaus-
Katz cqwtlen)
%d*n 73.2 151,2 190.2 229.2 307,2 424,2
Prosont wark 63.0 153.0 198.0 243.0 333,0 4t&o
(I,ydracerban units)

●Recommended values.

AcKNOWLEDGMENT R = 1.351
H= fll?) =/(1.351)
The support of the American Chemical Society
Petroleum Research Fund (Grant 635A) is gratefully H = 2.17162 (from tables)
acknowledged. IFT (g) (Density Difference) (Dmax~)
=
H
REFERENCES
(980) (0.6236) (0.22262) gm
1. Hough, E. W., Wood, B, B. and Rzaaa, M. J.: “Adaormion IFT =
at H ~0, -He, -CH4, -N2 Interface at Pressures to 15,000 2.17162 sq sec
psia”, ]our. Phys. Chem. (1952) Vol. 56, 996. IFT = 13,94 dynes/cm.
20 Weinaug, F. and Katz, D. L.: “Surface Tensions
C.
of Methane-Propane Mixtures”, lnd and Eng. Cbem. SAMPLE CALCULATION 2
(1943) Vol. 35, 239,
3. Hough, E. W. and Stegemeier, G. L.: “Comelation of SOLVfNGFORX1 ANDK2,
Surface and Interracial Tension of Light Hydrocarbons METHANE-n-HEPTANE SYSTEM
in the Critical Region”, Sot. Pet. Eng. Jew. (Dec.,
196 1) 259-263. Temperature 220F
4. ~amel, T, E.: ~fAdvanced !Matiatics fOr A,?icultllrid Pressure 400 psia
Economiata”, Class Notes for Agriculture Economics, Mole fraction of merhane in liquid 0.1003
Miesiaaippi State U,, State College, Miss. <1957) 210. Mole fraction of methane in gas 0.9305
5, Wamen, H, G,: ~lnterfacial Tension Meaaurementa of Molal volume of liquid 2.494 cu ft/lbmole
Methane-Normal Heptane and Ethylene-Normal Heptane Molal volume of gas 17.80 cu ft/lb mole
Systeme by the Pendant Drop Method”, PhD disserta-
tion, Miaaiasippi State U,, State College, Mks. (1965).
~ 0.1003 .— 0.9305
G. Bennington, B. F. and Hough, E. W.: “Interracial
Tension of the Methane-Normal Butane System’? Prod.
Monthl~ (July, 1965) Vol. 29, No. 7, 4.
XI (merhane) = —
62.43 [ 2.494 17.80 1
7. Stegemeier, G. L. and Hough,’ E. W.: ‘%terfacial
Tension of the Methane-Normsl Pentane System’~ Prad.
& .
(-0.01 189686)
Mor?tbty (Nov., 1961) Vol. 25, No. 11, 6.
8. Brauer, E. B. and Hough, E. W.: ‘ lnterfacial Tension -0.00019056
of the Normsl Bratene-Carbon Dioxide System”, prod.
hfontb~y (lkrs. , 196S) Vol. 29, No. S, 13.

S.: ~eA Relation Between !hrfaCe Tension, 1 0.8997 0.0695

9. Sugden,
De;aity,
SOC.
and Chemical
(1924) Vol. 16S, 11770
Composition”, jour. Cbem. X2(n-heptane) =~ —
[ 2.494
- —
17.80 1
APPENDIX = & (0.35829357)
.
SAMPLE CALCULATION 1
= 0.00573912
EXPf3RfMENTAL VALUE, INTERFACfAL
TENSION OF ETHYLENE-n-HEPTANE SYSTEM
SAMPLE CALCULATION 3
Temperature 100F
Pfessure 200 ps’ia SOLVING FOR P, AND P2
Minimum drop diameter, Dmin 0.1648 cm Four data points of rhe ●thylene-n-heptane
Maximum drop diameter, &Rx 0.2226 cm system were chosen for the sample calculation.
Liquid-vapor densirydiffcrence 0.6236 gin/cc The data are given below for temperature, pressure,
g 980 cm/eq sec IFT, Xl and X2 (X 1 aod X 2 were calculated as
D 0.2226 shown in sample calculation 2). A K value of 4.000
R=-=— was chosen.
Dmin 0.1648

S4s socItrTv OF •~TUOLEUM ENt2iNEERs JOURNAL

.

Experi- 0.017s6056 =P1(0.0000449) +P2(0.0000440)

Temper- Pres- mentalIFT 0.02504315 = P1(0.0W0440) + P2(0.0000680)
ature sure Values Pi =82.66
(W) (Psia) (dynes/cm) (etl$ene) (n-he%anct P2 =314.75
100 290 1:$ 0.001162260.00589873
100 600 0.003805540.00398029 The IBM computer solution using 52 data points
130 3:67 0.003549100.00346685 and l/K value of 0.2500 gave Pi R 87.93 aqd P2
130 l,R 1.46 0.004059070.00239553 = 314.29. A check of the calculation csn be made
by the R test.

IFT@Z5) s Y Y2 XIY ‘ X2 Y SSR = Pl ZXl Y+ P22X2Y-(ZY)2/n

1.9320 3.732624 0.00224548 0.01139634 = 1.449097 + 7.88233’1-8.929638.

1.5620 2.439844 0.00594425 0.00621721 = 0.401790
1.3840 L9154% 0.00491195 0.00479812
1.0985 1.206702 0.00445888 0.00263148 ~ Y~ZY)2/n = 9.294626-8.929638 = 0.364988
5.9765 9.294626 0.01756056 0.02504315 SSR 0“5
X12 X22 X1X*
—
R=
[ y2+y)2/~
1
0.0000347950 0.401790
0.0000013508 0.000006S558 s = 1.049
0.0000144782 0.0000154446 0.0000151471 0.364988
0.0000125961 0.0000120190 0,0000123041
0.0000057385 The value of R should never exceed 1 and, if
0.0000164719 0.0000096830
0.0000448970 no errors of roundicg are made in the computer, it
0.0000679971 0,0000439900
will not exceed 1. The R value for the 52 Jata
zxlr=p~zxlz +P2XX1X2 points and l/K = 0.2500 was 0.9994+,
***
2 X*Y = P~xx2x~+ P22x#

DECEMBER.1966 a49