Fluid Phase Equilibria 252 (2007) 6673

Vapourliquid interfacial tension of water and hydrocarbon mixture

at high pressure and high temperature conditions
A. Bahramian
a,
, A. Danesh
b
, F. Gozalpour
b
, B. Tohidi
b
, A.C. Todd
b
a
Institute of Petroleum Engineering, University of Tehran, Tehran, Iran
b
Institute of Petroleum Engineering, Heriot-Watt University, Edinburgh EH14 4AS, UK
Received 3 May 2006; received in revised form 5 November 2006; accepted 20 December 2006
Available online 5 January 2007
Abstract
Interfacial tension values of two liquidliquidvapour systems, a ternary waterdecanemethane and a quaternary watercyclo-
hexanedecanemethane, were measured using a pendant drop technique at 150

C and high pressures up to 28.1 MPa. The tested ternary mixture

showed a maximumliquidliquid interfacial tension by increasing pressure whereas it only slightly increased liquidliquid interfacial tension in the
quaternary system. The predicted interfacial tension values by some models are compared and the application of liquidliquid interfacial tension
models for predicting the liquidvapour interfacial tension at high pressure conditions is discussed.
2007 Elsevier B.V. All rights reserved.
Keywords: Interfacial tension; Liquidliquid equilibrium; Water; Methane; Decane; Cyclohexane; Experimental data
1. Introduction
The interfacial tension (IFT) values of waterhydrocarbon
systems affect important features of petroleum reservoir pro-
cesses, such as wateroil contact movement, water alternating
gas drive (WAG) [1], trapping of hydrocarbons by water ood
and oil recovery by depressurisation [2]. Interfacial tension data
are also required in calculations of transition zones in reservoirs.
Although data on waterhydrocarbon uids at two-phase con-
ditions have been reported in the literature [323], such data
at three-phase conditions, particularly at high pressurehigh
temperature (HPHT) conditions, are very scarce. Such data are
becoming more valuable as deeper, hence higher pressure and
temperature reservoirs are being exploited. At HPHTconditions,
the mutual solubility of water and hydrocarbon phases is higher;
therefore, the IFT of hydrocarbonwater systems at HPHT con-
ditions can be signicantly different from those in conventional
reservoirs.
In this work, novel measured IFT data on two liquidliquid
vapour systems of equilibrated waterhydrocarbon mixtures,
a ternary waterdecanemethane and a quaternary water

Corresponding author. Tel.: +98 21 88632975; fax: +98 21 88632976.

E-mail address: abahram@ut.ac.ir (A. Bahramian).
cyclohexanedecanemethane are presented. Predictive models
are employed and evaluated against the measured liquidliquid
and liquidvapour IFT data.
2. Experiments
Fig. 1 shows the conguration of the HPHT rig incorporating
a pendant drop facility for measurement of interfacial tension.
The pendant drop method for measuring IFT at high pressure
conditions is a well-established and documented procedure, with
details available in the literature [24]. The schematic diagram
shows a droplet of liquid suspended from the tip of a stainless
steel dropper, which was made oil-wet prior to being installed in
the window cell. The drop is viewed remotely by a camera con-
nected to a video monitor, where the drop is dimensioned using
a video scale device. The equilibrium phase densities are also
required in the calculation of IFT. These are measured by trap-
ping each of the phases, in turn inside the removable pressure cell
on the left of the diagram and by measuring the weight and vol-
ume of the sample its density can readily be calculated. Density
data were measured for the three equilibrium phases at lowest
and highest test pressures (3.4 and 28.1 MPa) and 150

C. The
measured density data were employed to adjust parameters of an
in-house phase behaviour model (Appendix A) for calculating
density at other pressures.
0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2006.12.013
A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673 67
Fig. 1. Schematic diagramof the HPHT equipment congured to measure inter-
facial tension by the pendant drop technique.
Tests uids were composed of decane (Sigma-Aldrich,
+99%) cyclohexane (Sigma-Aldrich, +99.9%, HPLC grade),
methane (Air Products, 99.995%) and triple distilled water.
Decane and cyclohexane were puried separately by passing
each six times through basic (as opposed to acidic) aluminium
oxide to remove surface-active components. Initial tests on
decanewater resulted in a data matching those in the literature
[22] within the error bands of the measurements.
All the components were individually added gravimetrically
to a previously cleaned and evacuated pressure vessel. Typical
loading of each compound was about 2030 g with a resolution
of 0.001 g using a Mettler Toledo PR5003 mass comparator. This
provided compositional data on the molar fraction of compo-
nents with a deviation of 0.0001. The vessel was then mounted
in the HPHT facility. The sample was pumped back and forth
between the high pressure cells to facilitate mixing and achiev-
ing equilibriumat the test pressure before attempting to perform
any measurements.
The oil-wet pendant dropper was used to form droplets of
hydrocarbon-rich liquid and water-rich liquid in the equilibrium
vapour phase for liquidvapour IFT data measurements. The
IFTof hydrocarbon-richliquid/water-richliquidwas determined
by suspending a droplet of water in the liquid hydrocar-
bon phase. It should be noted that all three phases (vapour
phase, hydrocarbon-rich liquid phase and water-rich liquid
phase) were present and they were at equilibrium during the
experiment.
2.1. Waterdecanemethane three-phase system
The three-phase interfacial tension of waterdecane
methane system was measured at 150

C and pressures of 3.4,

13.7, 24.0 and 28.1 MPa. Additional measurements were also
made on hydrocarbon-rich liquidvapour IFT, at three phase
conditions, at some pressure intervals, as shown in Table 1.
The interfacial tension between vapour (V) and hydrocarbon-
rich liquid (O) increases sharply from 0.088 mNm
1
at
28.1 MPa to 10.5 mNm
1
at 3.4 MPa. Similarly, the interfa-
cial tension between vapour and water-rich liquid (W) increases
from 30.1 to 41.7 mNm
1
over the above pressure range. Pres-
sure reduction, however, initially increases the IFT between the
two liquid phases, reaching to a maximumvalue before reducing
by further pressure reduction. However, changes in OW IFT are
relatively small in comparison with the other pairs. This is in
line with the effect of pressure on properties of liquids, which
is small, and the changes are considered to be mainly due to
compositional variations of the hydrocarbon-rich liquid phase.
A main application of three-phase IFT data is in determina-
tion of uid distribution in rock pores of petroleum reservoirs,
where the relative location of uid phases is controlled by the
characteristics of rock wetting and uid spreading, described by
the spreading coefcient, S, dened as:
S =
WV
(
VO
+
OW
) (1)
A negative spreading coefcient would allow a three-phase
uid contact, whereas full spreading where a liquid phase com-
pletely separates the second liquid fromthe vapour phase would
occur at S =0. The latter is equivalent to Antonows rule [25,26],
that is in a three-phase system at equilibrium, the sum of IFT
values of the two pairs more proximate phases is equal to
that of the largest one. The experimental data indicates that
the reduction of hydrocarbon-rich liquid/vapour IFT,
VO
, by
increasing pressure is almost equal to the increase in water-rich
liquid/vapour IFT,
WV
, with minimal changes in hydrocarbon-
rich liquid/water IFT,
OW
. The spreading coefcient remains
almost equal to zero, within the error band of IFT measurements
over the tested conditions.
2.2. Watercyclohexanedecanemethane three-phase
system
The sample was gravimetrically prepared and the resul-
tant mixture had the following molar composition: methane
63.13 0.01, decane 5.370 0.004, cyclohexane 8.43 0.01
and water 23.07 0.01. The tests were performed at 150

C and
at four pressures, 13.7, 17.1, 20.5 and 24.0 MPa using the HPHT
facility. The results are given in Table 2.
The hydrocarbon-rich liquid in equilibrium with the vapour
phase shows a wide range of interfacial tension from
0.22 mNm
1
at 24.0 MPa rising to 3.7 mNm
1
at 13.7 MPa.
The water-richliquidphase/vapour IFTincreasedonlyfrom30.5
to 32.4 mNm
1
over the above pressure range. The trend in the
interfacial tension between the liquid phases was opposite where
it reduced with increasing pressure. No IFT value was recorded
6
8
A
.
B
a
h
r
a
m
i
a
n
e
t
a
l
.
/
F
l
u
i
d
P
h
a
s
e
E
q
u
i
l
i
b
r
i
a
2
5
2
(
2
0
0
7
)
6
6

7
3
Table 1
Phase density and IFT of the waterdecanemethane three-phase system at 150

C
Pressure
(MPa)
Vapour density
(g cm
3
, 0.005)
Hydrocarbon-rich liquid
density (g cm
3
, 0.005)
Water-rich liquid density
(g cm
3
, 0.0001)
Vapourhydrocarbon-rich
liquid IFT (mNm
1
)
Vapourwater-rich
liquid IFT (mNm
1
)
Liquidliquid IFT
(mNm
1
)
S (mNm
1
)
3.4 0.025 0.619 0.9179 10.5 0.3 41.7 0.7 28.5 0.6 2.7 1.6
6.8 0.047 0.595 8.0 0.2
13.7 0.126 0.548 0.9214 4.1 0.1 34.9 0.6 31.1 0.6 0.3 1.3
20.5 0.227 0.493 1.6 0.1
24 0.256 0.462 0.9254 0.80 0.04 32.8 0.6 30.0 0.5 2.0 1.1
27.4 0.253 0.426 0.17 0.01
28.1 0.248 0.417 0.9270 0.088 0.01
a
30.1 0.5 29.6 0.5 0.412 1.01
a
The IFT value was measured by the meniscus height technique, described in ref. [51] as at this pressure the droplet was too small to be measured by the pendant drop method.
Table 2
Phase density and IFT of the watercyclohexanedecanemethane three-phase system at 150

C
Pressure (MPa) Vapour density
(g cm
3
, 0.005)
Hydrocarbon-rich liquid
density (g cm
3
, 0.005)
Water-rich liquid density
(g cm
3
, 0.0001)
Vapourhydrocarbon-rich
liquid IFT (mNm
1
)
Vapourwater-rich
liquid IFT (mNm
1
)
Liquidliquid IFT
(mNm
1
)
S (mNm
1
)
13.7 0.105 0.584 0.9237 3.7 0.1 32.4 0.6
17.1 0.139 0.549 0.9255 2.4 0.1 31.8 0.6 27.6 0.5 1.8 1.2
20.5 0.178 0.503 0.9273 1.11 0.05 30.5 0.5 29.0 0.5 0.39 1.05
24.0 0.225 0.423 0.9291 0.22 0.01 30.5 0.5 29.8 0.5 0.48 1.01
A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673 69
at 13.7 MPa because the water droplet could only be partially
seen as the refractive indices of the two phases became similar.
The spreading coefcient over the tested range almost remains
equal to zero, within the accuracy of IFT measurements, similar
to the previous case.
3. Prediction
There are a number of theoretical based equations and empir-
ical correlations to predict IFT of vapourliquid or liquidliquid
systems [2740]. The methods for vapourliquid systems are
generally applicable at low-pressure conditions as the properties
of the vapour phase are generally neglected. The methods used
for liquidliquid systems are mostly reliable for simple mix-
tures dominated by short range molecular forces. The reliability
of some of the most widely used methods for hydrocarbonwater
(polar compound) mixtures at three-phase HPHT conditions is
evaluated by comparing their predictions against the measured
data in this study.
3.1. Liquidvapour IFT
The most widely used correlation in the petroleumindustry is
the parachor method [2731], which is based on the observations
of Macleod [29] and the later work of Sugden [30]. The latter
was extended to multi-component systems by Weinaug and Katz
[31]:
(

)
1/4
=
c

i=1
[P
i
x

P
i
x

] (2)
where

is the interfacial tension between two phases and

, x the mole fraction, P
i
the parachor value of the compound i
and is the molar density.
Firoozabadi and Ramey [32] demonstrated that IFT
between water and pure hydrocarbons, over a wide range of
temperaturepressure, can be related to the phase density differ-
ence by a single curve, using the following IFT function:
IFTfunction
(
hw
)
0.25
(T/T
h
c
)
0.3125

h
(3)
where
hw
is the hydrocarbon (vapour or liquid)water-rich
liquid IFT and T
h
c
is the hydrocarbon phase critical temperature.
The reliability of correlation was demonstrated for various
compounds ranging from methane to dodecane. The curve can
be represented almost by the following equation [41]:

hw
= 111(
w

h
)
1.024
_
T
T
h
c
_
1.25
(4)
where IFT is in mNm
1
,
w
and
h
are the water and hydrocar-
bon phase density in g cm
3
, respectively.
3.2. Liquidliquid IFT
Amongst all the available methods to predict the liquidliquid
IFT [3440], only few of them relate IFT to mutual solubil-
ity [34,36,39,40]. The DonahueBartel correlation [34] is the
oldest, which is based on their observation that plotting the
liquidliquid IFT of binary systems versus the logarithm of the
sum of mutual solubility results in a linear relationship:

OW
= a b log(x
w
o
+x
o
w
) (5)
where
OW
is the oilwater IFT, x
w
o
and x
o
w
stand for mole
fraction of oil in the water-rich phase and water in the oil-rich
phase, respectively. Constants a and b, found by regression of
experimental data [42], are 3.31 and 15.61, respectively. It
should be noted that DonahueBartel, and the other models used
in this study, can also be used in non-aqueous systems.
Eq. (5) was modiedlater byTreybal [36] for ternarysystems:

OW
= a b log
_
x
w
o
+x
o
w
+
x
w
3
+x
o
3
2
_
(6)
The compound 3 in the above equation is the hydrocarbon
that is more soluble in the water-rich phase. Eqs. (5) and (6)
are the simplest equations of the kind but are limited to binary
and ternary systems. However, they have been found [42,43] to
be the most accurate methods as well as the Fu et al. equation,
which is as follow [39]:

OW
=
KRTX
A
w0
exp(X)(x
w
o
q
O
+x
o
w
q
W
+x
r
3
q
3
)
(7)
where,
X = ln(x
w
o
+x
o
w
+x
r
3
) (8)
Here the compound 3 is dened similar to that in Eq. (6), and
the letter r denotes the phase which is richer in compound 3.
A
w0
is the van der Waals area of a standard segment, q the pure
compound area parameter dened by the UNIQUAC model,
T temperature, R the universal gas constant and the empirical
parameter, K, found to be 0.9414 by regression using experimen-
tal IFT of binary systems [39]. Eq. (7) has the same limitation
of Eq. (6), that is, it cannot be used for systems with more than
three components.
Recently, employing the lattice theory and regular solution
assumptions, Bahramian and Danesh [40] proposed a simple
equation for predicting liquidliquid IFT of multi-component
systems. The equationdoes not include anyempirical parameters
and has no limitation with the number of components:
c

i=1
_
(x
o
i
x
w
i
)
0.5
exp
_
a
i
RT

OW
__
= 1 (9)
where c is the number of components and a
i
stands for the partial
molar surface area of the ith compound at the interface.
3.3. Results
The reviewed IFT models were evaluated against the mea-
sured liquidliquidvapour IFT data. The required composition
of equilibrated phases for IFT predictions was calculated using
an in-house phase behaviour thermodynamic model based on
the PengRobinson equation of state with non-random mix-
ing rules, to account for polarity of water (Appendix A). The
70 A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673
Fig. 2. Measured and predicted liquidliquid interfacial tension values of the
waterdecanemethane system at 150

C.
model and its reliability in predicting the mutual solubility of
waterhydrocarbons have been described elsewhere [44,45].
The predicted compositions were employed then to calculate
the liquidliquid and liquidvapour IFT of the both investigated
systems using the described IFT models. The required phase
densities were determined using the in-house phase behaviour
model with its parameters adjusted to match a limited number
of measured density data of equilibrium phases. The parachor
values can be found in the literature [41] or calculated from
the surface tension of the pure components. The area parame-
ter for methane in Eq. (9) can be calculated from the reported
LennardJones size parameter [46] and those of the others,
according to Bahramian and Danesh [40], from their molar pure
liquid volumes, except for water, which is suggested to be 32

A
2
per molecule [40,47,48]. The parameters in Eq. (7), that is A
w0
and q, are available in the literature [39,49]. The molar average
value of the critical temperature of phase components was used
in Eq. (4).
T
h
c
=

i=j
_
x
i

i=j
x
i
T
ci
_
(10)
where T
ci
is the critical temperature of component i, and j is
water component. In other words, the critical temperature of
hydrocarbon phase is calculated on a dry basis (water free).
Figs. 2 and 3 show the experimental liquidliquid IFT val-
ues of the investigated systems as well as the predicted results.
Fig. 3. Measured and predicted liquidliquid interfacial tension values of the
watercyclohexanedecanemethane system at 150

C.
While the BahramianDanesh model can reliably predict the IFT
values of the ternary and quaternary systems, with an average
absolute percentage deviation (AAD%) from the experimental
data of 3% and 6%, respectively, the deviations of the Trey-
bal (AAD=77%) and Fu et al. (AAD=57%) equations for the
ternary system indicate their lack of applicability at HPHT con-
ditions (Table 3). Their poor results, however, would be expected
as their empirical parameters have been calculated by matching
IFT values at 25

C and atmospheric pressure. The predictions

by the model of Fu et al., approach the measured value at
the lowest tested pressure of 3.4 MPa. Fig. 3 does not include
results of the Treybal and Fu et al. equations, owing to their
limitation for systems with more than three components. The
results of the Firoozabadi and Ramey model, as indicated in
Figs. 2 and 3, show a monotonically decrease in liquidliquid
IFT of the investigated ternary system (AAD=43%), whereas
for the quaternary system it shows a minimum with increasing
the pressure (AAD=24%).
The unacceptable predicted trends by Fu et al. and Trey-
bal models (Fig. 2) can be attributed to the limitations in the
correlated parameters of their models where they used data
at atmospheric pressure and 25

C. However, the deciency

of the FiroozabadiRamey model is mainly due to its depen-
dency to the solubility of the heavy component in the water
phase. The solubility of the heavy hydrocarbons in the aque-
ous phase is increased by the pressure increment. This results
the phase density difference to increase while reducing T
h
c
.
Therefore, according to FiroozabadiRamey model the IFTmay
Table 3
Average absolute percentage deviation (AAD%) of the predicted interfacial tension values from the measured data
BahramianDanesh [40] FiroozabadiRamey [32] Treybal [36] Fu et al. [39] Parachor [31]
Waterdecanemethane
Vapourhydrocarbon-rich liquid 673 903 103 51
Vapourwater-rich liquid 21 5 96 98 48
Water-rich liquidhydrocarbon-rich liquid 3 43 77 57
Watercyclohexanedecanemethane
Vapourhydrocarbon-rich liquid 68 16
Vapourwater-rich liquid 8 29 42
Water-rich liquidhydrocarbon-rich liquid 6 24
A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673 71
Fig. 4. Measured and the predicted hydrocarbon-rich liquidvapour interfacial
tension values of the watercyclohexanedecanemethane system at 150

C.
increase or decrease by increasing pressure (as it is evident from
Figs. 2, 3, 5 and 6).
At high pressure conditions the characteristics of vapour
approach that of liquid. Indeed at the critical point the prop-
erties of the vapour and the liquid become similar. Hence, it
would be reasonable to expect that a reliable liquidliquid IFT
model could produce reliable results for vapourliquid systems
at high pressure conditions.
Fig. 4 shows the measured and the predicted hydrocarbon-
rich liquidvapour IFT values of the investigated quaternary
system. The parachor method predicts the results reliably over
the full range with AAD=16%. The BahramianDanesh model
predicts the trend reasonably well and it approaches the mea-
sured value at the highest tested pressure. Such predictions of
vapourliquid IFT by a liquidliquid model are very encourag-
ing.
The predicted values for water-rich liquidvapour IFT of the
quaternary system are shown in Fig. 5. The predicted results
by the BahramianDanesh (liquidliquid) model are more reli-
able (AAD=8%) than those of the parachor (AAD=42%) and
FiroozabadiRamey (AAD=29%) correlations. However, the
BahramianDanesh model predicts a small increase in IFT by
Fig. 5. Measured and the predicted water-rich liquidvapour IFT values of the
watercyclohexanen-decanemethane system at 150

C.
Fig. 6. Measured and the predicted water-rich liquidvapour interfacial tension
values of the waterdecanemethane system at 150

C.
increasing the pressure contrary to the observed trend of mea-
sured data.
Fig. 6 compares the measured and predicted values of the
water-rich liquidvapour IFT of the investigated ternary system.
While at low pressure the BahramianDanesh model prediction
(AAD=21%) is unreliable (as expected), it predicts the results
reliably at high pressure conditions. The other two liquidliquid
models fail to give a reasonable prediction as their empirical
parameters have been determined at conditions vastly differ-
ent from those of the test. The parachor method (AAD=48%)
can only predict the data at low-pressure conditions. It is
interesting that the predicted IFT results by the parachor and
the FiroozabadiRamey (AAD=5%) models show a minimum
around 24.7 MPa. Such a trend has been experimentally obtained
and reported for binaries of watermethane and waterpropane
[50]. For some systems, e.g. waterhelium, even a continuous
increase of liquidvapour IFT with pressure at constant temper-
ature has been reported [50]. The average absolute percentage
deviations of the predicted interfacial tension values by all the
mentioned models are also presented in Table 3.
4. Conclusions
Measured data on three-phase IFTof two waterhydrocarbon
systems at high pressurehigh temperature have been presented.
The measured data were used to evaluate the capability of some
leading IFT models in the literature.
Amongst the predictive liquidliquid IFT models, the
BahramianDanesh model produced the most reliable results.
Furthermore, the model could also predict vapourliquid IFT
at high pressure conditions, where the behaviour of the vapour
phase approaches to the liquid phase.
The vapourliquid parachor model reasonably predicted the
vapourhydrocarbon-rich liquid IFT, but it failed to give a rea-
sonable prediction to the vapourwater-rich liquid IFT data.
Considering a zero spreading coefcient value at high pres-
sure conditions for waterhydrocarbon three-phase systems, a
combination of the BahramianDanesh liquidliquid model,
the parachor vapourhydrocarbon-rich liquid model and the
72 A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673
Antanow rule can provide reliable IFT data for all three pairs of
uids at HPHT conditions.
List of symbols
a constant in Eq. (5)
a
i
partial molar surface area of the ith compound
a
a
Eq. (A7)
a
c
Eq. (A2)
A
w0
van der Waals area of a standard segment
b constant in Eq. (5) and (A3)
c number of compounds
l
pi
non-random binary interaction coefcient between
polar and hydrocarbon compound
k
ij
random binary interaction coefcient
K constant in Eq. (7)
N number of compounds in Eq. (A4)
P pressure
P
i
parachor value of the compound i
q UNIQUAC pure compound area parameter
R ideal gas constant
S spreading coefcient
T temperature (K)
T
c
critical temperature (K)
molar volume
x mole fraction
X Eq. (8)
Greek letters
a function representing temperature dependency of the
attractive term in Eq. (A2)
molar density (mol cm
3
) in Eq. (2) and mass density
(g cm
3
) in Eqs. (3) and (4)
interfacial tension

ac
constant in Eq. (A2)

b
constant in Eq. (A3)
Subscripts
i ith compound
o hydrocarbon
p polar compound
r the richer phase in compound 3 at ternary system
w water
3 the more soluble hydrocarbon in the water-rich phase
at ternary system
Superscripts
h hydrocarbon
o hydrocarbon-rich phase (i.e. oil)
w water-rich phase
OW interface of water-rich liquid and hydrocarbon-rich liq-
uid
OV interface of vapour and hydrocarbon-rich liquid
VW interface of vapour and water-rich liquid
phase
phase
phase (interface of and )
Acknowledgements
The research work on which this paper is based was equally
sponsored by the UK Dept. of Trade and Industry, Total,
Marathon International (GB) Ltd., Norsk Hydro, Gaz de France,
Schlumberger Oileld UK Plc., and Shell US Exploration and
Production Ltd., which is gratefully acknowledged. The authors
wish to thank Mr. K. Bell for making the measurements, and
Mr. J. Pantling and Mr. C. Flockhart for manufacturing and
maintenance of the experimental facilities.
Appendix A
The van der Waals equation of state (EOS) has the following
generic form:
P =
RT
b

a
c

2
+ub +wb
2
(Al)
where P and are the pressure and the molar volume, respec-
tively. The parameter a (a
c
) is called the (conventional) attractive
term and b is the repulsive term. The u and w symbols are con-
stants in two-parameter forms of EOS. They are related to a third
parameter or some other property in three-parameter form EOS.
a
c
=
ac

R
2
T
2
c
P
c
(A2)
b =
b
RT
c
P
c
(A3)
where
ac
and
b
are EOS constants. T
c
and P
c
are the critical
temperature and the critical pressure of compound, respectively.
Parameter represents the temperature dependencyof the attrac-
tive term. The van der Waals conventional random mixing rules
to determine a
c
and b parameters of EOS for multi-component
systems are:
a
c
=
N

i=1
N

j=1
x
i
x
j
(a
c
i
a
c
j
)
0.5
(1 k
ij
) (A4)
b =
N

i=1
x
i
b
i
(A5)
where x
i
and N are the molar composition of component i and
the number of components in the mixture, respectively, k
ij
is the
conventional (random) binary interaction parameter (BIP). In
this study to simulate the interaction between water (polar) and
hydrocarbons (non-polar), an asymmetric (non-random) term
(a
a
) was added to the conventional (random) attractive term (a
c
)
of EOS:
a = a
c
+a
a
(A6)
where:
a
a
=

x
2
p

x
i
a
pi
l
pi
(A7)
The subscript p refers to polar components, and l
pi
is the
non-random BIP between polar and hydrocarbon compounds.
A. Bahramian et al. / Fluid Phase Equilibria 252 (2007) 6673 73
The conventional (random) (k
ij
) and the non-random(l
pi
) binary
interaction parameters (BIPs) for waterhydrocarbon have
been determined by matching the mutual solubility data of
hydrocarbonwater systems.
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