Fluid Phase Equilibria 355 (2013) 1225

Contents lists available at ScienceDirect

Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

A practical method for the estimation of oil and water mutual

solubilities
Marco A. Satyro a, , John M. Shaw b , Harvey W. Yarranton c
a
b
c

Virtual Materials Group, Inc., Calgary, Alberta, Canada

University of Alberta, Edmonton, Alberta, Canada
University of Calgary, Calgary, Alberta, Canada

a r t i c l e

i n f o

Article history:
Received 16 April 2013
Received in revised form 20 June 2013
Accepted 22 June 2013
Available online 2 July 2013
Keywords:
Solubility
Water
Hydrocarbon
Activity coefcient model
Equation of state

a b s t r a c t
A simple model is proposed for the calculation of oil and water mutual solubilities as a function of
temperature using the hydrocarbon specic gravity and Watson-K factor as correlating parameters. The
model parameters were determined using a single consistent set of high quality solubility data collected
at the water or hydrocarbon saturation pressures at temperatures from 273 K and 573 K but primarily
from 298 K to 398 K. The hydrocarbon in water solubilities ranged over 11 orders of magnitude while the
water in hydrocarbons solubilities ranged over 4 orders of magnitude. Hydrocarbon types ranged from
low molecular weight parafns such as n-pentane to heavy aromatics such as anthracene. The average
absolute error in the estimated solubilities of water in hydrocarbons over 621 data points was 34% and
approached the suggested underlying uncertainty in the reference data (30%). The average absolute error
in the estimated solubilities of hydrocarbons in water over 964 data points was 88% and exceeded the
suggested underlying uncertainty in the reference data (30%).
The model can be extended to higher temperatures using a procedure based on activity coefcients
or equations of state and is easily adapted to work with ill-dened hydrocarbon mixtures. Prediction
and correlation of solubilities of water in kerosene, heavy oils, and bitumen were made at temperatures, pressures, and compositions far removed from the original data used for model construction. The
correlation failed near the critical temperature of water because under these conditions, the properties
hydrocarbon-rich phases in the mixtures on which the correlation is based (Type II and Type IIIa phase
behaviour according to the van Konynenburg and Scott naming scheme) and those of water + heavy
hydrocarbons (Type IIIb phase behaviour) diverge. A separate NRTL based correlation is presented for the
mutual solubility of water + heavy oils at temperatures close to the critical temperature of water.
2013 Elsevier B.V. All rights reserved.

1. Introduction
The estimation of mutual solubilities of water and oil is an
important part of the development of reliable simulation models. The amount of water dissolved in hydrocarbons denes the
amount of water side draws from crude distillation towers while
the amount of dissolved hydrocarbons in aqueous streams is important for the design of water treatment systems. Water can also be
an attractive solvent for oil upgrading at high pressures and temperatures, and reasonable estimates for mutual solubilities under
these conditions are vital for the design of the reactor and associated water and hydrocarbon recovery systems. Thermodynamic
models used for the simulation of hydrocarbon processes can usually provide reliable estimates of water in hydrocarbon solubilities;

Corresponding author. Tel.: +1 403 397 2031.

E-mail address: marco.satyro@virtualmaterials.com (M.A. Satyro).
0378-3812/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2013.06.049

however, estimates for the solubility of hydrocarbons in water are

usually poor [1].
Several techniques for the estimation of water solubility are
available, based on empirical equations such as the ones found in
the API handbook [2], Tsonopoulos [3,4], and de Hemptinne et al.
[5]. In general, these techniques have some or all of the following
limitations: available only for n-alkanes; require constants to be
determined for individual compounds; limited to a single temperature, usually 25 C; parameters dependent on molecular structure
information [6]. On the other hand, simple cubic equations of state
do not suffer from these limitations and can be tuned to provide reasonable representations of water solubility in hydrocarbons using
interaction parameters in the vicinity of 0.5 [5].
The estimation of solubilities of hydrocarbons in water is more
complicated and few models are capable of predicting the solubility of hydrocarbons in water [5,7]. There are some models available
based on limited carbon number ranges at 25 C [5,818] with
specic constants determined based on chemical types or group

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Nomenclature
a
parameter for Eq. (15)
b
parameter for Eqs. (6) or (7) and (14) or (16)
c
parameter for Eqs. (6) or (7) and (14) or (17)
d
parameter for Eqs. (6) or (7) and (14) or (18)
e
parameter for Eq. (19)
f
Pade approximant term, Eq. (4)
g
Pade approximant term, Eq. (5)
h
enthalpy of solution
np
number of data points
OF
objective function for data regression
p0 , p1 , p2 empirical constants in Eq. (2)
R
gas constant
specic gravity
SG
T
absolute temperature
T0
reference temperature, 298.15 K
normal boiling point (K)
Tb
x
solute mole fraction
Watson (UOP) K
Wk
Subscripts
hc
hydrocarbon
I
data point index
solvent
s
w
water
Superscripts
calc
calculated value
IUPAC
experimental or recommended solubility value
from IUPAC

value at innite dilution

Greek symbols

parameter for Eq. (9)

parameter for Eq. (8)

Kw
Watson K departure from parafn reference, Eq. (8)
SG
specic gravity departure from parafn reference,
Eq. (9)
activity coefcient


NRTL interaction parameter

contributions [1921]. Currently available models are not easily

extended to oil and water mixtures where the oil is characterized
using distillation curves. The pseudo-components do not provide
enough information for the denition of a chemical type since they
actually represent the mixture of several compounds of different
chemical nature that boil at similar temperatures. The same handicap applies to group contribution based methods. Finally, currently
available methods do not provide much information for critical
evaluation of the quality of their predictions.
Simple cubic equations of state using classic quadratic mixing rules are not capable of predicting accurate mutual solubilities
because they use a symmetric interaction parameter. This inadequacy has been long known [22] and special interaction parameters
must be used for the correct representation of hydrocarbon solubilities in the water-rich phase. These interaction parameters are
usually much smaller than those required to model the solubility of
water in a hydrocarbon-rich phase and point to the need for more
advanced asymmetric mixing rules [23,24].
The recent publication of carefully screened water +
hydrocarbon mutual solubility data by Maczynski and coworkers
[818] provides an extensive and consistent set of data for the
development of solubility models and provided much of the

13

motivation for this study. The objective of this work is to develop

a fully predictive model for the estimation of oil and water mutual
solubilities applicable to petroleum and not just dened components. The model is to have a built-in temperature dependency and
must be easily integrated into a process simulation environment
where it can be used to provide information for the calculation of
model specic interaction parameters as are commonly used in
activity coefcient or equation of state methods.
2. Database
The construction of a consistent database for model development was greatly facilitated by the availability of an extensive,
critically evaluated series of papers on hydrocarbons and water solubility published by Maczynski and coworkers [818]. This data
compilation reviewed the previous extensive work done in the
IUPAC Solubility Series, Volumes 37 and 38 [25,26] with corrections
and included new published work up to 2006. This recent work
provides solubility data as a function of temperature for parafns,
naphthenes, aromatics, and other hydrocarbons ranging from C5 to
C36 hydrocarbons.
The available data points were individually examined and quality identiers were assigned to them. Reference data are provided
based on specially constructed correlation functions for specic
chemical families [8]. Experimental data differing from the reference data by less than 30% at similar temperatures from different
sources are classied as recommended while those that differ from the recommended data by more than 30% are classied
as doubtful. Their criteria, based on an analysis of cycloalkane,
alkane, isoalkanes and alkenes (hydrocarbon in water) and alkanes
and alkenes (water in hydrocarbons), were applied to solubilities
of hydrocarbons in water as well as water in hydrocarbons. If values from only a single laboratory are available, even if they agree
with the reference data, they are classied as tentative. If values are available but are deemed suspicious by the investigators,
they are classied as rejected. In this work only recommended
or tentative data points were used in the development of the
model. The uncertainty of individual data points is not accessible
and consequently statistical weighting cannot be applied to determine model parameters. Hydrocarbons lighter than C5 were not
included. Tables 1 and 2 summarize all the data as well the temperature and composition ranges used in the construction of the
model.
3. Model development
The principle objective is to develop a practical model that can
be used to estimate mutual solubilities for hydrocarbon + water
mixtures at temperatures found in common chemical processes.
The method should be easily implemented as an estimation procedure for the determination of interaction parameters for rigorous
thermodynamic models, based either on equations of state or activity coefcients. Further, restrictions and limitations dictated by
the diversity of phase behaviours exhibited by water + hydrocarbon
mixtures, data uncertainty (noted above), and hydrocarbon characterization must be recognized at the outset and are discussed
below.
Hydrocarbon compounds typically approach their critical temperatures remote from, and at lower temperatures than, the critical
temperature of water. For such cases the hydrocarbon-rich phase
is the more volatile phase and the phase diagrams are typically
Type IIIa [27] according to the naming scheme of van Konynenburg
and Scott [28]. There are also cases, such as 1-methylnaphthalene,
tetralin, naphthalene and biphenyl + water where the phase diagrams are Type II as reviewed by [29]. However, for a small but

14

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Table 1
Summary of components and conditions in the data set used for development of hydrocarbon in water solubility model (T, temperature; xhc , hydrocarbon mole fraction).
Components noted with an asterisk may have solubility data reported below their melting point.
Component

Tmin (K)

Tmax (K)

xhc, min

xhc, max

# points

1,3-Cyclopentadiene
2-Methyl-1,3-butadiene
1,4-Pentadiene
1-Pentyne
Cyclopentane
2-Methyl-2-butene
3-Methyl-1-butene
1-Pentene
2-Pentene
2,2-Dimethylpropane
2-methylbutane
n-Pentane
Benzene (*)
1,4-Cyclohexadiene
Cyclohexene
1,5-Hexadiene
1-Hexyne
Cyclohexane (*)
1-Hexene
Methylcyclopentane
2-Methyl-1-pentene
4-Methyl-1-pentene
2,2-Dimethylbutane
2,3-Dimethylbutane
Hexane
2-Methylpentane
3-Methylpentane
1,3,5-Cycloheptatriene
1,6-Heptadiyne
Toluene
Cycloheptene
1,6-Heptadiene
1-Heptyne
1-Methylcyclohexene
Cycloheptene
1-Heptene
2-Heptene
Methylcyclohexane
2,3-Dimethylpentane
2,4-Dimethylpentane
3,3-Dimethylpentane
n-Heptane
3-Methylhexane
Styrene
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene (*)
4-Vinyl-1-cyclohexene
1,7-Octadiene
1-Octyne
Cyclooctane
cis-1,2-Dimethylcyclohexane
1,4-Dimethylcyclohexane
trans-1,4-Dimethylcyclohexane
Ethylcyclohexane
1-Octene
Propylcyclopentane
1,1,3-Trimethylcyclopentane
n-Octane
2,2,4-Trimethylpentane
2,3,4-Trimethylpentane
Indan
1-Ethyl-2-methylbenzene
Isopropylbenzene
1,8-Nonadiyne
Propylbenzene
1,2,3-Trimethylbenzene
1,2,4-Trimethylbenzene
1,2,5-Trimethylbenzene
1-Nonyne
1-Nonene
1,1,3-Trimethylcyclohexane
4-Methyloctane
Nonane

298.20
293.20
298.15
298.20
273.20
288.20
298.20
298.20
298.20
298.20
273.20
273.20
273.20
278.30
278.30
286.20
298.20
278.30
293.20
283.20
298.20
298.20
273.20
273.20
273.20
273.20
298.20
278.30
298.20
273.20
298.20
298.20
298.20
298.20
298.20
293.20
296.70
283.20
298.20
273.20
298.15
273.20
273.20
279.20
273.20
273.20
273.20
273.20
298.15
293.15
298.15
298.15
298.15
330.15
298.15
310.90
298.20
298.15
298.15
273.20
273.20
273.20
298.15
298.15
273.20
298.15
273.20
288.20
288.20
288.20
298.15
298.15
298.15
298.15
298.20

308.40
333.20
298.15
298.20
426.30
333.20
298.20
298.20
298.20
298.20
313.20
308.20
527.20
318.40
318.40
298.20
298.20
482.20
494.30
298.20
298.20
298.20
298.20
422.80
425.00
422.70
298.20
318.40
298.20
548.20
298.20
298.20
298.20
298.20
303.20
303.20
298.20
410.50
298.20
298.20
423.55
423.60
298.20
338.20
506.70
318.20
543.80
555.70
298.15
360.15
298.15
298.15
298.15
513.15
298.15
552.80
477.60
298.15
298.15
552.80
298.20
298.20
298.15
298.15
353.40
298.15
359.00
318.20
318.20
373.20
298.15
298.15
298.15
298.15
298.20

1.410E04
1.440E04
1.480E04
2.780E04
4.000E05
6.060E05
3.340E05
3.800E05
5.210E05
8.300E06
1.170E05
9.600E06
3.350E04
1.570E04
4.670E05
3.700E05
7.890E05
1.100E05
9.200E06
8.950E06
1.700E05
1.000E05
3.850E06
3.990E06
2.090E06
2.720E06
2.680E06
1.136E04
3.230E04
9.200E05
1.200E05
8.200E06
1.760E05
9.700E06
4.990E06
3.340E06
2.700E06
2.700E06
9.430E07
6.500E07
1.060E06
4.070E07
8.890E07
4.300E05
2.480E05
2.850E05
2.400E05
2.650E05
8.300E06
3.000E04
4.400E06
1.270E06
9.600E07
2.700E06
6.160E07
2.400E06
4.000E07
3.270E07
5.990E07
8.260E08
1.800E07
3.620E07
1.350E05
1.122E05
8.920E06
1.900E05
6.860E06
8.970E06
7.770E06
5.910E06
1.000E06
1.600E07
2.530E07
1.600E08
1.710E08

4.620E04
2.290E04
1.480E04
4.150E04
2.040E04
9.300E05
3.340E05
3.800E05
5.210E05
8.300E06
1.810E05
1.640E05
1.540E02
2.270E04
6.810E05
3.700E05
7.890E05
4.930E04
7.300E04
9.600E06
1.700E05
1.000E05
4.970E06
3.370E05
2.320E05
2.360E05
2.740E06
1.495E04
3.230E04
1.290E02
1.200E05
8.200E06
1.760E05
9.700E06
5.500E06
5.700E06
2.750E06
2.550E05
9.430E07
1.170E06
1.548E05
7.860E06
9.410E07
1.000E04
1.930E03
4.080E05
5.000E03
7.624E03
8.300E06
1.490E02
4.400E06
1.270E06
9.600E07
4.120E04
6.160E07
2.370E03
9.100E05
3.270E07
5.990E07
6.000E04
3.880E07
3.690E07
1.665E05
1.122E05
2.420E05
1.900E05
1.980E05
1.280E05
1.040E05
2.910E05
1.000E06
1.600E07
2.530E07
1.600E08
1.710E08

4
6
1
2
10
7
1
1
1
1
7
16
153
6
10
2
1
19
10
4
1
1
4
9
23
12
3
7
1
113
1
1
1
1
2
5
2
9
1
6
8
17
3
12
82
11
30
25
1
3
1
1
1
4
1
5
4
1
1
16
5
3
2
1
19
1
29
6
7
17
1
1
1
1
2

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

15

Table 1 (Continued)
Component

Tmin (K)

Tmax (K)

xhc, min

xhc, max

2,2,5-Trimethylhexane
Naphthalene (*)
1,2,3,4-Tetrahydronaphthalene
Butylbenzene
sec-Butylbenzene
tert-Butylbenzene
p-Cymene
1,2-Diethylbenzene
1,3-Diethylbenzene
1,4-Diethylbenzene
Isobutylbenzene
1,2,4,5-Tetramethylbenzene (*)
d-Limonene
cis-Decalin
1-Butylcyclohexane
1-Decene
Pentylcyclopentane
Decane
1-Methylnaphthalene
2-Methylnaphtalene (*)
Pentylbenzene
tert-Pentylbenzene
2-Methyldecalin
Undecane
Acenaphthylene (*)
Biphenyl (*)
1,3-Dimethylnaphthalene
1,4-Dimethylnaphthalene
1,5-Dimethylnaphthalene (*)
2,3-dimethylnaphthalene (*)
2,6-Dimethylnaphthalene (*)
1-Ethylnaphthalene
2-Ethylnaphthalene
1,4-Diisopropylbenzene
Hexylbenzene
Dodecane
Fluorene (*)
Diphenylmethane (*)
4-Phenyltoluene (*)
1,4,5-Triphenylnaphthalene (*)
Anthracene
Phenanthrene (*)
trans-Stilbene (*)
4,4 -Dimethyl-1,1 -biphenyl (*)
Tetradecane
2-Methylanthracene (*)
9-Methylanthracene (*)
1-Methylphenanthrene (*)
Fluoranthene (*)
Pyrene (*)
9,10-Dimethylanthracene (*)
Hexadecane
Benzo[a]uorene (*)
Benzo[b]uorene (*)
Benz[a]anthracene (*)
Chrysene (*)
Naphthacene
Triphenylene (*)
1,2-Diphenylbenzene (*)
1,3-Diphenylbenzene (*)
1,4-Diphenylbenzene (*)
Octadecane (*)
1-Methylbenz[a]anthracene (*)
9-Methylbenz[a]anthracene (*)
10-Methylbenz[a]anthracene (*)
5-Methylchrysene (*)
Benzo[a]pyrene (*)
Benzo[e]pyrene (*)
Perylene (*)
Cholanthrene (*)
7,12-Dimethylbenz[a]anthracene (*)
9,10-Dimethylbenz[a]anthracene (*)
10-Ethylbenz[a]anthracene (*)
Eicosane (*)
5-Methylbenzo[a]pyrene (*)
Methylcholanthrene (*)
Benzo[ghi]perylene (*)

273.20
273.20
424.70
280.20
283.20
283.20
283.20
283.15
310.93
283.15
298.15
298.15
423.00
374.15
310.93
288.20
298.15
293.20
273.20
298.20
280.20
298.15
298.15
298.20
273.20
273.20
298.15
298.15
298.20
298.20
298.20
281.80
298.15
310.93
278.20
298.20
273.20
298.15
278.05
298.15
273.20
273.20
298.15
277.15
298.00
279.40
298.15
279.75
281.00
273.20
298.15
293.00
298.15
298.15
280.10
280.00
298.00
298.00
298.15
298.15
298.15
298.15
300.15
300.15
300.15
300.15
298.00
281.75
298.15
300.15
298.15
300.15
300.15
298.15
300.15
298.00
298.15

273.20
348.20
573.20
373.20
298.20
298.20
473.00
293.15
549.82
293.15
298.15
298.15
423.00
576.15
549.82
576.20
298.15
298.20
589.40
298.20
318.20
298.15
298.15
298.20
348.20
337.70
298.15
298.15
298.20
298.20
298.20
549.80
298.15
549.82
318.20
298.20
348.20
298.15
313.15
298.15
348.20
348.20
298.15
313.15
298.00
304.20
298.15
303.05
303.00
348.20
298.15
298.00
298.15
298.15
302.90
302.00
300.00
300.00
298.15
298.15
298.15
298.15
300.15
300.15
300.15
300.15
300.00
304.85
298.15
300.15
298.15
300.15
300.15
298.15
300.15
300.00
298.15

1.110E07
1.696E06
9.000E03
1.740E06
2.360E06
3.950E06
4.300E05
9.600E06
4.300E06
3.330E06
1.350E06
4.670E07
2.100E05
4.100E07
1.900E07
5.100E07
1.500E08
2.500E09
2.520E06
3.120E06
3.860E07
1.270E06
4.820E09
4.100E10
1.690E07
3.081E07
9.200E07
1.310E06
3.158E07
2.290E07
1.499E07
9.400E07
9.220E07
3.700E07
9.180E08
4.000E10
7.200E08
1.510E07
1.960E07
2.150E07
1.280E09
3.649E08
2.000E08
6.870E09
2.100E10
6.610E10
2.440E08
8.921E09
1.200E08
4.382E09
4.900E09
7.000E11
3.750E09
9.560E10
2.360E10
5.600E11
3.700E11
3.000E09
9.720E08
1.185E07
1.410E09
1.500E10
4.100E11
4.500E11
4.100E11
4.600E09
2.700E10
2.320E10
2.830E11
2.500E10
4.260E09
3.000E09
3.200E09
1.100E10
6.000E11
1.000E10
1.730E11

1.110E07
3.629E05
9.000E03
1.120E05
2.360E06
4.600E06
2.000E04
9.600E06
3.070E03
3.330E06
1.350E06
4.670E07
2.100E05
8.800E05
4.230E04
7.300E05
1.500E08
2.500E09
7.800E02
3.220E06
5.750E07
1.270E06
4.820E09
5.070E10
4.970E06
5.358E06
9.200E07
1.310E06
3.770E07
3.470E07
2.331E07
1.490E03
9.220E07
7.100E04
1.450E07
4.000E10
2.680E06
1.510E07
7.590E07
2.150E07
1.240E07
1.740E06
2.000E08
4.390E08
2.100E10
3.670E09
2.440E08
3.326E08
9.500E07
2.060E07
4.900E09
5.000E10
3.750E09
9.560E10
1.000E09
1.700E10
7.900E11
3.400E09
9.720E08
1.185E07
1.410E09
1.500E10
4.100E11
4.500E11
4.100E11
4.600E09
3.400E10
4.860E10
2.830E11
2.500E10
4.260E09
3.000E09
3.200E09
1.100E10
6.000E11
1.900E10
1.730E11

# points
2
63
2
25
2
3
3
2
7
2
1
1
1
5
6
8
1
3
23
2
12
1
1
3
23
25
1
1
2
2
2
22
1
8
33
2
28
1
3
1
49
49
1
3
1
10
1
7
14
38
1
5
1
1
15
9
2
4
1
1
1
1
1
1
1
1
3
12
1
1
1
1
1
1
1
2
1

16

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Table 1 (Continued)
Component

Tmin (K)

Tmax (K)

xhc, min

xhc, max

Dibenz[a,h]anthracene (*)
Dibenz[a,j]anthracene (*)
Picene (*)
10-Butylbenz[a]anthracene (*)
7-Pentylbenz[a]anthracene (*)
Coronene (*)
Hexacosane (*)
Hexatriacontane (*)

298.00
300.15
300.15
300.15
300.15
298.15
298.15
298.15

300.00
300.15
300.15
300.15
300.15
298.15
298.15
298.15

3.000E11
7.800E10
1.600E10
5.100E10
5.000E11
8.560E12
8.000E11
6.100E11

3.900E11
7.800E10
1.600E10
5.100E10
5.000E11
8.560E12
8.000E11
6.100E11

important subset of the experimental data, the hydrocarbon critical temperature is greater than that of water and these mixtures
exhibit Type IIIb phase behaviour; for example, large n-alkanes
(C26 and above), indene, and heavy oils [29]. For these latter
cases, simple models spanning from ambient conditions to conditions near the critical temperature of water are not valid because
they only account for the interactions of sub- or near-critical
hydrocarbon-rich liquid phases with a far from critical water-rich
liquid phase (Type II and Type IIIa behaviour). These interactions
with the water-rich liquid phase differ markedly from those of a
hydrocarbon-rich liquid phases remote from their critical points
with a near critical water-rich liquid phase (Type IIIb). Hence, at
high temperatures, the properties of mixtures exhibiting Type II
and Type IIIa phase behaviour are expected to diverge from Type
IIIb mixtures.
Heavy oils and bitumen are ill-dened and the uncertainty of
basic properties including their average molecular weight is signicant. Molecular weights are typically measured with vapour
pressure osmometry or freezing point depression methods and are
repeatable to only 15%. In addition, some asphaltenic components
in the oil self-associate and the nature of the association and its
dependence on temperature, pressure, and composition is not well
understood [30]. The solubility models reported in this work are
based on mole fractions which are determined from mass fractions and average molecular weights for these uids. Therefore,
systematic errors in molecular weights of ill-dened constituents
introduce bias into the model vis--vis experimental solubility
measurements.
With an initial focus on the Type II and Type IIIa data, a perturbation approach and an innite dilution activity coefcient approach
were tested. Perturbation methods have been used successfully for
the modelling of hydrocarbon systems [31] while innite dilution
activity coefcients provide a simple, thermodynamically based
way to estimate solubilities. The development of each approach
is described below.

ln x
h
=
R
(1/T )

ln x = p0 + p1

1
T

(1)

where x is mole fraction, T is absolute temperature, h is the heat

of solution, and R is the universal gas constant. Note, Eq. (1) is
a simplication of the actual thermodynamic process of dissolving materials in water since it neglects the formation of hydrogen
bonding and the resulting existence of a hydrocarbon solubility
minimum at around 298.15 K and 101.325 kPa. The shortcomings of
this equation can be alleviated by allowing the enthalpy of solution
to be a function of temperature as described below. It is also noted
that as temperatures and pressures increase the physico-chemical
nature of water changes due to the reduction of its dielectric

1
T0

+ p2

T

+ ln

T
1
T0

(2)

where p0 , p1 , and p2 are empirical constants unique to each

hydrocarbon and phase. To make the model universal for all
hydrocarbons, the empirical parameters in Eq. (2) are dened as
perturbations around values determined based on parafn data
only as:
pi = p0i fi2 gi2

(3)

The perturbation functions f and g are dened based on differences between the specic gravity and Watson-K factor between
the hydrocarbon of interest and an equivalent parafn that boils at
the same temperature as the hydrocarbon of interest. The specic
gravity SG is dened as the uid density divided by the density of
liquid water at 60 F and 1 atm. The Watson-K factor is dened as the
cubic root of the normal boiling point in R divided by the specic
gravity. The specic gravity provides a coarse measure of molecular size while the Watson-K factor provides a coarse measure of
the aromaticity of a hydrocarbon. They are also commonly available properties coming from the oil characterization procedure and
therefore available when using the method to estimate solubilities.
The perturbation functions take the form of Pade approximants as
suggested by Twu [31] where he successfully used perturbation
theory to correlate critical temperatures, pressures, and volumes
of many hydrocarbons:
fi =

gi =

fi0

This model for the solubility of both hydrocarbons in water

and water in hydrocarbons was based on the heat of solution as
expressed using standard thermodynamics:

2
1
1
1
1
1
1
1

constant, an effect not captured in the simple model proposed in

this work.
Eq. (1) can be expanded by allowing the enthalpy of solution to
vary with temperature as:

1 + 2fi0

(4)

1 2fi0
1 + 2gi0

(5)

1 2gi0

3.1. Model 1: Perturbation method

# points


bi

= SG

SG = e(SG

0 SG)

Kw = e

ci +

bi

= Kw

gi0

Tb

Tb

di

ci +

Tb

di

Tb

(Kw 0 Kw )


SG

(6)


Kw

(7)

(8)

(9)

The model parameters for the water in hydrocarbon solubility

model are bi , ci , di , and , where i goes from 1 to 3 in accordance
with Eq. (2). The parameters are determined through non-linear
regression using the objective function given by:
OFwater =

np

i=1

 
ln

calc
xi,water
IUPAC
xi,water

 2

(10)

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

17

Table 2
Summary of components and conditions in the data set used for development of water in hydrocarbon solubility model (T, temperature; xw , water mole fraction).
Component

Tmin (K)

Tmax (K)

xw, min

xw, max

# points

2-Methyl-1,3-butadiene
Cyclopentane
2-Methyl-2-butene
2-Methylbutane
n-Pentane
Benzene
Cyclohexene
1,5-Hexadiene
Cyclohexane
2,3-Dimethyl-1-butene
1-Hexene
Methylcyclopentane
2,2-Dimethylbutane
2,3-Dimethylbutane
Hexane
2-Methylpentane
3-Methylpentane
1,3,5-Cycloheptatriene
2,5-Norbornadiene
Toluene
Ethylcyclopentane
1-Heptene
Methylcyclohexane
2,4-Dimethylpentane
n-Heptane
2-Methylhexane
3-Methylhexane
2,2,3-Trimethylbutane
Styrene
Ethylbenzene
o-Xylene
m-Xylene
p-Xylene
1-Propenylcyclopentane
1,7-Octadiene
Ethylcyclohexane
Isopropylcyclopentane
1-Octene
2,4-Dimethylhexane
3-Methylheptane
n-Octane
2,2,4-Trimethylpentane
2,3,4-trimethylpentane
Isopropylbenzene
Butylcyclopentane
2,6-Dimethylheptane
2-Methyloctane
3-Methyloctane
Nonane
2,2,5-Trimethylhexane
1,2,3,4-Tetrahydronaphthalene
Butylbenzene
sec-Butylbenzene
tert-Butylbenzene
p-Cymene
Diethylbenzene
1,3-Diethylbenzene
cis-Decalin
1-Butylcyclohexane
1-Decene
Decane
2,7-Dimethyloctane
1-Methylnaphthalene
2-Ethyl-1,3,5-trimethylbenzene
Hexylcyclopentane
Undecane
1-Ethylnaphthalene
2-Allyl-1,3,5-trimethylbenzene
1,4-Diisopropylbenzene
2-Propyl-1,3,5-trimethylbenzene
Dodecane
(2-Ethylcyclopentyl)benzene
Cyclopentyloctane
Tridecane
1,4-Dicyclopentylbutane
2,4,6-Trimethyl-2-phenylheptane

293.20
273.20
293.20
283.20
278.70
276.20
293.20
286.20
283.20
303.15
293.20
283.20
273.20
273.20
273.20
273.20
298.20
303.20
293.15
273.20
283.15
293.20
283.20
273.20
273.20
283.15
273.20
273.15
279.20
273.20
273.20
273.20
298.20
298.15
293.15
310.90
283.15
310.90
283.15
298.15
273.20
273.20
273.20
273.20
283.15
283.15
283.15
283.15
298.20
273.20
424.70
283.20
283.20
283.20
283.20
273.15
310.93
374.15
310.93
374.20
298.20
283.15
273.20
293.15
283.15
298.20
366.50
293.15
310.93
293.15
298.20
283.15
283.15
298.15
283.15
283.15

333.20
313.20
333.20
333.20
298.00
523.20
313.20
293.20
473.20
303.15
420.40
303.20
273.20
313.20
477.60
273.20
298.20
323.20
323.15
548.20
303.15
303.20
303.20
273.20
313.20
303.15
273.20
323.15
324.20
568.10
298.20
473.40
373.20
298.15
360.15
561.40
303.15
549.80
303.15
298.15
550.40
298.20
298.20
323.20
303.15
323.15
303.15
303.15
298.20
298.20
595.90
373.20
303.20
283.20
303.20
323.15
582.54
599.09
584.32
475.20
576.20
303.15
589.40
313.15
303.15
313.20
594.40
313.15
589.98
313.15
313.20
303.15
303.15
313.15
303.15
303.15

2.260E03
1.790E04
1.510E03
2.370E04
1.440E04
1.300E03
1.440E03
2.810E03
1.600E04
2.140E03
1.600E03
3.400E04
1.530E04
1.400E04
1.340E04
1.380E04
4.500E04
3.210E03
1.510E03
1.170E03
3.870E04
1.360E03
3.330E04
1.730E04
1.450E04
3.120E04
1.390E04
1.500E04
1.800E03
2.600E05
1.090E03
1.110E03
2.590E03
2.340E03
2.000E04
8.100E04
3.680E04
1.680E03
3.360E04
1.250E07
1.460E04
1.460E04
1.270E04
1.040E03
3.930E04
3.770E04
3.700E04
3.560E04
5.600E04
1.780E04
4.400E02
1.740E03
2.230E03
2.030E03
1.660E03
1.570E03
3.420E03
9.700E03
7.390E04
1.330E02
5.200E04
3.790E04
1.590E03
2.130E03
4.450E04
6.000E04
2.120E02
1.150E03
1.570E03
2.290E03
6.100E04
1.000E03
4.860E04
6.100E04
9.400E04
1.160E03

5.530E03
1.548E03
3.520E03
2.340E03
4.810E04
3.940E01
2.560E03
4.370E03
7.930E02
2.140E03
4.329E02
9.580E04
1.530E04
1.540E03
1.403E01
1.380E04
4.500E04
5.060E03
3.440E03
5.690E01
1.014E03
2.040E03
1.920E03
1.730E04
9.570E04
1.012E03
1.390E04
2.815E03
7.100E03
6.910E01
2.680E03
1.510E01
2.020E02
2.340E03
5.000E04
6.030E01
9.900E04
5.380E01
1.141E03
1.250E07
5.490E01
5.070E04
4.690E04
4.720E03
1.058E03
3.302E03
1.110E03
1.103E03
5.600E04
5.340E04
9.390E01
1.990E02
4.200E03
2.030E03
3.080E03
7.430E03
7.760E01
7.910E01
7.500E01
1.280E01
6.060E01
1.200E03
9.220E01
3.780E03
1.207E03
1.130E03
9.270E01
2.040E03
8.330E01
4.090E03
1.200E03
2.640E03
1.234E03
1.260E03
2.590E03
3.050E03

3
5
4
5
4
127
3
2
22
1
4
3
1
6
25
1
1
3
3
69
3
2
5
1
10
4
1
6
10
35
3
15
11
1
2
7
3
6
3
1
12
5
2
6
3
5
3
3
1
2
4
11
3
1
3
6
7
6
7
3
15
3
13
3
3
2
6
3
7
3
2
3
3
2
3
3

18

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Table 2 (Continued)
Component

Tmin (K)

Tmax (K)

xw, min

xw, max

7,8-Dimethyltetradecane
Hexadecane
Coalinga
Huntington Beach
Peace River
Cat Canyon
Athabasca Bitumen

293.15
293.00
450.62
413.31
450.62
432.45
548.2

323.15
323.00
556.98
560.33
555.98
561.34
633.8

9.670E04
8.670E04
0.08927
0.1228
0.1683
0.2499
0.5398

4.309E03
4.160E03
0.5164
0.5026
0.5108
0.5913
0.8455

The model parameters for the hydrocarbon in water solubility

model are a different set of bi , ci , di , and determined using the
objective function given by:


np

OFhc =

i=1

 
ln

calc
xi,hc

 2
(11)

IUPAC
xi,hc

The optimized model parameters for Eqs. (8) and (9) for the solubility of hydrocarbon in water are summarized in Table 3. The
optimized exponents in Eqs. (8) and (9) are = 2.053 and = 4.531.
3.2. Model 2: Innite dilution activity coefcient approach
This model was developed based on the well-known fact that
for sparingly soluble mixtures the solubility can be estimated as
the inverse of the innite dilution activity coefcient,  :
1
xi
i

(12)

where i represents the solute, for example benzene in water or

water in benzene and i is the innite dilution activity coefcient
on i in solvent (water or hydrocarbon). An assumption implicit in
Eq. (12) is that both water and hydrocarbons are liquids. Thus,
solid hydrocarbons, designated with an asterisk (*) in Table 1,
were excluded from data regression and parameter evaluation for
the development of Model 2. The NRTL model [32] was selected
as the basic thermodynamic platform to determine the activity
coefcients. NRTL is a well-known model capable of representing
complex phase equilibria, including water and hydrocarbon mutual
solubilities. The activity coefcient at innite dilution when calculated using the NRTL model is given by:
ln i = is eis is + si

(13)

where  is is the interaction parameter between solute i and solvent s,  si is the interaction parameter between the solvent s and
solute i, is is the NRTL non-randomness parameter and subscript
s represents the solvent, for example water or benzene.
The interaction between solute and solvent requires an empirical temperature dependency given by:
is = ais +

bis
+ cis ln T
T

(14)

Finally the interaction energy between solvent and solute,  si , must

be dened. It was found that a simple, temperature independent
Table 3
Parameters for perturbation expansion specic gravity term (f) and Watson K term
(g).
Parameter

f0o
f1o
f2o
g0o
g1o
g2o

10.13
0.03103
4.320
1.386
0.4461
2.171

1.461
0.9219
3.254
0.01177
0.003946
0.3755

36.26
0.02603
0.1027
0.2144
0.008514
5.251

# points
4
4
6
7
6
7
8

Table 4
NRTL model parameters for the estimation of hydrocarbon (i) solubility in water (s).
Parameter

A
B
C
D
E

0.4264
295.9
1.4561
0.5850
475.3

5.086
187.4
0.9645
0.4342
277.0

0.2732
18.85
0.08160
0.07145
37.62

form was adequate for the correlation of both solubilities of hydrocarbons in water and solubilities of water in hydrocarbon. The
interaction parameters are generalized as a function of specic
gravity and Watson-K as follows.
ai,s = a1,s + a2,s SG + a3,s WK

(15)

bi,s = b1,s + b2,s SG + b3,s WK

(16)

ci,s = c1,s + c2,s SG + c3,s WK

(17)

i,s = d1,s + d2,s SG + d3,s WK

(18)

s,i = e1,s + e2,s SG + e3,s WK

(19)

The model was optimized using Eqs. (10) and (11) as described for
Model 1. The optimized parameters for hydrocarbon in water and
water in hydrocarbon solubilities are summarized in Tables 4 and 5,
respectively.
The NRTL interaction parameters used for the correlation of solubility data (Eqs. (15)(19)) are not directly applicable to a similar
NRTL model used for phase equilibrium calculations since the  s,i
term is used as a correlating parameter in the development of the
solubility model. From a purely thermodynamic point of view it
should be calculated through the use of the corresponding interaction parameters that would model the solubility of solvent in solute.
For example, the NRTL term  s,i (where i is for hydrocarbon and s
is for water) was used as a correlating parameter without worrying about the actual accuracy of the estimated solubility of water
in hydrocarbon. Ideally one should regress mutual solubility data
simultaneously over a range of temperatures to develop an entirely
self-consistent model. Unfortunately the state of the experimental
data does not allow for such a regression at this time. When using
the proposed model for phase equilibrium calculations as commonly found in process simulation one should use the method to
calculate mutual solubility data at desired temperatures and then
regress these data to the desired thermodynamic model as will be
shown later.
Table 5
NRTL model parameters for the estimation of water solubility in hydrocarbons.
Parameter

A
B
C
D
E

80.55
1393
6.912
0.01890
57.47

10.05
2966
7.097
0.01282
74.82

4.332
391.9
0.9115
0.001026
3.841

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

1.E+00

1.E-03

1.E-06

1.E-09

(a)

Calculated Solubility, Mole Fr.

Calculated Solubility, Mole Fr.

1.E+00

19

1.E-01

1.E-02

1.E-03

(b)

1.E-12

1.E-04

1.E-12

1.E-09

1.E-06

1.E-03

1.E+00

Measured Solubility, Mole Fr.

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

Measured Solubility, Mole Fr.

Fig. 1. Error dispersion plots for mutual solubilities of hydrocarbons and water from Model 1: (a) hydrocarbon in water and (b) water in hydrocarbon.

4. Results and discussion

4.1. Model 1: Perturbation approach
At rst glance, Table 6 and Fig. 1, the results for Model 1 were
encouraging with an average absolute percent error equal to 122%,
in the water-rich phase, and 45% in the hydrocarbon-rich phase. An
illustrative example, the predictions for the mutual solubilities of
cyclohexane and water are shown in Fig. 2. To put these deviations
in perspective, consider that the data span 10 orders of magnitude and include 160 different hydrocarbons for the modelling of
hydrocarbon in water solubilities and 78 different hydrocarbons
for the modelling of water in hydrocarbon solubilities as shown in
Table 1.
Although reasonably good results were obtained, recent simulation data [33] suggests that there is a problem with n-parafn
data for carbons numbers above approximately 10. Simulation data
suggests a smooth, regularly decreasing logarithm of solubility
with increasing carbon numbers but the data show a minimum
in solubility around carbon number equal to C16. There is significant dispersion in the data, undoubtedly caused by the very low
concentrations being measured and the associated experimental

Solute Mole Fraction

1.E+00
1.E-01

in HC
in water

1.E-02

Model 1
Model 2

difculties. Since the perturbation method is based on a reliable

reference system it was decided to focus on the innite dilution activity coefcient approach instead. The denition of the
correct solubility trend for parafns above C10 is an important
problem from a practical and theoretical point of view with obvious implications for new model development. If this problem is
resolved, then we recommend revisiting the perturbation modelling approach.

4.2. Model 2: Innite dilution activity coefcient approach

The second model avoids the problem with reference data
encountered with Model 1 and provides better results as shown
in Table 7 and Fig. 3, albeit with a reduced data set. For example, the predictions for the mutual solubilities of cyclohexane and
water compare well with the predictions from Model 1 (Fig. 2).
Two additional examples illustrate the performance of Model 2.
The data for water solubility in benzene are extensive and the
Model 2 t is within the error of the data (Fig. 4). The data for 1methylnaphthalene in water are sparse and inconsistent (Fig. 5). In
this case, the model systematically under-predicts the data but the
error is compounded by the inconsistencies in the data. The large
errors are caused by a relatively small number of compounds such
as 1,7-octadiene (1.49 102 versus 2.49 106 ) at 360.15 K and
1-decene (7.3 105 versus 4.9 108 ) at 298.2 K. The error and
bias for water solubility in hydrocarbons are both much smaller.
The solubility data set ranges over only 4 orders of magnitude and
the values themselves are larger. The error and bias are again dominated by a small fraction of the data. More than 360 points out of
621 points are t to within 15% with a bias of less than 4%.

1.E-03
4.3. Integration of Model 2 with other thermodynamic models

1.E-04
1.E-05
1.E-06
200

400
300
Temperature, K

500

Fig. 2. Mutual solubilities of n-hexane and water including data, and calculated
values based on Model 1 and Model 2.

The innite dilution activity coefcient approach, Model 2, can

be easily adapted for use within a process simulation environment
through the generation of mutual solubility tables as a function of
temperature. These synthetic datasets can then be regressed to
obtain equation of state or activity coefcient model parameters
and used directly in simulations. As the availability of data below
298 K and above 398 K is limited, Figs. 6 and 7, it is recommended
to perform these calculations within this temperature range and
to extrapolate outside this temperature range using a consistent
phase equilibrium model.

20

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Table 6
Summary of Model 1 optimization statistics.
Solvent phase

Number of points

Average absolute relative deviation (%)

Error bias (%)

Water
Hydrocarbon

1318
621

122
45

83
24

Table 7
Summary of Model 2 optimization statistics.
Solvent phase

Number of points

Average absolute relative deviation (%)

Error bias (%)

Water
Hydrocarbon

964
621

87
30

61
11

1.E+00
Calculated Solubility, Mole Fr.

Calculated Solubility , Mole Fr.

1.E+01

1.E-02

1.E-05

1.E-08

1.E-01

1.E-02

1.E-03

(a)

(b)
1.E-04

1.E-11
1.E-11

1.E-08

1.E-05

1.E-02

1.E+01

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

Measured Solubility, Mole Fr.

Measured Solubility, Mole Fr.

Fig. 3. Error dispersion plots for mutual solubilities of hydrocarbons and water from the innite dilution activity coefcient model (Model 2): (a) hydrocarbon in water and
(b) water in hydrocarbon.

4.4. Examples of Model 2 implementation

4.4.1. Example 1 solubility of water in kerosene
This example illustrates how to use solubility tables generated
with the innite dilution activity coefcient model in a process simulation involving a petroleum derived uid, specically kerosene.
The purpose is to demonstrate how the model can be integrated

1.E-01
1-Methyl Naphthalene Mole Fraction

1.E+00
data
Solute Mole Fraction

Model 2
1.E-01

1.E-02

1.E-03
200

with any thermodynamic model of interest capable of producing

two liquid phases. Solubilities of water in kerosene at high temperatures were reported by Griswold and Kasch [34]. The physical
properties of the kerosene are summarized in Table 8. From the
boiling curve, the critical temperature of the kerosene is expected
to be below that of water and the model is expected to conform

1.E-02

1.E-03

1.E-04

1.E-05

1.E-06

300

400

500

600

Temperature, K
Fig. 4. Solubility of water in benzene calculated using the innite dilution activity
coefcient model (Model 2).

200

300

400

500

600

Temperature, K
Fig. 5. Solubility of 1-methylnaphthalene in water calculated using the innite dilution activity coefcient model (Model 2).

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

(A)

21

600

Frequency

500
400
300
200
100

250
270
290
310
330
350
370
390
410
430
450
470
490
510
530
550
570
590
610
630
650

Temperature, K
0.4
0.35

10

data
NRTL

Saturation Pressure, MPa

Waer Solubility, Mole Fraction

(B)

0.3
0.25
0.2
0.15
0.1
0.05

(a)

data

NRTL

7
6
5
4
3
2
1

(b)

0
350

400

450

500

550

600

350

400

Temperature, K

450

500

550

600

Temperature, K

Fig. 6. (A) Temperature frequency distribution for experimental hydrocarbon solubility. (B) Measured [34] and modelled (Model 2) solubility of water in kerosene (a) and
saturation pressure (b). The kerosene was characterized using the four cuts described in Table 9.

with the data. The simulation was performed on the VMGSim process simulator [35] using the NRTL model for the phase equilibrium
calculations. Note that the NRTL model used for phase equilibrium calculations is not identical to the model used to correlate
the hydrocarbon in water and water in hydrocarbon solubilities
and previously discussed.
The recommended procedure to determine thermodynamic
model parameters from the solubility model is summarized below:

(A)

(B)

160

Calculated Solubility, Mole Fr.

140
120

Frequency

1. Characterize the petroleum into a set of pseudo-components.

In this case, the kerosene distillation data was cut into 4
pseudo-components and the properties of each cut were
determined using the oil characterization package from the
process simulator VMGSim (Table 9). Default values for
the determination of number of pseudo components and
pseudo component physical property information were used
[35].

100
80
60
40
20

0.8

0.6

0.4

0.2

0
250
270
290
310
330
350
370
390
410
430
450
470
490
510
530
550
570
590
610
630
650

Temperature, K

0.2

0.4

0.6

0.8

Measured Solubility, Mole Fraction

Fig. 7. (A) Temperature frequency distribution for experimental water solubility in hydrocarbons. (B) Error dispersion plot for measured solubilities of water in Coalinga,
Huntington Beach, Peace River and Cat Canyon calculated according to Model 2.

22

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

Table 8
Physical properties of kerosene [34].

Table 11
Heavy oil physical properties.

Property

Value

Oil

Specic gravity

Molecular weight (g/mol)

Reference

API gravity
Molecular weight (g/mol)
Watson K
IBP
10%
20%
30%
40%
50%
60%
70%
80%
90%
FBP

42
173
11.8
475.93 K
487.04 K
491.48 K
494.26 K
497.59 K
500.93 K
503.15 K
505.93 K
509.82 K
515.37 K
528.71 K

Coalinga
Huntington Beach
Peace River
Cat Canyon
Athabasca bitumen

1.00
0.97
1.02
1.03
1.02

439
442
571
678
550

[36]
[36]
[36]
[36]
[37]

water solubility and saturation pressures compare well with the

measured values, Fig. 6a and b respectively. The average absolute
relative deviation for the solubilities of water in kerosene is 46%
(0.03 mole fraction). The average absolute deviation for the saturation pressures is 122 kPa.

2. Generate a table of mutual solubilities from 25 C to 125 C for

each oil cut with water using the innite dilution activity coefcient model (four tables altogether). The temperature steps for
solubility calculations are arbitrary but we found out that 25 C
steps were adequate in most situations.
3. Regress the NRTL interaction parameters for each of the oil
cut/water binaries using an objective function constructed based
on liquidliquid equilibrium given by:



npoints nc

OF =

i=1

(xihc ihc xiw iw )

(20)

j=1

It is recommended that the interaction parameters,  ij be made

a function of temperature:
ij = aij +

bij
T

+ cij ln T

(21)

Note that any reasonable temperature dependency could be used

as commonly found in thermodynamic models supported by
different process simulators. In the case of NRTL one needs to
choose a value for the non-randomness parameter, or use it as a
tting parameter. Here a xed value, 0.2, was used.
4. Install the NRTL interaction parameters in the simulator for ash
calculations.
Note, once the solubility tables are generated, the proposed procedure can be applied to any thermodynamic model, be it activity
coefcient based or equation of state based.
The interaction parameters determined using this procedure
for kerosene and water are summarized in Table 10. With the
thermodynamic model completed, it is straightforward to calculate saturation conditions and mutual solubilities using standard
ow sheeting tools such as ashes and case studies. The estimated

4.4.2. Example 2 solubility of water in heavy oils

In this example, the applicability of the proposed method is
evaluated for uids (heavy oils) that consist of ill-dened components with properties outside the range of the data used to
construct the model; that is, pseudo binary mixtures exhibiting
Type IIIb behaviour. First, Model 2 predictions are computed for
Glandt and Chapmans [36] solubility data for water in several
heavy oils at temperatures well below the critical temperature of
water (Table 2). The oil physical property data are summarized in
Table 11. The oils were characterized as single pseudo-components
and Model 2 was directly used to calculate the solubility of water in
the hydrocarbon rich phase. The average absolute relative deviation
for the water solubility is 26% with a bias of 1.0%, as illustrated in
Fig. 7. A comparison of the model predictions with the measured
water solubility in Peace River bitumen, Fig. 8, also at temperatures
well below the critical temperature of water, demonstrates that
the model predicts water solubility within the error of the measurements and that much of the deviation reects scatter in the
data.
Alternately, Model 2 can be used to produce mutual solubility
points and then NRTL interaction parameters determined following the procedure used to construct the kerosenewater model. The
calculated NRTL interaction parameters are provided in Table 12a.
The average absolute relative deviation for the water solubility is
30.8% with a bias of 28.1%. This under-prediction is not surprising
given that Model 2 was used to estimate solubility data only from
298 K to 398 K and the NRTL parameters generated using this temperature range were then used to estimate the water solubility at
much higher temperatures.
The prediction of data from Amani et al. [38] for water solubility in Athabasca bitumen is an interesting test for the model
since the data were obtained at temperatures and pressures approaching the critical temperature of water as shown in Table 12a. The
highest temperature points were measured within a few degrees

Table 9
Kerosene pseudo-component properties.
Cut

Mole fraction

Standard density (kg/m3 )

Normal boiling point (K)

Tc (K)

Pc (kPa)

Watson K

1
2
3
4

0.1601
0.4773
0.2858
0.0768

805.8
812.9
819.0
826.9

483.85
497.15
508.95
523.15

672.5
685.6
679.3
711.2

2164
2082
2011
1935

11.9
11.9
11.9
11.9

Table 10
NRTL interaction parameters calculated for kerosene cuts and water. Mutual solubility data generated for each binary from 25 C to 125 C (hc, kerosene; w, water).
Cut

ahc,w

aw,hc

bhc,w

bw,hc

hc,w

1
2
3
4

6.945
6.845
6.754
6.636

6.105
6.021
5.951
5.867

3912
3892
3872
3844

2822
3045
3247
3485

0.2
0.2
0.2
0.2

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

23

Table 12a
NRTL interaction parameters calculated for heavy oils and water based on synthetic mutual solubility data generated for each binary from 25 C to 125 C (hc, heavy oil; w,
water).
Heavy oil

ahc,w

aw,hc

bhc,w

bw,hc

hc,w

Coalinga
Huntington Beach
Peace River
Cat Canyon

4.388
4.082
2.505
2.548

4.656
4.202
4.155
3.976

3082
2932
2418
2428

6963
6870
8835
8100

0.2
0.2
0.2
0.2

Table 12b
Solubility of water in the bitumen-rich liquid phase [38].
Temperature 0.3 (K)

Pressure 0.07 (MPa)

Measured water solubility 20% (wt.%)

548.2
573.1
583.2
593.1
603.5
613.4
623.2
633.8

6.1
9.0
10.7
12.7
15.9
21.1
26.4
32.7

3.7
5.3
6.2
7.7
8.8
11.3
13.5
15.2

of the critical temperature of water. For this case, the distinction

between Type II and Type IIIa phase behaviour in the data sets and
the Type IIIb behaviour of Athabasca bitumen + water is expected to
affect the accuracy of calculated outcomes because the interaction
of near critical water with a subcritical hydrocarbon (Type IIIb) is
expected to differ from subcritical water + subcritical hydrocarbons
(Type II, Type IIIa, Type IIIb), and subcritical water + near critical
hydrocarbons (Type IIIa). From an experimental perspective, the
impact of thermal decomposition on measured solubility values,
while compensated for in the measurement procedure, impacts
data precision and accuracy. Random uncertainties of these solubility data, based on measurement repetition and validation with
known compounds up to 573 K, of 20% are expected. Measurement bias, if present, underestimates solubility. Model 2, applied
directly, treats the Athabasca bitumen + water pseudo binary as a
Type II binary mixture and signicantly over-predicts the solubility of water in Athabasca bitumen as the critical point of water is
approached (Table 12b).
An alternative approach is to use an equation of state to
extrapolate solubilities to higher temperatures. The Advanced
PengRobinson (APR) equation of state, a modication of the Peng
and Robinson equation of state [22] described elsewhere [35] was

0.7
data

Solute Mole Fraction

0.6

Modelled water solubility (wt%)

Model 2

Model 2 + APR

High temperature Model 2

3.1
5.3
7.0
9.6
14.4
25.0
70.7
Soluble

2.2
3.1
3.7
4.3
5.1
6.1
7.2
8.5

4.1
6.0
7.0
8.2
9.6
11.2
13.1
15.7

Table 13
Water solubility estimates in Athabasca bitumen using Model 2.
Temperature ( C)

Mole fraction

APR interaction parameter, kij

25
125

0.00242
0.0481

0.3
0.25

used here. First solubilities were generated using Model 2 within

the 298398 K temperature range. Then, the APR was tuned to t
these solubilities using a simple temperature dependency for the
binary interaction parameter, kij , between water and Athabasca
bitumen,
kij = 0.1009 +

59.35
T

(22)

The tted interaction parameters are listed in Table 13 and the

estimated properties of Athabasca bitumen are shown in Table 14.
The tuned APR was then used to predict solubilities at higher
temperatures (Fig. 9 and Table 12b). In this case, Type IIIb phase
behaviour is predicted. There is qualitative agreement with the
data but the model systematically under-predicts the solubility. For
heavy oils the average molecular weights are not known exactly
and this is particularly true for bitumen. In this study, molecular
weight data were not adjusted to help match the experimental
data. However, the uncertainty in molecular weight is insufcient
to account for the model deviations which are more likely a result
of the different phase diagram for this system.

simulation
4.5. High temperature NRTL model for water solubility in heavy
oil

0.5
0.4

Since Model 2 based calculations fail above 600 K, a high temperature NRTL model was developed. Interaction parameters were

0.3

Table 14
Athabasca bitumen physical properties.

0.2
0.1
0
400

450

500

550

600

Temperature, K
Fig. 8. Measured [36] and calculated (Model 2) solubility of water in Peace River
bitumen.

Property

Value

Molecular weight [g/mol]

Normal boiling point [K]
Liquid density @ 298 K [kg/m3 ]
Critical pressure [kPa]
Critical volume [m3 /kmol]
Critical temperature [K]
Critical compressibility
Acentric factor

550
782.3
1019
1445
1.19
980.1
0.211
1.02

24

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

16

1.0

14

Calculated Solubility, Mole Fr.

data

Water Solubility, wt%

Model 2 + APR
12
10
8
6
4
2

Huntington Beach

0.9

Coalinga

0.8

Cat Canyon
Peace River

0.7

Athabasca

0.6
0.5
0.4
0.3
0.2
0.1
0.0

0
540

560

580

600

620

640

0.0

Temperature, K
Fig. 9. Measured [38] and predicted (Model 2 and APR) water solubility in Athabasca
bitumen.
Table 15
High temperature NRTL model parameters for the estimation of water solubility in
heavy oils.
Parameter

a
b
c
d
e

9.776
0.000
14.25
0.5896
0.4410

12.34
0.000
9.437
0.8993
10.58

18.53
0.000
3.027
0.1144
3.004

obtained by tting available solubility data for water in heavy

oils [36,38]. The tted high temperature interaction parameters,
Table 15, are tentative due to the small size of the data set available but can provide guidance for estimating the solubility of water
in heavy hydrocarbons at high temperatures and pressures. The
average error in the t is 7.6% with a bias of 0.8% over the temperature interval 400640 K. The quality of the t is illustrated in
Figs. 10 and 11, and estimated values for Athabasca bitumen in
particular are listed in Table 12b.
0.90

Water Mole Fraction in Bitumen

0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
540

560

580

600

620

640

Temperature, K
Fig. 10. Correlated solubility of water in Athabasca bitumen using the alternative
NRTL parameters from Table 15.

0.2
0.4
0.6
0.8
Measured Solubility, Mole Fr.

1.0

Fig. 11. Dispersion plot for correlated high-temperature water solubility in heavy
oils including data from [36,38]. NRTL parameters are presented in Table 15.

5. Conclusions
A simple and effective method for the estimation of mutual
solubilities of water and hydrocarbons, including undened hydrocarbons is presented. The method is based on the innite dilution
activity coefcients represented with the NRTL model. The method
can easily be integrated with process simulators providing the
necessary information for the determination of interaction parameters for any thermodynamic model capable of predicting the
existence of two liquids. The modelling approach works well for
water + hydrocarbon mixtures exhibiting Type II and Type IIIa
phase behaviour, and for mixtures exhibiting Type IIIb phase
behaviour below and remote from the critical temperature of water.
A tentative set of parameters for the estimation of water solubility
in heavy oils at high temperatures is also presented.
The method is easily adapted to work with more advanced characterization methods based on better structural characterization
of hydrocarbon fractions [39] and can provide useful background
support for the design of new chemically reactive solutions for
the upgrading of hydrocarbons using water at very high temperatures. In addition, the ability to estimate the amount of water in
oil rich phases reliably allows the use of more advanced viscosity
estimation methods, such as the Expanded Fluid model [40], for
hydrocarbon phases saturated with water or water phases saturated with hydrocarbons.
In addition the method model parameters can be easily revised
when new solubility data are made available. In particular, the measurement of more mutual solubility data of oils and water would
be a welcome addition to the experimental database, in particular
if some information about the nature of the oil solvent or dissolved
oil in water in terms of chemical species or boiling point fractions
were measured. The method should also be used with caution when
estimating solubilities of very heavy fractions at low temperatures
due to the paucity of available data. Issues related to the freezing
of an oil solvent or formation of solid hydrocarbon phases are not
taken into account by the method.
A perturbation method for estimating oil + water mutual solubilities was also considered based on a reference system dened
by n-parafns + water, but an inconsistency between the solubility
trend predicted by molecular simulation and data was found and
that approach was not pursued further. There is a signicant need
for clarication on the actual dependency of solubility on carbon

M.A. Satyro et al. / Fluid Phase Equilibria 355 (2013) 1225

number above decane, which offers a signicant opportunity for

research.
Acknowledgements
The authors are grateful to Virtual Materials Group, Inc. for
permission to publish this paper. The assistance of Mohammad
J. Amani (University of Alberta), J. van Dorp (Shell Canada) and
A. Panagiotopoulos (Princeton University) is gratefully acknowledged. Initial motivation for this work came from discussions with
P. House, J. van Dorp (Shell Canada), G. Hay (VMG Canada), H.
Iketani (VMG Japan) and G. Jacobs (VMG USA). Harvey Yarranton
and John M. Shaw also acknowledge the sponsors of the NSERC
(Natural Sciences and Engineering Research Council) Industrial
Research Chairs in Heavy Oil Properties and Processes (NSERC,
Petrobras, Schlumberger, and Shell), and in Petroleum Thermodynamics (NSERC, Alberta Innovates Energy and Environment
Solutions, British Petroleum, ConocoPhillips, Nexen, Shell, Total
E&P Canada) respectively.
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