Group Contribution Method For Henry's Law Constant of Aqueous Hydrocarbons

THERMODYNAMICS
Group Contribution Method for Henry’s Law

Constant of Aqueous Hydrocarbons
Josef Sedlbauer
Dept. of Chemistry, Technical University Liberec, 461 17 Liberec, Czech Republic
¨ Bergin and Vladimir Majer

Gaetan
`
Laboratoire de Thermodynamique des Solutions et des Polymeres, ´ Blaise PascalrCNRS,
Universite
` Cedex, France
63177 Aubiere
A functional group contribution scheme based on a hydration model predicts Henry’s

Law constant of aqueous hydrocarbons as a function of temperature and pressure. It
uses the direct link of Henry’s Law constant with the Gibbs free energy of hydration, as
well as its temperature and pressure deri®ati®es accessible from calorimetric and ®olu-
metric data. A semitheoretic model inspired by the fluctuation solution theory with fi®e
adjustable parameters was used for expressing the temperature and pressure dependence
of ten functional contributions. A consistent group contribution scheme for hydration
properties at 298 K and 0.1 MPa was taken from literature to constrain the model at
reference conditions. Parameters for hydrocarbon functional groups were adjusted by
simultaneous correlation of o®er 1,000 data points on Henry’s Law constant and about
550 ®alues on deri®ati®e hydration properties (enthalpy, heat capacity, and ®olume)
a®ailable in a wide range of temperature and pressure. The resulting group additi®ity
scheme can be used for predicting Henry’s Law constant for alkanes, alkenes, alkylcy-
cloalkanes, and alkylbenzenes up to 570 K and up to 100 MPa. A®erage accuracy of the
predictions ®aries from 20 to 40% at ambient to high temperatures, respecti®ely, and
semiquantitati®e estimates are possible up to the critical point of water.
Introduction
Reliable knowledge of solubility and vapor-liquid parti- waste. Importantly, many of these operations and processes
tioning of hydrocarbons in aqueous systems over a wide range occur at superambient conditions, thus creating a need for
of temperature and pressure is essential for conception of convenient estimation methods allowing to predict the re-
industrial operations, as much as for understanding environ- quired thermodynamic data. The property of high practical
mental and geological processes. These include, among oth- interest is Henry’s Law constant ŽHLC. which is a direct mea-
ers, modification of petroleum composition by oil field waters sure of volatility of a given solute in a solution. This property
in sedimentary basins, interaction between groundwaters and expressed as a function of temperature and pressure is also
reservoir fluids, pollution of aquatic and atmospheric envi- useful for correlating or predicting solubility of a hydrocar-
ronment during storage, transport and treatment of bon in water provided that the fugacity of the coexisting or-
petroleum and natural gas, depollution of petrochemical ef- ganic phase can be calculated.
fluents by air stripping, and the use of high-temperature wa- HLC is used in various contexts by physical chemists,
ter as a medium for decomposition of hazardous organic chemical and environmental engineers, and geochemists.
Each community developed its own terminology and ap-
Correspondence concerning this article should be addressed to V. Majer. proaches specific for the given field and a variety of HLC
2936 December 2002 Vol. 48, No. 12 AIChE Journal

definitions can be found in literature. Unfortunately, the Thermodynamic Background
thermodynamic background is not always well understood and The Henry’s Law constant K H is defined as the limit of
available information is sometimes confusing. This is particu- fugacityrconcentration ratio of a solute in a solution ŽPraus-
larly valid regarding the evolution of HLC with temperature nitz et al., 1999; Sandler, 1999. and has the dimension of
and pressure where extrapolations using simple empirical pressure
schemes can lead to important systematic errors.
Experimental results allowing calculation of HLC at ambi- fs
ent conditions are available for many common hydrocarbons;
much less information was published at superambient condi-
K H Ž T , p . s lim
xs™ 0 ž /
xs
Ž1.
tions and it is not always clear from literature how HLC was
determined. In the case of aqueous organic compounds Žand where f s is fugacity of the solute and x s is its molar fraction.
hydrocarbons particularly ., it is useful to adopt a functional This one-phase definition of HLC can be rewritten in two
group additive scheme. The reason is obvious: while the simple relationships. When considering the standard state of
number of these compounds is huge, they consist of just a ideal gas for the solute, it follows that
few functional groups. In the chemical thermodynamics of di-
lute aqueous solutions, this principle has been utilized with K H Ž T , p . s p␸T
s Ž2.
success at the temperature of 298 K, and several methods are
available that vary in the set of selected functional groups where ␸T s is the fugacity coefficient of solute at infinite dilu-
and in the type of thermodynamic property expressed. tion, which can be calculated from an equation of state for a
Extension of estimation techniques to elevated tempera- solution. Similarly, the introduction of the standard state of
tures faces more difficulty for two reasons. First, there is a pure liquid leads to relationship
lack of reliable experimental results for various solutes in a
range of conditions, and second, there is a need of a good
K H Ž T , p . s f s ␥s⬁
䢇
Ž3.
thermodynamic model for the description of temperature and
pressure dependence of HLC. For aqueous hydrocarbons, lit-
tle systematic experimental work was performed at superam- where f s and ␥s⬁ stand for fugacity of pure liquid solute Žreal
䢇
bient conditions with the exception of the major contribution or hypothetical . and the limiting activity coefficient in sym-
from Tsonopoulos and collaborators ŽTsonopoulos and Wil- metrical standard state convention, respectively. This latter
son, 1983; Heidman et al., 1985; Economou et al., 1997; parameter can be expressed from models characterizing non-
Tsonopoulos, 1999, 2001.. Attempts to correlate the data in a ideality of a solution in terms of molar excess properties.
range of conditions remained mainly on empirical grounds. HLC is also simply linked with the Gibbs free energy of
Only in the past decade or so, new approaches have ap- hydration ⌬GThyd corresponding to the transfer of a solute
peared inspired by statistical thermodynamics and the theo- from an ideal gas state at the reference pressure Ž pref s 0.1
ries of near critical dilute solutions that allowed to build MPa. to the standard state of infinitely dilute solution at
high-temperature correlations on a more solid basis. Also, the pressure p. ŽThe standard state adopted for aqueous species
high-temperature models developed by geochemists for pre- is unit activity in a hypothetical solution of unit molar frac-
dicting the standard molar properties of aqueous solutes can tion referenced to infinite dilution, denoted here with super-
be adopted for calculation of HLC. script o.. The relationship is obtained by writing relationships
The purpose of this work was to establish a new group for the chemical potential of a solute using the standard state
contribution scheme for aqueous hydrocarbons that would of infinite dilution and that of ideal gas and combining them
take into account all types of experimental results for these with the definition of K H ŽEq. 1.
solutes available in literature. Use of a thermodynamic model
related to fluctuation solution theory makes possible reliable K H ŽT , p.
sGTs Ž T , p . yGsi g Ž T , pref . s ⌬GThyd
calculation of HLC up to the temperature of 573 K and pres-
sures to 100 MPa, and provides realistic predictions in the
RT ln
ž pref / Ž4.
direction of the critical point of solvent. Practical use of the

This equation presents a straightforward connection of HLC
proposed method is facilitated by a user-friendly software tool
to the rigorous system of thermodynamic state functions, and
presented elsewhere ŽMajer et al., 2003., which can be ob-
any physicochemical theory of hydration yielding ⌬GThyd also
tained free of charge on request provided it will serve for a
allows calculation of HLC. The temperature derivatives of
noncommercial use.
Eq. 4 lead to the enthalpy and heat capacity of hydration
A thermodynamic framework is set relating HLC to the
basic thermodynamic functions and the different approaches
⭸ ln K H
used in literature for estimating this property are briefly re- RT 2 ž / sy HT ig T
s Ž T , p . y Hs Ž T . sy⌬ H hyd Ž 5 .
viewed. This is followed by a presentation of the group con- ⭸T p
tribution scheme and thermodynamic model used for func-
⭸ ⭸ ln K H
tional groups representation as a function of temperature and sy CTp, s Ž T , p . yC pi g, s Ž T .
pressure. Next, the databases are described which are em- ž ⭸T
RT 2
⭸T / p
ployed in correlation for establishing adjustable parameters
of the model. Finally, the new predictions are discussed and sy⌬CTp, hy d Ž6.
tested against representative high-temperature and high-
pressure data. and the pressure derivative gives the standard volume of a
AIChE Journal December 2002 Vol. 48, No. 12 2937

solute ity of hydrocarbon in organic and aqueous phases
⭸ ln K H f sorg Ž T , p . s f saq Ž T , p . ( K H Ž T , p . x sol Ž9.

sVsT Ž T , p .
RT
ž ⭸p / T
Ž7. s
Solubility of hydrocarbon in water x sol

s is combined with the
It follows from Eqs. 5 to 7 that the temperature andror pres- fugacity of hydrocarbon in the organic phase that can be solid,
sure evolution of HLC can be calculated by integration of liquid, or gaseous. For hydrocarbons in a fluid state, satisfac-
derivative hydration properties that can be obtained from tory results can be obtained from a cubic equation of state
calorimetric and volumetric data. The integral of Eq. 7 be- ŽEconomou and Tsonopoulos, 1997. with a classical mixing
tween saturation pressure of solvent and pressure of the sys- rule adjusted to at least one data point on solubility of water
tem is known as the Krichevskii-Kasarnovsky equation useful in the organic phase. For solid hydrocarbons or at conditions
for calculating evolution of solubility with pressure. where water solubility in an organic phase can be neglected,
Unlike GTs ŽT, p ., the standard derivative functions HT s T, p
Ž . HLC is calculated from the equation
and VsT ŽT, p . are equal to the partial molar properties at infi-
nite dilution and diverge at the critical point of solvent pssat␸ssat exp Vs Ž py pssat . rRT
ŽLevelt-Sengers, 1991.. For hydrophobic solutes, this diver- K H ŽT , p. ( Ž 10.
gence is generally positive so that the enthalpy of hydration x sol
s
of aqueous hydrocarbons is also positively divergent, and,

consequently, the partial temperature derivative of HLC is where pssat , ␸ssat , and Vs are vapor pressure, fugacity coeffi-
increasingly negative as T ™Tc,w . ⌬ HT hyd is most often ob- cient, and molar volume of pure hydrocarbon, respectively.
tained from the experimentally accessible enthalpies of disso- When pressure is low and close to the vapor pressure of so-
lution and vaporization Ž ⌬ HT hyd f ⌬ Hsol y ⌬ H vap . Since, at
. lute, Eq. 10 reduces to a simple ratio K H s pssatrx sol
s .
ambient conditions, enthalpy of dissolution of a nonelec- It should be also mentioned that the term Henry’s law con-
trolyte in water is much smaller than the enthalpy of vapor- stant is often used by environmental engineers for denoting
ization Ž< ⌬ HT < < T
<.
vap ) ⌬ Hsol , the enthalpy of hydration is nega- the air-water partition coefficient. This coefficient is defined
T
tive Ž ⌬ H hyd fy⌬ H vap - 0. near room temperature and the as a limiting ratio of molar concentrations C s in air and wa-
temperature slope of HLC is positive. The opposite sign of ter and is related to HLC as follows
⌬ HT hyd at ambient and near critical conditions implies exis-
tence of a maximum in HLC at a temperature where ⌬ HT hyd C sair K H ␳w
s 0, which is generally observed between 373 and 473 K. The
pressure derivative of HLC is always positive, increasing
K aw s lim
C saq ™ 0 ž /
C saq
(
RTMw
Ž 11.
strongly at p™ pc,w . Using Eq. 2 as a starting point, Japas

and Levelt-Sengers Ž1989. derived a two-parameter equation The relation is valid exclusively for sparingly soluble com-
expressing exactly the evolution of HLC along the saturation pounds at near ambient conditions where air can be approxi-
line of solvent Žw. near its critical point mately described by an ideal gas equation of state and the
density of a solution can be considered equal to that of pure
T ln K H Ž T . re sat
w sTc,w ln Ž pc ,w ␸T
c , srf c ,w .
solvent.
This outline of basic equations aimed at presenting HLC in
T
q Ž ⭸ pr⭸ x s . c ,V ,T r␳c,w
2
Ž ␳wsat y ␳c ,w . Ž8. a broader thermodynamic context going beyond its restrictive
viewing as vapor-liquid partition coefficient along the satura-
tion line of solvent.
The partial derivative of pressure with respect to composition
at state of infinite dilution is called the Krichevskii parame-
ter. Its value reflecting interactions between solvent and so- Review of Prediction and Correlation Approaches
lute is positive for volatile nonelectrolytes, and is well be- A number of empirical approaches to the estimation of
haved near the critical point of solvent, which means that Eq. HLC at 298 K and 0.1 MPa are available using grouprbond
8 reduces at the critical point to the first term with ␸T s being contribution or structural parameters. Promising methods for
the only property of solute affecting HLC ŽBeutier and correlation at superambient conditions are those making use
Renon, 1978.. Since temperature and pressure derivatives of of the above relationships for activity or fugacity coefficients
the solvent fugacity e w are well behaved at the critical point, or for the hydration properties that can be expressed from
the temperature derivative of HLC along the saturation line models for dilute aqueous solutions.
of solvent will diverge negatively. According to power laws,
the density difference < ␳wsat y ␳c,w < is proportional to < Twsat y
Tc,w < ␤ with the critical exponent having a universal value of Estimation methods at near ambient conditions
0.326 ŽSengers and Levelt-Sengers, 1986.. Thus, the diver- Limiting activity coefficients are popular in engineering ap-
gence along the saturation line will be governed by exponent plications ŽSandler, 1996. and lead directly to HLC after a
Ž1-␤ . and is weaker than that along the isothermal or iso- combination with vapor pressures ŽEq. 3.. They can be calcu-
baric path. lated at near ambient conditions from well-established group
For aqueous hydrocarbons that are sparingly soluble in wa- contribution schemes such as UNIFAC or ASOG, which,
ter at most conditions, it is possible to use data on mutual however, fail in describing aqueous systems ŽEckert and
miscibility for obtaining HLC from the equivalence of fugac- Sherman, 1996.. The specific schemes for limiting activity co-

efficients of aqueous hydrocarbons are less frequent and use Economou et al. Ž1997. and by Plyasunov and Shock Ž2000b.
structural rather than group parameters ŽTsonopoulos and for correlation of HLC for aqueous hydrocarbons.
Prausnitz, 1971; Medir and Giralt, 1982.. Several linear cor- The approaches based on the link between HLC and the
relations are available in the literature expressing directly Gibbs free energy of hydration ŽEq. 4. were explored first
HLC or its analogues such as K aw in terms of grouprbond using the scale particle theory ŽPierotti, 1976.
contributions ŽHine and Mookerjee, 1975; Meyland and
Howard, 1991., solvatochromic parameters ŽAbraham et al., K H ŽT , p.
1994; Sherman et al., 1996., and topological descriptors
ŽNirmalakhandan and Speece, 1988; Nirmalakhandan et al.,
RT ln
ž pref / sGc qGi q RT ln Ž V igrVw . Ž 14.
1997.. For the latter two groups of techniques, the determi-

nation of parameters is tedious. In this relationship the three terms express the contribution
The compilation of hydration properties for aqueous or- for creating a cavity in the solvent, the interaction between
ganics expressed in terms of group contributions at 298 K solvent and solute and the standard term, respectively.
and 0.1 MPa was established by Cabani et al. Ž1981. on the Schulze and Prausnitz Ž1981. have expressed Gc and Gi as a
basis of extensive experimental work performed by solution function of molecular parameters and temperature for corre-
chemists. These data, largely ignored by the engineering lating HLC of gases in water.
community, allow a straightforward calculation of HLC ŽEq. Another way of expressing hydration properties is inspired
4.. Plyasunov and Shock Ž2000a. published a comprehensive by the fluctuation solution theory based on the work of
update of Cabani’s work for hydrocarbons and alcohols pre- O’Connell and collaborators Žfor example, O’Connell, 1971;
senting the most exhaustive overview of experimental values O’Connell et al., 1996.. The spatial integral of the infinite
available, as well as new values of group contributions. dilution solute-solvent correlation function CTs,w can be re-
lated to the so-called modified Krichevskii parameter ATs,w
Correlation as a function of temperature and pressure defined as the ratio of VsT and the point mass volume
Since the HLC exhibits a maximum in temperature, any

VsT ⭸p V
extrapolation from near ambient data by a polynomial-like 1yCTs,w s ATs,w s
equation can be a failure. For a correlation or prediction over
a wide range of temperature andror pressure, it is necessary
␬ w RT
s lim
ns™ 0 ž / ⭸ ns T ,V
RT
Ž 15.
to use relationships giving a realistic description of the where ␬ w is the compressibility of water and n s is the mole
derivative hydration properties ŽEqs. 5 to 7.. Several authors number of solute in the volume of solution V. This dimen-
presented empirical equations for correlating HLC of gases sionless parameter changes much less with density of solvent
in water along the saturation line of solvent respecting nega- than the partial molar volume and is well behaved in the crit-
tive divergence of the temperature derivative of HLC at the ical region of water. It can be used for expressing the fugacity
critical point of solvent Žsee, for example, Krause and Benson coefficient of solute at infinite dilution ŽO’Connell et al., 1996.
Ž1989., Fernandez-Prini and Crovetto Ž1989., and Crovetto
allowing to calculate HLC from Eq. 2. When rewriting the
Ž1991...
ATs,w parameter in the form of a virial expansion in density,
Harvey and Levelt-Sengers Ž1990. added an empirical term we get
to Eq. 8, which allowed correlation of HLC down to room
temperature. They have also shown ŽHarvey et al., 1991. that
this relationship is not restricted to the solvent saturation line, ⭸ Ž pVrRT . 2
ATs,w s lim ␳w Bs,w q . . .
but can be applied for correlating HLC and hydration prop-
erties as a function of temperature and pressure
ns™ 0 ž ⭸ ns / T ,V
s1q
ž /
Mw
Ž 16.
T ln w K H Ž T , p . rf w x s Aq B Ž ␳w y ␳c,w .
where Bs,w is the second cross virial coefficient. An analo-
qCT␳w exp w Ž 273.15yT . r50 x Ž 12. gous procedure can be adopted for pure water where
solvent-solvent interactions are expressed in terms of a mod-
This simple three-parameter equation is not, however, flexi- ulus A w,w
ble enough for allowing quantitative description of the stan-
dard derivative hydration properties using Eqs. 5 to 7 ŽHarvey, 2
␳w Bw ,w q . . .
1998; Sedlbauer and Majer, 2000.. For engineering applica-
tions, Harvey Ž1996. proposed a simplified form of Eq. 12 for
A w,w s1q
ž /
Mw
Ž 17.
correlation along the saturation line of solvent, where calcu-

lation of water density is not necessary Subtracting Eq. 17 from 16 and introducing an empirical pa-
rameter d related to the ratio of cavity-creating sizes for
0.355 solute and solvent leads to the relationship
T ln K H Ž T . rpwsat s Aq B Ž T yTc,w .
qCT 0.59 exp Ž Tc,w yT . Ž 13. 2

ATs,w s dA w ,w q Ž 1y d . q ␳w
The parameters were presented for several gases in water
ž /
Mw
Ž Bs,w y dBw ,w . q . . .
including light hydrocarbons. This equation was also used by Ž 18.

Several ways have been proposed how to express ATs,w and to which can be rearranged in the form
obtain subsequently hydration properties by integration.
Plyasunov and collaborators ŽPlyasunov et al., 2000a,b; 2001. ⌬GThyd Ž T , p . s ⌬GThyd Ž Tref , pref .
have added an empirical term to approximate the contribu-
tion of higher virial terms resulting in a relationship with three T p re f
adjustable parameters. The necessity to know or to estimate y Ž T yTref . ⌬ SThyd w Tref , pref x q HT Ž ⌬CTp ,hyd . dT
re f
the second cross virial coefficient is a complication namely
for solutes of low volatility. Sedlbauer et al. Ž2000. have pro- T p re f p
posed a version of Eq. 18 where virial expansion is replaced yT HT Ž ⌬CTp,hyd . d ln T q Hp Ž VsT . T dp Ž 22 .
by a sum of exponentials in T and ␳w re f ref
ATs,w s dA w ,w q Ž 1y d . q ␳w aq b Ž exp w ␽␳w x y1 . where the superscripts pref and T indicate the constant vari-
able at which the integration is performed. The two refer-
q c exp w ⌰rT x q ␦ Ž exp w ␭␳w x y1 . 4 Ž 19. ence state terms are expressed from an independent scheme
available in literature Žlit. ŽPlyasunov and Shock, 2000a., while
where a, b, c, d are four adjustable parameters, ␦ s 0.35a the sum of three integrals is obtained from our temperature
and ®, ⌰ and ␭ are generalized constants that were obtained dependent model Žmod.. Then one can simplify Eq. 22 to
earlier ŽSedlbauer et al., 2000. from analysis of a large amount
of data on various aqueous solutes. This relationship has a
correct ideal gas limit for low densities and is analytically in- ⌬GThyd Ž T , p . s ⌬GThyd
lit
Ž Tref , pref . y Ž T yTref . ⌬ SThyd
lit
Ž Tref , pref .
tegrable to obtain properties on the Gibbs free energy level
Žsee the Appendix.. The particular functional form has been q ⌬GThyd
mod
Ž T , p . y ⌬GThyd
mod
Ž Tref , pref .
inspired by an older model of O’Connell et al. Ž1996.. Al-
though this development was originally made in connection y Ž T yTref . ⌬ SThyd
mod
Ž Tref , pref . Ž 23 .
with an application in geochemistry, we found this approach
appealing also as a basis for prediction of HLC over a wide
The entropy of hydration ⌬ SThyd
lit
ŽTref , pref . is calculated simply
range of temperature and pressure.
as
New Group Contribution Model

⌬ SThyd
lit
Ž Tref , pref . s ⌬ HThydlit Ž Tref , pref .
The basic idea of our approach is to calculate HLC from a
hydration model whose parameters are adjusted with the use
y ⌬GThyd
lit
Ž Tref , pref . rTref Ž 24.
of the Gibbs free energy data, resulting mainly from solubil-
ity measurements, and also with the use of data on the
derivative properties obtained from calorimetric and volu- from the group contributions tabulated for ⌬GThyd lit
ŽTref , pref .
T lit
metric measurements. The adopted model for expression of and ⌬ H hyd ŽTref , pref . by Plyasunov and Shock Ž2000a.. Re-
HLC as a function of temperature and pressure provides regarding the temperature-dependent model, ⌬GThyd mod
and
T mod
alistic behavior at near critical and low density conditions. ⌬ S hyd are obtained from equations
Because prevailing amount of existing accurate experimental
results is available at or near to ambient conditions, we con- 0 p
sidered it is also useful to constrain the model at the refer- ⌬GThyd
mod
s Hp RTdln pq H0 V T T cor
s dpq ⌬G hyd Ž 25.
ence conditions Tref s 298.15 K and pref s 0.1 MPa using re f
representative recommendations of ⌬GThydŽTref , pref . that

⭸ ⌬GThyd
mod
were taken from literature. For this purpose, we have se- ⌬ SThyd
mod
lected the recent group contribution method by Plyasunov and

s
ž ⭸T / p
Ž 26.
Shock Ž2000a., which is based on a very thorough evaluation
of all available data related to hydration of aqueous hydro- where VsT is expressed from Eq. 19. An empirical correction
carbons at 298.15 K and 0.1 MPa. term ⌬GThydcor
with one adjustable parameter e is needed since
A hydration property ⌬YT hyd T, p
Ž . Ž Y sG, H,S . can be ex-
the simple volumetric equation is not sufficient for describing
pressed by a relationship quantitatively the thermodynamic hydration properties at
subcritical conditions
⌬YT T T T, p
hyd Ž T , p . s ⌬Y hyd Ž Tref , pref . q ⌬Y hyd T re f , p ref Ž 20.
⭸ 2⌬GThyd
cor
⭸ ⌬ SThyd
cor
⌬CTp ,hyd
cor
where the second term corresponds to the change of hydra-
tion property between the reference state and T, p of inter-
y
ž ⭸T 2 / ž
p
s
⭸T / p
s
T
est. In the case of the Gibbs free energy of hydration Eq. 20
2
can be written as e Ž T yTc .
s T -Tc Ž 27.
T ŽT y ⌽ .
⌬GThyd Ž T , p . s ⌬GThyd Ž Tref , pref . q ⌬ HThyd T , p
T, p
re f ref
where ⌽ is again a general constant. The contribution of the

y T⌬ SThyd
T, p
T re f , p ref Ž 21.
correction term is decreasing with increasing temperature and

it vanishes at the critical temperature of solvent Ž ⌬GThyd
cor
s Table 1. Group Contributions for Calculating ⌬GT lit (
hyd Tref ,
T cor T cor
⌬ H hyd s ⌬C p,hyd s 0 T GTc thus providing integration con-
. pref ) and ⌬ HT lit ( T
hyd ref , pref
)( Plyasunov and Shock, 2000a)
stants for Eq. 27. Detailed expressions for thermodynamic Functional ⌬GThyd
lit
ŽTref , pref . ⌬ HThyd
lit
ŽTref , pref .
functions of hydration are available in the Appendix. Group ŽkJ ⴢ moly1 . ŽkJ ⴢ moly1 .
An assumption of functional group additivity allows to de- C y4.50 2.6
termine any thermodynamic function of hydration of an CH y1.79 y0.9
aqueous organic molecule as a sum of structural contribu- CH 2 0.72 y3.76
tions CH 3 3.63 y7.54
C sC y10.23 0.6
U
H␲ 3.91 y3.7
N UU
c-CH y1.03 y2.4
⌬YT
hyd sYSS q Ý n i Ys,iT Ž 28. c-CH 2 0.83 y5.36
is1 Car † y3.85 y0.67
CH ar y0.65 y5.00
IŽCyC. y1.01 2.0
where N is the total number of functional groups present in
YSS ‡ 17.92 y2.29
a given compound, n i is the number of occurrences of each
T U
specific functional group, and Ys,i stands for the Y property Hydrogen atom bound to alkene group.
UU
of the i-th group. YSS accounts for the intrinsic contribution Prefix c-denotes a cycloalkane group.
†
A group with subscript ar is a part of aromatic ring.
to the Y property that is equal to the contribution of a point ‡
Standard state term.
mass. This term is derived from theory ŽBen-Naim, 1987. and
can be evaluated using only thermodynamic functions of pure
solvent. used at Tref and pref , and the selection of group contribu-
There are two basic features crucial for success of any tions in both schemes should be as close as possible. In our
functional group contribution scheme operating over a range group contribution scheme we utilize the same set of func-
of conditions: a suitable selection of a set of functional groups tional groups as proposed by Cabani et al. Ž1981. and later
and the quality of thermodynamic model, representing the re-evaluated for hydrocarbons at ambient conditions by Plya-
T
evolution of Ys,i group properties with T and p. In the choice sunov and Shock Ž2000a.: C, CH, CH 2 and CH 3 for alkanes,
of appropriate functional groups one has to take into account c-CH and c-CH 2 for cycloalkanes, CH ar and C ar for benzene
several constraints. The first one is the validity of the as- and alkylbenzenes, C sC for alkenes, and H ␲ for a hydrogen
sumption of structural additivity. The more complex is the set atom attached to the double bond. The only correction for
of selected groups, the better the resulting scheme can reflect proximity effects in this first-order group contribution scheme
effects of different structures and the method is the more is considered for orthosubstituted dialkylbenzenes and cis-
accurate. The second constraint is that we are limited in the 1,2-dialkylcycloalkanes. For these compounds, Plyasunov and
selection of functional groups by the amount of available ex- Shock introduced a ‘‘pseudo-group’’ IŽC-C., which we have
perimental results, which may be used for model parameteri- not used in the T, p dependent model due to lack of data on
zation. This is often not compatible with the first require- relevant compounds. The functional group values at Tref s
ment, because the use of aggregated groups increases the 298.15 K and at pref s 0.1 MPa of Plyasunov and Shock
number of contributions and, hence, demands more data. The Ž2000a. that were used in this study are summarized in Table
third constraint is the fact that, for calculating HLC as a 1, while the five parameters for each functional group in the
function of temperature and pressure, we use also the values T, p dependent model are given in Table 2. The database of
of ⌬GThydŽTref , pref . and ⌬ HT
hyd Tref , pref resulting from some
Ž . hydration properties applied for adjusting parameters of the
previously established group contribution scheme taken over functional groups in the latter model and calculation proce-
from literature. The reliability of predictions at reference dure are described below.
conditions 298.15 K and 0.1 MPa is crucial since these values
largely affect accuracy of results at superambient conditions,
particularly through the term ⌬ SThydŽTref , pref .ŽT yTref . ŽEq. Experimental Database
23.. The complexity of a functional group selection applied For determining parameters of the temperature dependent
for T, p dependent model should not be higher than that model, we have established a database consisting of HLC and
Table 2. Group Contributions for Calculating Parameters of the T, p Dependent Model

Functional a i =10 3 bi =10 4 c i =10 6 e i =10
Group Žm3 ⴢ kgy1 ⴢ mol. Žm3 ⴢ kgy1 ⴢ mol. Žm3 ⴢ kgy1 ⴢ mol. di ŽJ ⴢ Ky2 ⴢ moly1 .
C y34.6310 9.4034 y53.9212 y7.3260 y13.7921
CH y6.5437 1.8156 y16.9215 y0.9492 y3.9136
CH 2 y0.0244 0.7216 y8.9576 0.3416 y1.8264
CH 3 7.2778 y0.1571 y1.9499 1.4268 y0.0177
C sC y10.2988 y9.5352 y12.9835 11.4045 1.4871
H␲ 2.8400 3.1911 9.2357 y3.1496 0.5847
c-CH y16.9864 4.8289 5.0487 y3.3563 y0.9028
c-CH 2 3.0612 0.1108 y7.6472 0.7839 y1.2200
Car y9.1549 2.2106 y21.3460 y1.3723 y4.9993
CHar 0.6924 0.5168 y5.0903 0.3337 y1.0754

Table 3. Database of Experimental Values has been found in test correlations that the amount of avail-
Total No. of Exp. Values ŽNo. of Compounds. able data for aqueous hydrocarbons was not sufficient to al-
low parameterization of the quaternary carbon functional
Compounds x ssol ⌬ HThyd CTp, s Vs⬚
group ŽC., and also parameters for CH, C sC and H ␲ func-
Alkanes 295 Ž8. 63 Ž6. 1 Ž1. 5 Ž1. tional groups were subject to substantial numerical instabil-
Alkenes 291 Ž5. 6 Ž3. 3 Ž3. ᎏ
Cycloalkanes 27 Ž3. 12 Ž2. ᎏ 6 Ž1. ity. To improve determination of these groups, we have in-
Alkylbenzenes 445 Ž7. 56 Ž6. 16 Ž2. 72 Ž6. cluded in the fit also the data on VsT and ⌬CTp,hyd of aqueous
Alcohols ᎏ ᎏ 44 Ž16. 286 Ž22. alcohols that are available in literature as a function of tem-
perature. The contribution for the alcoholic OH group was
Total 1,058 Ž23. 137 Ž17. 64 Ž22. 369 Ž30.
also evaluated, but is not presented in the context of this
publication.
Included in the database were primary literature sources,
related derivative properties Ženthalpies and heat capacities and, in several cases, also recommended data from represen-
of hydration and standard molar volumes ŽEqs. 5 to 7.. for tative compilations in order to strengthen the presence of less
aqueous alkanes, alkenes, cycloalkanes, and alkylbenzenes. It common groups. The numbers of compounds and data points
Table 4. Database of Hydrocarbon Solubility in Water

Hydrocarbon Temp. ŽK. Pres. ŽMPa. Solubility ŽMolar Fraction. No. of Points Ref.
Alkanes
Ethane 311᎐444 50 1.07=10y3 y2.79=10y3 5 Culberson and McKetta Ž1950.
573 30᎐100 2.0=10y2 ᎐2.5=10y2 2 Danneil et al. Ž1967.
273 ᎐ 573 0.1᎐ 8.6 ᎐ 13 Fernandez Prini and Crovetto Ž1989.
344 50 1.3=10y3 1 Dhima et al. Ž1998.
Propane 285᎐422 0.5᎐19.2 8=10y5 ᎐6.9=10y4 45 Kobayashi and Katz Ž1953.
288᎐411 0.1᎐3.5 1.2=10y5 ᎐3.1=10y4 71 Azarnoosh and McKetta Ž1958.
344 0.5᎐1.2 5.5=10y5 ᎐1.2=10y4 8 Wehe and McKetta Ž1961a.
Butane 311᎐511 50 7.8=10y5 ᎐1.6=10y3 7 Reamer et al. Ž1952.
273 ᎐ 523 0.1᎐ 3.4 ᎐ 11 Carroll and Mather Ž1997.
344 50 1.0=10y4 1 Dhima et al. Ž1998.
Pentane 573 15᎐70 3.3=10y3 ᎐4.3=10y3 5 Connoly Ž1966.
277᎐303 0.1 10=10y6 ᎐1.1=10y5 4 Nelson and De Ligny Ž1968.
278᎐309 0.1 3=10y5 y3=10y5 3 Pierotti and Liabastre Ž1972.
273 0.1 1.6=10y5 1 Polak and Lu Ž1973.
313᎐423 0.1᎐2.1 10=10y6 ᎐7.4=10y5 6 Price Ž1976.
367᎐589 0.62᎐20.7 2.3=10y5 ᎐5.1=10y3 19 Gillespie and Wilson Ž1982.
288᎐308 0.1 1.0=10y5 ᎐1.1=10y5 4 ¨
Jonsson et al. Ž1982.
273ᎏ453 0.02᎐3.6 1.0=10y5 ᎐1.9=10y4 8 Jou and Mather Ž2000.
n-Hexane 277᎐328 0.1 2.7=10y6 ᎐4.6=10y6 5 Nelson and De Ligny Ž1968.
273 0.1 3.4=10y6 1 Polak and Lu Ž1973.
293 0.1 3.1=10y6 1 Busantseva et al. Ž1976.
313᎐425 0.1᎐1.3 2.1=10y6 ᎐2.2=10y5 9 Price Ž1976.
288᎐308 0.1 2.1=10y6 ᎐2.2=10y6 4 ¨
313᎐333 0.1 1.5=10y6 ᎐1.7=10y6 2 Bittrich et al. Ž1983.
311᎐473 0.1᎐3.5 2.4=10y6 ᎐1.9=10y4 7 Tsonopoulos and Wilson Ž1983.
573 20 3.8=10y3 1 Brunner et al. Ž1993.
373᎐464 0.4᎐3 6.1=10y6 ᎐1.9=10y4 5 Barrufet et al. Ž1996.
2-Methylpentane 573 15᎐70 2.7=10y3 4 Connoly Ž1966.
273 0.1 4.0=10y6 1 Polak and Lu Ž1973.
313᎐423 0.1᎐1.4 2.9=10y6 ᎐2.4=10y5 6 Price Ž1976.
n-Heptane 568 17᎐70 2.0=10y3 4 Connoly Ž1966.
561᎐583 24.8 2=10y3 ᎐3.1=10y3 4 O’Grady Ž1967.
277᎐318 0.1 3.5=10y7 ᎐4.3=10y7 4 Nelson and De Ligny Ž1968.
273᎐298 0.1 7.9=10y7 ᎐6.1=10y7 2 Polak and Lu Ž1973.
293᎐313 0.1 3.0=10y6 ᎐1.0=10y5 2 Busantseva et al. Ž1976.
313᎐424 0.1᎐0.9 4.7=10y7 ᎏ7.9=10y6 6 Price Ž1976.
288᎐308 0.1 4.5=10y7 ᎐4.8=10y7 4 ¨
n-Octane 278᎐318 0.1 2.6=10y7 ᎐3.9=10y7 3 Nelson and De Ligny Ž1968.
273 0.1 2.1=10y7 1 Polak and Lu Ž1973.
293 0.1 1.9=10y7 1 Busantseva et al. Ž1976.
298᎐423 0.1᎐0.7 8.3=10y8 ᎐1.9=10y6 6 Price Ž1976.
288᎐308 0.1 9.6=10y8 ᎐1.0=10y7 4 ¨
293᎐343 0.1 1.4=10y7 ᎐2.7=10y7 3 Burris and MacIntyre Ž1985.
311᎐553 0.1᎐8.9 1.2=10y7 ᎐6=10y4 6 Heidman et al. Ž1985.
394᎐500 0.3᎐1.3 3.0=10y6 ᎐2=10y5 4 Rahman and Barrufet Ž1995.
298᎐473 6.5 1.4=10y4 ᎐3=10y5 5 Miller and Hawthorne Ž2000.

included for individual properties for different classes of hy- obtained. As a rule, we have calculated HLC systematically
drocarbons and for alcohols are given in Table 3. A detailed from experimental data on solubility of a hydrocarbon in wa-
listing of data sources with temperature and pressure inter- ter and the fugacity of organic phase using Eq. 9. The values
vals can be found in Tables 4᎐7. of x sols are typically between 10y4 and 10y8 at near ambient
conditions, but increase considerably with temperature. Also,
Henry’s Law constant deviations from the Henry’s Law must be expected. The solu-
The data on HLC have been retrieved from phase equilib- bility data above 573 K were therefore omitted due to large
rium determinations in water-hydrocarbon systems as a func- uncertainties connected with conversion of solubility mea-
tion of temperature. We tried to avoid using HLC published surements to HLC. Since methodology of calculating
in literature, since it is not usually clear how the values were f sorg ŽT, p . was similar to that used by Plyasunov and Shock
Table 4. Database of Hydrocarbon Solubility in Water (Continued)

Decane 298 0.1 2.0 = 10 y 9 1 Baker Ž1959.
298 0.1 2.5 = 10 y 9 1 Franks Ž1966.
298 0.1 6.6 = 10 y 9 1 Krasnoshchekova and Gubercrits Ž1973.
298 0.1 1.1= 10 y 9 2 Mackay and Shiu Ž1975.
298 0.1 2.3= 10 y 8 ᎐ 1.6 = 10 y 7 1 Becke and Quitzsch Ž1977.
374 ᎐ 576 0.1y 11.2 5.1= 10 y 7 ᎐ 5.0 = 10 y 5 4 Economou et al. Ž1997.
Alkenes
Ethene 308᎐379 0.8᎐53.1 2.0=10 ᎐4.8=10y3
y4
53 Bradbury et al. Ž1952.
297᎐346 0.10᎐0.13 4.5=10y5 ᎐1.1=10y4 14 Morrison and Billet Ž1952.
311᎐394 0.1᎐3.7 2.7=10y5 ᎐1.9=10y3 46 Davis and McKetta Ž1960.
311᎐411 3.4᎐34.4 1.3=10y3 ᎐5.6=10y3 35 Anthony and McKetta Ž1967.
439᎐573 10᎐94.5 4.0=10y3 ᎐4.9=10y2 12 Sanchez and Lentz Ž1973.
Propene 311᎐411 1.6y33 8.1=10y4 ᎐2.3=10y3 34 Li and McKetta Ž1963.
441᎐573 12.6᎐97 2.9=10y3 ᎐3.3=10y2 12 Sanchez and Lentz Ž1973.
293᎐323 0.1 5.7=10y5 ᎐1.2=10y4 12 Serra et al. Ž1998.
1-Butene 311᎐411 0.4᎐41.4 2.2=10y4 ᎐6.1=10y4 6
311᎐428 0.4᎐69 2.3=10y4 ᎐1.1=10y3 52 Leland et al. Ž1955.
311᎐378 0.4᎐2.1 2.2=10y4 ᎐ 4=10y4 3 Wehe and McKetta Ž1961b.
1-Hexene 293 0.1 1.0=10y5 1 Busantseva et al. Ž1976.
311᎐494 0.2᎐24.8 1.2=10y5 ᎐4.5=10y3 5 Economou et al. Ž1997.
1-Octene 311᎐550 0.1᎐9.3 5.0=10y7 ᎐9.8=10y4 6 Economou et al. Ž1997.
Alkylcyclohexanes
Cyclohexane 563᎐573 13.9᎐19 5.9=10y3 2 Rebert and Hayworth Ž1967.
274᎐323 0.1 1.3=10y5 ᎐1.5=10y5 8 de Hemptinne et al. Ž1998.
Methylcyclohexane 313 ᎐ 422 0.1᎐ 0.7 3.3= 10 y 6 ᎐ 4.5 = 10 y 5 6 Price Ž1976.
299 ᎐ 444 1.6 3.0 = 10 y 6 ᎐ 7.1= 10 y 5 6 Jose Ž2001.
Ethylcyclohexane 311᎐553 0.1᎐8.8 1.1=10y6 ᎐2.4=10y3 6 Heidman et al. Ž1985.
Butylcyclohexane 366᎐550 0.1᎐7.1 1.9=10 y7
᎐4.2=10 y4
5 Economou et al. Ž1997.
Alkylbenzenes
Benzene 278᎐314 0.1 4.0᎐10y4 ᎐4.6=10y4 8 Bohon and Claussen Ž1951.
273᎐342 0.1 3.9=10y4 ᎐6.0=10y4 23 Arnold et al. Ž1958.
274᎐338 0.1 4.1=10y4 ᎐5.9=10y4 11 Alexander Ž1959b.
298᎐336 0.1 3.9=10y4 ᎐5.4=10y4 15 Franks et al. Ž1963.
377᎐477 6.9᎐34.5 1.0=10y3 ᎐9.9=10y3 8 Thompson and Snyder Ž1964.
533᎐554 10᎐80 162=10y2 ᎐3.7=10y2 8 Connoly Ž1966.
277᎐295 0.1 3.9=10y4 ᎐4.1=10y4 10 Leinonen Ž1972.
298᎐328 0.1 4.2=10y4 ᎐5.6=10y4 2 Bradley et al. Ž1973.
273 0.1 3.9=10y4 1 Polak and Lu Ž1973.
278᎐293 0.1 4.1=10y4 ᎐4.2=10y4 9 Brown and Wasik Ž1974.
294 0.1 4.0=10y4 1 Chey and Calder Ž1975.
328᎐348 0.1 9.2=10y4 ᎐1.5=10y3 2 Price Ž1976.
273᎐299 0.1 4.0=10y4 ᎐4.2=10y4 7 May Ž1977.
283᎐293 0.1 3.8=10y4 ᎐4.0=10y4 2 Ben-Naim and Wiff Ž1979.
288᎐318 0.1 3.5=10y4 ᎐4.3=10y4 5 Sanemasa et al. Ž1981.
281᎐306 0.1 3.9=10y4 ᎐4.4=10y4 3 Dutta-Choudhury et al. Ž1982.
273᎐343 0.1 4.0=10y4 ᎐5.9=10y4 12 May et al. Ž1983.
374᎐477 0.3᎐3.2 1.0=10y3 ᎐6.1=10y3 8 Anderson and Prausnitz Ž1986.

Table 4. Database of Hydrocarbon Solubility in Water (Continued)
293᎐323 0.1 3.9=10y4 ᎐4.0=10y4 4 Cooling et al. Ž1992.
303᎐373 0.1᎐0.3 4.2=10y4 ᎐9.5=10y4 8 Chen and Wagner Ž1994.
472᎐523 3.5᎐7.7 5.0=10y3 ᎐1.5=10y2 3 Stevenson et al. Ž1994.
303᎐313 0.1 4.3=10y4 ᎐4.8=10y4 3 Zou et al. Ž1997.
473᎐548 2.7᎐17.2 5.7=10y3 ᎐2.6=10y2 6 Chandler et al. Ž1998.
279᎐323 0.1 3.8=10y4 ᎐4.5=10y4 6 de Hemptinne et al. Ž1998.
323᎐473 6.5᎐40 3.3=10y4 ᎐5.0=10y3 7 Miller and Hawthorne Ž2000.
Toluene 303 0.1 1.1=10y4 1 Gross and Saylor Ž1931.
273᎐318 0.1 1.2=10y4 ᎐1.4=10y4 12 Bohan and Claussen Ž1951.
553᎐573 15᎐60 1.2=10y2 ᎐3.2=10y2 7 Connoly Ž1966.
278᎐318 0.1 1.2=10y4 ᎐1.3=10y4 5 Pierotti and Liabastre Ž1972.
318᎐328 0.1 1.4=10y4 ᎐1.7=10y4 2 Bradley et al. Ž1973.
293 0.1 1.4=10y4 1 Polak and Lu Ž1973.
294 0.1 9.4=10y5 1 Chey and Calder Ž1975.
283᎐303 0.1 1.3=10y4 ᎐1.8=10y4 7 Schwarz and Miller Ž1980.
283᎐306 0.1 1.1=10y4 ᎐1.2=10y4 2 Dutta-Choudhury et al. Ž1982.
278᎐318 0.1 1.3=10y4 ᎐1.4=10y4 4 Smith et al. Ž1989.
298 0.1᎐ 200 1.09 = 10 y 4 ᎐ 1.28 = 10 y 4 5 Sawamura et al. Ž1989.
273᎐363 0.1 1.6=10y4 ᎐2.5=10y4 10 Stephenson Ž1992.
294᎐473 0.1᎐5 9.8=10y5 ᎐2.5=10y3 8 Yang et al. Ž1997.
473᎐548 2.5᎐17.2 2.4=10y3 ᎐1.3=10y2 5 Chandler et al. Ž1998.
553᎐573 15.1y30.5 1.4=10y2 ᎐2.7=10y2 8 Haruki et al. Ž2000.
298᎐473 5 1.1=10y4 ᎐1.9=10y3 5 Miller and Hawthorne Ž2000.
273 ᎐ 323 0.1᎐ 200 1.08 = 10 y 4 ᎐ 1.46 = 10 y 4 34 Sawamura et al. Ž2001.
Ethylbenzene 273᎐316 0.1 3.5=10y5 ᎐3.9=10y5 9 Bohon and Claussen Ž1951.
273 0.1 3.3=10y5 1 Polak and Lu Ž1973.
283᎐293 0.1 3.0=10y5 ᎐3.1=10y5 2 Schwarz and Miller Ž1980.
311᎐553 0.1᎐8.6 3.2=10y5 ᎐3.7=10y3 6 Heidman et al. Ž1985.
283᎐318 0.1 3.0=10y5 ᎐3.6=10y5 15 Owens et al. Ž1986.
298 0.1᎐ 150 2.9 = 10 y 5 ᎐ 3.6 = 10 y 5 6 Sawamura et al. Ž1989.
m-Xylene 273᎐313 0.1 3.3=10y5 ᎐3.7=10y5 8 Bohon and Claussen Ž1951.
344᎐540 0.15᎐6.8 5.9=10y5 ᎐4.9=10y3 7 Pryor and Jentoft Ž1961.
273 0.1 3.3=10y5 1 Polak and Lu Ž1973.
293᎐343 0.1 2.7=10y5 ᎐6.4=10y5 3 Chernoglazova and Simulin Ž1976.
298᎐473 6 2.9=10y5 ᎐8.8=10y4 5 Miller and Hawthorne Ž2000.
p-Xylene 273᎐316 0.1 2.6=10y5 ᎐3.8=10y5 11 Bohon and Claussen Ž1951.
360᎐556 0.14᎐8.8 7.8=10y5 ᎐7.6=10y3 5 Pryor and Jentoft Ž1961.
273 0.1 2.8=10y5 1 Polak and Lu Ž1973.
298᎐422 0.14᎐50 1.6=10y5 ᎐1.4=10y4 18 Knauss and Copenhaver Ž1995.
Propylbenzene 298 0.1᎐ 150 8.2 = 10 y 6 ᎐ 9.6 = 10 y 6 5 Sawamura et al. Ž1989.
Butylbenzene 280 ᎐ 318 0.1 1.7 = 10 y 6 ᎐ 2.5 = 10 y 6 11 Owens et al. Ž1986.
303 ᎐ 373 0.14 ᎐ 0.2 2.2 = 10 y 6 ᎐ 1.1= 10 y 5 8 Chen and Wagner Ž1994.
m-Diethylbenzene 311᎐550 0.1᎐7.07 4.3=10y6 ᎐3.0=10y3 6 Economou et al. Ž1997.
p-diisopropylbenzene 311᎐550 0.1᎐7.5 3.7=10y7 ᎐7.1=10y4 6 Economou et al. Ž1997.
Hexylbenzene 278 ᎐ 302 0.1 1.0 = 10 y 7 ᎐ 1.1= 10 y 7 23 May et al. Ž1983.
280 ᎐ 318 0.1 9.2 = 10 y 8 ᎐ 1.4 = 10 y 7 9 Owens et al. Ž1986.

Ž2000b., as well as the data used, we give here only the most Table 5. Standard Molar Enthalpies of Hydration
salient features of the procedure. The cubic equation of state Temp. Pres. No. of
of Strycek and Vera Ž1986. was used for 23 hydrocarbons in- Hydrocarbon ŽK. ŽMPa. Points Ref.
cluded in the database with the binary interaction parameter Hydrocarbons
k s adjusted to representative vapor pressure data. The van
Ethane 273᎐323 0.1 11 Naghibi et al. Ž1987.
der Waals mixing rule was applied with the parameter k sw 288᎐308 0.1 2 Dec and Gill Ž1985.
adjusted to the data on solubility of water in the organic 288᎐308 0.1 2 Olofsson et al. Ž1984.
phase. Recent measurements of solubilities of water in ethyl- Propane 273᎐323 0.1 11 Naghibi et al. Ž1987.
benzene at high temperature ŽGuillaume et al., 2001. com- 288᎐308 0.1 2 Dec and Gill Ž1985.
288᎐308 0.1 2 Olofsson et al. Ž1984.
pleted the data listed by Plyasunov and Shock. Since no in-
Butane 288᎐308 0.1 2 Dec and Gill Ž1985.
formation is available for solubility of water in 2-methylpen- 288᎐308 0.1 2 Olofsson et al. Ž1984.
tane and p-xylene above 298 K, the data for water in hexane 273᎐318 0.1 9 Naghibi et al. Ž1987.
and m-xylene were used instead, respectively. The cubic 2-Methylpropane 288᎐308 0.1 2 Dec and Gill Ž1985.
equation of state reproduces the data on water solubility in 273᎐318 0.1 9 Naghibi et al. Ž1987.
2,2-Dimethylpropane 288᎐308 0.1 2 Dec and Gill Ž1985.
organic phase within 10 to 20%, which is consistent with the Hexane 288᎐308 0.1 2 Gill et al. Ž1976.
typical scatter of experimental results. Once the parameters 573᎐643 20᎐30 5 Degrange Ž1998.
k s and k sw were determined, the fugacity was calculated at Ethene 288᎐308 0.1 2 Dec and Gill Ž1985.
T, p corresponding to experimental points of hydrocarbon 1-Propene 288᎐308 0.1 2 Dec and Gill Ž1985.
1-Butene 288᎐308 0.1 2 Dec and Gill Ž1985.
solubility in water for getting HLC. No data above the pres-
Cyclopropane 288᎐308 0.1 2 Dec and Gill Ž1985.
sure of 100 MPa were included since the fugacity calculation Cyclohexane 288᎐308 0.1 4 Gill et al. Ž1976.
by a cubic equation of state can fail at these extreme pres- 573᎐643 10᎐30 6 Degrange Ž1998.
sures. More detailed information on the procedure of calcu- Benzene 288᎐308 0.1 5 Gill et al. Ž1975.
lating HLC can be found in the thesis by Bergin Ž2002.. 573᎐643 10᎐30 12 Degrange Ž1998.
523᎐623 10᎐30 5 Pardo Ž2000.
The summary of calculated HLC is presented in Table 4. Toluene 288᎐308 0.1 4 Gill et al. Ž1976.
The bulk of the database consisted of 1,058 data points in- 573᎐643 10᎐30 8 Degrange Ž1998.
cluded in the regression calculations. These primary data were 523᎐623 10᎐30 4 Pardo Ž2000.
completed by six values of HLC for each of the three solutes Ethylbenzene 523᎐623 10᎐30 5 Pardo Ž2000.
Ž2,2-dimethylpropane, 2-methylpropene, 1,3-butadiene . cal- o-Xylene 523᎐623 10᎐30 5 Pardo Ž2000.
m-Xylene 523᎐623 10᎐30 4 Pardo Ž2000.
culated between 273 and 343 K from a correlation presented p-Xylene 523᎐623 10᎐30 4 Pardo Ž2000.
by Wilhelm et al. Ž1977.. No primary data on solubilities as a
function of temperature were found in literature for these
three compounds, yet they contain groups that are otherwise
underrepresented in the database. About 200 additional data determined from recent experimental data on ⌬ Hsol and the
points Žprinted in italics . were used as a testing set for assess- residual enthalpies of pure hydrocarbons ⌬ Hres s Hs y Hsig 䢇
ment of predictive capabilities of the new group contribution calculated using the corresponding state method of Lee and
scheme Žsee below.. Kesler Ž1975. as described by Degrange Ž1998.
Deri©ati©e properties ⌬ HT
hyd s lim Ž ⌬ Hsolrx s . q ⌬ Hres . Ž 29.
xs™ 0
The derivative properties ⌬ HT
hyd , ⌬CTp,hyd
and VsT
are ob-
tained from results of calorimetric and volumetric experi-
ments with dilute aqueous solutions. The data for aqueous Values of partial molar volumes at infinite dilution VsT
hydrocarbons are rare at near ambient conditions where their ŽTable 6. obtained mainly from density measurements on vi-
determination is complicated due to low solubility of hydro- brating tube densimeters are numerous and present over 20%
carbons in water; they are, however, quite frequent for aque- of the database with the data both at near ambient and high-
ous alcohols. Particularly, a limited amount of high tempera- temperature conditions. Heat capacities of hydration were
ture data is available due to measurements performed at the calculated as a difference between the experimental partial
University of Delaware ŽWood and collaborators. and at the molar heat capacity at infinite dilution CTp, s and the heat ca-
Blaise Pascal University in Clermont-Ferrand, France ŽMajer pacity of an ideal gas C p,igs estimated from the group contri-
and collaborators.. The data on derivative properties ex- bution method of Joback, as presented in the monograph of
tended in a few cases Žhexane, cyclohexane, benzene and Reid et al. Ž1988.. Most data for CTp, s resulted from flow
toluene. to 643 K and supercritical pressure of 30 MPa. The calorimetric experiments on the Picker-type flow calorime-
purpose of their inclusion was to guide correlation of HLC ters performed at near ambient conditions and for three
correctly in the direction of the critical point; however, no compounds also at elevated temperatures ŽTable 7.. For both
near critical experimental results were considered. VsT and CTp, s , we have mainly included primary data sources
Most data on enthalpies of hydration ŽTable 5. at near am- listing measurements at several temperatures. Multiple
bient conditions were derived from articles by the groups of sources presenting the data at 298.15 K only were avoided
I. Wadso¨ at the University of Lund and S. J. Gill at the Uni- with an exception of four compounds for volumes and 12
versity of Colorado. They obtained ⌬ HT hyd combining unique compounds for heat capacities where we also included values
calorimetric data on dissolution of hydrocarbons in water with from representative compilations by Hoiland Ž1986. and Ca-
enthalpies of vaporization. The high-temperature values were bani et al. Ž1981.. These secondary data were used for com-

Table 6. Standard Molar Volumes
Temp. Pres. No. of
ŽK. ŽMPa. Points Reference
Hydrocarbons
Hexane 373᎐643 20᎐30 5 Degrange Ž1998.
Cyclohexane 373᎐643 10᎐30 6 Degrange Ž1998.
Benzene 278᎐318 0.1 5 Sakurai Ž1990.
278᎐353 0.6 5 Makhatadze and Privalov Ž1988.
373᎐643 10᎐30 16 Degrange Ž1998.
523᎐623 10᎐30 4 Pardo Ž2000.
Toluene 278᎐318 0.1 5 Sakurai Ž1990.
373᎐643 10᎐30 7 Degrange Ž1998.
523᎐623 10᎐30 4 Pardo Ž2000.
Ethylbenzene 278᎐318 0.1 5 Sakurai Ž1990.
523᎐623 10᎐30 5 Pardo Ž2000.
o-Xylene 523᎐623 10᎐30 4 Pardo Ž2000.
m-Xylene 523᎐623 10᎐30 3 Pardo Ž2000.
p-Xylene 523᎐623 10᎐30 4 Pardo Ž2000.
Alcohols
Methanol 273᎐333 0.1 6 Alexander Ž1959a.
278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐348 0.1 4 Makhatadze et al. Ž1990.
278᎐318 0.1 5 Sakurai et al. Ž1994.
323᎐573 0.1᎐13.5 14 Xiao et al. Ž1997.
Ethanol 273᎐333 0.1 6 Alexander Ž1959a.
278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐318 0.1 5 Sakurai et al. Ž1994.
1-Propanol 273᎐333 0.1 6 Alexander Ž1959a.
278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐313 0.1 4 Hoiland Ž1980.
298᎐523 28 8 Criss and Wood Ž1996.
2-Propanol 278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐318 0.1 5 Sakurai Ž1988.
278᎐313 0.1 4 Hoiland Ž1980.
283᎐298 0.1 2 Roux et al. Ž1980.
301᎐523 0.1᎐28 7 Schulte et al. Ž1999.
1-Butanol 273᎐333 0.1 4 Alexander Ž1959a.
278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐313 0.1 4 Hoiland Ž1980.
274 0.1 1 Franks and Smith Ž1968.
2-Butanol 278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐313 0.1 4 Hoiland Ž1980.
274.15 0.1 1 Franks and Smith Ž1968.
2-Methyl-1-Propanol 278᎐318 0.1 5 Sakurai et al. Ž1994.
298 0.1 1 Hoiland Ž1986.
2-Methyl-2-Propanol 278᎐318 0.1 8 Sakurai et al. Ž1994.
278᎐318 0.1 7 Sakurai Ž1987.
274 0.1 1 Franks and Smith Ž1968.
298 0.1 1 Hoiland Ž1986.
1-Pentanol 273᎐333 0.1 4 Alexander Ž1959a.
278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐313 0.1 4 Hoiland Ž1980.
298᎐413 19 8 Inglese and Wood Ž1996.
2,2-Dimethyl-1-propanol 283 0.1 1 Roux et al. Ž1980.
2-Methyl-2-Butanol 278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐318 0.1 5 Sakurai Ž1989.
298 0.1 1 Cabani et al. Ž1981.
283᎐298 0.1 2 Roux et al. Ž1980.
1-Hexanol 278᎐318 0.1 5 Sakurai et al. Ž1994.
278᎐313 0.1 4 Hoiland Ž1980.
2-Pentanol 278᎐313 0.1 4 Hoiland Ž1980.
2-Hexanol 278᎐313 0.1 4 Hoiland Ž1980.
1,3-Propanediol 278᎐318 0.1 3 Nakajima et al. Ž1975.

Table 6. Standard Molar Volumes (Continued)
Temp. Pres. No. of
278᎐313 0.1 4 Hoiland Ž1980.
1,3-Butanediol 273᎐333 0.1 4 Alexander Ž1959a.
1,4-Butanediol 278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐313 0.1 4 Hoiland Ž1980.
298᎐523 28 8 Criss and Wood Ž1996.
1,5-Pentanediol 278᎐318 0.1 3 Nakajima et al. Ž1975.
301᎐523 0.1᎐28 7 Schulte et al. Ž1999.
1,6-Hexanediol 278᎐318 0.1 3 Nakajima et al. Ž1975.
278᎐313 0.1 4 Hoiland Ž1980.
298᎐523 28 8 Criss and Wood Ž1996.
1,7-Heptanediol 278᎐313 0.1 4 Hoiland Ž1980.
2-Propen-1-ol 298 0.1 1 Cabani et al. Ž1981.
Cyclohexanol 301᎐523 0.1᎐28 7 Schulte et al. Ž1999.
Benzyl alcohol 301᎐523 0.1᎐28 7 Schulte et al. Ž1999.
pounds including group contributions that are only scarcely terest, such as
present in the data set, namely the quaternary and ternary
carbon functional groups and the unsaturated bond, in order N
to improve representation of these functional groups in the as Ý n i ai and so on Ž 30.
correlation. is1
where a i is the parameter for i-th functional group. The point

Results and Discussion mass Žstandard state. contribution to a given property ŽEq.
The model equations from the Appendix can be used if all 28. is already included in the equations in the Appendix. Pa-
of the five adjustable parameters a, b, c, d, and e are known rameters of the functional groups were obtained by simulta-
for a given solute. Because the model linearly depends on neous correlation of data on hydration properties of aqueous
adjustable parameters, the group contribution scheme is ap- hydrocarbons and alcohols obtained as described above. For
plied most easily by calculating each parameter as a sum of the sake of consistency, the most abundant data on HLC were
parameters for functional groups present in the solute of in- converted before correlation to ⌬GThyd using Eq. 4. The ob-
Table 7. Standard Molar Heat Capacities

Temp. Pres. No. of
Hydrocarbons
2,2-Dimethylpropane 298 0.1 1 Cabani et al. Ž1981.
Ethene 298 0.1 1 Cabani et al. Ž1981.
1-Propene 298 0.1 1 Cabani et al. Ž1981.
2-Methyl-1-propane 298 0.1 1 Cabani et al. Ž1981.
Benzene 278᎐413 0.6 8 Makhatadze and Privalov Ž1988.
Toluene 278᎐413 0.6 8 Makhatadze and Privalov Ž1988.
Alcohols
Methanol 278᎐348 0.1 4 Makhatadze and Privalov Ž1990.
Ethanol 278᎐348 0.1 4 Makhatadze and Privalov Ž1989.
1-Propanol 278᎐348 0.1 4 Makhatadze and Privalov Ž1989.
303᎐523 28 3 Inglese and Wood Ž1996.
2-Propanol 283᎐298 0.1 2 Roux et al. Ž1980.
1-Butanol 278᎐348 0.1 4 Makhatadze and Privalov Ž1989.
2-Methyl-1-Propanol 298 0.1 1 Cabani et al. Ž1981.
2-Methyl-2-Propanol 298 0.1 1 Cabani et al. Ž1981.
1-Pentanol 278᎐348 0.1 4 Makhatadze and Privalov Ž1989.
2-Methyl-2-Butanol 298 0.1 1 Cabani et al. Ž1981.
283᎐298 0.1 2 Roux et al. Ž1980.
2,2-Dimethyl-1-Propanol 298 0.1 1 Cabani et al. Ž1981.
283 0.1 1 Roux et al. Ž1980.
1,4-Butanediol 303᎐523 28 4 Inglese and Wood Ž1996.
1,6-Hexanediol 303᎐523 28 4 Inglese and Wood Ž1996.
2-Propene-1-ol 298 0.1 1 Cabani et al. Ž1981.
2-Butene-1-ol 298 0.1 1 Cabani et al. Ž1981.
3-Butene-1-ol 298 0.1 1 Cabani et al. Ž1981.
4-Pentene-1-ol 298 0.1 1 Cabani et al. Ž1981.

Figure 2a. Henry’s Law constant calculated with the new model vs. experimental data along the saturation line of
water: pentane, hexane, octane, 1-hexene, 1-octene, cyclohexane, butylcyclohexane, benzene, toluene,
ethylbenzene, m-diethylbenzene, p-diisopropylbenzene.
References: pentane, ᎏ this work, 䢇 Jou and Mather Ž2000., ' Jonsson
¨ et al. Ž1982.; hexane, ᎏ this work, 䢇 Jonsson
¨ et al. Ž1982., '
Tsonopoulos and Wilson Ž1983 .; octane, ᎏ this work, 䢇 Heidman et al. Ž1985., ' Jonsson
¨ et al. Ž1982 .; 1-hexene, ᎏ this work, 䢇 Economou
et al. Ž1997 .; 1-octene, ᎏ this work, 䢇 Economou et al. Ž1997.; cyclohexane, ᎏ this work, 䢇 Tsonopoulos and Wilson Ž1983., ' de
Hemptinne et al. Ž1998 .; butylcyclohexane, ᎏ this work, 䢇 Economou et al. Ž1997.; benzene, ᎏ this work, 䢇 Tsonopoulos and Wilson
Ž1983 ., ' Anderson and Prausnitz Ž1986 ., B Chen and Wagner Ž1994a ., % Chandler et al. Ž1998 .; toluene, ᎏ this work, 䢇 Anderson and
Prausnitz Ž1986 ., ' Chen and Wagner Ž1994b ., B Chandler et al. Ž1998 .; ethylbenzene, ᎏ this work, 䢇 Heidman et al. Ž1985., ' Owens et
al. Ž1986 ., B Chen and Wagner Ž1994c .; m-diethylbenzene, ᎏ this work, 䢇 Economou et al. Ž1997.; p-diisopropylbenzene, ᎏ this work, 䢇
Economou et al. Ž1997 ..

Figure 2b. Henry’s Law constant calculated with the new model vs. experimental data along the saturation line of
water: pentane, hexane, octane, 1-hexene, 1-octene, cyclohexane, butylcyclohexane, benzene, toluene,
ethylbenzene, m-diethylbenzene, p-diisopropylbenzene.
References: pentane, ᎏ this work, 䢇 Jou and Mather Ž2000., ' Jonsson
¨ et al. Ž1982 .; hexane, ᎏ this work, 䢇 Jonsson
¨ et al. Ž1982., '
Tsonopoulos and Wilson Ž1983 .; octane, ᎏ this work, 䢇 Heidman et al. Ž1985., ' Jonsson ¨ et al. Ž1982 .; 1-hexene, ᎏ this work, 䢇
Economou et al. Ž1997 .; 1-octene, ᎏ this work, 䢇 Economou et al. Ž1997.; cyclohexane, ᎏ this work, 䢇 Tsonopoulos and Wilson Ž1983., '
de Hemptinne et al. Ž1998 .; butylcyclohexane, ᎏ this work, 䢇 Economou et al. Ž1997.; benzene, ᎏ this work, 䢇 Tsonopoulos and Wilson
Ž1983 ., ' Anderson and Prausnitz Ž1986 ., B Chen and Wagner Ž1994a ., % Chandler et al. Ž1998 .; toluene, ᎏ this work, 䢇 Anderson and
Prausnitz Ž1986 ., ' Chen and Wagner Ž1994b ., B Chandler et al. Ž1998 .; ethylbenzene, ᎏ this work, 䢇 Heidman et al. Ž1985., ' Owens et
al. Ž1986 ., B Chen and Wagner Ž1994c .; m-diethylbenzene, ᎏ this work, 䢇 Economou et al. Ž1997.; p-diisopropylbenzene, ᎏ this work, 䢇
Economou et al. Ž1997 ..

jective function for optimization had the following form
2
O ⌬GThyd
,exp
y ⌬GThyd
,calc
Fs Ýž
is1 ␴ ⌬GThyd / i
2 2
P ⌬ HThyd
,exp
y ⌬ HThyd
,calc Q
⌬CTp,exp
,hyd y ⌬C p ,hyd
T,calc
q Ýž ␴ ⌬ HT / q Ý ž ␴ ⌬CTp ,hyd /
js 1 hyd j k s1 k
T,exp T,calc 2
R Vs yVs
q Ý
ls1
ž ␴ VsT / l
Ž 31 .
where ␴ ⌬YT hyd is the estimated uncertainty of a given data

point, and O, P, Q and R are the numbers of data points for
each property. The variables Y T,exp were derived from experi-
mental data, while those denoted as Y T,calc were calculated
from Eq. 23 for ⌬GThyd and for ⌬ HT hyd analogously from the Figure 3b. Henry’s Law constant of benzene, ethylben-
relationship zene and m-diethylbenzene: test of ethyl
group substitution.
⌬ HT T lit T mod
hyd Ž T , p . s ⌬ H hyd Ž Tref , pref . q ⌬ H hyd Ž T , p . Displayed are experimental data from major sources.
y ⌬ HT mod
hyd Ž Tref , pref . Ž 32.
for maintaining consistency with the enthalpic data at the ref- temperature and, thus, the distinction is made for orthodi-
erence conditions generated from the group contributions alkylbenzenes and cis-dialkylcycloalkanes in our high-tem-
determined by Plyasunov and Shock Ž2000a.. Expressions used perature predictions.
for CTp,hyd and VsT are directly the model equations listed The estimated uncertainties ␴ YT in Eq. 31 play a role of
in the Appendix, without any constraint at the reference weighting factors reflecting reliability of experimental data
conditions. In this way we obtained five parameters of the and error margin within which we want to reproduce the given
temperature-dependent SOCW model for ten hydrocarbon property. In assignment of these weighting factors it is in-
functional groups in Table 2 Žthe value of the OH group is evitable to also take into account the inherent error of the
considered only as provisional.. Compared to the reference functional group additivity assumption. The weighting scheme
state group contribution scheme, we omitted the correction employed here intended to yield the most reliable predictions
for proximity effect IŽC-C. due to an insufficient amount of over the entire temperature and pressure range, and to bal-
data at elevated conditions for relevant hydrocarbon struc- ance the impact of different properties on the overall fit. The
tures. However, the correction at reference conditions also uncertainties were therefore assigned to each property in such
probably accounts for most of the proximity effect at higher a way that, on average, the data on this property were de-
scribed by our model at the limits of the estimated uncer-
tainty. In the case of ⌬GThyd the data sources on HLC were
divided into five classes depending on data quality Žwhich
sometimes changed with temperature . and the assignment of
uncertainties was done using a simple relation ␴ ⌬GThyd s 0.2
q0.1 ⴢ C wkJrmolx where C is the uncertainty class ranging
from 1 to 5. This error margin corresponds to about 10᎐40%
relative error in K H . The uncertainties assigned to derivative
properties were in most cases somewhat higher than the ex-
pected experimental errors in calorimetric and volumetric
data. The data of highest accuracy were those available for
standard molar volumes and heat capacities of aqueous alco-
hols near ambient conditions. However, directly using experi-
mental uncertainties associated with these data in our simul-
taneous correlation would lead to overweighting of derivative
properties at the expense of a good fit to HLC. The values of
␴ YT for derivative properties were finally set to 8% for
⌬ HT Ž . T
hyd but at least 1.2 kJrmol , 5% for ⌬C p,hyd at least 13
Ž
T 3
JrKrmol., and 0.8% for Vs Žat least 0.5 cm rmol.. It should
Figure 3a. Henry’s Law constant of homologous series be noted that the adopted weighting scheme at the same time
of alkylbenzenes: test of methylene group provides an assessment of the expected prediction uncertain-
addition. ties of K H and of the derivative hydration properties for
Displayed are experimental data from major sources. aqueous hydrocarbons which were treated by our group con-

Figure 4a. Tests of calculated Henry’s Law constant vs. experimental data excluded from regression along the satu-
ration line of water: ethane, butane, decane, methylcyclohexane, butylbenzene and hexylbenzene.
References: ethane, ᎏ this work, 䢇 Fernandez Prini and Crovetto Ž1989.; butane, ᎏ this work, 䢇 Carroll and Mather Ž1997.; decane, ᎏ
this work, 䢇 Baker Ž1959.; ' Franks Ž1966 ., % Krasnoshchekova and Gubercrits Ž1973 ., ` Mackay and Shiu Ž1975 ., ^ Becke and
Quitzsch Ž1977 ., I Economou et al. Ž1997 .; methylcyclohexane, ᎏ this work, 䢇 Jose Ž2001., ' Price Ž1976 .; butylbenzene, ᎏ this work, 䢇
Owens et al. Ž1986 ., Chen and Wagner Ž1994c .; hexylbenzene, ᎏ this work, 䢇 May et al. Ž1983., ' Owens et al. Ž1986 ..
tribution procedure, or which are reasonably similar by their along the saturation line of water are given in Figure 1.
structure to our training set used in correlation. Structural elements governing total ⌬GThyd for hydrocarbons
The plots of temperature evolution of the functional group Žmethyl, methylene, c-CH 2 and CH ar groups. exhibit a maxi-
contributions to ⌬GThyd and to its first derivatives calculated mum in the range from 400 K to 450 K that is consistent with

Figure 4b. Tests of calculated Henry’s Law constant vs. experimental data at elevated pressures.
Ethane, propane ŽKobayashi and Katz, 1953., 1-butene ŽLeland et al., 1955.: data for these three compounds were included in regression.
Toluene, ethylbenzene, propylbenzene Žall Sawamura et al., Ž2001..: data for these three compounds were not included in regression.
References: Ethane: 䢇 Culberson and McKetta Ž1950., '
Danneil et al. Ž1967 ., B Dhima et al. Ž1998 ., ᎏ this work.
the occurrence of maximum in HLC for hydrophobic solutes. pounds. This is, however, not surprising due to an easy polar-
The trend is reversed mainly for the C sC contribution of ization of the double bond. The temperature evolution of
alkenes, which mimics behavior of polar Žhydrophilic. com- functional groups for derivative properties also follows ex-

pected paths and are in accordance with our previous find- In concluding the discussion on expected errors, we would
ings ŽYezdimer et al., 2000.. Prevailing hydrophobic charac- like to emphasize once more what are the sources of uncer-
ter of hydrocarbons dictates positive divergence of the lead- tainties associated with high-temperature predictions of HLC.
ing functional groups for VsT and ⌬ HT hyd near the critical There are model errors and extrapolation uncertainty, con-
point of a solvent. nected mainly with functional groups for which only few data
Figure 2 compares predicted HLC with representative lit- were available at elevated conditions such as groups in
erature data along the saturation line of water for several branched chains. A major source of error is, however, the
compounds reflecting variety of hydrocarbon structures pre- assumption of group additivity in the adopted scheme, which
sent in the database. For convenience, the graphs also in- sets the limits for appropriate use of the group contribution
clude deviation plots in terms of percentage difference be- method. This uncertainty affects mainly the reference values
tween the literature and predicted HLC. It follows from Fig- of ⌬GThyd ,lit
ŽTref , pref . and ⌬ SThyd
,lit
ŽTref , pref . determining the error
ure 2 that our group contribution scheme provided predic- at both reference level by ⌬GThyd ,lit
ŽTref , pref . and at high tem-
tion of HLC in the limits of uncertainties, as estimated above, peratures additionally by T yTref . ⌬ SThyd
Ž ,lit
ŽTref , pref . term in
for all test solutes with the exception of ethylbenzene at ele- Eq. 23. Plyasunov and Shock Ž2000a. estimated these errors
vated temperatures. The reason for this discrepancy is that to be at least 0.5 kJrmol and 8 JrKrmol, respectively, which
data of Heidman et al. Ž1985. do not comply with the group transforms to 20% relative uncertainty in K H at 298 K, 40%
additivity assumption. Figure 3a displays in detail experimen- at 400 K, and about the same at 500 K Žrelative error in HLC
tal HLC for benzene, toluene, ethyl-, propyl- and butylben- ␦ K HrK H is given by Žexpw ␦ Ž ⌬GThyd .rRT xy1., in linear ap-
zene. Considering additivity of the CH 2 group addition, the proximation by ␦ Ž ⌬GThyd .rRT .. This effect is in most part in-
difference between toluene and any other higher alkylben- cluded in the estimate of uncertainties utilized in the regres-
zene should be the same at each temperature. This approxi- sion as stated above, but, in predictions beyond the classes of
mately holds true at lower temperatures, but the results of compounds considered in correlation, it may lead to impor-
Heidman et al. seem to deviate from this path at tempera- tant additional errors. This is true namely for alkanes with
tures over 400 K. Figure 3b shows variation of HLC of ben- over twelve carbon atoms, for which the predictions of
zene, ethylbenzene, and diethylbenzene where the differ- ⌬GThyd
,lit
ŽTref , pref . from the group contribution scheme by Plya-
ences between neighbor pairs should again be comparable at sunov and Shock Ž2000a. are inappropriate. While the method
the same conditions. The experimental data from both plots of Plyasunov and Shock suggests a continuing increase in hy-
on ethylbenzene at high temperatures seem to be much too drophobic nature with an increasing carbon number, avail-
high, although we do not dare to draw any final conclusion able experimental data on solubility of long chain alkanes
before some new experimental results supplement the only ŽBaker, 1959; Franks, 1966; Sutton and Calder, 1974; Bergin,
existing high-temperature study on this solute. 2002. indicate that this trend is much weaker for n-alkanes
The first part of Figure 4a displays comparison of pre- with over twelve carbon atoms. This effect may be explained
dicted and experimental results along the saturation line of by structural collapse of the long chains, which might be fold-
water for several data sets that were not included in correla- ing and thus decreasing their hydrophobic surface ŽTsono-
tion Žethane, butane, n-decane, methylcyclohexane, butylben- poulos, 1999.. A simple group contribution method is there-
zene, and hexylbenzene .. Predicted lines show a fair consis- fore not recommended for predicting HLC of hydrocarbons
tency with the experimental points, except for very large dis- containing more than twelve carbon atoms in the backbone
agreement with data on n-decane. This solute has been stud- aliphatic chain.
ied mainly at ambient conditions, but, even at those condi- The group contribution model presented in this article is
tions, the scatter of various reported results is in several or- rather complex. To facilitate its use in potential applications
ders of magnitude. The authors of the only available high- we decided to implement the equations and parameters re-
temperature data set ŽEconomou et al., 1997. noticed appeal- ported here into a software tool, which is free for a noncom-
ing inconsistency of their HLC with the homologous additiv- mercial use and is presented in a separate paper ŽMajer et
ity scheme, which is also a reason for the discrepancy with al., 2002..
our prediction. Since the model description of most experi-
mental data for n-alkanes is good up to octane and reason-
able even for dodecane Žfor which new experimental results Conclusions
were obtained by Bergin Ž2002.., we consider in agreement Available literature data for HLC and for the related
with Economou et al. the data for decane as doubtful. A sim- derivative properties of aqueous hydrocarbons at elevated
ilar problem, although in a lesser extent, was observed also conditions were collected and converted to standard molar
for 1-decene from the same literature source. thermodynamic functions of hydration. The prepared
Finally, Figure 4b includes a set of plots for HLC by the databases were used for establishing a group contribution
group contribution scheme compared to data for ethane, method, based on the SOCW thermodynamic model. Param-
propane, 1-butene, toluene, ethylbenzene, and propylben- eters of the model equations are reported for ten hydrocar-
zene at pressures remote from the saturation line of water bon functional groups: C, CH, CH 2 , CH 3 , c-CH, c-CH 2 ,
Žhigh-pressure data for the three alkylbenzenes are also new CH ar , C ar , C sC, and H ␲ , leading to predictions of HLC
database additions and were not included in correlation.. and of the related standard molar thermodynamic properties
Predictions tend to somewhat shifted pressure effects com- of hydration at elevated temperature and pressure for aque-
pared to experimental values, namely at very low tempera- ous alkanes, alkenes, cycloalkanes, and Žalkyl.benzenes. The
tures, but the differences are within estimated uncertainty predictions are provided to at least 570 K and 100 MPa and
limits to at least 150 MPa for all test solutes. for compounds including up to twelve carbon atoms in the

aliphatic backbone chain. Our interest was not to quantita- ␬ sisothermal compressibility, Pay1
tively reproduce the behavior of HLC in the close vicinity of ␳ sdensity, kgrm3
␴ sabsolute error
the critical point of water. In such a case the approach pro- ␸ sfugacity coefficient
posed here by Japas and Levelt-Sengers Ž1989. should be
preferred. However, considering the physically reasonable Subscripts
temperature extrapolation of presented group contributions, air sair
we believe that in most cases the results provided by our aq saqueous
scheme will be semiquantitatively correct even at near critical awsair-water
conditions. cscritical
In addition to practical calculations the group contribution sssolute
SSsstandard state
scheme can be employed as a consistency check for new ex- sol sdissolution
perimental determinations on HLC, solubility or other re- hyd shydration
lated properties for alkanesralkenes up to C 12 , and for Žal- ref sreference conditions
kyl.cyclohexanesrbenzenes with one to three alkyl chains up res sresidual
vapsvaporization
to typically C 6 . While it is clear that group additivity assump- w swater
tion has its limitations, it is well-established thermodynamic
regularity and any large disagreement calls for a physically Superscripts
sound explanation. T sstandard state of unit concentration referenced to infinite dilu-
The new group contribution method is intended as a basis tion
for later extensions, covering also polar and ionic organic ⬁sinfinite dilution in the symmetrical standard state convention
functional groups. An important advantage of our scheme re- calc scalculated value
garding this task is a consistent methodology and data repre- cor scorrection
expsexperimental value
sentation in terms of hydration properties. The employed ig sideal gas standard state
thermodynamic model is capable of the description of all types lit sliterature value
of solutes and since the hydrocarbon functional group contri- modscalculated from model
butions were evaluated here with a high confidence level, it sat ssaturation
sol sdissolution
will be possible to keep them unchanged in the correlations
of data for any newly included groups.
Literature Cited
Acknowledgments Abraham, M. H., J. Andonian-Haftvan, G. S. Whithing, A. Leo, and
S. Taft, ‘‘Hydrogen Bonding. Part 34. The Factors that Influence
This work was partly supported by the American Chemistry Coun-
the Solubility of Gases and Vapors in Water at 298 K, and a New
cil ŽJ. S. and V. M.. and by TotalFinaElf and GDF ŽPhD stipend of
Method for its Determination,’’ J. Chem. Soc. Perkin Trans., 2, 1777
G. B... Mobility costs between Czech Rep. and France ŽJ. S. and V.
Ž1994..
M.. were covered under Barrande exchange program 968QB. J. S.
Alexander, D. M., ‘‘Apparent Molar Volumes of Alcohols in Dilute
acknowledges also support by the Research Plan MSM 254100303
Aqueous Solutions,’’ J. Chem. Eng. Data, 4, 252 Ž1959a..
and by the International Association for the Properties of Water and
Alexander, D. M., ‘‘The Solubility of Benzene in Water,’’ J. Phys.
Steam ŽIAPWS Fellowship .. The authors thank Andrey Plyasunov
Chem., 63, 1021 Ž1959b..
and Everett Shock for sharing their collection of solubility data on
Anderson, F. E., and J. M. Prausnitz, ‘‘Mutual Solubilities and Va-
hydrocarbon-water systems. G. B. benefited from the expertise of
por Pressures for Binary and Ternary Aqueous Systems Contain-
Stanley Sandler in use of the equations of state Ž6-month stay at the
ing Benzene, Toluene, m-Xylene, Thiophene and Pyridine in the
University of Delaware ..
Region 100᎐200T C,’’ Fluid Phase Equilibria, 32, 63 Ž1986..
Anthony, R. G., and J. J. McKetta, ‘‘Phase Equilibrium in the Eth-
Notation ylene-Water System,’’ J. Chem. Eng. Data, 12, 17 Ž1967..
Asmodified Krichevskii parameter Arnold, D. S., C. A. Plank, E. E. Ericson, and F. P. Pike, ‘‘Solubility
Bssecond virial coefficient, m3rkg of Benzene in Water,’’ Chem. Eng. Data Ser., 3, 253 Ž1958..
C smolar concentration, molrdm3 Azarnoosh, A., and J. J. McKetta, ‘‘The Solubility of Propane in Wa-
C s,w sintegral of the solute-water direct correlation function ter,’’ Petrol. Refin., 37, 275 Ž1958..
C p sheat capacity, JrKrmol Baker, E. G., ‘‘Origin and Migration of Oil,’’ Science, 129, 871 Ž1959..
f sfugacity, Pa Barrufet, M. A., K. Liu, S. Rahman, and C. Wu, ‘‘Simultaneous Va-
GsGibbs free energy, Jrmol por-Liquid-Liquid Equilibria and Phase Molar Densities of a Qua-
H senthalpy, Jrmol ternary System of Propane q Pentane q Octane q Water,’’ J.
K H sHenry’s law constant, Pa Chem. Eng. Data, 41, 918 Ž1996..
M smolar mass, kg Becke, A., and G. Quitzsch, Chem. Techn., 29, 49 Ž1977..
nsnumber of moles Ben-Naim, A., and J. Wiff, ‘‘A Direct Measurement of Intramolecu-
pspressure, Pa lar Hydrophobic Interactions,’’ J. Chem. Phys., 70, 771 Ž1979..
Rsgas constant, JrKrmol Ben-Naim, A., Sol®ation Thermodynamics, Plenum Press, New York
Ssentropy, JrKrmol Ž1987..
T stemperature, K Bergin, G., ‘‘Prevision de la Solubilite ´ des Hydrocarbures dans l’Eau
V svolume, m3 en Fonction de la Temperature´ et de la Pression,’’ PhD Thesis,
x smolar fraction University Blaise Pascal, Clermont-Ferrand, France Ž2002..
Beutier, D., and H. Renon, ‘‘Gas Solubilities Near the Solvent Criti-
Greek letters cal Point,’’ AIChE J., 24, 1122 Ž1978..
¨
Bittrich, H.-J., A. Fahl, and F. Hartwig, ‘‘Zur Loslichkeitsbeeinflus-
␣ scoefficient of thermal expansion, Ky1 sung von Kohlenwasserstoffen in Wasser. II. Der Einfluss von
␦ srelative error Guarternaren Ammoniumsalzen,’’ Z. phys. Chem. (Leipzig), 264, 891
␥ sactivity coefficient Ž1983..
⌬ sfinite change Bohon, R. L., and W. F. Claussen, ‘‘The Solubility of Aromatic Hy-

drocarbons in Water,’’ J. Am. Chem. Soc., 72, 1751 Ž1951.. Pascal, Clermont-Ferrand, France Ž1998..
Borisover, M. D., F. D. Baitalov, and B. N. Solomonov, ‘‘Enthalpies ´
de Hemptinne, J. C., H. Delepine, C. Jose, and J. Jose, ‘‘Aqueous
and Gibbs Energies of Hydration of Aromatic Hydrocarbons and Solubility of Aqueous Mixtures,’’ Re®ue de l’institut français du
Their Halogen Derivatives Žin Russian.,’’ Zh. Obsh. Khim., 61, 2629 ´
petrole, 53, 409 Ž1998..
Ž1991.. Dhima, A., J.-C. de Hemptinne, and G. Moracchini, ‘‘Solubility of
Bradbury, E. J., D. McNulty, R. L. Savage, and E. E. McSweeney, Light Hydrocarbons and Their Mixtures in Pure Water under High
‘‘Solubility of Ethylene in Water, Effect of Temperature and Pres- Pressure,’’ Fluid Phase Equil., 145, 129 Ž1998..
sure,’’ Ind. Eng. Chem., 44, 211 Ž1952.. Dutta-Choudhury, M. K., N. Miljevic, and W. A. Van Hook, ‘‘Iso-
Bradley, R. S., M. J. Dew, and D. C. Munro, ‘‘The Solubility of Ben- tope Effects in Aqueous Systems. 13. The Hydrophobic Interac-
zene and Toluene in Water and Aqueous Salt Solutions under tion. Some Thermodynamic Properties of BenzenerWater and
Pressure,’’ High Temp.-High Press., 5, 169 Ž1973.. ToluenerWater Solutions and Their Isotope Effects,’’ J. Phys.
Brown, R. L., and S. P. Wasik, ‘‘A Method of Measuring the Solubil- Chem., 86, 1711 Ž1982..
ities of Hydrocarbons in Aqueous Solutions,’’ J. Res. NBS, 78A, 453 Eckert, C. A., and S. R. Sherman, ‘‘Measurement and Prediction of
Ž1974.. Limiting Activity Coefficients,’’ Fluid Phase Equilib., 116, 333 Ž1996..
Brunner, G., A. Steffen, and R. Dohrn, ‘‘High Pressure Liquid-Liquid Economou, I. G., J. L. Heidman, C. Tsonopoulos, and G. M. Wilson,
Equilibria in Ternary Systems Containing Water, Benzene, ‘‘Mutual Solubilities of Hydrocarbons in Water: III. 1-Hexene, 1-
Toluene, n-Hexane and n-Hexadecane,’’ Fluid Phase Equil., 82, 165 Octene, C 10 -C 12 Hydrocarbons,’’ AIChE J., 43, 535 Ž1997..
Ž1993.. Economou, I. G., and C. Tsonopoulos, ‘‘Associating Models and
Burris, D. R., and W. G. MacIntyre, ‘‘Water Solubility Behavior of Mixing Rules in Equations of State for WaterrHydrocarbon Mix-
Binary Hydrocarbon Mixtures,’’ En®iron. Toxicol. Chem., 4, 371 tures,’’ Chem. Eng. Sci., 52, 511 Ž1997..
Ž1985.. Fernandez-Prini, R., and R. Crovetto, ‘‘Evaluation of Data on Solu-
Busantseva, L. S., T. M. Lesteva, and M. S. Nemstov, Zh. Fiz. Khim., bility of Simple Apolar Gases in Light and Heavy Water at High
50, 1344 Ž1976.. Temperature,’’ J. Phys. Chem. Ref. Data, 18, 1231 Ž1989..
Cabani, S., P. Gianni, V. Mollica, and L. Lepori, ‘‘Group Contribu- Franks, F., ‘‘Solute-Water Interactions and the Solubility Behaviour
tions to the Thermodynamic Properties of Non-Ionic Organic So- of Long-Chain Paraffin Hydrocarbons,’’ Nature, 20, 87 Ž1966..
lutes in Dilute Aqueous Solution,’’ J. Sol. Chem., 10, 563 Ž1981.. Franks, F., and H. T. Smith, ‘‘Precision Densities of Dilute Aqueous
Carroll, J. J., and A. E. Mather, ‘‘A Model for the Solubility of Light Solutions of the Isomeric Butanols,’’ J. Chem. Eng. Data, 13, 538
Hydrocarbons in Water and Aqueous Solutions of Alkanolamines,’’ Ž1968..
Chem. Eng. Sci., 52, 545 Ž1997.. Franks, F., M. Gent, and H. H. Johnson, ‘‘The Solubility of Benzene
Chandler, K., B. Eason, C. Liotta, and C. A. Eckert, ‘‘Phase Equilib- in Water,’’ J. Chem. Soc., 2716 Ž1963..
ria for Binary Aqueous Systems from a Near-Critical Water Reac- ¨ ‘‘Calorimetric Determination
Gill, S. J., N. F. Nichols, and I. Wadso,
tion Apparatus,’’ Ind. Eng. Chem. Res., 37, 3515 Ž1998.. of Enthalpies of Solution of Slightly Soluble Liquids: I. Applica-
Chen, H., and J. Wagner, ‘‘An Apparatus and Procedure for Measur- tion to Benzene in Water,’’ J. Chem. Thermodyn., 7, 175 Ž1975..
ing Mutual Solubilities of Hydrocarbons q Water: Benzene q ¨ ‘‘Calorimetric Determination
Gill, S. J., N. F. Nichols, and I. Wadso,
Water from 303 to 373 K,’’ J. Chem. Eng. Data, 39, 470 Ž1994a.. of Enthalpies of Solution of Slightly Soluble Liquids: II. Enthalpy
Chen, H., and J. Wagner, ‘‘An Efficient and Reliable Gas Chomato- of Solution of Some Hydrocarbons in Water and Their Use in Es-
graphic Method for Measuring Liquid-Liquid Mutual Solubilities tablishing the Temperature Dependence of Their Solubilities,’’ J.
in Alkylbenzene q Water Mixtures: Toluene q Water from 303 Chem. Thermodyn., 7, 175 Ž1976..
to 373 K,’’ J. Chem. Eng. Data, 39, 475 Ž1994b.. Gillespie, P. C., and G. M. Wilson, ‘‘Vapor-Liquid and Liquid-Liquid
Chen, H., and J. Wagner, ‘‘Mutual Solubilities of Alkylbenzene q Equilibria: Water-Methane, Water-Carbon Dioxide, Water-Hydro-
Water Systems at Temperatures from 303 to 373 K: Ethylbenzene, gen Sulfide, Water-n-Pentane, Water-Methane-n-Pentane,’’ Re-
p-Xylene, 1,3,5-Trymethylbenzene, and Butylbenzene,’’ J. Chem. search Report, RR-48, Gas Processor Association Ž1982..
Eng. Data, 39, 679 Ž1994c.. Gross, P. M., and J. H. Saylor, ‘‘The Solubilities of Slightly Soluble
Chernoglazova, F. S., and Yu N. Simulin, ‘‘Mutual Solubility in the Organic Compounds in Water,’’ J. Amer. Chem. Soc., 53, 1744
System m-Xylene-Water Žin Russian.,’’ Zh. Fiz. Khim., 50, 809 Ž1931..
Ž1976.. Guillaume, D., S. Tkachenko, J. Dubessy, and J. Pironon, ‘‘High-
Chey, W., and G. V. Calder, ‘‘Method for Determining Solubility of Temperature and High-Pressure Water Solubility in Ethylbenzene
Slightly Soluble Organic Compounds,’’ J. Chem. Eng. Data, 17, 199 to 200⬚C and 1 kbar and the Acetic Acid Effect,’’ Geochim. Cos-
Ž1975.. mochim. Acta, 65, 3319 Ž2001..
Connoly, J.F., ‘‘Solubility of Hydrocarbons in Water Near the Criti- Haruki, M., Y. Iwai, S. Nagao, Y. Yahiro, and Y. Arai, ‘‘Measure-
cal Solution Temperatures,’’ J. Chem. Eng. Data, 11, 13 Ž1966.. ment and Correlation of Phase Equilibria for Water Hydrocarbon
Cooling, M. R., B. Khalfaoui, and D. M. T. Newsham, ‘‘3Phase Equi- Systems Near the Critical Temperature and Pressure of Water,’’
libria in Very Dilute Mixtures of Water and Unsaturated Chlori- Ind. Eng. Chem. Res., 39, 4516 Ž2000..
nated Hydrocarbons and of Water and Benzene,’’ Fluid Phase Harvey, A. H., and J. H. M. Levelt Sengers, ‘‘Correlation of Aqueous
Equilib., 81, 217 Ž1992.. Henry’s Constants from 0⬚C to the Critical Point,’’ AIChE J., 36Ž4.,
Criss, C. M., and R. H. Wood, ‘‘Apparent Molar Volumes of Aque- 539 Ž1990..
ous Solutions of Some Organic Solutes at the Pressure 28 MPa Harvey, A. H., J. H. M. Levelt Sengers, and J. C. Tanger IV, ‘‘Uni-
and Temperatures to 598 K,’’ J. Chem. Thermodyn., 28, 723 Ž1996.. fied Description of Infinite-Dilution Thermodynamic Properties for
Crovetto, R., ‘‘Evaluation of Solubility Data on the System CO 2-H 2 O Aqueous Species,’’ J. Phys. Chem., 95, 932 Ž1991..
from 273 K to the Critical Point of Water,’’ J. Phys. Chem. Ref. Harvey, A. H., ‘‘Semiempirical Correlation for Henry’s Constants
Data, 20, 575 Ž1991.. Over Large Temperature Ranges,’’ AIChE J., 42, 1491 Ž1996..
Culberson, O. L., and J. J. McKetta, Jr., ‘‘Phase Equilibria in Hydro- Harvey, A. H., ‘‘Applications of Near-Critical Dilute-Solution Ther-
carbon-Water Systems: II. The Solubility of Ethane in Water at modynamics,’’ Ind. Eng. Chem. Res., 37, 3080 Ž1998..
Pressures to 10,000 Psi,’’ Petroleum Trans., AIME, 189, 319 Ž1950.. Heidman, J. L., C. Tsonopoulos, C. J. Brady, and G. M. Wilson,
¨
Danneil, A., K. Todheide, and E. U. Franck, ‘‘Verdamp- ‘‘High-Temperature Mutual Solubilities of Hydrocarbons and Wa-
fungsgleichgewichte und kritische Kurven in den Systemen ter. Part II: Ethylbenzene, Ethylcyclohexane, and n-Octane,’’
ÄthanrWasser und n-ButanrWasser bei hohen Drucken,’’¨ Chemie AIChE J., 31, 376 Ž1985..
Ing. Techn., 30, 816 Ž1967.. Hill, P. G., ‘‘A Unified Fundamental Equation for the Thermody-
Davis, J. E., and J. J. McKetta, ‘‘Solubility of Ethylene in Water,’’ J. namic Properties of H 2 O,’’ J. Phys. Chem. Ref. Data, 19, 1233 Ž1990..
Chem. Eng. Data, 5, 374 Ž1960.. Hine, J., and P. K. Mookerjee, ‘‘The Intrinsic Character of Organic
Dec, S. F., and S. J. Gill, ‘‘Heats of Solution of Gaseous Hydrocar- Compounds: Correlations in Terms of Structural Contributions,’’ J.
bons in Water at 15, 25, and 35T C,’’ J. Sol. Chem., 14, 827 Ž1985.. Org. Chem., 40, 292 Ž1975..
´
Degrange, S., ‘‘Nouvelle Procedure ´
de Determination ´ des
Simultanee Hoiland, H., ‘‘Partial Molal Volumes, Expansibilities and Compress-
´ ´ Enthalpiques et Volumiques des Systemes
Proprietes ` Fluides: Ap- iblities for Aqueous Alcohol Solutions Between 5⬚C and 40⬚C,’’ J.
plication ` ´
a l’etude des Solutions Aqueuses d’Hydrocarbures Sol. Chem., 9, 857 Ž1980..
jusqu’au Domaine Critique de l’eau,’’ PhD Diss. Universite ´ Blaise Hoiland, H., ‘‘Partial Molar Volumes of Biochemical Compounds in
Aqueous Solution,’’ Thermodynamic Data for Biochemistry and Estimating Henry’s Law Constants,’’ En®iron. Toxicol. & Chem., 10,
Biotechnology, H. J. Hinz, ed., Springer-Verlag Ž1986.. 1283 Ž1991..
Inglese, A., P. Robert, R. De Lisi, and S. Milioto, ‘‘Apparent Molar Miller, D. J., and S. B. Hawthorne, ‘‘Solubility of Liquid Organics of
Volumes of 1-Pentanol in Water from T s 298 K to T s 413 K Environmental Interest in Subcritical ŽHotrLiquid. Water from 298
at ps 0.1 MPa and ps19 MPa,’’ J. Chem. Thermodyn., 28, 873 K to 473 K,’’ J. Chem. Eng. Data, 45, 78 Ž2000..
Ž1996.. Morrison, T. J., and F. Billet, ‘‘The Salting-out of Non-electrolytes.
Inglese, A., and R. H. Wood, ‘‘Apparent Molar Heat Capacities of Part II. The Effect of Variation in Non-electrolyte,’’ J. Chem. Soc.,
Aqueous Solutions of 1-Propanol, Butane-1,4,-diol, and Hexane- 1952, 3819 Ž1952..
1,6-diol at Temperatures from 300 K to 525 K and a Pressure of 28 Naghibi, H., S. F. Dec, and S. J. Gill, ‘‘Heat of Solution of Ethane
MPa,’’ J. Chem. Thermodyn., 28, 1059 Ž1996.. and Propane in Water from 0⬚C to 50⬚C,’’ J. Phys. Chem., 91, 245
Japas, M. L., and J. M. H. Levelt-Sengers, ‘‘Gas Solubility and Henry’s Ž1987..
Law Near the Solvent’s Critical Point,’’ AIChE J., 35, 705 Ž1989.. Naghibi, H., D. W. Ownby, and S. J. Gill, ‘‘Enthalpies of Solution of
¨
Jonsson, J. A., J. Vejrosta, and J. Novak, ‘‘AirrWater Partition Coef- Butanes in Water from 5 to 45⬚C,’’ J. Chem. Eng. Data, 32, 422
ficients for Normal Alkanes Ž n-Pentane to n-Nonane.,’’ Fluid Phase Ž1987..
Equil., 9, 279 Ž1982.. Nakajima, T., T. Komatsu, and T. Nakagava, ‘‘Apparent Molal Vol-
Jose J., private communication Ž2001.. umes and Adiabatic Compressibilities of n-Alkanols and Alpha,
Jou, F.-Y., and A. E. Mather, ‘‘Vapor-Liquid-Liquid Locus of the Omega-Alkane Diols in Dilute Aqueous Solutions at 5, 25, and 45
System Pentane q Water,’’ J. Chem. Eng. Data, 45, 728 Ž2000.. C. I. Apparent Molal Volumes,’’ Bull. Chem. Soc. Jpn., 48, 783
Knauss, K. G., and S. A. Copenhaver, ‘‘The Solubility of p-Xylene in Ž1975..
Water as a Function of Temperature and Pressure and Calculated Nelson, H. D., and C. L. De Ligny, ‘‘The Determination of the Solu-
Thermodynamic Quantities,’’ Geochim. Cosmochim. Acta, 59, 2443 bilities of some n-Alkanes in Water at Different Temperatures, by
Ž1995.. Means of Gas Chromatography,’’ Rec. Tra®. Chim., 87, 528
Kobayashi, R., and D. L. Katz, ‘‘Vapor-Liquid Equilibria for Binary Ž1968..
Hydrocarbon-Water Systems,’’ Ind. Eng. Chem., 45, 440 Ž1953.. Nirmalakhandan, N., and R. E. Speece, ‘‘QSAR Model for Predict-
Krasnoshchekova, R. Ya., and M. Ya. Gubercrits, ‘‘Solubility of ing Henry’s Constant,’’ En®iron. Sci. Technol., 22, 1349 Ž1988..
Paraffin Hydrocarbons in Fresh and Salt Water Žin Russian.,’’ Nirmalakhandan, N., R. A. Brennan, and R. E. Speece, ‘‘Predicting
Neftekhimiya, 13, 885 Ž1973.. Henry’s Law Constant and the Effect of Temperature on Henry’s
Krause, D., and B. B. Benson, ‘‘The Solubility and Isotopic Fraction- Law Constant,’’ Wat. Res., 31, 1471 Ž1997..
ation of Gases in Dilute Aqueous Solution. IIa. Solubilities of the O’Connell, J. P., ‘‘Thermodynamic Properties of Solutions Based on
Noble Gases,’’ J. Sol. Chem., 18, 823 Ž1989.. Correlation Functions,’’ Mol. Phys., 20, 27 Ž1971..
Lee, B. I., and M. G. Kesler, ‘‘A Generelized Thermodynamic Corre- O’Connell, J. P., A. V. Sharygin, and R. H. Wood, ‘‘Infinite Dilution
lation Based on Three-Parameter Corresponding States,’’ AIChE Partial Molar Volumes of Aqueous Solutes over Wide Ranges of
J., 21, 510 Ž1975.. Conditions,’’ Ind. Eng. Chem. Res., 35, 2808 Ž1996..
Leinonen, P. J., ‘‘The Solubility of Hydrocarbons in Water,’’ M.A.Sc. O’Grady, T. M., ‘‘Liquid-Liquid Equilibria for the Benzene-n-
Thesis, University of Toronto, Toronto, Canada Ž1972.. Heptane-Water System in the Critical Solution Region,’’ J. Chem.
Leland, Th. W., Jr., J. J. McKetta, Jr., and K. A. Kobe, ‘‘Phase Equi- Eng. Data, 12, 9 Ž1967..
librium in 1-Butene-Water System and Correlation of Hydrocar- Olofsson, G., A. A. Oshodj, E. Qvarnstrom, and I. Wadso, ¨ ‘‘Calori-
bon-Water Solubility Data,’’ Ind. Eng. Chem., 47, 1265 Ž1955.. metric Measurements on Slightly Soluble Gases in Water. En-
Levelt-Sengers, J. H. M., ‘‘Thermodynamics of Solutions Near the thalpies of Solution of Helium, Neon, Argon, Krypton, Xenon,
Solvent’s Critical Point,’’ Supercritical Fluid Technology: Re®iews in Methane, Ethane, Propane, n-Butane, and Oxygen at 288.15,
Modern Theory and Applications, T. J. Bruno and J. F. Ely, eds., 298.15, and 308.15 K,’’ J. Chem. Thermodyn., 16, 1041 Ž1984..
CRC Press, Boca Raton, FL Ž1991.. Owens, J. W., S. P. Wasik, and H. DeVoe, ‘‘Aqueous Solubilities and
Li, C. C., and J. J. McKetta, ‘‘Vapour-Liquid Equilibrium in the Enthalpies of Solution of n-Alkylbenzenes,’’ J. Chem. Eng. Data,
Propylene-Water System,’’ J. Chem. Eng. Data, 8, 271 Ž1963.. 31, 47 Ž1986..
Mackay, D., and W. Y. Shiu, ‘‘Determination of the Solubility of Pardo, M., ‘‘Rapport de D.E.A.,’’ Universite ´ Blaise Pascal,
Hydrocarbons in Aqueous Sodium Chloride Solutions,’’ Can. J. Clermont-Ferrand, France Ž2000..
Chem. Eng., 53, 239 Ž1975.. Pierotti, R. A., and A. A. Liabastre, ‘‘Structure and Properties of
Majer, V., G. Bergin, and J. Sedlbauer, ‘‘Predicting the Henry’s Law Water Solutions,’’ U.S. Nat. Tech. Inform. Ser., PB Rep., No. 21263
Constant and Related Partition Coefficients of Aqueous Hydrocar- Ž1972..
bons: A Software Tool for Calculations in a Wide Range of Tem- Pierotti, R. A., ‘‘A Scaled Particle Theory of Aqueous and Non-
peratures and Pressures,’’ Fluid Phase Equilib., in press Ž2003.. aqueous Solutions,’’ Chem. Re®., 76, 717 Ž1976..
Makhatadze, G. I., and P. L. Privalov, ‘‘Heat Capacity of Alcohols in Plyasunov, A. V., J. P. O’Connell, and R. H. Wood, ‘‘Infinite Dilu-
Aqueous Solutions in the Temperature Range from 5 to 125⬚C,’’ J. tion Partial Molar Properties of Aqueous Solutions of Nonelec-
Sol. Chem., 18, 927 Ž1989.. trolytes: I. Equations for Partial Molar Volumes at Infinite Dilu-
Makhatadze, G. I., and P. L. Privalov, ‘‘Partial Specific Heat Capac- tion and Standard Thermodynamic Functions of Hydration of
ity of Benzene and of Toluene in Aqueous Solution Determined Volatile Nonelectrolytes over Wide Ranges of Conditions,’’
Calorimetrically for a Broad Temperature Range,’’ J. Chem. Ther- Geochim. Cosmochim. Acta, 64, 495 Ž2000a..
modyn., 20, 405 Ž1988.. Plyasunov, A. V., J. P. O’Connell, R. H. Wood, and E. L. Shock,
Makhatadze, G. I., V. N. Medvedkin, and P. L. Privalov, ‘‘Partial ‘‘Infinite Dilution Partial Molar Properties of Aqueous Solutions
Molar Volumes of Polypeptides and Their Constituent Groups in of Nonelectrolytes: II. Equations for the Standard Thermodynamic
Aqueous Solution over a Broad Temperature Range,’’ Biopolymers, Functions of Hydration of Volatile Nonelectrolytes over Wide
30, 1001 Ž1990.. Ranges of Conditions Including Subcritical Temperatures,’’
Makhatadze, G. I., and P. L. Privalov, ‘‘Heat Capacity of Proteins. I. Geochim. Cosmochim. Acta, 64, 2779 Ž2000b..
Partial Molar Heat Capacity of Individual Amino Acid Residues in Plyasunov, A. V., and E. L. Shock, ‘‘Thermodynamic Functions of
Aqueous Solution: Hydration Effect,’’ J. Mol. Biol., 213, 375 Ž1990.. Hydration of Hydrocarbons at 298.15 K and 0.1 MPa,’’ Geochim.
May, W. E., ‘‘The Solubility Behavior of Polynuclear Aromatic Hy- Cosmochim. Acta, 64, 439 Ž2000a..
drocarbons in Aqueous Systems,’’ PhD Thesis, University of Mary- Plyasunov, A. V., and E. L. Shock, ‘‘Standard State Gibbs Energies
land Ž1977.. of Hydration of Hydrocarbons at Elevated Temperatures as Evalu-
May, W. E., S. P. Wasik, M. M. Miller, Y. B. Tewari, and J. M. ated from Experimental Phase Equilibria Studies,’’ Geochim. Cos-
Brown-Thomas, ‘‘Solution Thermodynamics of Some Slightly Solu- mochim. Acta, 64, 2811 Ž2000b..
ble Hydrocarbons in Water,’’ J. Chem. Eng. Data, 28, 197 Ž1983.. Plyasunov, A. V., J. P. O’Connell, R. H. Wood, and E. L. Shock,
Medir, M., and F. Giralt, ‘‘Correlation of Activity Coefficients of Hy- ‘‘Semiempirical Equation of State for the Infinite Dilution Ther-
drocarbons in Water at Infinite Dilution with Molecular Parame- modynamic Functions of Hydration of Nonelectrolytes over Wide
ters,’’ AIChE J., 28, 341 Ž1982.. Ranges of Temperature and Pressure,’’ Fluid Phase Equilib., 183-
Meylan, W. M., and P. H. Howard, ‘‘Bond Contribution Method for 184, 133 Ž2001..

Polak, J., and B.C.-Y. Lu, ‘‘Mutual Solubilities of Hydrocarbons and Sengers, J. V., and J. M. H. Levelt-Sengers, ‘‘Thermodynamic Behav-
Water at 0 and 25⬚C,’’ Can. J. Chem., 51, 4018 Ž1973.. ior of Fluids Near the Critical Point,’’ Ann. Re®. Phys. Chem., 37,
Prausnitz, J. M., R. N. Lichtenthaler, and E. G. de Azevedo, Molecu- 189 Ž1986..
lar Thermodynamics of Fluid Phase Equilibria, 3rd ed., Prentice Hall, Serra, M. C. S., M. M. R. D. Fonseca, J. C. G. Calado, and A. M. F.
NJ Ž1999.. Palavra, ‘‘Solubility of Propene in Water and in a Mineral Medium
Price, L. C., ‘‘Aqueous Solubility of Petroleum as Applied to Its Ori- for the Cultivation of a Xanthobacter Strain,’’ J. Solut. Chem., 27,
gin and Primary Migration,’’ Amer. Assoc. Petrol. Geol. Bull., 60, 455 Ž1998..
213 Ž1976.. Sherman, S. R., D. B. Trampe, D. M. Bush, M. Schiller, C. A. Eck-
Pryor, W. A., and R. E. Jentoft, ‘‘Solubility of m- and p-Xylene in ert, A. J. Dallas, J. Li, and P.W. Carr, ‘‘Compilation and Correla-
Water and in Aqueous Ammonia from 0⬚ to 300T C,’’ J. Chem. Eng. tion of Limiting Activity Coefficients of Nonelectrolytes in Water,’’
Data, 6, 36 Ž1961.. Ind. Chem. Eng. Res., 35, 1044 Ž1996..
Rahman, S., and M. A. Barrufet, ‘‘A New Technique for Simultane- Smith, R. R., N. W. Charon, and W. J. Canady, ‘‘Thermodynamics of
ous Measurement of PVT and Phase Equilibria Properties of Flu- Solution of Aromatic Hydrocarbons in Water and in Water-Ethanol
ids at High Temperatures and Pressures,’’ J. Petrol. Sci. Eng., 14, Solutions: Comparison of Some Methodologies,’’ J. Phys. Chem.,
25 Ž1995.. 93, 5938 Ž1989..
Reamer, H. H., B. H. Sage, and W. N. Lacey, ‘‘Phase Equilibria in Stephenson, R. M., ‘‘Mutual Solubilities: Water-Ketones, Water-
Hydrocarbon Systems. n-Butane-Water System in the Two-Phase Ethers, and Water-Gasoline-Alcohols,’’ J. Chem. Eng. Data, 37, 80
Region,’’ Ind. Eng. Chem., 44, 609 Ž1952.. Ž1992..
Rebert, C. J., and K. E. Hayworth, ‘‘The Gas and Liquid Solubility Stevenson, R. L., D. S. LaBracio, T. A. Beaton, and M. C. Thies,
Relations in Hydrocarbon-Water Systems,’’ AIChE J., 13, 118 ‘‘Fluid Phase Equilibria and Critical Phenomena for the Dode-
Ž1967.. cane-Water and Squalane-Water Systems at Elevated Tempera-
Reid, R. C., J. M. Prausnitz, and B. E. Poling, The Properties of Gases tures and Pressures,’’ Fluid Phase Equilib., 93, 317 Ž1994..
and Liquids, 4th ed., McGraw-Hill, New York Ž1999.. Stryjek, R., and J. H. Vera, ‘‘An Improved Peng-Robinson Equation
Roux, G., D. Roberts, G. Perron, and J. E. Desnoyers, ‘‘Microhet- of State with New Mixing Rules for Pure Compounds and Mix-
erogenity in Aqueous-Organic Solutions: Heat Capacities, Vol- tures,’’ Can. J. of Chem. Eng., 64, 323 Ž1986..
umes and Expansibilities of some Alcohols, Aminoalcohol and Sutton, C., and J. A. Calder, ‘‘Solubility of Higher-Molecular-Weight
Tertiary Amines in Water,’’ J. Sol. Chem., 9, 629 Ž1980.. n-Paraffins in Distilled Water and Seawater,’’ En®ir. Sci. Technol.,
Sakurai, M., ‘‘Partial Molar Volumes in Aqueous Mixtures of Non- 8, 654 Ž1974..
electrolytes: I. t-Butyl Alcohol,’’ Bull. Chem. Soc. Jpn., 60, 1 Ž1987.. Thompson, W. H., and J. R. Snyder, ‘‘Mutual Solubilities of Benzene
Sakurai, M., ‘‘Partial Molar Volumes in Aqueous Mixtures of Non- and Water. Equilibria in the Two Phase Liquid-Liquid Region,’’ J.
electrolytes: II. Isopropyl Alcohol,’’ J. Sol. Chem., 17, 267 Ž1988.. Chem. Eng. Data, 9, 516 Ž1964..
Sakurai, M., ‘‘Partial Molar Volumes in Aqueous Mixtures of Non- Tsonopoulos, C., and J. M. Prausnitz, ‘‘Activity Coefficients of Aro-
electrolytes: III. t-Pentyl Alcohol,’’ J. Sol. Chem., 18, 37 Ž1989.. matic Solutes in Dilute Aqueous Solutions,’’ Ind. Eng. Chem. Fun-
Sakurai, M., ‘‘Partial Molar Volumes in Aqueous Mixtures of Non- dam., 10, 593 Ž1971..
electrolytes: IV. Aromatic Hydrocarbons,’’ Bull. Chem. Soc. Jpn., Tsonopoulos, C., and G. M. Wilson, ‘‘High-Temperature Mutual
63, 1695 Ž1990.. Solubilities of Hydrocarbons and Water: Benzene, Cyclohexane
Sakurai, M., K. Nakamura, and K. Nitta, ‘‘Volumetric Properties of and n-Hexane,’’ AIChE J., 29, 990 Ž1983..
Dilute Aqueous Alcohol Solutions at Different Temperatures,’’ Tsonopoulos, C., ‘‘Thermodynamic Analysis of the Mutual Solubili-
Bull. Chem. Soc. Jpn., 67, 1580 Ž1994.. ties of Normal Alkanes and Water,’’ Fluid Phase Equilib., 156, 21
Sanchez, M., and H. Lentz, ‘‘Phasengleichgewichte der Systeme Ž1999..
Wasser-Propen und Wasser-Athen ¨ ¨
bei hohen Drucken und Tem- Tsonopoulos, C., ‘‘Thermodynamic Analysis of the Mutual Solubili-
peraturen,’’ High Temp.-High Pres., 5, 687 Ž1973.. ties of Hydrocarbons and Water,’’ Fluid Phase Equilib., 186, 185
Sandler, S. I., ‘‘Infinite Dilution Activity Coefficients in Chemical Ž2001..
Environmental and Biochemical Engineering,’’ Fluid Phase Equilib., Wehe, A. H., and J. J. McKetta, ‘‘Method for Determining Total
116, 343 Ž1996.. Hydrocarbons Dissolved in Water,’’ Anal. Chem., 33, 291 Ž1961a..
Sandler, S. I., Chemical Engineering Thermodynamics, 3rd ed., Wiley, Wehe, A. H., and J. J. McKetta, ‘‘N-Butane-1-Butene-Water System
New York Ž1999.. in the Three-Phase Region,’’ J. Chem. Eng. Data, 6, 167 Ž1961b..
Sanemasa, I., M. Araki, T. Deguchi, and H. Nagai, ‘‘Solubilities of Wilhelm, E., R. Battino, and R. J. Wilcock, ‘‘Low-Pressure Solubility
Benzene and the Alkylbenzenes in Water-Method for Obtaining of Gases in Liquid Water,’’ Chem. Re®., 77, 219 Ž1977..
Aqueous Solutions Saturated with Vapours in Equilibrium with Xiao, C., H. Bianchi, and P. R. Tremaine, ‘‘Excess Molar Volumes
Organic Liquids,’’ Chem. Lett., 225 Ž1981.. and Densities of ŽMethanol q Water. at Temperatures Between
Sanemasa, I., M. Araki, T. Deguchi, and H. Nagai, ‘‘Solubility Mea- 323 K and 573 K and Pressures of 7.0 MPa and 13.5 MPa,’’ J.
surements of Benzene and the Alkylbenzenes in Water by Making Chem. Thermodyn., 29, 261 Ž1997..
Use of Solute Vapour,’’ Bull. Chem. Soc. Jpn., 55, 1054 Ž1982.. Yang, Y., D. J. Miller, and S. B. Hawthorne, ‘‘Toluene Solubility in
Sawamura, S., K. Nagaoka, and T. Machikawa, ‘‘Effects of Pressure Water and Organic Partitioning from Gasoline and Diesel Fuel
on the Solubility of Alkylbenzenes in Water: Volumetric Property into Water at Elevated Temperatures and Pressures,’’ J. Chem. Eng.
of Hydrophobic Hydration,’’ J. Phys. Chem. B, 105, 2429 Ž2001.. Data, 42, 908 Ž1997..
Sawamura, S., K. Kitamura, and Y. Taniguchi, ‘‘Effect of Pressure Yezdimer, E. M., J. Sedlbauer, and R. H. Wood, ‘‘Predictions of
on the Solubilities of Benzene and Alkylbenzenes in Water,’’ J. Thermodynamic Properties at Infinite Dilution of Aqueous Or-
Phys. Chem., 93, 4931 Ž1989.. ganic Species at High Temperatures via Functional Group Additiv-
Schulte, M. D., E. L. Shock, M. Obsil, and V. Majer, ‘‘Volumes of ity,’’ Chem. Geology, 164, 259 Ž2000..
Aqueous Alcohols, Ethers, and Ketones to T s 523 K and ps 28 Zou, L., B. Han, R. Liu, and H. Yan, ‘‘Solubilities of Benzene and
MPa,’’ J. Chem. Thermodyn., 31, 1195 Ž1999.. Diphenyl in Žt-Butyl Alcohol1water. and Hydrophobic Interaction,’’
Schulze, G., and J. M. Prausnitz, ‘‘Solubilities of Gases in Water at J. Chem. Thermodyn., 29, 1289 Ž1997..
High Temperatures,’’ Ind. Eng. Chem. Fundam., 20, 175 Ž1981..
Schwarz, F. P., and J. Miller, ‘‘Measurement of the Solubilities of Appendix: Summary of the SOCW Thermodynamic
Slightly Soluble Organic Liquids in Water by Elution Chromatog- Model
raphy,’’ Anal. Chem., 52, 2161 Ž1980..
Sedlbauer, J., and V. Majer, ‘‘Data and Models for Calculating the Equation 19 in the main text can be rearranged into a vol-
Standard Thermodynamic Properties of Aqueous Nonelectrolyte umetric form using the definition of the modified Krichevskii
Solutes Under Hydrothermal Conditions,’’ Eur. J. Mineral., 12, 1109 parameter ŽEq. 15.
Ž2000..
Sedlbauer, J., J. P. O’Connell, and R. H. Wood, ‘‘A New Equation of
State for Correlation and Prediction of Standard Molal Properties VsT s RT␬ w q d Ž Vw y RT␬ w . q RT␬ w ␳w aq b Ž exp w ␽␳w x y1 .
of Aqueous Electrolytes and Nonelectrolytes at High Tempera-
tures and Pressures,’’ Chem. Geology, 163, 43 Ž2000.. q c exp w ␪rT x q ␦ Ž exp w ␭␳w x y1 . 4 Ž A1.

where Vw , ␳w , and Mw are molar volume, specific density, where Gw , Hw , and C p,w are the molar Gibbs free energy,
and molar mass of water, respectively, and general coeffi- enthalpy and heat capacity of water, Gwig , Hwig , and C p,w
ig
are
cients valid for all solutes are ® s 0.005 m3rkg, ␪ s1,500 K, the same properties of water in ideal gas standard state at
and ␭ sy0.01 m3rkg. Adjustable parameters are a, b, c, and temperature T, and ␣ w syw1r␳w Ž ⭸␳wr⭸ T . p x is the coeffi-
d, and parameter ␦ is determined depending on the charge cient of thermal expansion. Thermodynamic properties of
of a particle Ž ␦ s 0.35a for neutral molecules.. Equation A1 pure water needed in calculations were obtained in this study
is in fact modeling a series of perturbation effects due to from the equation of state by Hill Ž1990.. Correction terms in
insertion of a point mass into water solvent Ž RT␬ w ., growing Eqs. A2᎐A5 apply at temperatures below critical tempera-
it to a ‘‘ water-like’’ molecule with size adjusted to mimic the ture of water Tc s647.126 K and arise due to inadequacy of
intrinsic volume of a solute w dŽ Vw y RT␬ w .x, and then chang- the simple volumetric Eq. A1 to describe accurately pressure
ing its potential field from solvent-solvent to solute-solvent change of K H in both gas and liquid phases in a two-phase
interaction Žthe third term on the righthand side of Eq. A1.. subcritical region. For nonelectrolyte solutes, this correction
The process of hydration is defined as a transfer of solute is expressed by an empirical function with one additional ad-
molecule from the ideal gas standard state at given T and justable parameter e
pressure pref s 0.1 MPa to aqueous solution at T, p. Corre-
sponding change in the Gibbs free energy is expressed by Eq.
25. Full form of Eq. 25 in the framework of the SOCW model
is given by Sedlbauer et al. Ž2000. Tc2 T Ž Tc y ⌽ . 2 T y⌽
⌬ SThyd
␳w RT
cor
se
ž T yTc y
⌽
ln
Tc
q
⌽
ln
Tc y ⌽ /
⌬GThyd s ⌬GThyd
cor
q RT ln Ž A6.
Mw pref
␳w RT
ž
q d Gw yGwig y RT ln
Mw pref / ⌬ HT ½
hyd s e Ž 2Tc y ⌽ .Ž Tc yT . q1r2 Ž T yTc .
cor 2 2
b
q RT ␳w Ž aq c exp w ␪rT x y by ␦ . q
½ Ž exp w␽␳w x y1.
␽ T y⌽
q
␦
Ž exp w ␭␳w x y1. 5 Ž A2.
2
q Ž Tc y ⌽ . ln
Tc y ⌽ 5 Ž A7.
␭
⌬GThyd
cor
s ⌬ HT cor T cor
hyd yT⌬ S hyd Ž A8.
Appropriate derivations of ⌬GThyd lead to other thermody-
namic properties of hydration
2
e Ž T yTc .
⌬ HT T cor ⌬CTp,hyd
cor
s Ž A9.
hyd s ⌬ H hyd q RT Ž T␣ y1. q d Hw y Hwig ŽT y ⌽ .
␳w
y RT Ž T␣ y1 . x q RT␪ c exp w ␪rT x
T
⭸␳w where ⌽ s 228 K is a general constant. Correction functions
y RT 2 ž / aq b Ž exp w␽␳w x y1. q c exp w ␪rT x are zero by definition at T GTc . All thermodynamic proper-
⭸T p
ties that appear in the above equations should be applied in
q ␦ Ž exp w ␭␳w x y1 . 4 Ž A3. their basic SI units when using parameters from Table 2 in
the text.
⌬ SThyd s Ž ⌬ HT T
hyd y ⌬G hyd . rT Ž A4.
⭸␣ w ⭸␣ w
⌬CTp,hyd s ⌬CTp ,hyd
cor
q 2 RT␣ w q RT 2 ž / / ½ y R q d C p ,w yC pig,w y 2 RT␣ w q RT 2
ž ⭸T p
ž /
⭸T p
yR
°2 R ⭸␳w
aq b Ž exp w ␽␳w x y1 . q c exp w ␪rT x q ␦ Ž exp w ␭␳w x y1 4 y c exp w ␪rT x
␪ ¶
ž /Ž
⭸T p T
␳w ⭸␳w 2
yT q Rc exp w ␪rT x ␪ ␽ b exp w ␽␳w x q ␭␦ exp w ␭␳w x .

2
T 3
q RT ž /Ž
⭸T p
Ž A5.
⭸ 2␳w
aq b Ž exp w ␽␳w x y1 . q c exp w ␪rT x q ␦ Ž exp w ␭␳w x y1 . 4
¢ q RT
ž /
⭸T 2 p
ß
Manuscript recei®ed May 21, 2002, and re®ision recei®ed Sept. 17, 2002.

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THERMODYNAMICS

Group Contribution Method for Henry’s Law

¨ Bergin and Vladimir Majer

A functional group contribution scheme based on a hydration model predicts Henry’s

2936 December 2002 Vol. 48, No. 12 AIChE Journal

direction of the critical point of solvent. Practical use of the

AIChE Journal December 2002 Vol. 48, No. 12 2937

⭸ ln K H f sorg Ž T , p . s f saq Ž T , p . ( K H Ž T , p . x sol Ž9.

Solubility of hydrocarbon in water x sol

of aqueous hydrocarbons is also positively divergent, and,

strongly at p™ pc,w . Using Eq. 2 as a starting point, Japas

2938 December 2002 Vol. 48, No. 12 AIChE Journal

1997.. For the latter two groups of techniques, the determi-

Since the HLC exhibits a maximum in temperature, any

correlation along the saturation line of solvent, where calcu-

qCT 0.59 exp Ž Tc,w yT . Ž 13. 2

including light hydrocarbons. This equation was also used by Ž 18.

AIChE Journal December 2002 Vol. 48, No. 12 2939

New Group Contribution Model

representative recommendations of ⌬GThydŽTref , pref . that

lected the recent group contribution method by Plyasunov and

where ⌽ is again a general constant. The contribution of the

2940 December 2002 Vol. 48, No. 12 AIChE Journal

Table 2. Group Contributions for Calculating Parameters of the T, p Dependent Model

AIChE Journal December 2002 Vol. 48, No. 12 2941

Table 4. Database of Hydrocarbon Solubility in Water

2942 December 2002 Vol. 48, No. 12 AIChE Journal

Table 4. Database of Hydrocarbon Solubility in Water (Continued)

AIChE Journal December 2002 Vol. 48, No. 12 2943

2944 December 2002 Vol. 48, No. 12 AIChE Journal

AIChE Journal December 2002 Vol. 48, No. 12 2945

2946 December 2002 Vol. 48, No. 12 AIChE Journal

where a i is the parameter for i-th functional group. The point

Table 7. Standard Molar Heat Capacities

AIChE Journal December 2002 Vol. 48, No. 12 2947

AIChE Journal December 2002 Vol. 48, No. 12 2949

2950 December 2002 Vol. 48, No. 12 AIChE Journal

where ␴ ⌬YT hyd is the estimated uncertainty of a given data

AIChE Journal December 2002 Vol. 48, No. 12 2951

2952 December 2002 Vol. 48, No. 12 AIChE Journal

AIChE Journal December 2002 Vol. 48, No. 12 2953

2954 December 2002 Vol. 48, No. 12 AIChE Journal

AIChE Journal December 2002 Vol. 48, No. 12 2955

AIChE Journal December 2002 Vol. 48, No. 12 2957

2958 December 2002 Vol. 48, No. 12 AIChE Journal

yT q Rc exp w ␪rT x ␪ ␽ b exp w ␽␳w x q ␭␦ exp w ␭␳w x .

AIChE Journal December 2002 Vol. 48, No. 12 2959

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