Fluid Phase Equilibria 272 (2008) 6574

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Fluid Phase Equilibria

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Henrys law constant and related coefcients for aqueous hydrocarbons,

CO2 and H2 S over a wide range of temperature and pressure
Vladimir Majer a, , Josef Sedlbauer b, , Gaetan Bergin a
a
Laboratoire de Thermodynamique des Solutions et des Polymres, Universit Blaise Pascal Clermont-Ferrand/CNRS, 63177 Aubire, France
b
Department of Chemistry, Technical University of Liberec, 46117 Liberec, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: This article presents three interrelated topics. First, the Henrys law constant (HLC) and its use are reviewed
Received 7 April 2008 in a broader thermodynamic context reaching beyond the restricted image of HLC as a coefcient reecting
Received in revised form 14 July 2008 partitioning between liquid and vapor phases. The relationships of HLC to the vaporliquid distribu-
Accepted 29 July 2008
tion coefcient and the airwater partition coefcient are discussed as well as the interrelation between
Available online 6 August 2008
expressions of HLC in terms of different concentration scales. Second, the previously published group
contribution method for estimation of HLC of hydrocarbons [J. Sedlbauer, G. Bergin, V. Majer, AIChE J. 48
Keywords:
(2002) 2936] is extended by adding the newly determined parameters for CH4 , CO2 and H2 S. Inclusion of
Henrys law constant
Aqueous
these three major constituents of the natural gas makes the method more versatile in application to sys-
Hydrocarbons tems where oil and/or natural gas coexist with an aqueous phase. When establishing the parameters of the
CO2 model the representative HLCs from literature were combined with the data on the derivative properties
H2 S available over a wide range of conditions from the calorimetric and volumetric experiments. An attention
is paid particularly to the effect of pressure on the HLC. Third, a convenient user-friendly software package
is described allowing calculation of HLC and of other related coefcients over a wide range of temperature
and pressure on the basis of the presented model. This package is available on request in an executable
form on a shareware basis for non-commercial users.
2008 Elsevier B.V. All rights reserved.

1. Introduction
The Henrys law constant KH is a quantity frequently applied
in the thermodynamic description of dilute aqueous solutions. It
was originally proposed more than 200 years ago [1] as a mea-
sure of gas solubility in a liquid, and expressed as a ratio of the
partial pressure of a gaseous solute to its equilibrium concentra-
tion in the liquid phase. The perception and use of the Henrys
law constant today is, however, much broader; from the physico-
chemical point of view KH is basically a coefcient relating the
fugacity of a dissolved nonelectrolyte to its concentration in a solu-
tion. The solute can be in the pure state gaseous, liquid or solid and
solvent is often water. The Henrys law constant is namely used
in environmental chemistry and atmospheric physics as a major
criterion for describing airwater partitioning of solutes at near-
ambient conditions. It plays a major role in evaluating the transport
of pollutants between atmosphere and aquatic systems, rain water
Corresponding author. Tel.: +33 4 73 40 71 88; fax: +33 4 73 40 71 85.
Corresponding author. Tel.: +420 48 535 3375; fax: +420 48 510 5882.
E-mail addresses: vladimir.majer@univ-bpclermont.fr (V. Majer),
josef.sedlbauer@tul.cz (J. Sedlbauer).
and aerosols. The Henrys law constant is also used extensively in
chemical engineering and geochemistry for designing or describing
processes where dilute aqueous systems are involved, often over
a wide range of temperature and pressure. In this case it is nec-
essary to adopt some theoretically founded concepts allowing a
realistic calculation of the Henrys law constant at superambient
conditions.
The use of the Henrys law constant by different communities
is reected by the establishment of multiple and alternative def-
initions of this quantity, leading to a considerable confusion in
literature. Thus, the Henrys law constant is certainly a coefcient
the most frequently applied in phase equilibrium calculations con-
cerning dilute solutions, but its thermodynamic essence is often
misunderstood or misinterpreted. For that reason we have found
useful to present in the rst part of this paper a concise review
of the thermodynamics regarding the Henrys law constant and to
show how the different versions of KH and other related coefcients
are interconnected.
An effort has been made over the past years to use the QSPR1
concepts for building up linear prediction schemes for the Henrys
1
QSPR quantitative structureproperty relationship.

0378-3812/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2008.07.013
66 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574

law constant, covering a variety of organic solutes in water. After condition. For that reason it is a function of two independent vari-
the pioneering work of Hine and Mookerjee [2] this approach ables, temperature and pressure.2
has become namely popular in environmental chemistry where The chemical potential of a solute in a solution (the partial molar
different methods using fragmentary contributions [3], topologi- Gibbs energy, Gs ) can be expressed depending on the choice of
ig
cal descriptors [4,5] or solvochromic parameters [68] have been the standard state (Gs [T, pref ] for ideal gas at a reference pressure
used for estimations at 298 K. In addition, more sophisticated, yet pref = 0.1 MPa, or Gs [T, p] for innitely dilute solution3 ) as
mainly empirical, computational models were introduced recently  f 
using quantum mechanical descriptors [911] and advanced sta- ig
Gs [T, p] = Gs [T, pref ] + RT ln
s
= Gs [T, p] + RT ln(xs sH ) (2)
tistical techniques based on neural networks [1214]. While all pref
these schemes are designed for predictions at near-ambient con-
The symbol sH stands for the dimensionless activity coefcient
ditions, the methods for estimation of the Henrys law constant as
compatible with the Henrys law, i.e. limxs 0 sH = 1 Combination
a function of temperature are limited. Sedlbauer et al. [15] have
of Eqs. (1) and (2) in the limit of innite dilution leads to the expres-
published a model allowing calculation of the Henrys law con-
sion
stant for aqueous C2 to C12 hydrocarbons over a wide range of
temperature (273 < T < 573 K) and pressure (0.1 < p < 100 MPa). The
 K [T, p] 
= Gs [T, p] Gs [T, pref ] = Ghyd

H ig
RT ln [T, p] (3)
group contribution approach was used for calculating the param- pref
eters of a thermodynamically sound model for innite dilution
where Ghyd is the Gibbs energy of hydration corresponding to the
properties [16] allowing to obtain KH via the Gibbs energy of
hydration. transfer of a solute from an ideal gas state to an innitely dilute
Besides clarifying various concepts of the Henrys law con- solution.
stant this article has basically two objectives. First, the previously For description of solutions, other concentration variables are
published estimation method of Sedlbauer and collaborators sometimes preferred to the molar fraction xs . These are namely
is extended by adding the parameters for CH4 , CO2 and H2 S. molality ms (mol/kg) popular with geochemists or molarity cs
Inclusion of these three major constituents of the natural gas (mol/m3 ) used often in environmental science. It holds in the limit
encountered frequently in the presence of other hydrocarbons of innite dilution
(NC > 2) makes the method more versatile for phase equilib- xs xs w
rium calculations in systems where oil and/or natural gas coexist lim ms = and lim cs = (4)
xs 0 Mw xs 0 Mw
with an aqueous phase. When establishing the parameters for
these three gaseous solutes we have combined the representa- where Mw (kg/mol) and w (kg/m3 ) are the molar mass and density
tive Henrys law constants selected recently by Fernandez-Prini of water, respectively. The values of the standard state chemical
et al. [17] with the data on the derivative properties available potentials are therefore affected by the choice of the concentration
over a wide range of conditions from the calorimetric and vol- variable as follows
umetric experiments. An attention is paid particularly to the M c 
w o
effect of pressure on the Henrys law constant of gases and liq- Gsm = Gsx + RT ln(Mw mo ) and Gsc = Gsx + RT ln (5)
w
uids.
Second, a convenient user-friendly software package is Since activity coefcients are always dimensionless, the standard
described allowing calculation of the Henrys law constant and concentrations mo = 1 mol/kg and co = 1 mol/m3 must be introduced
several related coefcients characterizing vaporliquid equilib- for converting molality and molarity to dimensionless concentra-
ria over a wide range of conditions. This package is available tion variables. Introduction of Eq. (5) into Eq. (3) then leads to
on request in an executable form on a shareware basis for non- the relationship between KH and the alternative denitions of the
commercial users. Availability of such a software tool is important Henrys law constant in terms of molality KHm and molarity KHc . It
for implementation of the method. The reprogramming of the holds:
model would be complex, requiring, e.g. the use of the same  fs

fundamental EOS for water as that applied when establishing KHm = lim = KHx Mw mo and
ms 0 ms /mo
the group contributions for calculating the parameters of the
model.  f  co
s
KHc = lim = KHx Mw (6)
cs 0 cs /co w
2. Thermodynamic background
This means that both KHm and KHc have also dimension of pressure
The aim of the following outline of basic equations is to present and are thus consistent with Eqs. (3) and (5). In practical use, the
the Henrys law constant in a broader thermodynamic context alternative Henrys law constants are, however, usually expressed
going beyond its restrictive viewing as a coefcient reecting parti- simply as a ratio of pressure to molality or molarity. While this
tioning between the liquid and vapor phases, as well as to elucidate is not strictly rigorous in the light of the above relationships, this
the interrelation between the related coefcients dened in terms simplied convention allows to distinguish immediately what con-
of different concentration scales. centration scale was selected and is therefore generally used in
The Henrys law constant KH is dened in modern chemical applications.
thermodynamics as the limiting fugacity/molar fraction ratio of
a solute in a solution [18,19] and has therefore the dimension of
pressure 2
The denition of the Henrys law constant introduced here is of course more
f  general than that resulting from the historical understanding of KH exclusively as
s
KH [T, p] = lim (1) a parameter reecting the gas solubility. When the Henrys law constant is obtained
xs 0 xs experimentally from the vaporliquid equilibrium measurements it is related logi-
cally to the vapor pressure of the solvent due to the limit of innite dilution.
Fugacity of the solute fs and its molar fraction xs relate to the same 3
This standard state adopted for aqueous species is unit activity in a hypothet-
phase, thus this is a one-phase denition of the Henrys law con- ical solution of unit concentration referenced to innite dilution (denoted with
stant without assumption of any kind of the phase equilibrium superscript ).
 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574
The derivatives of Eq. (3) allow establishing the exact thermo-
dynamic relationships describing the temperature and pressure
dependence of the Henrys law constant. It holds:
 
lnKH
= (Hs [T, p] Hs [T, pref ]) = Hhyd
2 ig
RT
T stant with the Gibbs energy of hydration and implying a general
p
  
2 lnKH ig
RT = (Cp,s [T, p] Cp,s [T, pref ]) = Cp,hyd (8)
T T
p
 
ln KH
RT = Vs [T, p].
p (10) the effect of pressure on the Henrys law constant from the
T
The standard thermodynamic properties (enthalpy, heat capac-
ig ig
ity and volume) of solute relate to an ideal gas (Hs , Cp,s ) or an
innitely dilute solution (Hs , Cp,s , Vs ). It follows from Eqs. (7) and
(8) that the temperature dependence of the Henrys law constant
can be calculated by integrating the derivative hydration properties
, C
(Hhyd ) that are accessible from calorimetric and spectro-
p,hyd
scopic measurements. Enthalpy of hydration Hhyd is calculated as
a combination of heat of solution and the residual enthalpy (dif-
ference between the enthalpy of pure solute and that of an ideal
gas) that is in absolute value close to the enthalpy of vaporization
for liquid solutes. The heat capacity of hydration Cp,hyd , calcu-
lated as a difference of solute heat capacity at innite dilution and
that of an ideal gas, is positive and increasing with temperature
for volatile nonelectrolytes [20]. Hhyd values, generally negative
at near-ambient conditions, become positive at high temperatures,
scaling with water expansivity and diverging when approaching
the critical point of water. The Henrys law constant is therefore at
rst increasing with temperature, exhibiting a maximum typically
between 373 and 473 K, and decreasing with temperature when
approaching the critical point of water.
Similarly the change of the Henrys law constant with pressure
can be calculated by integrating Eq. (9) where the partial molar
volume at innite dilution of a solute Vs is accessible from den-
sitometric measurements. Its value is proportional to the molar
mass of solute at room temperature and scales with compressibil-
ity of water at conditions remote from ambient, diverging positively
at the critical point of water for volatile nonelectrolytes [20]. The
Henrys law constant is therefore generally increasing with increas-
ing pressure. The integral of Eq. (9) between saturation pressure
of the solvent and pressure of the system is identical with the
KrichevskiKasarnovsky equation used in the chemical engineering
literature for calculating the so-called Poynting correction express-
ing the change of fugacity with pressure.
It is apparent from the combination of Eqs. (6)(9) that KHm and
KH have identical temperature and pressure slopes while a minor
difference is observed in the case of KHc where the mechanical
coefcients of water (expansivity and compressibility) play a role.
The Henrys law constant is used mainly for the description of
vapor (or gas)liquid equilibria and the compositions of coexisting
phases (ys and xs ) obtained from experiments are at the same time
also the major data source for determining KH of volatile solutes:

of a solute and water
p
Vs [T, p]
pys s = KH [T, psat
w ] exp dp xs sH .
RT
psat
w psat
The symbols p, s and psat
w denote the overall pressure, the fugacity
coefcient of a solute in the vapor and the saturation pressure of
water, respectively. Since the Henrys law constant is dened in the
limit of innite dilution (Eq. (1)), it can be obtained from experi-
mental vaporliquid equilibrium data when p psat s . Then in the
above relationship both the exponential term (the Poynting correc-
tion) and sH approach unity. The temperature dependence of the
67
Henrys law constant is therefore mostly presented in the litera-
ture along the saturation line of water and for that reason some
authors maintain that KH is a function of one independent variable
onlytemperature (e.g. [2123]). This statement is, however, not
(7) quite correct considering the direct link of the Henrys law con-
validity of Eq. (9). It is in principle always possible to construct
the thermodynamic surface of KH [T, p] with two independent state
variables. The limited amount of the volumetric data for aqueous
solutes, especially at superambient conditions, is, however, a major
(9) obstacle. Without this information it is difcult to separate in Eq.
nonideality of aqueous solution since the concentration of solute
xs is increasing due to increasing pressure and the solution cannot
then be considered as ideal (sH =/ 1). This interconnection between
the Poynting and nonideality corrections hampers the use of high-
pressure vaporliquid equilibrium data for KH determination [65].
The Henrys law constant of sparingly soluble liquids or solids in
water is determined from their solubilities xssol in water as follows:
 
Vs (p psat
s )
psat
s s
sat
exp = KH [T, p]xssol (11)
RT
where psat
s and Vs are the vapor pressure and molar volume of
pure solute, respectively. This equation is valid for low solubilities
where sH 1 and in the cases where the solubility of water in the
nonaqueous phase can be neglected. Since the volume of a con-
densed solute changes little with pressure, this equation is a good
approximation that allows to calculate the Henrys law constant as
a function of both temperature and pressure. At low pressures it
simply holds that KH = psat sol
s /xs , this relationship being the main
avenue used for calculating the Henrys law constant of low volatil-
ity solutes that are sparingly soluble in water.
The symmetrical limiting activity coefcients sR complying
with the Raoults law (limxs 1 sR = 1) are extensively used in
engineering thermodynamics for describing nonideality of dilute
solutions at temperatures up to 373 K and at ambient pressure.
Their determination from the phase equilibrium data is carried
out typically via the Henrys law constant or related coefcients
dened below. Since the fugacity of a solute in the liquid phase can
be expressed as fs = fs l xs sR , the combination with Eq. (1) gives
KH = fs l sR = psat,l
s sR (12)
l
where fs and psat,l
are the fugacity and saturation vapor pressure
s
of a real or hypothetical liquid solute.
Several other coefcients closely related to KH were introduced
for describing the partitioning of solutes between the vapor and
liquid phases. This is the case of the vaporliquid distribution coef-
cient Kd (denoted sometimes also as the limiting relative volatility
) that is dened as
y 
s
Kd = lim (13)
xs 0 xs
It follows immediately from Eq. (10) for a binary system consisting
KH [T, psat
(10) Kd = w ]
(14)
w w
sat
where wsat is the fugacity coefcient of saturated water vapor.
It means that Kd corresponds simply to the ratio of the Henrys
law constant and saturation vapor pressure at conditions where
vapor phase nonideality can be neglected. Coefcient Kd is logically
dened exclusively along the saturation line of solvent.
The Henrys law constant is often considered in geochemistry
and atmospheric physics as a thermodynamic reaction constant
68 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574

corresponding to a hydration process where the solute is trans- Table 1

Group contributions for calculating Ghyd [Tref , pref ] and Shyd [Tref , pref ]; values of
ferred from an ideal gas state to an ideal aqueous solution with the
group contributions for hydrocarbons C2 and higher are from lit [25]; values for CH4 ,
standard states dened in terms of unit molality or molarity. Thus,
CO2 and H2 S are obtained from the data in lit [17,26]
the following two coefcients
1 1
Functional group
Ghyd [Tref , pref ] (kJ mol )
Shyd [Tref , pref ] (J mol K1 )
 ms mo  cs co
KHm = = and KHc = = (15)
ps KHm ps KHc YSS a 17.92 67.78
C 4.50 23.81b
are encountered in literature. The symbol ps is the partial pres- CH 1.79 2.99b
sure of a solute in the vapor phase and the concentration variables CH2 0.72 15.03b
express concentration of the solute in the aqueous phase. CH3 3.63 37.46b
C C 10.23 36.32b
The airwater partition coefcient Kaw characterizing equilib-
H c 3.91 25.52b
rium distribution of a solute between the atmospheric and aqueous c-CHd 1.03 4.60b
phases is dened as the limiting molarity ratio c-CH2 0.83 20.76b
 ca  Car e 3.85 10.67b
Kaw = lim s
, (16) CHar 0.65 14.59b
csw 0 csw I(CC)f 1.01 10.10b
CH4 8.283 64.04b
where csa and csw are the equilibrium concentrations of a solute CO2 0.421 59.80b
in air and water, respectively. This coefcient is sometimes called H2 S 2.358 44.78b
N
in environmental chemistry the dimensionless Henrys law con- a
The standard state term to be used as Yhyd [Tref , pref ] = YSS +
ni Ys,i where
i=1
stant. In the limit of innite dilution it holds for the aqueous phase
Ys,i are individual group contributions and ni is the number of their occurrences
csw = xsw w /Mw and the atmospheric phase can be approximated in the molecule. Standard state term is also used in the case of CH4 , CO2 and H2 S.
by an ideal gas equation of state, csa = pas /RT where pas is the par- b
Entropic group contributions were calculated from Eq. (20).
c
tial pressure of solute in the air. Since at atmospheric conditions Hydrogen atom bound to alkene group.
d
Prex c denotes a cycloalkane group.
pas = KH xsw , it holds e
Group with subscript ar is a part of aromatic ring.
KH Mw KHm KHc f
Correction for ortho position on aromatic ring.
Kaw = = = (17)
RTw RTw mo RTco
[T , p ] and S [T , p ], and the second for expressing
Ghyd
This coefcient Kaw is presented typically at 298 K or over a lim- ref ref hyd ref ref
ited temperature interval at near-ambient conditions. Taking into the three integrals in Eq. (19).
account Eq. (7) it follows for the temperature dependence of Kaw : The Gibbs energy and entropy of hydration at the reference
    /RT + T 1 state Tref , pref are obtained for hydrocarbons (C2 and higher) from
lnKaw ln KH 1 Hhyd w [T , p ] and S [T , p ]
= + w = the group contributions for Ghyd ref ref hyd ref ref
T T T T
p p tabulated by Plyasunov and Shock [25]. In the case of CH4 ,
(18) CO2 and H2 S Ghyd [T , p ] was calculated from the Henrys
ref ref

where w is water compressibility. At temperatures close to ambi- law constant at 298.15 K obtained from the evaluated data by
/RT and T are of the order of 10 and 0.1, respectively. Fernandez-Prini et al. [17] using Eq. (3). The Shyd [T , p ] val-
ent Hhyd w ref ref

Then the above relationship suggests that the temperature slope of ues are those recommended by Plyasunov et al. [26]. Table 1
Kaw is about 10% lower compared to that for KH . lists the concrete Gibbs energy and entropy of hydration values:
the rst line contains the intrinsic YSS values that correspond to
3. Description of the group contribution method for KH the material point contribution to the Gibbs energy and entropy
of hydration. This term is derived from statistical mechanics
The Henrys law constants is calculated as a function of temper- [27] and can be calculated using only the properties of pure
ature and pressure via the Gibbs energy of hydration that can be solvent:
 RT 
expressed as follows [24]
GSS = RT ln
K  p Vw
RT ln
H
= Ghyd
[T, p] = Ghyd [Tref , pref ]     RT  
pref GSS
SSS = = R ln + 1 w T (21)
T T p Vw
p p
(T Tref )Shyd [Tref , pref ] + (Cp,hyd ) ref dT
Tref where p = 0.1 MPa and Vw and w are the molar volume and the
T p
coefcient of thermal expansion of water, respectively.
T
(Cp,hyd )
pref
d ln T + (Vs )T dp (19) The sum of the three integrals on the right-hand side of Eq.
Tref pref (19) is calculated from the high-temperature hydration model
[T , p ] and S [T , p ] are the terms relating
(SedlbauerOConnellWood, SOCW) proposed by Sedlbauer et al.
where Ghyd ref ref hyd ref ref [16]. Since the integration of the standard heat capacity equation is
to the reference state at Tref = 298.15 and pref = p = 0.1 MPa. The complex within this model it is more convenient to rearrange Eq.
entropic term is typically obtained as (19) as follows:
[T , p ] G [T , p ]
Hhyd
ref ref hyd ref ref Ghyd [T, p] = Ghyd [Tref , pref ] (T Tref )Shyd [Tref , pref ]
Shyd [Tref , pref ] = (20)
Tref
mod mod
+Ghyd [T, p] (Ghyd [Tref , pref ]
using the Gibbs energy and enthalpy reference state data. The
three integrals express the change with temperature and pres- mod
(T Tref )Shyd [Tref , pref ]) (22)
sure, the superscripts pref and T indicate the constant variable at
which the integration is performed. We have adopted an approach It is apparent that the sum of integrals is replaced by a com-
combining two distinct schemes; one for calculating the values of bination of three terms (denoted by superscript mod) using the
 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574 69

Table 2
Group contributions for calculating parameters of the T, p dependent (SOCW) model

Functional group a 103 (m3 kg1 mol) b 104 (m3 kg1 mol) c 106 (m3 kg1 mol) d e 10 (J K2 mol1 )

Ca
34.6310 9.4034 53.9212 7.3260 13.7921
CHa 6.5437 1.8156 16.9215 0.9492 3.9136
CH2 a 0.0244 0.7216 8.9576 0.3416 1.8264
CH3 a 7.2778 0.1571 1.9499 1.4268 0.0177
C Ca 10.2988 9.5352 12.9835 11.4045 1.4871
H a 2.8400 3.1911 9.2357 3.1496 0.5847
c-CHa 16.9864 4.8289 5.0487 3.3563 0.9028
c-CH2 a 3.0612 0.1108 7.6472 0.7839 1.2200
Car a 9.1549 2.2106 21.3460 1.3723 4.9993
CHar a 0.6924 0.5168 5.0903 0.3337 1.0754
CH4 b 3.90203 2.09843 2.4163 0 0.746493
CO2 b 3.15041 1.5963 9.65805 0.407478 1.90856
H2 Sb 1.36697 1.69674 12.8815 0.443516 2.81635
a
Group contributions for hydrocarbons reported by Sedlbauer et al. [15].
b
Parameters for individual compounds determined in this work.

expressions for the Gibbs energy and entropy of hydration from where Vs is expressed from Eq. (23). An additional empirical correc-
the high-temperature model. cor is needed at subcritical conditions since the simple
tion term Ghyd
The equation for the standard molar volume of an aqueous volumetric Eq. (23) is not sufcient for describing quantitatively the
solute is the basic relationship of the SOCW model: integration across the vaporliquid saturation line. This correction
 is dened on the heat capacity level and for nonelectrolytes has the
Vs = RTw + d(Vw RTw ) + RTw w a + b(exp[w ] 1) form

 
   cor
2 Ghyd cor
Shyd cor
Cp,hyd e(T Tc )2

= = = ,
+ c exp + (exp[w ] 1) (23) T 2 T T T (T 228)
T p
p

T < Tc (25)
where  = 0.005 m3 /kg,
= 1500 K and  = 0.01 m3 /kg are the pre-
determined general constants valid for all solutes. The solute
specic adjustable parameters are a, b, c and d, while = 0.35a where e is an additional adjustable parameter. Contribution of the
holds for all nonelectrolytes. This equation is in fact modeling a correction term is decreasing with increasing temperature and it
cor = H cor =
vanishes at the critical temperature of solvent (Ghyd
series of perturbation effects due to: (i) insertion of a material hyd
cor
Cp,hyd = 0, T Tc ) thus providing integration constant for Eq.
point into water solvent (VSS = RTw ), (ii) growing it to a water-
like molecule with size adjusted to mimic the intrinsic volume of mod is available, the model equa-
(24). Once the expression for Ghyd
a solute (d(Vw RTw )), and (iii) then changing its potential eld tion for the entropy of hydration also required in Eq. (22) is simply
from solventsolvent to solutesolvent interaction. This last con- obtained as
tribution is modeled by the third term on the right-hand side of
Eq. (23) that is purely empirical. This equation has correct limiting


mod
Ghyd
behavior, i.e. it reduces to the virial equation truncated after the mod
Shyd = (26)
second virial coefcient at low densities and diverges at the critical T
p
point of water [16].
Since the process of hydration is dened as an isothermal trans- mod , S mod and other thermody-
Full expressions for Ghyd hyd
fer of a solute molecule from an ideal gas state at pref = 0.1 MPa to
aqueous solution at a pressure p it is possible to write the Gibbs namic functions within the SOCW model can be found in
energy of hydration as Appendix A.
The ve parameters a, b, c, d, e of the temperature and pres-
0 p sure dependent model are obtained for hydrocarbons (NC > 1) from
mod
Ghyd = RT d ln p + Vs dp + Ghyd
cor
(24) the group contributions tabulated in Table 2. Each parameter for
pref 0 the solute of interest is calculated as a linear combination of the

Table 3
Survey of the database of experimental values

Compound type Total number of experimental values (number of compounds)

KH Hhyd Cp,s Vs

Alkanes (NC > 1) 295 (8) 63 (6) 1 (1) 5 (1)

Alkenes 291 (5) 6 (3) 3 (3)
Cycloalkanes 27 (3) 12 (2) 6 (1)
Alkylbenzenes 445 (7) 56 (6) 16 (2) 72 (6)
Alcohols 44 (16) 286 (22)

Total 1058 (23) 137 (17) 64 (22) 369 (30)

CH4 45 17 6 18
CO2 73 1 7 17
H2 S 27 1 9 19
70 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574

appropriate parameters of constituting groups, e.g. Table 4

Survey of data sources to determine the parameters of the SOCW model

N

a= ni ai (27) Literature sources in chronological Prop. Npoints T (K) p (MPa)

order
i=1
CH4
where N is the total number of structural groups present in the given Michels et al. [28] KH 4 323423 sat
solute, ni is the number of occurrences of each specic group, and Culberson and McKetta [29] KH 6 298444 sat
ai stands for the a parameter of the ith group taken from Table 2. Sultanov et al. [30] KH 5 423633 sat
Rettich et al. [31] KH 16 275328 sat
The molecular fragments are dened in an identical way as the
Cramer [32] KH 7 297518 sat
group contributions used for the calculation at the reference con- Crovetto et al. [33] KH 7 334554 sat
ditions Tref , pref (Table 1), the proximity effect I(CC) on aromatic Dec and Gill [34] H 1 298 0.1
ring is not, however, considered. The material point contribution Dec and Gill [35] H 2 288308 0.1
(Eq. (21)) that is temperature dependent appears explicitly in Eq. Oloffson et al. [36] H 3 288308 0.1
Naghibi et al. [37] H 11 273323 0.1
(24) and therefore it is not listed in Table 2. The group contribu- Hnedkovsky and Wood [38] Cp 6 303623 28
tions for C2 and higher hydrocarbons were taken over from the Tiepel and Gubbins [39] V 1 298 0.1
article by Sedlbauer et al. [15]. For illustration Table 3 gives the Moore et al. [41] V 1 298 0.1
number of data points and compounds that were considered per Hnedkovsky et al. [42] V 16 298623 2835
class of hydrocarbons when determining the group contributions CO2
by simultaneous correlation of the experimental Henrys law con- Wiebe and Gaddy [43] KH 3 323373 sat
stants and their derivative properties. A certain amount of data on Wiebe and Gaddy [44] KH 3 304313 sat
Morrison and Billet [45] KH 19 286347 sat
derivative properties (Cp,hyd , Vs ) for alcohols were also included
Malinin [46] KH 4 473603 sat
that was helpful for increasing numerical stability of the group con- Ellis and Golding [47] KH 9 450582 sat
tribution determination for the less frequent functional groups (for Takenouchi and Kennedy [48] KH 9 423623 sat
more information see reference [15]). Murray and Riley [49] KH 8 274308 sat
Cramer [32] KH 3 306405 sat
Using analogous simultaneous correlation procedure like for Shagiakhmetov and Tarzimanov KH 2 323373 sat
hydrocarbons, the parameters were newly determined for CH4 , [50]
CO2 and H2 S. These three aqueous solutes belong to experimen- Mller et al. [51] KH 6 373473 sat
tally well-studied systems with data available for most properties Nishswander et al. [52] KH 2 353471 sat
Crovetto and Wood [53] KH 3 623643 sat
characterizing hydration at elevated temperatures and extending
Bamberger et al. [54] KH 2 333353 sat
in the case of Vs and Cp,hyd to supercritical conditions. When Berg and Vanderzee [55] H 1 298 0.1
establishing the parameters of the SOCW model we have used the Barbero et al. [56] Cp 1 298 0.1
Henrys law constants along the saturation line of water deter- Hnedkovsky and Wood [38] Cp 6 304623 28
Moore et al. [41] V 1 298 0.1
mined from the gas solubility data reported in a variety of literature
Hnedkovsky et al. [42] V 16 298623 2035
sources listed in Table 4. Major sources of derivative properties
H2 S
were the papers by Hnedkovsky and Wood [38] and by Hnedkovsky
Selleck et al. [57] KH 3 377444 sat
et al. [42], reporting the standard heat capacities obtained by the Lee and Mather [58] KH 11 283453 sat
Picker-type ow calorimetry and the standard volumes from mea- Gillespie and Wilson [59] KH 3 422533 sat
surements by vibrating tube densimetry, respectively. These data Carroll and Mather [60] KH 10 273333 sat
were included for the three gases up to 623 K and 35 MPa in the Cox et al. [61] H 1 298 0.1
Barbero et al. [62] Cp 3 283313 0.1
case of volumes and at one isobar (28 MPa) for the heat capacities.
Hnedkovsky and Wood [38] Cp 6 304623 28
The enthalpies of hydration are available for CH4 at temperatures Barbero et al. [56] V 3 283313 0.1
to 323 K, originating from the unique measurements carried out by Hnedkovsky et al. [42] V 16 304623 2035
the groups of Gill et al. [34,35,37] and Wads and co-workers [36].
Only one enthalpic data point at 298 K is, however, reported for
CO2 and H2 S. The properties of the solutes in the ideal gas phase,
, C
where Xj and Xj stand for KH , Hhyd , Vs and their errors,
needed for converting Cp,s to C , were taken from the JANAF p,hyd
p,hyd
Thermochemical Tables [40]. Overall numbers of data points relat- respectively, and nj are the numbers of data points for the four
ing to individual thermodynamic properties are presented for the properties. Explicit equations for the thermodynamic functions
three gases in Table 3 and a detailed survey is given in Table 4. resulting from the SOCW model (denoted with the upper index
The parameters of the SOCW model were obtained by the mod in Eqs. (24)(26)) are presented in Appendix A. The adjustable
simultaneous correlation of the Henrys law constants and the parameters of the SOCW model obtained for aqueous CH4 , CO2
data on the three derivative properties using the weighted least and H2 S are summarized in Table 2 along with parameters for the
squares procedure with weights reecting the expected experi- hydrocarbon functional groups evaluated earlier [15]. A quantita-
mental uncertainties. They were estimated at 2% for KH of CH4 and tive comparison is made in Table 5 between the data calculated for
at 3% for CO2 and H2 S, based on the root-mean-square deviations of the three gases from the SOCW model and the values resulting from
the data from the correlation of Fernandez-Prini et al. [17]. For the the other two recently published models valid along the saturation
derivative properties the expected errors were set between 1% and line of water [17,63]. It is apparent that the agreement among the
3% for Hhyd and Vs , and between 3% and 5% for Cp,hyd , accord- models at psat
w is quantitative for CH4 and CO2 . Some differences are
observed for H2 S due to higher uncertainty in the Henrys law con-
ing to the error estimates in the original data sources and the fact
stants that are not quite consistent at elevated temperatures with
that the relative error increases with the temperature. The objective
the Cp,hyd and Vs data.
minimized function O was dened as
nj mod,j 2 Figs. 14 illustrate the changes in the Henrys law constant with

4 
Xi
exp,j
Xi the structure of the solute and with temperature and pressure up to
O= (28)
j 623 K and 80 MPa for hydrocarbons having eight carbon atoms and
Xi
j=1 i=1 for the three gases. First the results of the calculation for KH from
 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574 71

Table 5
Henrys law constants calculated along the saturation line of water and at elevated
pressures from the presented model for octane, methane, carbon dioxide and hydro-
gen sulde

p (MPa) ln KH at 298 K ln KH at 373 K ln KH at 473 K ln KH at 573 K

n-Octane
psat 9.60 11.25 9.77 6.73
10 10.21 11.78 10.20 6.82
40 12.02 13.36 11.69 8.51
80 14.42 15.43 13.58 10.45

CH4
psat 8.28 8.79 8.20 7.07
Ref. [17] at psat 8.28 8.77 8.20 7.09
Ref. [63] at psat 8.33 8.82 8.27 7.12
10 8.43 8.92 8.32 7.10
40 8.88 9.32 8.73 7.70
80 9.49 9.83 9.24 8.30

CO2
psat 5.11 6.23 6.34 5.78
Ref. [17] at psat 5.11 6.23 6.35 5.81
Fig. 1. The Henrys law constants calculated along the saturation line of water from Ref. [63] at psat 5.08 6.27 6.50 5.98
the group contribution model [15] for C8 hydrocarbons: n-octane (full), 1-octene 10 5.25 6.36 6.45 5.81
(long-dashed), ethylcyclohexane (short-dashed) and ethylbenzene (dashed-dot 40 5.66 6.72 6.82 6.32
line). 80 6.22 7.20 7.28 6.84

H2 S
psat 3.99 5.08 5.32 4.96
Ref. [17] at psat 3.99 5.03 5.33 5.00
Ref. [63] at psat 3.99 5.08 5.23 4.78
10 4.13 5.21 5.42 4.98
40 4.55 5.58 5.79 5.45
80 5.12 6.07 6.25 5.95

Comparison for CH4 , CO2 and H2 S at psat with the values (in italics) calculated from
the formulations of Fernandez-Prini et al. [17] and of Akinev and Diamond [63].

the group contributions are presented along the saturation line of

Fig. 2. The Henrys law constants for n-octane calculated as a function of tempera-
ture along the saturation line of water (full) and at pressures of 40 MPa (long-dashed)
and 80 MPa (short-dashed line).
water for four different C8 hydrocarbons (Fig. 1) and for n-octane as
a function of temperature and pressure (Fig. 2). Second, analogous
plots are in Figs. 3 and 4 for the aqueous gases.
Table 6 listing the ratios KH (p)/KH (psat
w ) for octane, methane,
carbon dioxide and hydrogen sulde at three pressures and four
temperatures summarizes quantitatively the change of the Henrys
law constant with pressure for the four solutes. It is apparent
from Eq. (9) that the standard molar volume of a solute plays a
major role in determining this factor. Thus, the pressure effect is
much stronger for octane than for the three gaseous solutes due to

Fig. 3. The Henrys law constants calculated along the saturation line of water from Fig. 4. The Henrys law constants for carbon dioxide calculated as a function of
the presented model for methane (full), carbon dioxide (long-dashed) and hydrogen temperature along the saturation line of water (full) and at pressures of 40 MPa
sulde (short-dashed line). (long-dashed) and 80 MPa (short-dashed line).
72 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574

Table 6
Ratios KH (p)/KH (psat
w ) for octane, methane, carbon dioxide and hydrogen sulde

KH (p)/KH (psat
w ) w 0.1 MPa)
323 K (psat w 0.1 MPa)
373 K (psat w 1.6 MPa)
473 K (psat w 8.7 MPa)
573 K (psat

10 MPa 50 MPa 100 MPa 10 MPa 50 MPa 100 MPa 10 MPa 50 MPa 100 MPa 10 MPa 50 MPa 100 MPa

Octane 1.8 17 289 1.7 14 181 1.5 11 114 1.1 10 101

CH4 1.2 2.0 4.0 1.1 1.9 3.6 1.1 1.9 3.6 1.0 2.2 4.5
CO2 1.1 1.9 3.7 1.1 1.8 3.3 1.1 1.8 3.2 1.0 2.0 3.6
H2 S 1.1 1.9 3.8 1.1 1.8 3.4 1.1 1.8 3.2 1.0 1.9 3.4

the difference in the Vs values (about 100 cm3 /mol for C8 H18 and
close to 35 cm3 /mol for the three gases at 298.15 K). At superambi-
ent conditions, the standard molar volume increases substantially
with increasing temperature and decreases with pressure, it scales
approximately with the compressibility of water and diverges at
the critical point of the solvent. For the pressures dependence of
KH the increase in volume at high temperatures is, however, partly
compensated by dividing with temperature in Eq. (9). Therefore,
the relative pressure effect on KH does not change much with tem-
perature at conditions remote from the critical point of water.
instead of fugacity. This simplifying assumption of an ideal gas
behavior of the vapor phase can lead to an increase of uncertainty
in Kd at high temperatures where the fugacity coefcient of water
can differ signicantly from unity.
The code is available on request as shareware for non-
commercial users from academia (contacts: vladimir.majer@univ-
bpclermont.fr and josef.sedlbauer@tul.cz). The preparation of input
les, the operation of the code and a few illustrative examples of
the input and output les are described in the README document
that is distributed along with the software.

4. Software package for calculating the Henrys law List of symbols

constant and related distribution coefcients c molarity
C heat capacity
As apparent from the equations listed in Appendix A, the applied f fugacity
model is rather complex and requires the use of a fundamental G Gibbs energy
equation of state allowing calculation of the thermodynamic prop- H enthalpy
erties of water. A programming effort would be necessary before Kaw airwater partition coefcient
using the method. In addition, the Henrys law constant or another Kd vaporliquid distribution coefcient
related coefcients are required in varying pressure and concen- KH Henrys law constant
tration units depending on the users and erroneous conversions m molality
often lead to confusion. For that reason we have prepared a com- M molar mass
puter code with a user-friendly interface allowing generation of the N total number of functional groups in a molecule
Henrys law constants from the model as a function of temperature O minimized objective function
and pressure in several types of units as well as the calculation of p pressure
other two coefcients dened by Eqs. (13) and (16) that are closely R universal gas constant
related to the Henrys law constant. Using the group contributions S entropy
listed in Tables 1 and 2 the estimations can be performed for normal SS intrinsic value
and branched alkanes and alkenes C2 to C12 and for the mono- T thermodynamic temperature
cyclic saturated or aromatic hydrocarbons (typically for C6 ring V volume
compounds) with one or several alkyl groups up to C8 . In addition, x molar fraction liquid phase
the software uses specic parameters for methane, carbon dioxide X partial molar property (X = G, H, S, V, C)
and hydrogen sulde. The calculations can be made at temperatures y molar fraction gaseous phase
up to 623 K either along the saturation line of water or at distinct
pairs of temperature and pressure (psat
w < p < 100 MPa). When run-
Greek letters
ning the program the user chooses from several options allowing expansivity
the calculation of one of the following parameters: the Henrys law  activity coefcient change
constant KH dened in terms of the mol fraction (Eq. (1)), its mod- fugacity coefcient
ications KHm and KHc (Eq. (6)) using as concentration variables  compressibility
molality (mol/kg) or molarity (mol/m3 ), respectively, the airwater  density
partition coefcient Kaw (Eq. (16)) and the vaporliquid distribution absolute error
constant (relative volatility) Kd (Eq. (13)). The airwater partition
coefcient is used for expressing the partition of a solute between Superscripts
air and water at near-ambient conditions and the calculation is a air phase
made therefore only at pressures below 0.5 MPa. Similarly due to its calc calculated
denition the vaporliquid distribution constant can be calculated cor correction term
solely along the saturation line of water. The ve coefcients are in exp experimental
the code interconnected by the limiting conversion expressions as g gas phase
follows H property compatible with the Henrys law
KHm KHc w Kaw RTw Kd ig ideal gas
KH = = = = (29) l liquid phase
mo Mw co Mw Mw psat,w
mod high-temperature model
where the meaning of individual symbols was explained above (see R property compatible with the Raoults law
Eqs. (6), (14) and (17)). Compared to Eq. (14) it is apparent that the sat saturation
saturation pressure of water is used in the conversion (Eq. (29)) sol solubility
 V. Majer et al. / Fluid Phase Equilibria 272 (2008) 6574 73

    
w aqueous phase


w
+(exp[w ]1) c exp +Rc exp
2
standard state of innite dilution T T T T3
limiting value
 2
pure compound w
+RT (b exp[w ] +  exp[w ])
T
p
Subscripts
    
c relating to molarity 2 w

hyd hydration + RT a + b(exp[w ] 1) + c exp

T 2 T
p
m relating to molality
 cor
o unit value +(exp[w ] 1) + Cp,hyd (A.4)
ref reference state
s solute where Gw, Hw , Cp,w are the molar Gibbs energy, enthalpy and heat
ig ig ig
sol dissolution capacity of water, Gw , Hw , Cp,w are the same properties of water in
SS intrinsic value an ideal gas standard state and w = 1/w (w /T )p is the iso-
w water baric coefcient of thermal expansion. Thermodynamic properties
x relating to molar fraction of water were obtained in this study from the equation of state
by Hill [64]. The correction terms are expressed by an empirical
Acknowledgements function with one additional adjustable parameter, e

cor e(T Tc )2
The authors thank Roberto Fernandez-Prini and Jorge L. Alvarez Cp,hyd = (A.5)
T
for providing the direct values of the Henrys law constant for CH4 ,    2  
CO2 and H2 S used for establishing parameters of the correlations cor Tc2 T (Tc ) T
Shyd =e T Tc ln + ln (A.6)
published in ref. [17]. J.S. acknowledges the support by the Research Tc Tc
Centre Advanced Remediation Technologies and Processes.
 1 2
cor
Appendix A. Thermodynamic functions of hydration from Hhyd = e (2Tc )(Tc T ) + (T Tc2 )
2
the SOCW model  T 
2
+(Tc ) ln (A.7)
The Gibbs energy of hydration is expressed in the SOCW model Tc
[16] as:
  RT     RT  cor
Ghyd cor
= (Hhyd cor
T Shyd ) (A.8)
w ig w
Ghyd = RT ln + d Gw Gw RT ln
Mw pref Mw pref
where = 228 K is a general constant. Correction terms dened by
    

b Eqs. (A.5)(A.8) apply only at temperatures below the critical tem-
+RT w a + c exp b + (exp[w ] 1) perature of water Tc = 647.1 K and are by denition equal to zero
T
at Tc 0. All thermodynamic properties that appear in the above

equations should be applied in their basic SI units when using
cor
+ (exp[w ] 1) + Ghyd (A.1) parameters from Table 2 of the main text.


Appropriate temperature derivations of Ghyd (see Eqs. (3), (7) and References
(8) in the main text) lead to other thermodynamic properties of
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