J.

of Supercritical Fluids 37 (2006) 333–341

Using solute structure to predict solubility of organic molecules

in supercritical carbon dioxide
B. Tomberli a,∗ , S. Goldman b , C.G. Gray a , M.D.A. Saldaña c , F. Temelli c
a
Department of Physics, University of Guelph, Guelph, Ont., Canada N1G 2W1
b
Department of Chemistry and Biochemistry, University of Guelph, Guelph, Ont., Canada N1G 2W1
c Department of Agricultural, Food and Nutritional Science, University of Alberta, Edmonton, Alta., Canada T6G 2P5

Received 17 June 2005; received in revised form 21 September 2005; accepted 30 October 2005

Abstract
Predictions of critical parameters and the Pitzer factor for three different group contribution methods are compared and used in correlative
predictions of virial coefficients. These virial coefficients are then used to determine the chemical potential of a solute in supercritical carbon
dioxide as a function only of the solute structure. Experimental chemical potentials are determined from measured solubility data and compared
to calculated chemical potentials by using both experimental vapour pressures and vapour pressures estimated from the solute structure by group
contribution methods. The group contribution method of Marrero and Gani is shown to best reproduce experimental solubility data with an average
absolute relative deviation of 10.4% (“exact” experimental input data only yields an accuracy of 10.7% for the molecules studied here). The
obtained accuracy for several common organic pollutants (naphthalene, benzoic acid, anthracene, phenanthrene, naphthol-2 and pyrene) suggests
that the method is applicable for predictions on previously unmeasured systems as long as the molecule has fewer than 20 non-hydrogenic atoms
and is relatively rigid.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Chemical potential; Fluctuation theory; Group estimation methods; Organic pollutants; Solid–fluid equilibria; Supercritical carbon dioxide

1. Introduction expansion of fluctuation theory. This theory does not require sol-
ubility data to estimate cross parameters and can thus provide
Recent interest in using supercritical fluids (SCFs) for extrac- real predictions of solubility. A specific goal is to estimate the
tion and fractionation processes [1–3] requires tractable and accuracy of this method when extended to solutes for which little
accurate predictions for the solubility of a low-volatility solute, or no input data are known.
B, in a SCF, A. However, for many systems of commercial inter-
est, theoretical methods are difficult to apply because input data 2. Theory
are lacking. Such data can be estimated using group contribution
methods, in which an additive function of the quantity desired The mole fraction of solute dissolved in the supercritical
(e.g. critical temperature, TC ) is formulated with the terms phase, xB , is related to the residual chemical potential by:
contributed by each molecular subunit or “group” within the

  
molecule (e.g. COOH within benzoic acid). While pure solute PBVAP µB (P − PBVAP )v̄sB
and pure solvent parameters can be estimated using group con- xB = exp − exp − (1)
ρkT kT kT
tribution methods, solute–solvent interaction parameters such
as the solubility parameter (e.g. ref. [3]) often require solubility
where T is the temperature, k Boltzmann’s constant, P the applied
data for accurate estimates. Therefore, the main objective of this
pressure and, for low solubility, ρ is the number density of the
study is to test the effect of using group contribution methods on
SCF (infinite dilution limit). The molecular volume of the solid
a previously published theoretical method [4] employing a virial
species (assumed to be pure), v̄sB , is assumed to remain con-
stant as pressure is changed and it is readily calculated from
∗ Corresponding author. Tel.: +1 519 824 4120x52625; fax: +1 519 836 9967. the density of the pure solute and its molecular weight. The
E-mail address: tomberli@physics.uoguelph.ca (B. Tomberli). key quantities are the vapour pressure of the solute, PBVAP , and

0896-8446/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2005.10.008
334 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341

of the nature and derivation of such expansions are given in stan-

Nomenclature
A solvent
AARD absolute average relative deviation
B solute
Bxy (T) second xy cross virial coefficient
Cxyx (T) third xyz cross virial coefficient
Dwxyx (T) fourth wxyz cross virial coefficient
dard statistical mechanics texts (see Chapter 12 of [5]). The Nth
virial coefficient can be directly related to the N-body potential
energy function [5]. For example, for classical rigid molecules
interacting via a pairwise potential, uxy (r12 , ω1 , ω2 ) = uxy (12),
the second virial coefficient, Bxy (T), is:

1  
Bxy (T ) = − exp(−βuxy (r12 , ω1 , ω2 )) − 1 ω ω dr12
2 1 2

EOS equation of state (2)

f fitting parameter for alkane flexibility
where β = 1/kT and the · · ·ω,ω2 denotes an unweighted aver-
GXY Kirkwood–Buff factor of species X and Y
age over all orientations ω1 and ω2 of molecules 1 and 2 (of
gxy (12) ≡ gxy (r12 , ω1 , ω2 ) pair correlation function
type x and y, respectively) of the function contained within the
between molecule 1 of species x and molecule
pointed brackets and dr12 denotes a volume element. Higher
2 of species y
order virial coefficients, (Cxyz (T), Dwxyz (T), etc.. . .) are most
gxy(i) (12) ith order term in density expansion of g (12)
xy
easily expressed graphically and are given in standard statistical
I first ionization potential
mechanical texts [5].
k Boltzmann’s constant
When virial coefficients are used in the virial expansion for
Nx number of molecules of species, x
the residual chemical potential of an infinitely dilute solute, B,
P pressure
in a solvent A, i.e.
PBVAP vapour pressure of solute B
r position vector µB 3
lim = 2BAB (T )ρ + CAAB (T )ρ2
SCF supercritical fluid xB →0 kT 2
T temperature
4
T* reduced temperature, T* = kT/ε + DAAAB (T )ρ3 + · · · , (3)
TC , PC , ρC , vC critical temperature, pressure, density and 3
volume per molecule where xB ≡ NB /N is the mole fraction of the solute, terms
uxy (12) ≡ uxy (r12 , ω1 , ω2 ) pair potential between to order Dwxyz (T) in (3) are required to achieve satisfactory
molecule 1 of species x and molecule 2 of species (∼5%) numerical accuracy at SCF extraction conditions [4,6].
y Because calculating DAAAB (T) can be extremely difficult for
v̄sB ≡ (∂v/∂NB )T,P,NA partial molecular volume of species real molecules, a method is required that can achieve compara-
B in solid phase ble accuracy with fewer virial coefficients.
V volume Using fluctuation theory and well-known expressions for v̄sB
xB mole fraction of solute, B and κT in terms of Kirkwood–Buff factors one obtains [7]:
 ρ
µB GAB
Greek symbols =− dρ (4)
· · · average of . . . kT 0 1 + ρ GAA
µB residual chemical potential of solute B where the GXY are Kirkwood–Buff factors which can be
β 1/kT given in terms of the radial distribution function, gxy (r12 , ω1 ,
ε well depth for Lennard–Jones potential ω2 ) ≡ gxy (12), or the thermodynamical averages of the number
κT isothermal compressibility of molecules of each species, Nx ,
ρ number density 
ρ* reduced number density, ρ* = ρσ 3 GXY ≡ gxy (r12 , ω1 , ω2 ) − 1ω1 ,ω2 dr 12
σ molecular diameter for Lennard–Jones potential
ω acentric Pitzer factor Nx Ny  − Nx Ny  − δxy Nx 
ωi angular orientation of molecule i =V (5)
Nx Ny 

The density dependence of gxy (12) can be expressed as a

solute’s residual (i.e. excess over the ideal gas) chemical poten- density series similar to the pressure virial expansion [4,6]:
tial, µB , in the supercritical phase. The remaining exponential
factor in Eq. (1) is of the order of unity at supercritical conditions gxy (12) = gxy
(0)
(12) + ρgxy
(1)
(12) + ρ2 gxy
(2)
(12) + · · · (6)
and therefore of less interest.
where gxy
(i) (12) is given in terms of the pair potential, for example:
Virial coefficients are used in an expression from fluctuation
theory. The virial coefficients form the terms in an expansion gxy
(0)
(12) = exp(−βuxy (12)). (7)
breaking the interactions of the N molecules in the SCF into a
series composed of a one body term (the ideal gas term), a two Higher order expressions are available in standard thermody-
body interaction term, a three body interaction term, etc. Details namic texts [5]. Substitution of such expressions into Eq. (4) for
 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341 335

a two component fluid in the infinite dilution limit for compo- Table 1
nent B (xB → 0) and integrating the resulting expressions yields Comparison of critical temperatures (K) estimated by three different group con-
tribution methods to experimental values
an expression distinct from Eq. (3) for the residual chemical
potential in terms of the virial coefficients [4]: Substance MGa CGa JRa Exp. [Ref.]


 Naphthalene 746.60 739.02 737.28 748.4 [16]
µB 2BAB − BAA (a3 /a2 ) a2 ρ − BAA
= tan−1 Benzoic Acid 749.99 751.00 750.90 752 [16]
kT a1 a1 Biphenyl 826.03 760.55 777.19 789 [16]

 Phenanthrene 870.8 826.54 877.24 878 [16]
−BAA a3
− tan−1 − ln[1 − 2BAA ρ + a2 ρ2 ], Anthracene 873.00 826.54 877.10 883 [16]
a1 2a2 Pyrene 934.97 874.81 943.41 936 [13]
(8) Decane 612.93 623.69 590.67 617.6 [16]
n-Heneicosane 777.23 768.75 841.70 778b
where AARD (%) 1.0 3.2 2.2 0.0
⎛ ⎞
a MG stands for Marrero–Gani [10], CG for Constantinou–Gani [11] and JR
1
a1 = ⎝  ⎠, (9) for Joback–Reid [12].
2 − 3C
3BAA
b Interpolated from data in [16] and [17].
AAA

a2 = 4BAA
2
− 3CAAA , (10) contribution method of Marrero and Gani [10] is clearly bet-
ter than the others. The other thermodynamic parameters used
and
(PC , vC , ω) show similar trends in accuracy.
a3 = 4BAB BAA − 3CAAB . (11) Virial coefficients calculated using experimental critical
parameters and ionization potentials are compared to mea-
Only terms to order gxy (1) (order C (T)) are kept in Eq. (6) to
xyz sured virial coefficients [15] to estimate the accuracy of the
get Eq. (8). An expression for gxy (1) is given in [5]. The expres- virial coefficient correlations. For carbon dioxide, experimen-
sion to second order is much simpler, but less accurate [4]. The tal values are used everywhere in this work: TC = 304.2 K,
expression to fourth order is more complicated and not useful PC = 73.8 bar, vC = 94 cm3 /mol, ω = 0.225 and I = 13.773 eV
due to the difficulty of determining the higher order virial coeffi- [14,18]. In Fig. 1, correlated BAB (T)’s determined using exper-
cients. When used to predict the residual chemical potential for imental values for TC , PC , vC , ω and I for both solute and
Lennard–Jones systems, Eq. (8) has been shown to be accurate solvent are compared to measurements of the second virial coef-
to within 6% when accurate virial coefficients (to order Cxyz (T)) ficient [14] for pure CO2, CO2 –naphthalene, CO2 –anthracene
are used. and CO2 –phenanthrene with absolute average relative deviation
(AARD) of the correlated values of 0.53%, 9.0%, 10.4% and
3. Determination of virial coefficients 8.7%, respectively. The pure virial coefficients are clearly more
accurate than the mixed ones. This is due to the difficulty of
The proposed test requires solutes for which both CO2 –solute estimating unlike pair interactions and a corresponding lack of
cross virial coefficients and solubility data are known. For
this reason, naphthalene, phenanthrene, anthracene and the n-
alkanes were chosen for this study. Naphthol-2, pyrene and
benzoic acid were also studied because the Tsonopoulous corre-
lation [8] is shown in Fig. 1 to be accurate for polycyclic aromatic
pollutants and because enough experimental data existed for
these compounds to allow accuracy to be tested with confidence.
The empirical correlations of Tsonopoulous for the second
virial coefficient Bxy (T) [8] and of Orbey and Vera for Cxyx (T) [9],
requiring the critical parameters, TC , PC , vC , the Pitzer factor ω
and the first ionization potential, I, of both the solute and solvent
as input, were used. Critical parameters and Pitzer factors were
obtained using a program calculating the group contributions by
the methods of Marrero and Gani (MG) [10], Constantinou and
Gani (CG) [11] and Joback and Reid (JR) [12] available via the
Internet [13] and ionization potentials are taken from ab initio
calculations and used to determine Bxy (T) and Cxyz (T).
Cross virial coefficients require mixed critical parameters and Fig. 1. Experimental second virial coefficients for pure CO2 (×) and exper-
imental cross virial coefficients for naphthalene–CO2 , ( ) anthracene–CO2
Pitzer factors that are determined as outlined by Prausnitz et al.
(
) and phenanthrene–CO2 (
) from [14] are shown with error bars. The
[14]. The program outputs for the estimated critical temperatures phenanthrene–CO2 data are shown displaced by −100 cm3 /mol for clarity. The
of eight different compounds based on the three different meth- smooth curves are the predicted second virial coefficients from the correlation
ods are compared to experimental data in Table 1. The group of Tsonopoulous [8].
336 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341

Fig. 2. Experimental third virial coefficients for pure CO2 [15] are compared
to the results from [9] using both the predicted (thin line) and measured (thick
line) value of Cxyz (TC ).

Fig. 3. Experimental cross virial coefficients for decane–CO2 (
) [15] and
data. Therefore, the accuracy of Eq. (8) will benefit from the C21 H44 –CO2 ( ) [19] systems. The upper smooth curves are the predicted
increased accuracy of the pure virial coefficients while Eq. (3) second virial coefficients from the correlation of Tsonopoulous [8]. The thick
will not. This is in addition to the increased accuracy shown in line is for C21 H44 . The thin line denotes decane. The thick line passing approx-
Lennard–Jones systems [4] where both pure and mixed virial imately through the C21 H44 data is the Tsonopoulous data multiplied by 2.5 to
coefficients were calculated to equal accuracy. account for the increased flexibility of the longer alkane.
Experimental data for the third virial coefficient of CO2
are compared to results using the method of Orbey and
Vera [9] with the known value [15] of CAAA (TC ) = CAAA
(304.2 K) = 5112 ± 100 cm6 mol−2 in Fig. 2 (taken from [4]).
The AARD is 2.7%: not as low as that for the pure second virial
coefficient but considerably better than that for the mixed sec-
ond virial coefficient. There are no experimental data for mixed
third virial coefficients available for further comparisons. Given
the reduced effect of successively higher coefficients in Eq. (8),
this level of agreement is deemed satisfactory.
The accuracy of the virial coefficients determined using
experimental data indicate that the Tsonopoulous correlation
is suitable for relatively rigid molecules with less than 20 non-
hydrogenic atoms.
Cross second virial data for n-alkanes with CO2 are available Fig. 4. Plot of flexibility factor, f, used to correct Tsonpoulous [8] correlation to
in the literature [19]. Given the spotty availability of experi- force agreement with experimental Bxy (T) [19] vs. carbon number for n-alkanes.
mental input parameters, the MG method, shown to be the best The curve joining the points is included only to guide the eye.
in Table 1, was used for all alkanes. In Fig. 3, CO2 –n-decane
and CO2 –C21 H44 cross coefficients from the Tsonopoulous cor- ted against carbon number clearly shows the increasing trend
relation are compared to experimental data [19]. Experimental in error as the carbon number increases. However, for rigid
critical parameters and Pitzer factors are used here [16]. Ion- molecules of similar size, the Tsonopoulous correlation does
ization potentials are extrapolated from [20]. The correlation considerably better. For example, the accuracy for phenanthrene
agrees well with measured results for n-decane CO2 , while the and anthracene is much better than that for C14 H30 (not shown).
agreement is very poor for the CO2 –C21 H44 . Accuracy of mixed Therefore, the inaccuracy can be attributed to molecular flexi-
second virial coefficients for alkanes with more than 21 carbons bility.
is also poor. The Tsonopoulous correlation is more accurate for
the rigid molecules (CO2 , naphthalene, to a lesser extent decane) 4. Comparison of predictions of the residual chemical
but visibly less accurate for the flexible alkanes. In Fig. 4 the potential to experimental results
results for the Tsonopoulous correlation using MG input data
and ionization potential data extrapolated from [20] are summa- Using the well-known experimental results for carbon diox-
rized. A factor, f, is introduced into Eq. (2) to force agreement ide’s critical parameters, Pitzer factor and ionization potential
between the BAB (T) predicted by the Tsonopoulous correlation given above and using the group contribution methods of Mar-
and experimental values. The increasing value of f when plot- rero and Gani (MG) [10], Constantinou and Gani (CG) [11] and
 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341 337

Table 2
Absolute average relative deviations (AARD’s) for residual chemical potentials calculated using three different group contribution (GC) methods or experimental
data as input compared with residual chemical potentials from Eq. (1) with measured vapour pressures and vapour pressures from [22]
Solute [ref. for solubility] T (K) AARD (%)

Only CG with CG with GC JR with JR with GC MG with MG with GC

experimental experimental PBVAP experimental PBVAP experimental PBVAP
input PBVAP PBVAP PBVAP

Naphthalene [24] 308 9.4 9.0 6.9 9.1 8.9 8.3 16.7
323 5.9 6.3 22.8 8.9 8.7 7.7 4.5
328 7.1 7.1 20.2 8.9 8.8 7.3 8.2
Phenanthrene [25,26] 318 11.2 25.8 14.7 15.0 15.1 11.0 14.3
323 9.3 24.1 11.6 13.3 13.2 9.3 12.6
328 12.7 26.8 14.3 16.6 16.2 12.8 15.8
338 14.6 28.0 13.7 18.3 17.2 14.9 17.4
Anthracene [27] 308 10.2 26.1 18.0 15.3 13.2 11.2 9.3
323 13.0 28.0 30.3 18.3 16.1 14.5 13.1
343 15.8 29.2 37.1 20.1 17.0 11.6 16.2
Pyrene [26] 313 14.5 8.8 13.2 12.3 14.2 11.3 14.3
323 8.8 12.8 12.3 7.0 14.9 6.6 14.9
333 4.4 17.2 11.4 4.2 16.2 4.0 15.9
Benzoic acid [28] 308 7.3 6.5 4.7 9.4 3.0 8.0 6.4
318 9.7 8.9 6.8 11.6 3.5 10.2 8.9
328 12.5 11.9 10.3 14.3 5.5 12.9 11.9
343 15.4 15.0 13.7 17.2 7.6 15.7 15.4
Averages AARD (%) 10.7 17.1 15.4 12.9 11.7 10.4 12.7

Joback and Reid (JR) [12] to determine solute critical parame-
ters and Pitzer factors with ab initio ionization potentials, Bxy (T)
and Cxzy (T) can be estimated using the Tsonopoulous [8] and
Orbey and Vera [9] correlations, respectively. The resulting virial
coefficients, when substituted into Eq. (8) will yield predic-
tions for the residual chemical potential that can be compared
to the experimental values calculated from experimental solu-
bility data using Eq. (1) and experimental values for the solvent
pressure, solvent density, solute molecular volume and vapour
pressure. Molecular volume is in all cases estimated from the
experimental density of the solute. The solid molar volume of
the solute has a weak effect on the chemical potential and will
not be discussed further. Solvent density is a key parameter.
Where it is not provided as part of the experimental data, it
can be estimated quite accurately with the Ely equation of state
[21] for pure CO2 as long as the infinite dilution approximation

Table 3
Vapour pressures for group contribution method of Coustikos [22] with melting point from three other group contribution methods compared to experimental data

Solute T (K) Measured PBVAP (Pa) CG PBVAP (Pa) JR PBVAP (Pa) MG PBVAP (Pa)

Naphthalene 308 65.7 [29] 168.6 153.0 25.7

323 179.0 [29] 536.5 488.9 89.3
328 243.6 [29] 768.9 701.8 131.5
Phenanthrene 318 0.227 [30] 0.992 0.2197 0.143
323 0.368 [30] 1.646 0.3733 0.245
328 0.598 [30] 2.687 0.6234 0.411
338 1.463 [30] 6.832 1.655 1.11
Anthracene 308 0.0029 [31] 0.341 0.07195 0.0033
323 0.0186 [31] 1.646 0.3733 0.0198
343 0.173 [31] 10.655 2.6348 0.1655
Pyrene 313 0.090 [32] 0.0544 0.00446 0.00482
323 0.151 [32] 0.1589 0.01409 0.0152
333 0.242 [32] 0.4334 0.04131 0.0444
Benzoic acid 308 0.367 [31] 0.4881 0.9718 0.448
318 1.105 [31] 1.401 2.728 1.289
328 3.110 [31] 3.743 7.145 3.454
343 13.11 [31] 14.52 26.94 13.44
AARD (%) 0.0 1700 410 37
338 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341

holds. On the other hand, the vapour pressure strongly affects

the values for the residual chemical potential obtained from the
experimental solubility data. While vapour pressure predictions
are not the emphasis of this work, to truly predict solubility using
Eq. (1), vapour pressure data are required. In keeping with the
theme of this work that only the solute structure needs to be
known, a group contribution method for the vapour pressure
according to Coustikos et al. [22] was used rather than the more
common correlations [23], which require a fitted constant and a
boiling point. The method of Coustikos et al. [22] requires only
the structure and melting point. The melting point is calculated
using the same group contribution techniques as for the critical
parameters.
In Table 2, results are summarized for the AARD’s of predic-
tions with measured residual chemical potential calculated using
Eq. (1) from experimental solubility data. All group contribu- Fig. 5. Theoretical predictions of µB /kT from fluctuation theory to order
tion methods should be compared to the third column, which Cxyz (T) using only solute structure are compared to values calculated from exper-
contains the errors when all inputs for Eq. (8) are from exper- imental data for naphthalene at 308.2 ( ), 323.2 K (
) and 328.2 K (
) [24].
imental sources. Within the error bars from the experimental The 323.2 K data are shown displaced by +5 and the 328 K data are shown
displaced by +10 for clarity.
measurements, this column indicates the underlying accuracy
of the theory for these molecules.
The vapour pressures used in Table 2 are presented in Table 3. tion potentials are required, they were obtained from [18]. The
The Marrero and Gani [10] melting point clearly gives the best loss of accuracy apparent in Fig. 5 at higher densities is caused
vapour pressure data using the correlation of Coustikos et al. by two underlying effects for naphthalene. Firstly, the theory
[22]. itself is less accurate at higher densities [4]. Secondly, at the
In Table 2, the method of Marrero and Gani [10] is demon- highest temperatures, the mole fraction of naphthalene reaches
strated to be slightly more accurate than the method of Joback up to 5%, which may render the infinite dilution approximation
and Reid [12] and much more accurate than the method of Con- inadequate. The larger deviation of the leftmost experimental
stantinou and Gani [11]. For predicting vapour pressures, it is data point in the 308 K isotherm may be due to experimental
apparent in Table 3 that the MG melting point is far superior error. Nonetheless, it has been included in the analysis.
to the others. Therefore, most of the remaining discussion will Plots of predictions of the residual chemical potential from
focus on the MG method. Eq. (8) for pyrene in CO2 at T = 313, 323 and 333 K are com-
In a previous work [4], comparisons to Lennard–Jones sim- pared to the chemical potential calculated from experimental
ulation results were found to agree very well for reduced den- results [26] using Eq. (1) in Fig. 6. In this case, the vapour
sities, ρ* ≡ ρσ 3 ≤ 0.6, where σ is the molecular radius of the pressures were taken from literature values [32] for Antoine
Lennard–Jones potential. This density corresponds to about coefficients determined from experiment. Ionization potentials
twice the critical density. If the discussion is restricted to experi- are taken from [18,34]. The agreement with experimental data
mental densities less than 0.021 g/cm3 for CO2 then the AARD’s
when the Marrero and Gani Group contribution method is used
to generate the required input for Eq. (8) drop to below 5%.
This is consistent with the experimental error bars induced by
uncertainty in the vapour pressure and with the comparison to
simulated results in [4].
Fig. 5 shows predictions of the residual chemical potential
from Eq. (8) using the Marrero and Gani input data [5] for
naphthalene in CO2 at T = 308, 323 and 328 K compared to
the chemical potential calculated from experimental results [24]
using Eq. (1). Experimental vapour pressures were used in Eq.
(1) to calculate µB /kT; however, the results did not differ sub-
stantially when they were determined using the correlation of
Coustikos et al. [22]. The first ionization potential was from ab
initio quantum chemical calculations that used only the struc-
ture as input [33]. The critical density of CO2 on this scale is
Fig. 6. Theoretical predictions of µB /kT from fluctuation theory to order
0.01063 mol/cm3 . The experimental data agree very well with
Cxyz (T) (curves) using only solute structure are compared to experimental val-
the theoretical predictions. The AARD’s for naphthalene from ues for pyrene at 313 K (
), 323 K (♦) and 333 K ( ) [26] calculated using
Table 2 are 8.3%, 7.7% and 7.3% for all data points in [24] at experimental vapour pressures. The 323 K and 333 K results are offset by −4
308, 323 and 328 K, respectively. Where experimental ioniza- and −8, respectively.
 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341
Fig. 7. Theoretical predictions of µB /kT from Eq. (8) (thick line) and Eq. (3)
(thin line) using only solute structure are compared to values calculated from
experimental data [35] for anthracene at 343 K.
is excellent because the necessary approximations for these
methods apply best to pyrene. It has low solubility in CO2 ,
and it is a very rigid molecule without any large multipolar
moments. If densities above 0.16 g/cm3 are excluded from the
analysis – the region where Eq. (8) is less accurate – then the
AARD’s reported in Table 2 for the MG method fall signifi-
cantly to 3.1%, 1.3% and 4.6%. In other words, the calculation
is well within experimental error bars for moderate to low den-
sities. It is only at high densities that the approximations break
down. This effect was less apparent for naphthalene and ben-
zoic acid where the infinite dilution approximation was not as
good.
In Fig. 7, calculated values for the residual potential of
anthracene in supercritical CO2 are compared to values calcu-
lated using Eq. (1) from the solubility measured in [35]. The
thick line in Fig. 7 shows predictions using Eq. (8) for anthracene
at 343 K using the MG method to generate the critical param-
eters and Pitzer factor and ionization potentials are from [35].
Five percent error bars corresponding to the approximate error
induced by the uncertainty in the vapour pressure are shown.
This uncertainty in the vapour pressure is approximated by the
discrepancy between various measurements. Similar sized error
bars apply to the other data. Even with the error bars, the agree-
ment between theory (Eq. (8)) and experiment (Eq. (1)) is much
poorer for anthracene than those shown in Figs. 5 and 6. It
was chosen as a representative from Table 2 to illustrate what
the worst cases studied looked like. What is surely a fortuitous
cancellation of errors at higher densities reduces the AARD to
about 15%. The reasons for this poor agreement are best seen
in Table 1. The group contribution methods give poorer results
for TC (and other parameters) for anthracene than for the other
molecules. This is probably caused by the difficulties that group
contribution methods have in accounting for the difference in the
properties between isomers like anthracene and phenanthrene.
The µB results for phenanthrene show trends very similar to
anthracene in accuracy. Ionization potentials used to calculate
the phenanthrene–CO2 cross virial coefficients are taken from
[18,34].
339
Nearly all solubility predictions of the type seen in recent
literature [1–3] involve adjustable parameters based upon other
solubility data. Truly predictive methods tend to be very labori-
ous, e.g. simulation. One of the few available predictive methods
that Eq. (8) can be compared to is the virial expansion (Eq. (3))
[6]. The thin line in Fig. 7 shows the predictions of Eq. (3)
for anthracene. Even though the same input data were used as
for Eq. (8), the agreement is markedly worse. Similar trends are
observed for phenanthrene, naphthalene and pyrene. For benzoic
acid and naphtol-2, predictions from Eq. (3) were quantitatively
and qualitatively similar to those from Eq. (8). On this basis, Eq.
(8) is deemed to be superior to Eq. (3).
Results on µB for benzoic acid (shown only in Table 2)
look qualitatively similar to those for naphthalene; however, a
vertical shift between theory and experiment is more apparent at
all densities. Ionization potentials used to calculate virial coef-
ficients are taken from [18,36]. The results are slightly worse,
probably due to complexing of the benzoic acid with the sur-
rounding solvent medium facilitated by the hydroxyl group and
increased polarity of the molecule.
The residual chemical potential from Eq. (8) for naphthol-2
in CO2 at T = 318 and 328 K compared to the chemical poten-
tial calculated from experimental results [37,28] using Eq. (1)
is shown in Fig. 8. This is an example that typifies the way the
methods outlined in this work are most often applied—with par-
tial sets of data compiled from a combination of experimental,
correlated and theoretical data. Experimental ionization poten-
tials and solid molar volumes are taken from [18] and [37],
respectively. The vapour pressures are estimated using the cor-
relation of Grain [23] because the method of Coustikos et al.
[22] in this case gives answers that are at odds with measured
data for naphthol. Other input data are once again from the MG
[10] method. No fittings of any kind are done and the method
reported was simply the most expedient path to reasonable self-
consistent data. Once again, the agreement between our theory
and experimental data is very good. Furthermore, the compari-
Fig. 8. Theoretical prediction of µB /kT from Eq. (8) is compared to values
calculated from experimental data [37,28] for naphthol-2 at 318 K (closed sym-
bols) and 328 K (open symbols). The 328 K data (thick line) are shown displaced
by +4 for clarity.
340 B. Tomberli et al. / J. of Supercritical Fluids 37 (2006) 333–341
son with the results of two different experiments indicates that
this is not due to a fortuitous cancellation of errors. The data
were not included in the AARD analysis only due to the lack
of independence between experimental and estimated correlated
data.
5. Conclusions
An accurate and tractable theory for making supercritical sol-
ubility predictions has been presented. It is based on combining
the virial expansion and fluctuation theory. The theory is derived
from first principles and is systematically improvable through
the inclusion of higher order terms in the expansion. The required
virial coefficients can be calculated from first principles when
sufficient computing resources exist. In this work, it has been
shown that they can be estimated using well-known and accu-
rate empirical correlations with little or no loss of accuracy and
that the CG method [11] is inferior to both the MG [10] and
JR [12] group contribution methods with the MG method being
marginally superior. Using experimental data for TC , PC , vC and
ω and the experimental ionization potential as inputs to Eq. (8),
the AARD for the studied data sets was 10.7%. Using only
the structure of the solutes to estimate these same parameters
via the MG method [10] and literature results from molecular
structure based quantum mechanical calculations improved the
agreement to 10.4%. This small discrepancy is within the under-
lying error inherent in the approximative theory and the small
improvement almost surely represents a fortuitous cancellation
of errors. When the vapour pressures required to determine µB
are estimated by group contribution methods, the accuracy falls
slightly to 12.9% for the MG method.
A decrease in accuracy is apparent as density is increased
in all data. This is consistent with the decreasing accuracy of
the virial expansion as the density is increased. Agreement is
significantly better if only experimental data for densities less
than about twice the critical density are used.
The overall accuracy indicates that the method is suitable
for predictions on previously unmeasured systems as long as
the molecule has fewer than 20 non-hydrogenic atoms and is
relatively rigid. This includes many anti-oxidant molecules of
current interest. Therefore, future work in this field will be
directed towards solubility predictions for anti-oxidants.
Acknowledgements
We gratefully acknowledge the financial support of the Nat-
ural Sciences and Engineering Research Council of Canada
(NSERC) and the Advanced Foods and Materials Network of
Canada (AFMNet). Jorge Marrero and Rafiqul Gani are thanked
for allowing the use of their program Propred 3.6 in carrying out
these calculations and J.H. Dymond is thanked for providing
virial coefficient data from [15].
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