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