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Abstract
Isobaric vapor–liquid equilibrium measurements are reported for the binary system (−)-beta-pinene + (+)-fenchone at the constant pressure
of 13.33 kPa in the temperature range from 341.60 K to 393.25 K. The boiling temperatures of the mixtures were also measured at seven
constant compositions in the pressure range from 2.56 kPa to 20.80 kPa. The experimental data were found to be thermodynamically consistent.
Reduction of the vapor–liquid equilibrium data was carried out by means of the Wilson, NRTL and UNIQUAC equations. Our data on
vapor–liquid equilibria for mixtures containing terpenoids are examined in terms of the DISQUAC and modified UNIFAC (Dortmund) group
contributions models. Interaction parameters of the DISQUAC model are reported.
© 2004 Elsevier B.V. All rights reserved.
Keywords: Vapor–liquid equilibria; Terpenoids; DISQUAC; Modified UNIFAC (Dortmund); Gibbs energy
0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.10.032
114 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124
The purpose of the present work was to measure VLE structures of all the terpenes and terpenoids refered to in this
of binary mixtures of (−)-beta-pinene + (+)-fenchone and to paper are presented in Fig. 1.
check the predictive capability of two group contribution
models, DISQUAC and modified UNIFAC (Dortmund), for
this mixture and for the previous reported mixtures contain- 2. Experimental
ing terpenoids.
No experimental VLE data are available in the literature 2.1. Chemicals
for the binary system (−)-beta-pinene + (+)-fenchone [7].
(−)-Beta-pinene is a bicyclic terpene hydrocarbon while (−)-Beta-pinene, CAS RN 18172-67-3, ACROS OR-
(+)-fenchone is a bicyclic terpenoid ketone. The chemical GANICS (Ney Jersey, USA) material of stated purity
The direct experimental boiling temperatures T of the pure where N is the number of experimental points, Pie , Tie , xie
terpenoids were measured previously and published [1–6,8] and yie are the experimental data and Pic , Tic , xic and yic are
A series of isobaric T–x–y measurement was performed the corresponding calculated values for pressure, tempera-
at (13.33 ± 0.030) kPa (Table 1). The experimental activity ture, and the liquid and vapor compositions, respectively. In
116 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124
Fig. 4. Variation of the molar excess Gibbs energy, GE with mole fraction xi ,
Fig. 2. Experimental vapor–liquid equilibrium diagram for the binary
for the binary system n-decane (1) + (+)-fenchone (2) at a constant pressure
system. (−)-Beta-pinene (1) + (+)-fenchone (2) at constant pressure
P = 6.67 kPa: (), experimental; ( ), DISQUAC model;(夽), mod.UNIFAC
P = 13.33 kPa, temperature T (K) as a function of the liquid phase, xi (),
(Do) model.
or vapor phase yi (*), mole fraction composition of component 1.
4. Discussion
Table 3
Binaries parameters A12 and A21 of the Wilson and NRTL and UNIQUAC models for the binary system (−)-beta pinene (1) + (+)-fenchone (2)
T–P–x–y MD (y) MD (P) (Pa) T–P–x MD (P) (Pa)
Fig. 5. Variation of the molar excess Gibbs energy, GE with mole fraction xi , Fig. 7. Variation of the molar excess Gibbs energy, GE with mole fraction
for the binary system n-decane (1) + (−)-menthone (2) at a constant pressure xi , for the binary system (+)-limonene (1) + (S)-(+)-carvone (2) at a con-
P = 6.67 kPa: (), experimental; ( ), DISQUAC model; (夽), mod.UNIFAC stant pressure P = 6.53 kPa: (), experimental; ( ), DISQUAC model; (夽),
(Do) model. mod.UNIFAC (Do) model.
In the mixture with n-decane at ca. 372 K, the equimolar GE In the binary system eucalyptol + (R)-(−)-carvone, the like
is ca. 660 J mol−1 (Fig. 6). dipole/dipole CO/CO and O / O interactions compensate
(S)-(+)-Carvone and (+)-limonene having similar molec- the unlike dipole/dipole CO/ O and dipole/induced dipole
ular structures and the same number of double bonds, the like O /C C interactions. Accordingly, at 375 K, the equimolar
and unlike dipole/induced dipole CO/C C interactions com- GE of the mixture is ca. 418 J mol−1 (Fig. 8), much smaller
pensate. At ca. 376 K, the equimolar GE is ca. 510 J mol−1 than for n-decane + (R)-(−)-carvone (Fig. 6).
(Fig. 7), as expected for a cyclic ketone + n-alkane mixtures. The binary system n-octane + (+)-limonene exhibits rela-
The binary system (−)-beta-pinene + (+)-fenchone tively small deviations from ideality. The contribution to the
(Fig. 3) exhibits a relatively smaller deviation from ideality, nonideality of the mixture comes from the like C C/C C in-
compared to n-decane + (+)-fenchone (Fig. 4), due to the teractions. At ca. 372 K the equimolar GE is ca. 191 J mol−1
compensation of the like dipole/dipole CO/CO with the (Fig. 9).
unlike dipole/induced dipole CO/C C interactions in the The binary system (−)-beta-pinene + eucalyptol is almost
mixture. The equimolar GE at ca. 379 K is ca. 340 J mol−1 . ideal with an equimolar GE of ca. 15 J mol−1 (Fig. 10). This
Fig. 6. Variation of the molar excess Gibbs energy, GE with mole frac- Fig. 8. Variation of the molar excess Gibbs energy, GE with mole frac-
tion xi , for the binary system n-decane (1) + (R)-(−)-carvone (2) at a con- tion xi , for the binary system eucalyptol (1) + (R)-(−)-carvone (2) at a con-
stant pressure P = 6.67 kPa: (), experimental; ( ), DISQUAC model; (夽), stant pressure P = 6.67 kPa: (), experimental, ( ), DISQUAC model; (夽),
mod.UNIFAC (Do) model. mod.UNIFAC (Do) model.
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 119
Table 5
Volumes ri , total surfaces qi , and molecular surface fractions αsi
ri qi αei αai αki /αfi
Alkanes
n-Hexane 3.9871 3.3241 0.0000 1.0000
n-Octane 5.1822 4.2552 0.0000 1.0000
n-Decane 6.3773 5.1862 0.0000 1.0000
Alkenes
1-Hexene 3.7836 3.1414 0.1339 0.8661
Cyclohexene 3.3359 2.4759 0.1699 0.8201
1-Methylcyclohexene 3.9320 3.0448 0.1382 0.8618
Limonene 5.5190 4.3586 0.1930 0.8070
Beta-pinene 5.3107 3.9397 0.1068 0.8932
Ketones
Butan-2-one 2.8779 2.4793 0.0000 0.7775 0.2225a
Menthone 6.0041 4.5673 0.0000 0.8792 0.1208a
Fenchone 5.6121 4.2839 0.0000 0.8712 0.1288a
Carvone 5.6159 4.4776 0.1879 0.6889 0.1232a
Ethers
Eucalyptol 5.7313 4.2949 0.0000 0.9518 0.0482b
Oxane 3.1484 2.3708 0.0000 0.9127 0.0873b
Oxolane 2.5619 2.0920 0.0000 0.9011 0.0989b
DISQUAC model.
a These values are of α .
ki
b These values are of α .
fi
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 121
Table 6
quac
Dispersives Cstdis and the quasichemicals Cst interchange coefficients
Substances Dispersives Quasichemicals References
Table 7 Table 10
Molar excess Gibbs energies (GE ) of the alkenes or cycloalkenes with n- Molar excess enthalpies (HE ) of the cycloalkenes with ketones
alkanes (m is the number of C atomes in the n-alkane) Cycloalkene Ketones T (K) E (J mol−1 )
Hexp References
Alkenes/cycloalkenes m T (K) GEexp (x = 0.5) References
Cyclohexene Butan-2-one 298.06 860 (x = 0.532) [33]
(J mol−1 ) 298.15 877 (x = 0.50) [33]
1-Hexene 6 328.15 25 [29] 343.15 910 (x = 0.532) [33]
Cyclohexene 6 278.15 96 [28]
283.15 55
288.15 85 4.1.1.2.3. Terpenoid ketones + monocyclic and bicyclic
293.15 102 terpene hydrocarbons. In the mixture of (S)-(+)-carvone
298.15 102 + (+)-limonene we have considered four types of surfaces
with the following types of contacts: (k, a), (k, e), (k,
Table 8 c–e), (e, c–e), (e, a) and (c–e, a) while the mixture of (+)-
Molar excess enthalpies (HE ) of the alkenes or cycloalkenes with n-alkanes fenchone + (−)-beta-pinene is characterized by three types of
(m is the number of C atomes in the n-alkane) surfaces and the following types of contacts: (k, a), (k, e) and
Alkenes/cycloalkenes m T (K) Hexp
E (x = 0.5) References (e, a).
(J mol−1 ) 4.1.1.2.4. Terpenoid oxaalkanes + bicyclic terpene hy-
1-Hexene 6 298.15 61 [31] drocarbons. The mixture of eucalyptol + (−)-beta-pinene
Cyclohexene 6 298.15 165 [30] is characterized by three types of surfaces and by the fol-
lowing types of contacts: (f, e), (f, a), and (e, a). The dis-
persive parameters Cf,e dis have been estimated on the basis
two double bonds, one of them in relation of mesomery E E
of G and H listed in Tables 11 and 12. For the con-
with the ketone group. In mixtures with n-decane the bi-
nary systems are characterised by the following types of Table 11
contacts: (k, a) in (−)-menthone and (+)-fenchone, respec- Molar excess Gibbs energies (GE ) of the alkenes with oxaalkanes
tively (k, a), (k, e), (k, c–e) (e, a), (c–e, a) in (R)-(−)- Alkenes Oxaalkenes T (K) GEexp (x = 0.5) References
carvone. The dispersive interchange coefficients,Ck,c dis
–e for (J mol−1 )
ketone + cycloalkenes have been estimated on the basis of 1-Hexene Oxane 263.15 170 [34]
GE and HE listed in Tables 9 and 10. For the contact ke- 333.15 163 [34]
tone + alkene we used the same dispersive interchange coef- 1-Hexene Oxolane 263.15 245 [34]
ficients, Ck,c
dis . For the contact (k, a), we used the dispersive
–e
333.15 232 [34]
dis and quasichemical C dis interchange coefficients pub-
Ck,a k,a
lished in the literature [25,27]. Table 12
Molar excess enthalpies (HE ) of the alkenes or cycloalkenes with oxaalkanes
Alkenes/ Oxaalkenes T (K) Hexp
E (x = 0.5) References
Table 9 cycloalkenes (J mol−1 )
Molar excess Gibbs energies (GE ) of the cycloalkenes with ketones
1-Hexene Oxane 333.15 197 [34]
Cycloalkene Ketones T (K) GEexp (x = 0.5) (J mol−1 ) References
Cyclohexene Oxane 298.15 148 [35]
Cyclohexene Butan-2-one 293.15 670 [32] 1-Hexene Oxolane 333.15 290 [34]
313.15 643 [32] Cyclohexene Oxolane 298.15 286 [35]
122 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124
Table 13
Rk and Qk parameters and group assignment for mod. UNIFAC (Do) method [36]
Main group Subgroup No. Rk Qk
1 ‘CH3 ’ CH3 1 0.6325 1.0608
CH2 2 0.6325 0.7081
CH 3 0.6325 0.3554
C 4 0.6325 0.0000
9 ‘CH2 CO’ CH3 CO 18 1.7048 1.6700
CH2 CO 19 1.7048 1.5542
42 ‘c-CH2 ’ c-CH2 78 0.7136 0.8635
c-CH 79 0.3479 0.1071
c-C 80 0.3470 0.0000
43 ‘c-CH2 O’ c-CH2 OCH2 27 1.7023 1.8784
c-CH2 O[CH2 ]1/2 83 1.4046 1.4000
c-[CH2 ]1/2 O[CH2 ]1/2 84 1.0413 1.0116
Table 14
Modified UNIFAC (Do) group interaction parameters [36] and revised modified UNIFAC (Do) group interaction parameters [38] for the main group 42 (c-CH2 )
with the main groups 1, 2, 9
n m anm (K) bnm (K) cnm (K) amn (K) bmn (K) cmn (K)
1 42 −680.95 4.0194 −0.6878 × 10−2 1020.8 −6.0746 0.1015 × 10−1
a1 42 −117.10 0.5481 −0.00098 170.90 −0.8062 0.00129
2 42 −78.19 0.1327 0.00 182.40 −0.3030 0.00
a2 42 2.4060 −0.1882 0.00 60.20 0.1565 0.00
9 42 156.53 −0.7135 0.00 498.92 −0.4400 × 10−1 0.00
a9 42 168.20 −0.8197 0.00 464.50 0.1542 0.00
a Revised modified UNIFAC (Do) group interaction parameters.
I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124 123
lar excess Gibbs energy, GE , in all the systems refered to in systems comparative with experimental GE values. A new
this paper, except the binary system (−)-beta-pinene + (+)- c-COC structural group should be defined for eucalyptol.
fenchone (Fig. 3), where the prediction is unsatis-
factory.
5. Conclusions
4.1.3. Comparison with experiment
A detailed comparation between experimental data and Isobaric vapor–liquid equilibrium (VLE) measurements
calculated values of the molar excess Gibbs energy, GE , (T–x–y) are reported for the binary system (−)-beta-
from DISQUAC and mod. UNIFAC (Do) is presented in pinene + (+)-fenchone.
Figs. 3–10. More discussions are necessary for each chemical We have realized a comparative study about the predictive
structure. capability of two group contribution models, DISQUAC and
mod. UNIFAC (Do), in mixtures containing terpenoids. Ter-
4.1.3.1. Terpenes and terpenoids + n-alkanes. The exami- penoids are complicated molecules, saturated or unsaturated,
nation of the terpenes and terpenoids + n-alkane mixtures is acyclic, monocyclic or bicyclic, containing various functional
of importance in order to test the validity of the model param- groups, the ketone group, sometimes being in relation of me-
eters for each individual terpene. As a matter of fact, various somery with the double bonds in the cycle. The literature [7] is
intramolecular effects such as group proximity, steric and very poor in vapor–liquid equlibria experimental data in mix-
cyclization may seriously affect the model parameters. tures containing terpenoids. The mod. UNIFAC (Do) does
The DISQUAC model, using the dispersive and qua- not define some subgroups, like CCO, from (+)-fenchone, re-
sichemcal interchange coefficients, taken from previous pub- spectively c-COC, from eucalyptol. Thus, the GE predictions
lications and redetermined with the new definition of >C C< in the binaries systems containing eucalyptol are unsatisfac-
group, is appropiate for all the investigated terpenes and ter- tory. The GE predictions in the binary systems containing
penoids + n-alkanes mixtures, except the binary system n- (+)-fenchone depend of the other component in mixture and
octane + (+)-limonene (Fig. 9) where the prediction is rather of the group interaction parameters. Thus, in mixture with
poor. an inert component, like n-decane, the GE predictions is very
A very good prediction of the mod. UNIFAC (Do) model good while in mixtures with (−)-beta-pinene the GE predic-
was found for the mixtures of n-decane with (R)-(−)-carvone tions depend of the group interaction parameters.
(Fig. 6) and (+)-fenchone (Fig. 4) while in the systems con- The GE predictions using DISQUAC model are appropiate
taining (−)-menthone (Fig. 5) and (+)-limonene (Fig. 9) the for all the studied binary systems.
agreement is satisfactory. A new CCO structural group should
be defined for (+)-fenchone. List of symbols
A12 , A21 binary parameters of the models Wilson, NRTL,
4.1.3.2. Terpenoids + terpenoids. The examination of the UNIQUAC
GE predictions using the DISQUAC model containing only Bii , Bjj pure component second virial coefficient
terpenoids is appropiate for all the binary systems, ex- Bij cross second virial coefficient
cept binary system (+)-limonene + (S)-(+)-carvone (Fig. 7) GE molar excess Gibbs energy
where calculated GE is smaller than exp. GE values. We HE molar excess enthalpy
note a very good prediction in the binary system (−)-beta- P total vapor pressure
pinene + eucalyptol (Fig. 10) comparative with the mod. Pio saturated vapor pressure of pure component i
UNIFAC (Do), where the calculated GE values are very high. R universal gas constant
The examination of the GE predictions using the mod. S objective functions in Eqs. (4) and (5)
UNIFAC (Do) is appropiate for the binary system (+)- T absolute temperature
limonene + (S)-(+)-carvone (Fig. 7). In this system, the ViL molar volumes of the saturated liquid
original UNIFAC model [37] predicts more accurate the x, y liquid and vapor composition mole fraction, respec-
VLE experimental data than mod. UNIFAC (Do) model tively
[1,36,38]. Cstdis dispersive interchange coefficients (DISQUAC
In the binary system (−)-beta-pinene + (+)-fenchone model)
quac
(Fig. 3) the GE predictions is appropiate using the original Cst quasichemical interchange coefficients (DISQUAC
group interaction parameters mod. UNIFAC (Do) [36] and model)
unsatisfactory using the revised group interaction parameters ri , qi relative molecular volumes or surfaces, respectively
mod. UNIFAC (Do) [38]. (DISQUAC model)
In the others two binary systems of terpenoids: (−)- rG , qG relative volumes or surfaces group increments, re-
beta-pinene + eucalyptol (Fig. 10) and eucalyptol + (R)-(−)- spectivey (DISQUAC model)
carvone (Fig. 8) the GE predictions values are unsatisfac- anm ,amn ,bnm ,bmn ,cnm ,cmn group interaction parameters
tory. The GE calculated values are very high in both binary (mod. UNIFAC (Do) model)
124 I. Batiu / Fluid Phase Equilibria 227 (2005) 113–124
VCH4 , ACH4 volumes or surfaces of methane, respectively [12] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases and
(DISQUAC model) Liquids, fourth ed., Mc Graw-Hill, Book Company USA, New York,
1987 (ISBN: 0-07-051799-1).
Rk , Qk van der Waals volumes or surfaces, respectively
[13] G.M. Panaitescu, Int. Chem. Eng. 25 (1985) 68–71.
(mod. UNIFAC (Do) model) [14] Aa. Fredenslund, J. Gmehling, P. Rasmussen, Vapor–Liquid Equilib-
ria using UNIFAC, Elsevier, Amsterdam, 1977 (ISBN: 0-444-41621-
Greek letters 8).
γ 1 , γ 2 activity coefficients [15] G.M. Wilson, J. Am. Chem. Soc. 86 (1964) 127–130.
δij mixture parameter in Eq. (2) [16] H. Renon, J.M. Prausnitz, AIChE J. 14 (1968) 135–144.
[17] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116–128.
σ standard deviation in Eq. (4) [18] H. Renon, Int. DATA Ser., Sel. Data Mixtures, Ser. A 1 (1973)
ψnm group interaction parameters in Eqs. (6) and (7) 59–67.
(mod. UNIFAC (Do) model) [19] E. Matteoli, L. Lepori, J. Chem. Eng. Data 33 (1988) 247–250.
[20] H.V. Kehiaian, B. Marongiu, Fluid Phase Equilib. 40 (1988) 23–78.
[21] A. Bondi, Physical Properties of Molecular Crystals, Liquids and
Gases, Wiley, New York, 1968.
Acknowledgments [22] H.V. Kehiaian, J.-P.E. Grolier, G.C. Benson, J. Chim. Phys. 75 (1978)
1031–1048.
The author gratefully aknowledges Dr. H.V. Kehiaian [23] M.R. Tine, H.V. Kehiaian, Fluid Phase Equilib. 32 (1987) 211–248.
(ITODYS, University VII Paris, France) for his interest in [24] M.A. Villamañan, H.V. Kehiaian, Fluid Phase Equilib. 42 (1988)
this work and for helpful discussions. Thanks are also due to 165–172.
[25] H.V. Kehiaian, S. Porceda, B. Marongiu, L. Lepori, E. Matteoli,
Dr. G. M. Panaitescu (Petroleum-Gas University of Ploieşti, Fluid Phase Equilib. 63 (1991) 231–257.
Romania) and Dr. Gabriela Bârzan (NACHEMA Comp. S.A. [26] H.V. Kehiaian, M.R. Tine, L. Lepori, E. Matteoli, B. Marongiu, Fluid
Făgăraş, Romania) for their helpful assistance in the compu- Phase Equilib. 46 (1989) 131–177.
tation and analytical work, respectively. Financial support [27] J.A. Gonzales, J.M. Fernandez Martinez, I. Garcia de la Fuente, J.C.
from Romanian CNCSIS, Project 76/2001, 39/2002, 7/2003. Cobos, Can. J. Chem. 74 (1996) 1815–1823.
[28] H.J. Gumpert, H. Köhler, W. Schill, H.J. Bittrich, Wiss. Z. Tech.
Hochsch. Chem. Carl Schorlemmer Leuna-Merseburg 15 (1973)
179–187.
References [29] H. Kirss, L. Kudryavsteva, O. Eisen, Eesti NSV Tead. Akad. Toim.
Keem. Geol. 24 (1975) 15–22.
[1] I. Batiu, L.E. Jimenez, ELDATA: Int. Electron. J. Phys. -Chem. Data [30] K. Günzel, H.J. Bittrich, Z. Phys. Chem. Leipzig 258 (1977)
2 (1996) 59–66. 1073–1080.
[2] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 2 (1996) [31] W. Woycicki, J. Chem. Thermodyn. 7 (1975) 77–81.
231–238. [32] H.C. Van Ness, F. Kohler, Int. DATA Ser., Sel. Data Mixtures, Ser.
[3] I. Batiu, J. Jose, L. Mokbel, L.E. Jimenez, A.P. Bonsfills, ELDATA: A (1990) 254.
Int. Electron. J. Phys. -Chem. Data 4 (1998) 67–74. [33] J. Gmehling, B. Meents, Int. DATA Ser., Sel. Data Mixtures, Ser. A
[4] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 5 (1999) 1–4. (1992) 165.
[5] I. Batiu, ELDATA: Int. Electron. J. Phys. -Chem. Data 5 (1999) [34] R. Hani, G. Ghanem, A. Ait-Kaci, J. Jose, ELDATA: Int. Electron.
191–195. Phys. -Chem. Data 5 (1999) 149–156.
[6] I. Batiu, Fluid Phase Equilb. 198 (2002) 111–121. [35] J.-P.E. Grolier, A. Inglese, E. Wilhelm, J. Chem. Eng. Data 27 (1982)
[7] I. Wichterle, J. Linek, Z. Wagner, H.V. Kehiaian, Vapor–Liquid 333–335.
Equilibrium in Mixtures and Solutions. Bibliographic Database. [36] J. Gmehling, J. Li, M. Schiller, Ind. Eng. Chem. Res. 32 (1993)
EVLM’2002, ELDATA, Paris, France, 2002, CD-ROM ISBN 2- 178–193.
9507664-9-8 (2002). [37] Aa. Fredenslund, R.L. Jones, J.M. Prausnitz, AIChE J. 21 (6) (1975)
[8] T. Guetachew, I. Mokbel, I. Batiu, Z. Cisse, J. Jose, ELDATA: Int. 1086–1099.
Electron. J. Phys. -Chem. Data (1999) 43–53. [38] J. Gmehling, J. Lohmann, A. Jakob, J. Li, R. Joh, Ind. Eng. Chem.
[9] H.C. Van Ness, M.M. Abbott, Classical Thermodynamics of Res. 37 (1998) 4876–4882.
Non-electrolyte Solutions, Mc Graw-Hill Book Co., New York, [39] J. Lohmann, R. Joh, J. Gmehling, Ind. Eng. Chem. Res. 40 (2001)
1982. 957–964.
[10] K.S. Pitzer, R.F. Curl, J. Am. Chem. Soc. 79 (1957) 2369–2370. [40] J. Lohmann, J. Gmehling, J. Chem. Eng. Jpn. 34 (2001) 43–54.
[11] H.K. Bae, S.Y. Lee, A.S. Teja, Fluid Phase Equilib. 66 (1991) [41] J. Gmehling, R. Wittig, J. Lohmann, R. Joh, Ind. Eng. Chem. Res.
225–232. 41 (2002) 1678–1688.