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A New Group Contribution Method based

on Equation of State Parameters to Evaluate


the Critical Properties of Simple and
Complex Molecules
Jos O. Valderrama1, 2* and Vctor H. Alvarez2
1. Faculty of Engineering, Mechanical Engineering Department, University of La Serena, Casilla 554, La Serena, Chile
2. Centro de Informacin Tecnolgica, Casilla 724, La Serena, Chile

A new group contribution method to evaluate the critical properties (temperature, pressure and volume) is presented and applied to estimate
the critical properties of biomolecules. Similar to other group contribution methods, the one proposed here divides the molecule into conveniently defined groups and evaluates the properties as the sum of the different contributions according to a specified model equation for each
of the properties. The proposed method consists of a one-step calculation that uses simple model equations and does not require additional
data besides the knowledge of the structure of the molecule, except for isomers. For these substances the normal boiling temperature, the
molecular mass and the number of atoms in the molecule are used to distinguish among isomers. The method is applicable to high molecular
weight compounds, as most biomolecules and large molecules present in natural products.
On prsente une nouvelle mthode de contribution de groupe pour valuer les proprits critiques (temprature, pression et volume) de
biomolcules. Comme dans le cas dautres mthodes de contribution de groupe, celle quon prsente ici divise la molcule en groupes dfinis de
manire pratique et value les proprits comme la somme des diffrentes contributions selon une quation de modle spcifique pour chacune
des proprits. La mthode propose consiste en un calcul en une tape qui utilise des quations de modle simple et, except pour les isomres,
ne requiert pas de donnes supplmentaires hormis la structure de la molcule. Pour ces substances, on utilise la temprature dbullition normale,
la masse molculaire et le nombre datomes dans la molcule pour distinguer entre les isomres. La mthode est applicable des composs de
poids molculaire lev, comme la plupart des biomolcules et des molcules larges prsentes dans les produits naturels.
Keywords: group contribution, critical properties, molecular structure, van der Waals

INTRODUCTION

upercritical fluid extraction has experienced important


developments during the last decades, especially with the
use of carbon dioxide as an extracting fluid of biomolecules.
The subject has become then an interesting source for chemical,
thermodynamic and process research (Brennecke and Eckert,
1989; McHugh and Krukonis, 1994). Modelling and simulation of
supercritical fluid separation processes have also received some
attention and several equations of state models have been
proposed. These nowadays commonly used methods require of the
knowledge of the critical properties of the fluids involved in the
supercritical mixtures and of the acentric factor. However, in many
cases these properties cannot be evaluated in experimental form,
but still the values are required for the application of equations of
state to the calculation of properties of pure fluids and mixtures
(Valderrama, 2003). The so-called group contribution methods
have been commonly used to estimate the critical properties of
those substances for which these properties are not available.

VOLUME 84, AUGUST 2006

Among the several proposals presented in the literature, the


method developed by Lydersen (1955) is perhaps the most widely
used group contribution method to estimate critical properties.
Similar proposals were presented by Ambrose (1978) and
Klincewicz and Reid (1984). Later, Joback and Reid (1987)
developed a method that is frequently mentioned in the literature
and used in several applications. In all these methods, the property
of a compound is calculated by summing up the contributions of
certain defined groups of atoms, considering at the same time the
number frequency of each group occurring in the molecule.
Although all these methods have been questioned in the literature
(Poling et al., 2001), they have the advantage of quick estimates
without requiring sophisticated computational calculations.
Lydersen (1955) defined 43 structural groups and proposed
the following model equations for the critical properties:

* Author to whom correspondence may be addressed.


E-mail address: jvalderr@userena.cl

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431

Tc =

Pc =

Tb

AL +

ni T ( ni T )

(1)

M
C L +

Vc = E L +

ni PL

(2)

ni V

(3)

In these equations ni is the number of times that a group appears


in the molecule, Tb is the normal boiling temperature, TL is the
contribution to the critical temperature, PL is the contribution
to the critical pressure, VL is the contribution to the critical
volume, M is the molecular mass, and AL, CL and EL are
constants. The values of these constants are: AL=0.567, CL=0.34
and EL=40.
Joback and Reid (1987) defined 41 structural groups and
proposed the following model equations for the critical
properties:
Tc =

Pc =

Tb

AJ + B J

ni TJ

( ni T )
2

C J + D J N

Vc = E J +

ni PJ

(4)

ni V

(5)

(6)

In these equations ni is the number of times that a group appears


in the molecule, N is the number of atoms in the molecule, Tb is
the normal boiling temperature, TJ is the contribution to the
critical temperature, PJ is the contribution to the critical
pressure, VJ is the contribution to the critical volume, and AJ,
BJ, CJ, DJ and EJ are constants. The values of these constants are:
AJ=0.584, BJ=0.965, CJ=0.113, DJ=0.0032 and EJ=17.5.
Constantinou et al. (1993), proposed a complex estimation
technique, which is based on conjugate forms (alternative
formal arrangements of valence electrons). This technique
provides reasonable estimations of several properties of pure
compounds and allows capturing the differences among isomers.
However, the generation of conjugate forms is a nontrivial issue
and requires a symbolic computing environment. Another
somewhat complex method has been proposed by Constantinou
and Gani (1994). The method considers the molecular structure
of the molecule and estimates a given property at two levels. The
primary level uses contributions from simple groups that allow
describing a wide variety of organic compounds while the
higher level involves polyfunctional and structural groups that
provide more information about molecular fragments whose
description through first-order groups is not possible. Joback
(2003) has shown that the method of Constantinou and Gani
(1994) gives errors a little higher than Lydersens method.
Marrero and Pardillo (1999), proposed another technique that
considers the contributions of interactions between bonding
groups instead of the contributions of simple groups, method
that allows distinguishing among isomers.
Group Contribution Methods have also been proposed for
mixture properties, being the most recent one that proposed by

432

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Jaubert and coworkers to estimate the binary interaction


parameter kij for the Peng-Robinson equation of state (Jaubert
and Mutelet, 2004; Jaubert et al., 2005; Vitu et al., 2006). To the
best of our knowledge the most recent Group Contribution
Method proposed in the literature to estimate the critical properties is that of Skander and Chitour (2003). The authors considered the estimation of critical properties, heat of vaporization,
refractive index parameter and molar volume of hydrocarbons
and petroleum fractions. In another development, Kolsk (2005)
presented a group contribution method to estimate the enthalpy
and entropy of vaporization of pure organic compounds. Stefanis
et al. (2004) have extended the method of Constantinou and
Gani (1994), and applied it to the calculation of the octanolwater partition coefficient, the solubility parameters at 25C,
and the flash point.
As described above, group contribution methods have been
commonly used to estimate critical properties. However, most
applications of equations of state also require the knowledge of
the acentric factor , which can be calculated from the vapour
pressure and the definition of the acentric factor: =-Log[Pvap/
Pc] at T/Tc=0.7-1 (Prausnitz et al., 1999). If vapour pressure
data are not available to calculate the acentric factor, a good
estimation can be done using the critical properties and the
normal boiling temperature, assuming that the vapour pressure
and the temperature follow the classical relation Log Pvap=AB/T. Applying this equation to both the normal boiling point and
the critical point, and using the definition of the acentric factor,
this can be estimated as: =(3/7)TbxLog[Pc/Pb]/(Tc-Tb) - 1.
Here, Pc is in MPa, Pb=0.101325 MPa, Tb and Tc are in Kelvin.
In this paper, the 180 substances shown in Table 1, for which
the critical properties are known, have been considered to
propose a new simple and accurate group contribution method.
Most of the values are those indicated as experimental data in
the DIPPR compilation of Daubert et al. (1996). The substances
designated with (1) in Table 1 were obtained from the Korean
Data Base available on Internet (KBD, 2003).
The proposed one-step method does not require the normal
boiling temperature (except to distinguish among isomers), and
uses simple expressions for the critical temperature, the critical
pressure and the critical volume. The model equations are based
on an idea of group contribution applied to estimate the force
and the volume constants of the van der Waals equation of state
presented by Vukalovich and Novikov (1948). Large molecules
have been considered in the proposed method to determine the
contributions for each of the defined groups so the technique
could be applied to large complex substances such as those
present in many natural products.

THE NEW METHOD


Vukalovich and Novikov (1948) presented an extensive analysis
of the van der Waals equation of state. In that analysis the
authors discussed the characteristic of the equation of state
constants a and b and related them to atoms and groups that
form a given molecule. From a theoretical analysis, they
concluded that the volume constant b could be determined by
summing up the values of certain defined groups bi while for a
the contributions are for a . That is:

ni
b = ni bi
a =

ai

(7)
(8)

VOLUME 84, AUGUST 2006

Here, ni is the number of times that the atom or group i


appears in the molecule, ai and bi are the contributions to a
and b. These contributions are given by Vukalovich and Novikov
for atoms and groups of atoms (25 for a and 35 for b).
The relations (7) and (8) are based on the van Laar concepts
about the van der Waals constants for the case of mixtures:
b=xibi and
a = xi ai , being xi the mole fraction of
component i in the mixtures. Vukalovich and Novikov considered xi as the number of groups in the molecule.
The expressions for a and b for the van der Waals equation
of state written in terms of the critical properties and the ideal
gas constant R, are (Prausnitz et al., 1999):
2

a=

27R Tc
64 Pc

b=

RTc
8 Pc

(9)

(10)

Replacing Equations (9) and (10) into Equations (7) and (8) and
cancelling the constants, it can be seen that the groups to be
defined in a group contribution method are Tc / Pc , [Tc/Pc]
and [Vc].
It should be mentioned here that the van der Waals equation
is not directly used but only the relation between the constants
a and b with the critical properties. The relation between the
a and b parameters with the critical properties is the same
for all equations of state derived from van der Waals equation:
a= aR2Tc2/Pc; b=bRTc/Pc (being a and b different for each
equation of state). Thus, there is no need of using more complex
or accurate equations of state.
As any group contribution method, the one proposed here not
only requires the values of the contributions Tc / Pc , [Tc/Pc]
and [Vc], but also a model to add in some way those contributions. After exploring several models, the following equations for
these groups are defined:

Tc
= 1 +
Pc

Tc
= 2 +
Pc

T 1
ni c
Pc i

(11)

T
ni c
Pc i

(12)

For the critical volume, a similar expression is used:

3
Vc = 3 +
ni [Vc ]i
(13)

In these equations, ni is the number of times that a group i


appears in a molecule, i and i are constants, and Tc / Pc i,
[Tc/Pc]i and [Vc]i are the contributions to Tc / Pc , [Tc/Pc]and
[Vc], respectively. These contributions and the constants i and
i are determined from regression analysis of experimental data
of Tc, Pc and Vc. Once the groups (Tc / Pc )i and (Tc/Pc)i are
known, the critical temperature and the critical pressure are
directly obtained. Data for the 180 substances shown in Table 1
were used in the regression analysis and 39 groups were defined
as shown in Table 2.

ISOMER CORRECTIONS
The proposed method has been extended to predict critical
properties of isomers. We have found that the main properties

VOLUME 84, AUGUST 2006

that affect the critical properties of isomers are the normal


boiling point and the predicted critical properties (Tc, Pc and Vc),
calculated using Equations (11) to (13). To distinguish between
groups of isomers the variables to consider are the molecular
mass (M) and the number of atoms in the molecule (N).
Thus, the critical properties for isomers are estimated as for
any other compound and then correction functions Tc, Pc and
Vc are added. These correction functions include the properties
Tc, Pc and Vc, calculated using Equations (11) to (13).
Tc = aT 1 1 + aT 2(Tb / Tc ) + aT 3 M + aT 4 N

(14)

Pc = a P1 1 + a P 2(Tb / Tc ) + a P 3 M + a P 4 N

(15)

Vc = aV 1 1 + aV 2(Tb / Tc ) + aV 3 M + aV 4 N

(16)

It should be noticed that the terms containing the molecular


mass (M) and the number of atoms in the molecule (N) allow
distinguishing between groups of isomers (for instance the
group of dimethyl hexanes from the group of xylenes). The term
containing the normal boiling temperature allows distinguishing
among a group of isomers of the same substance (for instance
between o-xylene, m-xylene and p-xylene). It should be also
noticed that for isomers the method loses its predictive capabilities since the normal boiling temperature is needed.
Finally, the critical properties for the isomers are calculated
as:
Tciso = Tc + Tc

(17)

Pciso = Pc + Pc

(18)

Vciso = Vc + Vc

(19)

The parameters aTi, aPi, and aVi in Equations (14) to (16) were
determined using data for 40 isomers, already included among
the 180 substances shown in Table 1.

Results and Discussion


A computer program to evaluate these contributions and
constants was specially developed. The program considers the
use of a Modified Marquardt method (Reilly, 1972) as a basic
numerical algorithm, and explores for multiple acceptable
solutions to choose as a final optimum solution that which give
the lowest deviation of an established objective function, F. In
the proposed method the objective function considers the
Ns=180 compounds listed in Table 1 and is defined as:
Ns

F=

(Qcal Qexp )

(20)

It should be observed that the variables Q used for the regression analysis are Tc / Pc , Tc/Pc and Vc. However, to analyze the
results obtained using the new method, a percent deviation has
been defined for each of the critical properties, as follows:
%Tc =

%Pc =

Tcexp Tccal

Tcexp

(21)

Pcexp Pccal

Pcexp
i

(22)

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433

%Vc =

Vcexp Vccal

exp
Vc
i

(23)

Using the designed program, the contributions shown in Table 3


for the groups Tc / Pc i , [Tc/Pc]i and [Vc]i and for the parameters
i and i were calculated. The parameters are: 1 = 38.91, 1 =
0.88, 2 = 5.84, 2 = 1.27, 3 = 26.86 and 3 = 1.06. A
summary of the method is given in Table 4, while Table 5 gives
the average deviations and the average absolute deviations
obtained for the 180 substances using the model summarized in
Table 4.
For the 40 isomers included in the list of 180 substances
considered in this study the results are also separately shown
in Table 6. In this Table, Tc, Pc, and Vc are the values calculated
without the correction for isomers while Tciso, Pciso, and Vciso
are the values calculated with the corrections of Equations (14)
to (16). It can be observed that overall deviations are lower for
the three properties when values are compared with the overall
deviations given by the method without isomer corrections.
The deviations are also lower than those found for the 180
compounds given in Table 4. More important, however, is that
the corrected values are different for the different isomers, as
experimentally found.
The results shown in Table 5 indicate that for most substances
deviations between experimental and calculated values are
lower than 5% for all properties (%S<5% is 91.7% for Tc,
71.7% for Pc and 83.9% for Vc). Also, the substances showing
deviations higher than 10% (%S>10% in the Table 5), are 2.2%
for Tc, 10.6% for Pc and 3.9% for Vc. The average deviations %
are 0.1% for Tc, 0.3% for Pc and 0.2% for Vc. The absolute
average deviations %|| are 2.2% for Tc, 4.5% for Pc and 2.6%
for Vc. These results are similar to those found using more
sophisticated methods as shown in Table 7. The Lydersen and
Joback-Reid results shown in Table 7 were also evaluated in this
work for the 180 selected substances presented in Table 1. For
the Constantinou-Gani and the Marrero-Pardillo methods the
results shown in the Table were taken from Poling et al. (2000).
It should be noticed that the Lydersen and the Joback-Reid
methods employ the normal boiling temperature to estimate the

critical temperature, reason that explains the low average


deviation in the prediction of this property. For Pc and Vc,
however, the proposed method does not use the normal boiling
temperature as input data, and give lower deviations.
The deviations shown in Table 5 depend not only on the type
of substances but also on the so-called occurrence, that is the
number of substances in which a given defined group appears in
the list of 180 substances considered in the analysis. When
solving the system of equations those groups having higher
occurrence have greater influence in determining the values of
the group contributions. Apart from this there is no other
numerical or convergence problem when determining the values
of the 117 groups (3 values for each of the 39 groups).
Finally, as an additional test, eighteen substances, mostly
biomolecules such as -pinene, cholesterol, capsaicin or astaxantin, not used in the calculation of the 39 groups and the six
parameters i and i, have been used to evaluate the applicability of the proposed method. The results are shown in Table 8. Of
the substances shown in the Table, only three of them have
experimental values in the literature. For the other substances,
true experimental values are not available, so the values
predicted by the Joback-Reid method were used for comparison
only. Deviations for these cases are not given since the experimental values are unknown.

CONCLUSIONS
According to the results, the following conclusions are drawn:
(i) a new simple method has been proposed to estimate the
critical properties of biomolecules; (ii) the method can be
applied to any organic substance that contain any of the 39
groups defined by the method; (iii) the method requires only the
molecular mass and the structure of the molecule, and does not
need the normal boiling temperature, except if corrections for
isomers are introduced; (iv) the average deviations are below
0.3% for Tc, Pc and Vc while the average absolute deviations are
2.2% for Tc, 4.5% for Pc and 2.6% for Vc; and (v) it is shown
that the proposed method gives results similar to other more
sophisticated methods that use different levels of calculations
and properties not readily available in the literature.

Table 1. Critical properties of the 180 substances chosen to evaluate the 39 group contributions and the model parameters. In the Table,
the substances designated with (1) were obtained from the Korean Data Base, available on the Internet (KBD, 2003).
NS

Substances

Formula

M (g/gmol)

Tc (K)

Pc (bar)

Vc (cc/mol)

Tb

Methyl_hydrazine (1)

CH6N2

46.072

567.00

82.400

271.00

360.60

Nitromethane

CH3NO2

61.040

588.15

63.126

173.41

374.35

Carbon_Tetrafluoride

CF4

88.005

227.50

37.400

140.00

145.09

Chloroform

CHCl3

119.377

536.40

54.720

239.00

334.33

Trichlorofluoromethane

CCl3F

137.368

471.20

44.076

248.00

296.97

Acetonitrile

C2H3N

41.052

545.50

48.500

173.00

354.80

Ketene (1)

C2H2O

42.037

380.00

65.000

145.00

232.00

Ethylene_oxide

C2H4O

44.053

469.15

71.900

140.30

283.60

Acetaldehyde (1)

C2H4O

44.053

466.00

55.700

154.00

293.20

10

Dimethylamine (1)

C2H7N

45.084

437.22

53.400

182.50

280.03

11

Ethanol

C2H6O

46.069

513.92

61.480

167.00

351.44

12

Methyl_Isocyanate (1)

C2H3NO

57.052

491.00

55.700

196.98

312.00

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VOLUME 84, AUGUST 2006

Table 1 (continued)
NS

Substances

Formula

M (g/gmol)

Tc (K)

Pc (bar)

Vc (cc/mol)

Tb

13

Acetic_acid

C2H4O2

60.053

591.95

57.860

179.70

391.05

14

Methyl_formate

C2H4O2

60.053

487.20

59.984

172.00

304.90

15

Ethylenediamine (1)

C2H8N2

60.099

593.00

62.800

206.00

390.40

16

Monoethanolamine (1)

C2H7NO

61.083

614.00

44.500

196.00

443.50

17

1_1-Difluoroethane

C2H4F2

66.051

386.60

44.988

181.00

247.35

18

Nitroethane (1)

C2H5NO2

75.067

595.00

48.500

269.00

387.20

19

Acetyl_chloride (1)

C2H3ClO

78.498

508.00

58.700

204.00

323.90

20

Bromoethane

C2H5Br

108.966

503.80

62.315

214.92

311.50

21

1_2-Diiodoethane

C2H4I2

281.863

749.90

47.300

323.50

473.20

22

Methylacetylene

C3H4

40.065

402.39

56.276

164.00

249.94

23

Acrylonitrile (1)

C3H3N

53.063

536.00

45.600

210.00

350.50

24

Propionitrile

C3H5N

55.079

564.40

41.847

229.00

370.50

25

Acetone

C3H6O

58.080

508.20

47.015

209.00

329.44

26

1_2-Propylene_oxide

C3H6O

58.080

482.25

49.244

186.00

307.05

27

Allyl_alcohol (1)

C3H6O

58.080

545.00

53.100

203.50

370.23

28

Trimethylamine

C3H9N

59.111

433.25

40.733

254.00

276.02

29

Isopropylamine

C3H9N

59.111

471.85

45.400

221.00

304.90

30

Isopropanol

C3H8O

60.096

508.31

47.643

220.13

355.41

31

Methyl_ethyl_ether

C3H8O

60.096

437.80

44.000

221.00

280.50

32

1-Propanol

C3H8O

60.096

536.78

51.750

219.00

370.35

33

Acrylic_acid (1)

C3H4O2

72.063

615.00

56.700

210.00

414.00

34

Propionic_acid

C3H6O2

74.079

600.81

46.170

233.00

414.32

35

Ethyl_formate

C3H6O2

74.079

508.40

47.420

229.00

327.46

36

Methyl_acetate

C3H6O2

74.079

506.55

47.500

228.00

330.09

37

Methylal

C3H8O2

76.095

480.60

39.517

213.00

315.00

38

1_2-Propylene_glycol (1)

C3H8O2

76.095

625.00

60.700

237.00

460.50

39

1-Nitropropane (1)

C3H7NO2

89.094

606.00

40.000

328.66

404.70

40

2-Nitropropane (1)

C3H7NO2

89.094

597.00

41.500

316.10

393.30

41

Glycerol (1)

C3H8O3

92.094

726.00

66.800

255.00

563.00

42

Hexafluoroacetone

C3F6O

166.023

357.14

28.371

329.00

245.88

43

2-Iodopropane (1)

C3H7I

169.990

574.60

43.300

285.50

362.60

44

1_2-Butadiene (1)

C4H6

54.091

443.70

44.900

219.00

284.00

45

Isobutene

C4H8

56.107

417.90

39.990

238.88

266.25

46

Furan

C4H4O

68.075

490.15

55.000

218.00

304.50

47

Isobutyronitrile (1)

C4H7N

69.106

566.00

38.200

279.50

377.00

48

Pyrrolidine

C4H9N

71.122

568.55

56.134

248.68

359.72

49

Methyl_ethyl_ketone

C4H8O

72.107

535.50

41.543

267.00

352.79

50

Diethyl_ether

C4H10O

74.123

466.70

36.400

280.00

307.58

51

2-Butanol

C4H10O

74.123

536.05

41.790

269.00

372.70

52

2-Methyl-2-propanol

C4H10O

74.123

506.21

39.730

275.00

355.57

53

2-Methyl-1-propanol

C4H10O

74.123

547.78

43.000

273.00

380.81

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435

Table 1 (continued)
NS

Substances

Formula

M (g/gmol)

Tc (K)

Pc (bar)

Vc (cc/mol)

Tb

54

Tetrahydro-furan

C4H8O

72.107

540.15

51.878

223.93

338.00

55

Tert-butylamine

C4H11N

73.138

483.90

38.400

293.00

317.55

56

Diethylamine

C4H11N

73.138

496.60

37.085

301.00

328.60

57

Vinyl_acetate (1)

C4H6O2

86.090

525.00

43.500

265.00

346.00

58

Methyl_acrylate (1)

C4H6O2

86.090

536.00

43.000

265.00

353.50

59

Morpholine (1)

C4H9NO

87.121

618.00

54.700

253.00

401.40

60

Ethyl_acetate

C4H8O2

88.106

523.30

38.800

286.00

350.21

61

Methyl_propionate

C4H8O2

88.106

530.60

40.040

282.00

352.60

62

N-propyl_formate

C4H8O2

88.106

538.00

40.631

285.00

353.97

63

1_4-Dioxane

C4H8O2

88.106

587.00

52.081

238.00

374.47

64

1_2-Dimethoxyethane

C4H10O2

90.122

536.15

38.706

270.64

357.20

65

1_3-Butanediol

C4H10O2

90.122

676.00

40.200

305.00

481.38

66

1-Nitrobutane (1)

C4H9NO2

103.121

624.00

38.000

347.94

426.10

67

2-Nitrobutane (1)

C4H9NO2

103.121

615.00

36.000

372.76

412.90

68

2-Bromobutane (1)

C4H9Br

137.019

558.70

43.000

315.50

364.40

69

3-Methyl-1-butyne (1)

C5H8

68.118

476.00

42.100

271.50

299.50

70

3-Methyl-1_2-butadiene (1)

C5H8

68.118

496.00

41.100

267.00

314.00

71

1_2-Pentadiene (1)

C5H8

68.118

503.00

40.700

276.00

318.00

72

2-methyl-1-butene

C5H10

70.134

465.00

34.000

292.00

304.30

73

2-methyl-2-butene

C5H10

70.134

471.00

34.000

292.00

311.71

74

n-Methylpyrrole

C5H7N

81.117

596.00

48.500

271.90

385.80

75

Cyclopentanone (1)

C5H8O

84.118

624.50

46.000

268.00

403.72

76

Piperidine

C5H11N

85.149

594.10

49.400

288.00

379.37

77

1-Pentanal

C5H10O

86.134

566.10

39.700

313.00

376.15

78

Diethyl_ketone

C5H10O

86.134

560.95

37.389

336.00

375.14

79

2-Pentanone

C5H10O

86.134

561.08

36.943

301.00

375.46

80

Pyridine (1)

C5H5N

79.101

620.00

56.700

243.00

388.38

81

1-Pentanal

C5H10O

86.134

566.10

39.700

313.00

376.15

82

2-Methyl_tetrahydrofuran (1)

C5H10O

86.134

537.00

37.600

267.00

351.00

83

n-Methyl-2-Pyrrolidone

C5H9NO

99.133

721.60

45.200

310.00

477.42

84

Ethyl_acrylate (1)

C5H8O2

100.117

552.00

37.400

320.00

373.00

85

Ethyl_propionate

C5H10O2

102.133

546.00

33.620

345.00

372.25

86

Methyl_n-butyrate

C5H10O2

102.133

554.50

34.730

340.00

375.90

87

Benzene

C6H6

78.114

562.05

48.950

256.00

353.24

88

1-Hexene

C6H12

84.161

504.03

31.400

354.00

336.63

89

Aniline

C6H7N

93.128

699.00

53.094

270.00

457.60

90

2-Methylpyridine

C6H7N

93.128

621.00

46.000

335.00

402.55

91

4-Methylpyridine

C6H7N

93.128

646.15

46.610

325.62

418.50

92

Phenol

C6H6O

94.113

694.25

61.300

229.00

454.99

93

Fluorobenzene

C6H5F

96.104

560.09

45.505

269.00

357.88

94

Cyclohexanone (1)

C6H10O

98.144

653.00

40.000

346.99

428.58

95

2-Hexanone

C6H12O

100.161

587.61

32.870

378.00

400.70

436

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 84, AUGUST 2006

Table 1 (continued)
NS

Substances

Formula

M (g/gmol)

Tc (K)

Pc (bar)

Vc (cc/mol)

Tb

96

3-Hexanone

C6H12O

100.161

582.82

33.200

378.00

396.65

97

Triethylamine

C6H15N

101.192

535.15

30.398

390.00

361.92

98

Diisopropyl_ether

C6H14O

102.177

500.05

28.800

386.00

341.45

99

1-Hexanol

C6H14O

102.177

611.35

35.100

381.00

430.55

100

Monochlorobenzene

C6H5Cl

112.558

632.35

45.191

308.00

404.87

101

Isobutyl_acetate (1)

C6H12O2

116.160

561.00

31.600

414.00

389.70

102

Hexanoic_acid

C6H12O2

116.160

659.10

33.080

377.20

478.85

103

2-Butoxy_ethanol

C6H14O2

118.176

633.90

32.700

423.57

444.47

104

Bromobenzene

C6H5Br

157.010

670.15

45.191

324.00

429.24

105

Iodobenzene

C6H5I

204.010

721.15

45.191

351.00

461.60

106

1-Methylcyclohexene (1)

C7H12

96.172

584.20

35.690

353.60

383.20

107

1-Heptene

C7H14

98.188

537.29

28.300

413.00

366.79

108

1_1-Dimethylcyclopentane

C7H14

98.188

547.00

34.450

360.00

361.00

109

Benzonitrile

C7H5N

103.123

699.35

42.150

313.20

464.15

110

p-Toluidine

C7H9N

107.155

693.15

40.000

346.00

473.57

111

m-Cresol

C7H8O

108.140

705.85

45.600

312.00

475.43

112

o-Cresol

C7H8O

108.140

697.55

50.055

282.00

464.15

113

p-Cresol

C7H8O

108.140

704.65

51.500

277.00

475.13

114

2-Heptanone

C7H14O

114.188

611.40

29.400

434.00

424.18

115

1-Heptanol

C7H16O

116.203

631.90

31.500

435.00

449.45

116

Benzoic_acid (1)

C7H6O2

122.123

752.00

45.600

341.00

523.00

117

Heptanoic_acid

C7H14O2

130.187

676.84

30.430

429.70

496.15

118

Diethylene_Glycol_monopropyl_ether

C7H16O3

148.202

679.80

30.020

489.00

487.99

119

Perfluoromethylcyclohexane (1)

C7F14

350.055

485.91

20.190

570.00

349.50

120

Perfluoroheptane (1)

C7F16

388.051

474.80

16.200

664.00

355.66

121

m-Xylene

C8H10

106.167

617.00

35.410

375.00

412.27

122

o-Xylene

C8H10

106.167

630.30

37.320

370.00

417.58

123

p-Xylene

C8H10

106.167

616.20

35.110

378.00

411.51

124

1-octene

C8H16

112.215

566.60

25.500

472.00

394.44

125

1_1-Dimethylcyclohexane

C8H16

112.215

591.15

29.384

450.00

392.70

126

n-Propylcyclopentane (1)

C8H16

112.215

603.00

30.000

425.00

404.10

127

2_2-Dimethylhexane

C8H18

114.231

549.80

25.300

478.00

379.99

128

2_3-Dimethylhexane

C8H18

114.231

563.40

26.300

468.20

388.76

129

2_4-Dimethylhexane

C8H18

114.231

553.50

25.600

472.00

382.58

130

2_5-Dimethylhexane

C8H18

114.231

550.00

24.900

482.00

382.26

131

Acetophenone (1)

C8H8O

120.151

709.50

40.600

386.00

475.00

132

n_n-Dimethylaniline (1)

C8H11N

121.182

687.00

36.300

406.17

467.30

133

1-octanol

C8H18O

130.230

652.50

28.600

490.00

468.35

134

Methyl_benzoate (1)

C8H8O2

136.150

692.00

36.400

396.00

472.20

135

Octanoic_acid

C8H16O2

144.214

694.26

27.790

499.00

512.85

136

Phthalic_anhydride (1)

C8H4O3

148.118

810.00

47.600

368.00

560.00

137

n-propylbenzene

C9H12

120.194

638.35

32.000

440.00

432.39

VOLUME 84, AUGUST 2006

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

437

Table 1 (continued)
NS

Substances

Formula

M (g/gmol)

Tc (K)

Pc (bar)

Vc (cc/mol)

Tb

138

Cumene

C9H12

120.194

631.00

32.090

434.00

425.56

139

Mesitylene

C9H12

120.194

637.30

31.270

433.00

437.89

140

n-Propylcyclohexane

C9H18

126.242

639.15

28.067

477.00

429.90

141

2_2_4_4-Tetramethylpentane

C9H20

128.258

571.35

23.609

504.00

395.44

142

2_2_3_3-Tetramethylpentane

C9H20

128.258

610.85

27.358

478.00

413.44

143

2_2_5-trimethylhexane

C9H20

128.258

568.05

23.305

519.00

397.24

144

Isoquinoline (1)

C9H7N

129.161

803.00

51.000

374.00

516.37

145

Quinoline (1)

C9H7N

129.161

782.00

48.600

437.00

510.31

146

5-Nonanone

C9H18O

142.241

640.00

23.200

560.00

461.60

147

1-Nonanal (1)

C9H18O

142.241

640.00

24.800

556.50

461.60

148

Naphthalene

C10H8

128.171

748.40

40.500

407.00

491.10

149

1_2_3_4-Tetrahydronaphthalene

C10H12

132.205

720.00

36.500

408.00

480.77

150

n-butylbenzene

C10H14

134.221

660.50

28.900

497.00

456.46

151

Isobutylbenzene (1)

C10H14

134.221

650.00

30.500

480.00

445.94

152

p-cymene

C10H14

134.221

652.00

28.000

497.00

450.28

153

cis-Decahydronaphthalene

C10H18

138.253

702.25

32.424

480.00

468.97

154

trans-Decahydronaphthalene

C10H18

138.253

687.05

28.371

480.00

460.46

155

1-decene

C10H20

140.269

617.05

21.684

585.00

443.75

156

1-Decanal (1)

C10H20O

156.267

674.20

22.600

612.50

481.60

157

n-Pentylbenzene

C11H16

148.248

679.90

26.040

550.00

478.61

158

n-Butyl_benzoate (1)

C11H14O2

178.230

723.00

26.000

561.00

523.00

159

Biphenyl

C12H10

154.211

773.00

33.800

497.00

528.15

160

1_2-Dimethylnaphthalene (1)

C12H12

156.227

775.30

30.100

521.50

539.50

161

1_3-Dimethylnaphthalene (1)

C12H12

156.227

773.80

30.100

521.50

538.40

162

1_4-Dimethylnaphthalene (1)

C12H12

156.227

776.80

30.100

521.50

540.50

163

1_5-Dimethylnaphthalene (1)

C12H12

156.227

773.50

30.100

521.50

538.20

164

1_6-Dimethylnaphthalene (1)

C12H12

156.227

770.60

30.100

521.50

536.20

165

1_7-Dimethylnaphthalene (1)

C12H12

156.227

770.60

30.100

521.50

536.20

166

2_3-Dimethylnaphthalene (1)

C12H12

156.227

777.80

30.100

521.50

541.20

167

2_6-Dimethylnaphthalene (1)

C12H12

156.227

769.20

30.100

521.50

535.20

168

Dibenzopyrrole (1)

C12H9N

167.210

901.80

39.300

502.00

627.85

169

Di-n-hexyl_ether (1)

C12H26O

186.337

657.00

18.200

720.00

499.60

170

Diphenylmethane

C13H12

168.238

760.00

27.100

563.00

537.42

171

n-Nonylbenzene

C15H24

204.356

741.00

18.950

790.00

555.20

172

Pyrene (1)

C16H10

202.255

938.20

27.210

626.00

666.00

173

1-Hexadecanol (1)

C16H34O

242.444

770.00

16.100

950.50

607.00

174

Undecylbenzene

C17H28

232.409

764.00

16.720

910.00

586.40

175

m-Terphenyl

C18H14

230.309

883.00

24.800

724.00

648.15

176

o-Terphenyl

C18H14

230.309

857.00

29.900

731.00

609.15

177

p-Terphenyl

C18H14

230.309

908.00

29.900

729.00

655.15

178

Triphenylene (1)

C18H12

228.293

1013.20

25.110

700.00

698.00

179

n-Tridecylbenzene (1)

C19H32

260.462

784.00

15.000

1040.00

614.40

180

1-Nonadecanol (1)

C19H40O

284.524

775.30

11.500

1118.50

631.00

438

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 84, AUGUST 2006

Table 2. Defined groups for


the proposed method

Table 3. Values for the contributions to Tc / Pc , Tc/Pc and Vc for the 39 groups and values of the constants
in the model Equations (11) to (13)

Non-ring groups

Non-ring groups

Tc / Pc

Tc/Pc

Vc

-CH3

-CH3

8.26

0.8446

45.42

-CH2-

-CH2-

20.07

1.2910

37.60

>CH-

>CH-

27.11

1.4806

30.00

>C<

>C<

35.81

1.6350

13.28

=CH2

=CH2

3.27

0.4418

41.36

=CH-

=CH-

18.81

1.1606

33.48

=C<

=C<

26.64

1.4472

21.93

=C=

=C=

15.40

0.6119

21.56

=(-)CH

6.46

0.2734

28.60

=(-)CH

10

=(-)C-

6.46

0.2734

28.60

10

=(-)C-

11

-OH

11.21

0.0881

20.75

11

-OH

12

-O-

9.93

0.3628

10.81

12

-O-

13

>C=O

34.18

1.5195

47.41

13

>C=O

14

-CHO

21.98

0.7953

52.80

14

-CHO

15

-COOH

50.52

1.9871

60.10

15

-COOH

16

-COO-

40.07

1.9804

56.69

16

-COO-

17

-HCOO-

28.83

1.3779

65.87

18

=O(Any_other)

-7.64

-0.9769

26.61

19

-NH2

13.70

0.4922

32.98

20

-NH-

15.00

0.2946

51.67

21

>N-

24.66

0.9936

17.34

22

=N-

26.42

1.8782

32.62

17

HCOO-

18

=O(Any_other)

19

-NH2

20

-NH-

21

>N-

23

-CN

49.30

2.5229

58.84

22

=N-

24

-NO2

48.83

2.0970

83.38

23

-CN

25

-F

-7.25

0.0210

21.46

24

-NO2

26

-Cl

8.28

0.5375

41.72

25

-F

27

-Br

16.07

0.5006

51.66

26

-Cl

28

-I

41.78

1.7649

68.45

27

-Br

28

-I
Ring groups

Ring groups
29

-CH2-

15.09

0.9240

34.69

30

>CH-

21.92

1.0535

20.42

31

=CH-

11.23

0.6178

28.49

32

>C<

31.39

1.3134

11.00

33

=C<

27.40

1.2796

20.63

29

-CH2-

30

>CH-

31

=CH-

34

-O-

2.13

-0.0201

10.59

32

>C<

35

-OH(Phenols)

1.17

-0.4922

-11.19

33

=C<

36

>C=O

27.48

1.0798

40.67

34

-O-

37

-NH-

4.28

-0.4429

19.04

35

-OH(Phenols)

38

>N-

33.80

1.2695

16.14

36

>C=O

39

=N-

9.23

-0.0791

29.24

37

-NH-

1 = 38.91

2 = 5.84

3 = 26.86

38

>N-

1 = 0.88

2 = 1.27

3 = 1.06

39

=N-

VOLUME 84, AUGUST 2006

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

439

Table 4. Summary of the equations that describe the proposed


group contribution method
All compounds

Tc
= g1 = 1 +
Pc

Tc
= g 2 = 2 +
Pc

T 1
c

Pc i

ni

ni Pcc

Pc = (g1 / g2)2
Tc = Pc x g2

Vc = 3 +

ni [Vc ]i

Table 5. Deviations for the calculated critical properties using the


new method for the 180 compounds. In the table, %S>10% is the
number of substances with average absolute deviation greater than
10%, %S<5% is the number of substances with average absolute
deviation lower than 5%.
Components

%Tc

%Pc

%Vc

Methyl hydrazine

-9.9

-19.5

-25.3

Nitromethane

-5.3

-9.7

15.7

Carbon Tetrafluoride

10.2

-14.4

13.2

Chloroform

-6.3

-8.5

-0.1

Trichlorofluoromethane

5.9

9.4

-1.0

Acetonitrile

-4.4

2.3

-4.2

Ketene

-0.5

-1.0

0.0

-3.7

-21.4

-6.2

1 = 38.91

2 = 5.84

3 = 26.86

Ethylene oxide

1 = 0.88

2 = 1.27

3 = 1.06

Acetaldehyde

-3.5

4.7

2.1

10

Dimethylamine

-1.1

-1.6

20.8

11

Ethanol

-6.8

-9.4

-1.2

12

Methyl Isocyanate

0.1

0.1

0.0

Tc = aT 1 1 + aT 2(Tb / Tc* ) + aT 3 M + aT 4 N

Pc = a P1 1 + a P 2(Tb / Tc ) + a P 3 M + a P 4 N

13

Acetic acid

-1.7

4.9

-6.8

14

Methyl formate

3.6

1.9

0.3

15

Ethylenediamine

-2.3

-15.1

6.0

Vc = aV 1 1 + aV 2(Tb / Tc* ) + aV 3 M + aV 4 N

16

Monoethanolamine

-2.3

32.7

2.5

17

1-1-Difluoroethane

-16.7

-18.9

2.6

aT1 = - 281.22

aP1 = - 20.47

aV1 = +105.82

18

Nitroethane

-1.1

0.4

-5.2

aT2 = - 1.587

aP2 = - 1.460

aV2 = -1.505

19

Acetyl chloride

0.4

-10.5

2.4

aT3 = - 0.1931

aP3 = 0.0106

aV3 = 0.0856

20

Bromoethane

-4.1

-16.4

-2.7

aT4 = 0.0531

aP4 = - 0.0464

aV4 = - 0.4402

21

1-2-Diiodoethane

-2.1

-1.9

-0.4

22

Methylacetylene

-3.3

-6.0

-0.3

23

Acrylonitrile

3.9

2.7

-1.1

24

Propionitrile

-1.7

2.8

-4.2

25

Acetone

-4.8

0.5

2.5

26

1-2-Propylene oxide

2.1

4.8

-5.7

27

Allyl alcohol

-3.9

0.1

1.7

28

Trimethylamine

3.8

2.2

-6.9

29

Isopropylamine

4.9

-1.2

7.1

30

Isopropanol

0.5

3.8

-0.5

31

Methyl ethyl ether

1.1

-4.0

-2.4

32

1-Propanol

-2.4

-6.0

-0.1

33

Acrylic acid

0.2

-0.4

-0.2

34

Propionic acid

1.8

11.4

-5.0

35

Ethyl formate

-0.5

-1.0

0.3

36

Methyl acetate

-3.4

-6.9

-0.2

37

Methylal

1.0

10.4

8.6

38

1-2-Propylene glycol

1.9

-7.0

0.3

39

1-Nitropropane

1.1

4.8

-5.6

40

2-Nitropropane

1.0

3.1

-1.8

41

Glycerol

4.4

-7.5

0.6

Isomers

Tciso = Tc + Tc Pciso = Pc + Pc Vciso = Vc + Vc

440

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 84, AUGUST 2006

Table 5 (continued)
Components

%Tc

%Pc

%Vc

Components

%Tc

%Pc

%Vc

42

Hexafluoroacetone

22.5

15.1

-6.3

87

Benzene

0.6

3.8

2.2

43

2-Iodopropane

1.7

0.4

1.1

88

1-Hexene

1.6

0.4

-0.2

44

1-2-Butadiene

3.3

2.3

45

Isobutene

1.7

-2.5

0.2

89

Aniline

-3.6

-4.6

10.5

-0.7

90

2-Methylpyridine

1.5

8.8

-2.3

46

Furan

6.4

5.8

-10.7

91

4-Methylpyridine

-0.8

8.9

-0.6

47

Isobutyronitrile

1.0

0.1

-1.8

92

Phenol

-1.8

-2.7

2.2

48

Pyrrolidine

49

Methyl ethyl ketone

3.3

1.4

-2.5

93

Fluorobenzene

1.6

0.9

4.7

-2.6

-0.4

0.7

94

Cyclohexanone

-2.8

6.0

-6.3

50

Diethyl ether

3.7

3.4

-3.5

95

2-Hexanone

-0.1

-0.4

-0.8

51

2-Butanol

3.7

2.9

0.5

96

3-Hexanone

0.2

-2.0

-0.5

52

2-Methyl-2-propanol

2.7

1.1

-1.8

97

Triethylamine

2.3

-3.0

3.3

53

2-Methyl-1-propanol

-0.4

-0.1

0.3

98

Diisopropyl ether

5.0

6.8

-1.0

54

Tetrahydro-furan

-1.6

-7.5

2.9

99

1-Hexanol

-1.2

-7.1

1.0

55

Tert-butylamine

10.0

7.4

-4.9

100

Monochlorobenzene

-0.2

4.3

1.1

56

Diethylamine

5.2

10.7

9.8

101

Isobutyl acetate

1.3

-1.8

-4.8

57

Vinyl acetate

-0.6

-4.1

3.1

102

Hexanoic acid

1.3

1.5

2.7

58

Methyl acrylate

-1.5

-2.0

2.3

103

2-Butoxy ethanol

0.0

0.2

-5.4

59

Morpholine

-1.9

7.8

2.0

104

Bromobenzene

2.9

14.7

0.6

60

Ethyl acetate

0.3

-0.4

-1.0

105

Iodobenzene

3.0

3.6

0.0

61

Methyl propionate

-0.7

-3.1

0.2

106

1-Methylcyclohexene

3.0

2.2

0.0

62

N-propyl formate

0.5

0.9

-0.2

107

1-Heptene

0.4

0.2

-0.9

63

1 4-Dioxane

-6.5

-4.5

3.2

108

1-1-Dimethylcyclopentane

7.5

0.1

1.2

64

1-2-Dimethoxyethane

-2.8

-0.8

5.7

109

Benzonitrile

3.1

-2.0

7.5

65

1 3-Butanediol

-2.9

19.0

-4.1

110

p-Toluidine

0.6

6.6

2.3

66

1-Nitrobutane

1.4

-3.8

5.2

111

m-Cresol

-0.1

8.2

-7.2

67

2-Nitrobutane

1.5

3.5

-1.8

112

o-Cresol

0.1

-2.4

3.6

68

2-Bromobutane

-2.5

-6.1

1.2

113

p-Cresol

0.1

-4.2

4.5

69

3-Methyl-1-butyne

1.9

3.5

0.2

114

2-Heptanone

-2.3

-1.9

0.5

70

3-Methyl-1-2-butadiene

-2.2

-1.8

0.6

115

1-Heptanol

-1.3

-7.6

1.4

71

1-2-Pentadiene

-0.7

-0.3

-0.7

116

Benzoic acid

3.6

4.7

-0.7

72

2-methyl-1-butene

0.4

3.1

0.0

117

Heptanoic acid

0.8

-1.7

3.3

73

2-methyl-2-butene

0.1

0.1

0.0
118

-2.3

-3.1

n-Methylpyrrole

5.2

1.2

-1.3

Diethylene Glycol
monopropyl ether

-0.4

74
75

Cyclopentanone

-1.5

1.8

2.3

119

Perfluoromethylcyclohexane

-1.6

-1.5

0.8

76

Piperidine

3.1

3.4

1.8

120

Perfluoroheptane

-6.6

-5.0

-0.3

77

1-Pentanal

0.7

-1.6

2.4

121

m-Xylene

1.0

2.6

0.2

78

Diethyl ketone

-0.5

-2.6

-4.2

122

o-Xylene

-0.5

-1.9

1.2

79

2-Pentanone

-0.5

-1.4

6.9

123

p-Xylene

1.1

3.4

-0.5

80

Pyridine

-0.2

10.3

8.1

124

1-octene

-0.6

0.7

-1.3

81

1-Pentanal

0.7

-1.6

2.4

125

1-1-Dimethylcyclohexane

2.8

8.5

-7.5

82

2-Methyl tetrahydrofuran

3.4

14.6

3.2

126

n-Propylcyclopentane

1.0

0.1

-0.5

83

n-Methyl-2-Pyrrolidone

-4.5

-1.8

1.1

127

2-2-Dimethylhexane

1.2

0.4

-2.7

84

Ethyl acrylate

0.4

-1.3

1.8

128

2 3-Dimethylhexane

-0.3

-2.4

0.3

85

Ethyl propionate

1.3

2.0

-2.1

129

2 4-Dimethylhexane

0.6

-1.1

-0.1

86

Methyl n-butyrate

0.3

-0.7

-1.0

130

2 5-Dimethylhexane

1.2

1.7

-2.1

VOLUME 84, AUGUST 2006

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

441

Table 5 (continued)
Components

%Tc

%Pc

%Vc

Components

%Tc

%Pc

%Vc

131

Acetophenone

-2.4

-0.4

0.3

159

Biphenyl

0.5

3.3

2.0

132

n n-Dimethylaniline

-4.2

1.8

1.0

160

1-2-Dimethylnaphthalene

-0.8

5.3

-0.8

133

1-octanol

-1.7

134

Methyl benzoate

-0.4

-8.2

1.6

161

1-3-Dimethylnaphthalene

-0.2

2.9

-0.7

4.5

1.3

162

1-4-Dimethylnaphthalene

-0.1

2.8

-0.7

135

Octanoic acid

0.3

-3.2

0.3

163

1-5-Dimethylnaphthalene

-0.3

3.0

-0.7

136

Phthalic anhydride

4.6

-1.5

1.7

164

1-6-Dimethylnaphthalene

-0.1

2.7

-0.6

137

n-propylbenzene

0.7

3.4

-2.5

165

1-7-Dimethylnaphthalene

0.2

2.5

-0.6

138

Cumene

0.6

4.9

-1.1

166

2-3-Dimethylnaphthalene

0.2

2.5

-0.6

139

Mesitylene

3.5

3.4

-1.0

167

2-6-Dimethylnaphthalene

-0.4

3.1

-0.8

140

n-Propylcyclohexane

-2.0

-0.3

-0.3

168

Dibenzopyrrole

-0.3

-3.1

-0.8

141

2-2-4-4-Tetramethylpentane

0.9

3.5

-0.2

169

Di-n-hexyl ether

0.6

-1.8

0.8

142

2-2-3-3-Tetramethylpentane

-3.4

-7.3

4.2

170

Diphenylmethane

2.0

16.4

-2.3

143

2-2-5-trimethylhexane

0.4

0.7

0.7

171

n-Nonylbenzene

-1.5

0.0

-1.9

144

Isoquinoline

-3.2

-10.9

10.6

172

Pyrene

-0.3

0.9

-1.1

145

Quinoline

-1.0

-7.0

-5.1

173

1-Hexadecanol

-1.8

-9.2

1.5

146

5-Nonanone

-0.8

2.2

-1.7

174

Undecylbenzene

-1.2

-0.8

-1.9

147

1-Nonanal

1.5

0.3

-1.8

175

m-Terphenyl

1.4

15.3

0.5

148

Naphthalene

0.3

2.4

0.8

176

o-Terphenyl

2.2

-8.7

0.5

177

p-Terphenyl

-1.1

-3.6

-0.3

149

1-2-3 4Tetrahydronaphthalene

-1.1

-2.7

0.0

178

Triphenylene

-6.1

1.6

1.0

150

n-butylbenzene

1.2

-7.3

8.9

179

n-Tridecylbenzene

-0.6

-1.7

-2.7

151

isobutylbenzene

-0.2

2.1

-2.3

180

1-Nonadecanol

2.2

9.2

2.3

152

p-cymene

0.3

-1.8

1.3

Average Deviation, %

0.1

0.3

0.2

153

cis-Decahydronaphthalene

1.3

5.9

-2.2

Absolute Average Deviation, %||

2.2

4.5

2.6

154

trans-Decahydronaphthalene

-1.7

-8.4

-0.2

%S<5%

91.7

71.7

83.9

155

1-decene

-0.4

3.4

0.2

%S>10%

2.2

10.6

3.9

156

1-Decanal

-2.0

-0.7

-0.8

157

n-Pentylbenzene

-1.3

0.6

-1.3

158

n-Butyl benzoate

-0.8

2.1

-1.3

442

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

VOLUME 84, AUGUST 2006

Table 6. Predicted critical properties for the 40 isomers included in the list of 180 substances considered in this study. Here, Tc*, Pc*, and Vc*
are the values without isomer correction and Tc, Pc, and Vc are the values calculated with isomer correction.
Substance

Tc*

Tc

Pc*

Pc

Vc*

Vc

2-Butanol

545.58

555.72

42.98

43.02

273.69

270.44

2-Methyl-1-propanol

545.58

562.35

42.98

43.46

273.69

268.07

Vinyl_acetate

524.76

521.82

42.11

41.70

270.41

273.29

Methyl_acrylate

524.76

528.20

42.11

42.13

270.41

271.02

Ethyl_acetate

524.54

525.02

38.88

38.65

282.39

283.24

Methyl_propionate

524.54

527.05

38.88

38.79

282.39

282.51

Diethyl_ketone

551.17

557.92

36.37

36.42

324.09

321.82

2-Pentanone

551.17

558.18

36.37

36.43

324.09

321.73

Ethyl_propionate

552.88

553.32

34.32

34.28

337.82

337.65

10

Methyl_n-butyrate

552.88

556.27

34.32

34.47

337.82

336.59

11

2-Methylpyridine

653.85

630.15

51.76

50.04

317.86

327.42

12

4-Methylpyridine

653.85

641.04

51.76

50.77

317.86

323.53

13

2-Hexanone

575.93

586.88

32.23

32.74

379.96

375.17

14

3-Hexanone

575.93

583.74

32.23

32.53

379.96

376.29

15

m-Cresol

706.16

705.38

49.28

49.34

288.71

289.50

16

o-Cresol

706.16

698.25

49.28

48.87

288.71

292.04

17

p-Cresol

706.16

705.19

49.28

49.33

288.71

289.57

18

m-Xylene

633.90

623.39

37.08

36.35

372.49

375.88

19

o-Xylene

633.90

627.13

37.08

36.60

372.49

374.55

20

p-Xylene

633.90

622.86

37.08

36.31

372.49

376.07

21

2_3-Dimethylhexane

546.17

561.94

24.85

25.67

479.01

469.78

22

2_4-Dimethylhexane

546.17

556.89

24.85

25.33

479.01

471.58

23

2_5-Dimethylhexane

546.17

556.63

24.85

25.31

479.01

471.68

24

2_2_4_4-Tetramethylpentane

572.29

576.22

24.23

24.43

509.07

503.04

25

2_2_3_3-Tetramethylpentane

572.29

590.26

24.23

25.37

509.07

498.03

26

Isoquinoline

791.45

777.37

45.81

45.43

408.17

413.64

27

Quinoline

791.45

773.95

45.81

45.20

408.17

414.86

28

cis-Decahydronaphthalene

695.50

690.00

29.83

29.69

481.27

479.19

29

trans-Decahydronaphthalene

695.50

684.54

29.83

29.32

481.27

481.14

30

1_2-Dimethylnaphthalene

771.79

773.65

30.01

30.98

520.61

517.89

31

1_3-Dimethylnaphthalene

771.79

773.01

30.01

30.93

520.61

518.12

32

1_4-Dimethylnaphthalene

771.79

774.23

30.01

31.01

520.61

517.68

33

1_5-Dimethylnaphthalene

771.79

772.90

30.01

30.93

520.61

518.16

34

1_6-Dimethylnaphthalene

771.79

771.74

30.01

30.85

520.61

518.57

35

1_7-Dimethylnaphthalene

771.79

771.74

30.01

30.85

520.61

518.57

36

2_3-Dimethylnaphthalene

771.79

774.63

30.01

31.04

520.61

517.54

37

2_6-Dimethylnaphthalene

771.79

771.16

30.01

30.81

520.61

518.78

38

m-Terphenyl

896.06

894.89

26.48

28.59

731.60

727.83

39

o-Terphenyl

896.06

875.47

26.48

27.29

731.60

734.76

40

p-Terphenyl

896.06

898.38

26.48

28.82

731.60

726.59

Average Deviation (%)

-0.03

0.04

-0.80

0.20

0.30

0.10

Absolute Average Deviation (%)

1.40

0.90

3.90

4.00

2.00

1.90

VOLUME 84, AUGUST 2006

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

443

Table 7. Overall comparison between the proposed methods and others presented in the
literature. The results for the methods Constantinou-Gani and Marrero-Pardillo have been
taken from Poling et al. (2000).
Property

Tc

Pc

Vc

Method

%S>10%

%S<5%

%||

Lydersen

98.3

1.0

Joback-Reid

98.6

0.9

Constantinou-Gani

1.4

59.3

2.5

Marrero-Pardillo

0.4

98.0

2.6

This work

2.2

91.7

2.2

Lydersen

17.8

59.4

5.7

Joback-Reid

12.8

68.9

4.6

Constantinou-Gani

12.1

59.3

5.5

Marrero-Pardillo

13.9

67.1

5.4

This work

10.6

71.7

4.5

Lydersen

7.2

78.9

3.3

Joback-Reid

5.6

82.2

2.9

Constantinou-Gani

5.6

75.6

3.5

Marrero-Pardillo

6.3

83.3

3.3

This work

3.9

83.9

2.6

Table 8. Deviations for the critical properties using the new method for the 18 new compounds not used in calculating the 39 groups
and the constants included in the proposed method. The values with * are the only experimental data.
%

TcLit

Tc

Cal

VcLit

Vc

3.00

604.40*

601.67

0.45

384.5

381.53

36.20

1081.41

1026.97

563.5

546.91

27.56

28.60

657.45

653.62

496.5

490.8

-pinene

28.91

29.95

655.13

712.21

484.5

459.14

Carvone

28.6

30.46

742.52

707.25

503.5

499.78

Linalool

25.82

25.05

697.84

676.55

565.5

563.13

Lauric_acid

19.22

19.43

582.15

758.49

731.5

724.40

Phenantrene

32.43

31.47

869.00*

869.28

0.03

554.00*

550.55

0.62

Anthracene

32.43

31.47

869.30*

869.28

0.01

554.00*

550.55

0.62

10

Myristic_acid

16.35

16.99

598.62

783.32

843.5

840.39

11

Palmitic_acid

14.08

15.10

614.22

807.18

955.5

957.33

12

Linoleic_acid

13.19

14.05

951.23

835.71

1027.5

1049.23

13

Oleic_acid

12.71

13.82

943.11

832.98

1047.5

1062.16

14

Stearic_acid

12.25

13.60

627.92

830.49

1067.5

1075.10

15

Capsaicin

17.92

18.23

1092.78

935.82

934.5

1012.61

16

Arachidic_acid

10.76

12.38

985.65

852.90

1179.5

1193.64

17

Cholesterol

10.79

13.18

1168.48

1000.29

1321.5

1334.91

18

Astaxantina

6.68

8.88

1957.95

1156.85

1983.5

2104.39

444

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING

Cal

Substance

PcLit

Pc

2-Methyl-1Pentanol

34.5*

33.46

Caffeine

41.78

Limonene

Cal

VOLUME 84, AUGUST 2006

ACKNOWLEDGEMENT

REFERENCES

The authors thank the support of the Direction of Research of the


University of La Serena for the permanent support of the Center
for Technological Information of La Serena-Chile and of the
National Council for Scientific and Technological Research
(CONICYT), through the research grant FONDECYT 1040285.

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NOMENCLATURE
a, b

force and volume parameters in van der Waals


equation of state
ai, bi
contributions of atoms and groups for the van der
Waals constants
aTi, aPi, aVi coefficients in the model for the isomers
AL, CL, EL coefficients in Lydersens method
AJ, BJ, CJ, DJ, EJ coefficients in Joback-Reids method
F
objective function
g1, g2 auxiliary variables in Table 4
M
molecular mass
ni
number of times that an atom or group i appears
in a molecule
N
number of atoms in a molecule (Equations (5) and
(14) to (16))
Ns
number of substances considered in this study
(Equation (20))
Pc
critical pressure
Pc*
critical pressure calculated with the proposed method
Pciso
calculated critical pressure for isomers
Pcexp
experimental critical pressure for the isomers
PcLit
literature value for critical pressure
Q
variable in the objective function F (Equation (20))
R
ideal gas constant
%S
percent of substances (%S>10 and %S<5 in Table 7)
Tb
normal boiling temperature
Tc
critical temperature
Tc*
critical temperature calculated with the proposed
method
Tciso
calculated critical temperature for the isomers
Tcexp
experimental critical temperature for the isomers
TcLit
literature value for the critical temperature
Vc
critical volume
Vc*
critical volume calculated with the proposed method
Vciso
calculated critical volume for the isomers
Vcexp
experimental critical volume for the isomers
VcLit
literature value for critical volume

Greek Symbols
i , i
%
%||
Pc, Tc, Vc
TL, PL, VL
TJ, PJ, VJ

constants in the model equations


percent relative deviation
average percent absolute deviation
contribution to the critical properties for isomer
contributions (Equations (14) to (16))
contribution to the critical properties in
Lydersens method (Equations (1) to (3))
contribution to the critical properties in JobackReids method (Equations (4) to (6))

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Temperature Dependent kij Calculated Through a Group
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Vukalovich, M. P. and I. I. Novikov, Equation of State of Real
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U.R.S.S. (1948).

Manuscript received February 11, 2006; revised manuscript received


May 10, 2006; accepted for publication May 10, 2006.

446

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VOLUME 84, AUGUST 2006