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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
431
Tc =
Pc =
Tb
AL +
ni T ( ni T )
(1)
M
C L +
Vc = E L +
ni PL
(2)
ni V
(3)
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)
432
ni
b = ni bi
a =
ai
(7)
(8)
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)
3
Vc = 3 +
ni [Vc ]i
(13)
ISOMER CORRECTIONS
The proposed method has been extended to predict critical
properties of isomers. We have found that the main properties
(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)
(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.
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)
433
%Vc =
Vcexp Vccal
exp
Vc
i
(23)
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
434
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
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
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
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
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-
439
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
%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
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
440
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
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
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
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
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
-0.03
0.04
-0.80
0.20
0.30
0.10
1.40
0.90
3.90
4.00
2.00
1.90
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
Cal
Substance
PcLit
Pc
2-Methyl-1Pentanol
34.5*
33.46
Caffeine
41.78
Limonene
Cal
ACKNOWLEDGEMENT
REFERENCES
NOMENCLATURE
a, b
Greek Symbols
i , i
%
%||
Pc, Tc, Vc
TL, PL, VL
TJ, PJ, VJ
445
446