PHYSICAL PROPERTIES Version 5.

Users Guide

DEFINING A COMPONENT WITH THE JOBACK/LYDERSON METHOD

The Joback Method is a group contribution method which will estimate the following properties:

Molecular weight (if not given by the user)

Critical temperature
Critical pressure
Critical volume
Acentric Factor
Normal boiling point (if not given by the user)
Ideal gas heat of formation at 25C and later.
Ideal gas Gibbs Free Energy of Formation at 25C and one atm
Ideal gas heat capacity coefficients for the polynomial equation
Solubility parameter
Specific gravity at 60F (if not given by the user)
Heat of Vaporization at the normal boiling point
Liquid volume constant
Watson Factor

MOLECULAR WEIGHT BY THE JOBACK METHOD

Each functional group has a molecular weight of its own. Therefore, the molecular weight of the
molecule is the sum of the molecular weights of the functional groups.
CRITICAL PROPERTIES BY THE JOBACK METHOD
One of the first very successful group contribution methods to estimate critical properties was developed
by Lyderson in 1955. Joback reevaluated Lydersens scheme, added several functional groups, and
determined the values of the group contributions. His proposed relations are

Tc = Tb 0.584 + 0.965 T ( T )
Pc = (0.113 + 0.0032n A P )

2 1

Vc = 17.5 + V

The units are Kelvin, Bar, and cubic centimeters per mole. nA is the number of atoms in the molecule.
The values are given in Table 2-2.
NORMAL BOILING POINT BY THE JOBACK METHOD
A number of methods to estimate the normal boiling point have been proposed. More recent techniques
are usually specific for a given homologous series as, for example, the work of Ambrose on alkanols.
Others attempt to use Londons theory to relate Tb to basic molecular parameters such as ionization
potential, molar refraction, and shape. None in this latter class yield accurate estimations.

To obtain a very approximate prediction of Tb, one may use the group contributions for Tb in Table 4.1
with the relation:
Tb = 198 + b
47

PHYSICAL PROPERTIES Version 5.6

Users Guide

where Tb is in Kelvin. The group increments were developed by Joback and these were tested on 438
diverse organic compounds. The average absolute error found was 12.9 K, and the standard deviation
of the error was 17.9 K. The average of the absolute percent errors was 3.6%. Whereas these errors
are not small, this simple technique may be useful as a guide in obtaining approximate values of Tb
should no experimental value be available.
THERMOCHEMICAL PROPERTIES BY THE JOBACK METHOD
Choosing the same atomic and molecular groups as in Table 4.1 to estimate critical properties, Joback

has used the values given in Stull et al. to obtain group contributions for Hof (298 K), Gof (298 K), and
polynomial coefficients to relate C po to temperature.

His group values are shown in Table 4.2 and they are to be used in the equations below.
With Hof and Gof in kJ/mol and Cpo in J/(mol K),
Hof (298 K) = 68.29 + ( n j H
j

Gof (298 K) = 53.88 + ( n j G

j
&
#
# &
Cpo = $ ( n j a 37.93 ! + $ ( n j b + 0.210 !T
$ j
!
! $ j
%
"
" %
&
&
#
#
+ $ ( n j c 3.91 10- 4 !T 2 + $ ( n j d + 2.06 10 7 !T3
$ j
$ j
!
!
%
%
"
"

where nj is the number of groups of the jth type and the contributions are for the jth atomic or molecular
group. The temperature T is in Kelvin.
Point Table 4.1 Joback Group Contributions for Critical Properties, the Normal Boiling Point, and
Freezing

Nonring groups:
CH3
>CH2
>CH
>C<
=CH2
=CH
=C<
=C=
CH
C

Tc

Pc

Vc

Tb

Tf

0.0141
0.0189
0.0164
0.0067
0.0113
0.0129
0.0117
0.0026
0.0027
0.0020

-0.0012
0
0.0020
0.0043
-0.0028
-0.0006
0.0011
0.0028
-0.0008
0.0016

65
56
41
27
56
46
38
36
46
37

23.58
22.88
21.74
18.25
18.18
24.96
24.14
26.15
9.20
27.38

-5.10
11.27
12.64
46.43
-4.32
8.73
11.14
17.78
-11.18
64.32

48

PHYSICAL PROPERTIES Version 5.6

Users Guide

Ring groups:
CH2
>CH
>C<
=CH
=C<
Halogen groups:
F
Cl
Br
I
Oxygen groups:
OH (alcohol)
OH (phenol)
O (nonring)
O (ring)
>C=O (nonring)
>C=O(ring)
O=CH (aldehyde)
COOH (acid)
COO (ester)
=O (except as
above)
Nitrogen groups:
NH2
>NH (nonring)
>NH (ring)
>N (nonring)
N= (nonring)
N= (ring)
CN
NO2
Sulfur groups:
SH
S (nonring)
S (ring)

Tc

Pc

Vc

Tb

Tf

0.0100
0.0122
0.0042
0.0082
0.0143

0.0025
0.0004
0.0061
0.0011
0.0008

48
38
27
41
32

27.15
21.78
21.32
26.73
31.01

7.75
19.88
60.15
8.13
37.02

0.0111
0.0105
0.0133
0.0068

-0.0057
-0.0049
0.0057
-0.0034

27
58
71
97

-0.03
38.13
66.86
93.84

-15.78
13.55
43.43
41.69

0.0741
0.0240
0.0168
0.0098
0.0380
0.0284
0.0379
0.0791
0.0481
0.0143

0.0112
0.0184
0.0015
0.0048
0.0031
0.0028
0.0030
0.0077
0.0005
0.0101

28
-25
18
13
62
55
82
89
82
36

92.88
76.34
22.42
31.22
76.75
94.97
72.24
169.09
81.10
-10.50

44.45
82.83
22.23
23.05
61.20
75.97
36.90
155.50
53.60
2.08

0.0243
0.0295
0.0130
0.0169
0.0255
0.0085
0.0496
0.0437

0.0109
0.0077
0.0114
0.0074
-0.0099
0.0076
-0.0101
0.0064

38
35
29
9

34
91
91

73.23
50.17
52.82
11.74
74.60
57.55
125.66
152.54

66.89
52.66
101.51
48.84

68.40
59.89
127.24

0.0031
0.0119
0.0019

0.0084
0.0049
0.0051

63
54
38

63.56
68.78
52.10

20.09
34.40
79.93

49

PHYSICAL PROPERTIES Version 5.6

Users Guide

Table 4.2 Joback Group Contributions for Ideal-Gas Properties

Nonring groups
CH3
>CH2
>CH
>C<
=CH2
=CH
=C<
=C=
CH
C
Ring groups
CH2
>CH
>C<
=CH
=C<
Halogen groups
F
Cl
Br
I
Oxygen groups
OH (alcohol)

OH (phenol)
O (nonring)
O (ring)
>C=O (nonring)
>C=O (ring)
O=CH
(aldehyde)
COOH (acid)
COO (ester)
=O (except as
above)

Values
a
b
J/mol K

H
kJ/mol

G
kJ/mol

-76.45
-20.64
29.89
82.23
-9.63
37.97
83.99
142.14
79.30
115.51

-43.96
8.42
58.36
116.02
3.77
48.53
92.36
136.70
77.71
109.82

1.95E+1
-9.09E-1
-2.30E+1
-6.62E+1
2.36E+1
-8.00
-2.81E+1
2.74E+1
2.45E+1
7.87

-8.08E-3
9.50E-2
2.04E-1
4.27E-1
3.81E-2
1.05E-1
2.08E-1
5.57E-2
2.71E-2
2.01E-2

1.53E-4
-5.44E-5
-2.65E-4
-6.41E-4
1.72E-4
-9.63E-5
-3.06E-4
1.01E-4
1.11E-4
-8.33E-6

-9.67E-8
1.19E-8
1.20E-7
3.01E-7
-1.03E-7
3.56E-8
1.46E-7
-5.02E-8
-6.78E-8
1.39E-9

-26.80
8.67
79.72
2.09
46.43

-3.68
40.99
87.88
11.30
54.05

-6.03
-2.05E+1
-9.09E+1
-2.14
-8.25

8.54E-2
1.62E-1
5.57E-1
5.74E-2
1.01E-1

-8.00E-6
-1.60E-4
-9.00E-4
-1.64E-6
-1.42E-4

-1.80E-8
6.24E-8
4.69E-7
-1.59E-8
6.78E-8

-251.92
-71.55
-29.48
21.06

-247.19
-64.31
-38.06
5.74

2.65E+1
3.33E+1
2.86E+1
3.21E+1

-9.13E-2
-9.63E-2
-6.49E-2
-6.41E-2

1.91E-4
1.87E-4
1.36E-4
1.26E-4

-1.03E-7
-9.96E-8
-7.45E-8
-6.87E-8

-208.04

-189.20

2.57E+1

-6.91E-2

1.77E-4

-9.88E-8

-221.65
-132.22
-138.16
-133.22
-164.50
-162.03

-197.37
-105.00
-98.22
-120.50
-126.27
-143.48

-2.81
2.55E+1
1.22E+1
6.45
3.04E+1
3.09E+1

1.11E-1
-6.32E-2
-1.26E-2
6.70E-2
-8.29E-2
-3.36E-2

-1.16E-4
1.11E-4
6.03E-5
-3.57E-5
2.36E-4
1.60E-4

4.94E-8
-5.48E-8
-3.86E-8
2.86E-9
-1.31E-7
-9.88E-8

-426.72
-337.92
-247.61

-387.87
-301.95
-250.83

2.41E+1
2.45E+1
6.82

4.27E-2
4.02E-2
1.96E-2

8.04E-5
4.02E-5
1.27E-5

-6.87E-8
-4.52E-8
-1.78E-8

50

PHYSICAL PROPERTIES Version 5.6

Nitrogen groups
NH2
>NH (nonring)
>NH (ring)
>N (nonring)
N= (nonring)
N= (ring)
=NH
CN
NO2
Sulfur groups
SH
S (nonring)
S (ring)

Users Guide

Values
a
b
J/mol K

H
kJ/mol

G
kJ/mol

-22.02
53.47
31.65
123.34
23.61
55.52
93.70
88.43
-66.57

14.07
89.39
75.61
163.16

79.93
119.66
89.22
-16.83

2.69E+1
-1.21
1.18E+1
-3.11E+1

8.83
5.69
3.65E+1
2.59E+1

-4.12E-2
7.62E-2
2.30E-2
2.27E-1

-3.84E-3
-4.12E-3
-7.33E-2
-3.74E-3

1.64E-4
-4.86E-5
1.07E-4
-3.20E-4

4.35E-5
1.28E-4
1.84E-4
1.29E-4

-9.76E-8
1.05E-8
-6.28E-8
1.46E-7

-2.60E-8
-8.88E-8
-1.03E-7
-8.88E-8

-17.33
41.87
39.10

-22.99
33.12
27.76

3.53E+1
1.96E+1
1.67E+1

-7.58E-2
-5.61E-3
4.81E-3

1.85E-4
4.02E-5
2.77E-5

-1.03E-7
-2.76E-8
-2.11E-8

ACENTRIC FACTOR BY THE JOBACK METHOD

The Joback method itself does not provide estimations for the acentric factor. When the Joback method
is selected, CHEMCAD uses the Lee-Kesler method to estimate the acentric factor:

where

= lnPc 5.97214 + 6.09648 O -1 + 1.28862ln O - 0.169347 O 6

= 15.2518 - 15.6875 O -1 13.4721ln O + 0.43577 O 6

O =

Tb
Tc

Pc [=]atm.
HEAT OF VAPORIZATION BY THE JOBACK METHOD
When the Joback method is selected the following equation is used to estimate the heat of vaporization
at the normal boiling point:

.
(ln Pc 1)
H v b = 1.093RTc ,Tb r
0.930 Tb r
,51

+
)
)*

PHYSICAL PROPERTIES Version 5.6

Users Guide

where

H v b

the heat of vaporization at the normal boiling point

R
Tc
Pc
Tbr

=
=
=
=

the gas law constant

critical temperature
critical pressure
reduced normal boiling point =

Tb
Tc

LIQUID VOLUME CONSTANT BY THE JOBACK METHOD

When the Joback method is selected, the liquid volume constant is estimated using the following
procedure:

i.

Estimate the Rackett Constant, ZRA:

Z RA = 0.29056 0.08775

ii.

Estimate the Liquid Molar Volume , V, at 77F:

V =

iii.

27
RTc
(Z RA )[1+ (1Tr ) ]
Pc

Calculate the Liquid Volume Constant, LVC:

LVC =

V
&
1611 #
$ 5.7 +
!
$
Tc !"
%

THE SPECIFIC GRAVITY AT 60F BY THE JOBACK METHOD

The specific gravity at 60F is calculated using the Cavett equation. The Cavett equation has the form:
liquid volume = Vol Con * (5.7 + 3Tr)

where

Liquid volume
Vol Con
Tr

=
=
=

is in cc/gmole
Liquid mole volume constant
Reduced temperature

The inverse of this value is divided by the density of water at 60F to get the specific gravity.
SOLUBILITY PARAMETER BY THE JOBACK METHOD
The solubility parameter is calculated from its definition like so:

. H298 +
=, v )
, VL )
*

0 .5

WATSON FACTOR BY THE JOBACK METHOD

52

[=]

& cal #
$
!
$! !
% c"

PHYSICAL PROPERTIES Version 5.6

Users Guide

The Watson Factor, K, is calculated like so:

K =

(NBP)0.333
S.G.

DEFINING A COMPONENT WITH THE UNIFAC (ELLIOTT) METHOD

The following method alternately called the "Elliott" or "UNIFAC" methods also estimate pure component
physical properties from a tabulation of its functional groups. The method is called the "UNIFAC" method
because it uses the same functional groups as the UNIFAC activity coefficient method.
CRITICAL PROPERTIES BY THE UNIFAC METHOD
-1
Tc=Tb*[1+(1.28+T) ]

[=] K

-2

Pc=MW*(0.346+P)

[=] bars

Vc=172+V

[=] cc/gmole

Tb=1000/(0.5+35.7/sqrt[Tb)

[=] K

+1000/(142+Tb)]

THERMOCHEMICAL PROPERTIES BY THE UNIFAC METHOD

ELLIOTT GROUP CONTRIBUTION ESTIMATION FORMULAS IN CHEMCAD

Property

Equation

% error

Tc [K ]

Tb 1 + (1.28 + i )

Pc [bar ]

MW (0.346 + i )

Vc [cc/mol]

172 + i

14.6

20.1

Tb [K ]
(760mmHg)

1000 / 0.5 + 35.7 / ( i )

Tb [K ]
(10mmHg)

1000 / 0.5 + 66 / ( i )

H vap (298)

6.829 + i

6.1

[
[

0.9

12

12

+ 1000 / (142 + i )

+ 1000 / (158 + i )

4.7
3.6

3.2

kJ / mole
53

Literature Source
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Zuppo and Elliott, Ind. Eng.
Chem. Res. Submitted
(1999).
Constantinou & Gani,
AIChEJ, 40: 1704 (1994).

PHYSICAL PROPERTIES Version 5.6

Users Guide

H f (298)
Gf

(298)

8.3
kJ mol
7.3
kJ mol
8.9

10.835 + i

14.828 + i

Tm [K ]

102.425 exp ( i )

V L (298)

Cp o

A + BT + CT 2 + DT 3

(cal/cc )1 2

[ (H

SG

MW / V L

7.7

vap

298R / V L

)]

12

Constantinou & Gani,

AIChEJ, 40: 1704 (1994).
Constantinou & Gani,
AIChEJ, 40: 1704 (1994).
Constantinou & Gani,
AIChEJ, 40: 1704 (1994).
Fedors, Poly. End. Sci,
14:147 (1974) (cf. Van
Krevelen, Elsevier, NY,
1990)
Joback, MIT thesis, Boston,
1984 (cf. Reid et al., Prop.
Gas & Liq; 1987).
Definition
Definition

CRITICAL PROPERTIES BY THE UNIFAC METHOD

Critical properties are estimated by an adaption of the Ambrose method described by Reid et. al. (1987,
pp.12, 13). The equations are of the form:

Equation
Tc = Tb [1 + (1.28 + T ) 1 ]
Pc = M(0.346 + p ) 2 ]
Vc = 172 + v

Units
Kelvin

Avg. % error
0.934

Bar

6.11

Cm /gmole

15

The group contributions have been regressed in terms of UNIFAC group contibutions since these are
normally required by other parts of the CHEMCAD program. Note that the Lydersen/Joback method
predicts negative values for the critical temperature at high molecular weights.
BOILING TEMPERATURE BY THE UNIFAC METHOD

Tb = 1000 /[0.5 + 35.7 / sqrt( TB ) + 1000 /(142 + TB )] [=] Kelvin; Avg. error = 4.67%
The form of this equation was suggested by a study of the critical point of the ESD equation of state in
conjunction with the molecular simulations of the dePablo and coworkers, and the experimental studies
of Schultz and Flory. All of these works indicate a dependency on the molecular weight that follows the
reciprocal square-root + reciprocal form consistent with this equation. Other popular forms for the boiling
temperature (e.g. Joback, Fedors, Gani) indicate improper asymptotic behavior at high molecular
weights. The Lydersen and Joback methods even indicate negative boiling temperatures at high
molecular weights. The group contributions have been regressed in terms of UNIFAC group
contributions since these are normally required by other parts of the CHEMCAD program.

54

PHYSICAL PROPERTIES Version 5.6

Users Guide

ENERGIES OF VAPORIZATION AND FORMATION BY THE UNIFAC METHOD

These correlations have been adopted without further review from the paper Gani, AIChE. J., 40:1704
(1994). First-order group contributions from conventional UNIFAC groups were well-defined in the
correlations as reported. Interested readers are referred to the original article for more in-depth
discussion of these methods.

Equation
H 298
= 6.829 + HV
v

Units
kJ/gmole

H 298
= 10.835 + Hf
f

kJ/gmole

G 298
= 14.828 + Gf
f

kJ/gmole

The group contributions are taken from Table 4.3 below.

TABLE 4.3 GROUP CONTRIBUTIONS FOR THE UNIFAC METHOD

Values marked as "NA" are amides, for which we had no Tc values in the database. Values marked as
"error" represent groups that correspond to a complete pure component, so they should not be treated
as group contributions. "Error" values should prompt flags if users try to indicate these groups as part of
a new component.
rms%err=

0.934

6.112

15

4.67

These 3 from Gani, AIChEJ, 40:1704

GRP ID

FORMULA

Tb

Hf298

Gf298

Hv298

1
2
2.5
3
3.5
4
4.5
5
6
7
8
9
9.5
10
11
12
13
14
15
16
17
18
19
20

CH3CH2<
RCH2<
CH
>RCH>C<
>RC<
CH2=CH
CH=CH
CH2=C
CH=C
C=C
CH2=C=CH
ACH
ACACCH3
ACCH2
ACCH
OH
CH3OH
H2O
ACOH
CH3CO
CH2CO

0.135
0.131
0.077
0.073
0.070
-0.015
0.070
0.169
0.169
0.169
0.169
0.169
0.338
0.069
0.099
0.221
0.207
0.136
0.554
error
error
0.278
0.387
0.383

0.232
0.224
0.177
0.186
0.195
0.143
0.204
0.360
0.360
0.360
0.360
0.360
0.720
0.153
0.173
0.375
0.370
0.356
0.075
error
error
0.126
0.513
0.504

40
41
25
30
37
5
55
32
32
32
32
32
64
16
87
68
95
107
-25
error
error
-20
77
78

123
121
138
97
107
74
20
257
257
257
257
257
514
124
247
282
303
191
474

525
514
512

-45.947
-20.763
-20.763
-3.766
-3.766
17.119
17.119
53.712
69.939
64.145
82.528
104.293
197.322
11.189
27.016
-19.243
9.404
27.671
-181.422

-164.609
-182.329
-164.41

-8.03
8.231
8.231
19.848
19.848
37.977
37.977
84.926
92.9
88.402
93.745
116.613
221.308
22.533
30.485
22.505
41.228
52.948
-158.589

-132.097
-131.366
-132.386

4.116
4.65
4.65
2.771
2.771
1.284
1.284
6.714
7.37
6.797
8.178
9.342
12.318
4.098
12.552
9.776
10.185
8.834
24.529

40.246
18.999
20.041

55

PHYSICAL PROPERTIES Version 5.6

Users Guide

TABLE 4.3 (CONT.) GROUP CONTRIBUTIONS FOR THE UNIFAC METHOD

GRP ID

FORMULA

Tb

Hf298

Gf298

Hv298

21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64

CHO
CH3COO
CH2COO
HCOO
CH3O
CH2O
CH-O
FCH2O
CH3NH2
CH2NH2
CHNH2
CH3NH
CH2NH
CHNH
CH3-RN
CH2-RN
ACNH2
C5H5N
C5H4N
C5H3N
CH3CN
CH2CN
COOH
HCOOH
CH2CL
CHCL
CCL
CH2CL2
CHCL2
CCL2
CHCL3
CCL3
CCL4
ACCL
CH3NO2
CH2NO2
CHNO2
ACNO2
CS2
CH3SH
CH2SH
FURFURAL
<CH2OH>2
I

0.299
0.457
0.453
0.305
0.234
0.230
0.175
0.140
error
0.301
0.247
0.306
0.301
0.247
0.148
0.144
0.270
error
0.433
0.433
error
0.512
0.615
error
0.236
0.178
0.090
error
0.283
0.196
error
0.326
error
0.165
error
0.440
0.440
0.440
error
error
0.203
error
error
0.056

0.324
0.712
0.704
0.455
0.367
0.358
0.311
0.249
error
0.316
0.269
0.324
0.316
0.269
0.313
0.304
0.211
error
0.869
0.869
error
0.564
0.511
error
0.542
0.504
0.461
error
0.822
0.779
error
1.161
error
0.460
error
0.617
0.617
0.617
error
error
0.476
error
error
0.816

-8
102
103
-6
41
42
27
-57
error
78
62
77
78
62
111
112
24
error
107
107
error
27
-31
error
79
68
43
error
107
82
error
124
error
47
error
34
34
34
error
error
65
error
error
-7

396
451
573
426
288
286
262
323

437
412
444
442
418
293
291
655

942
942

794
858

360
336
313

575
552

598

358

692
668
818

515

525

-129.158
-389.737
-359.258
-332.822
-163.569
-151.143
-129.488
-140.313

-15.505
3.32
5.432
23.101
26.718
54.929
69.885
20.079

134.062
139.758

88.298
-396.242

-73.568
-63.795
-57.795

-82.921

-107.188

-16.752

-66.138
-59.142
-7.365

-8.253

57.546

-107.858
-318.616
-291.188
-288.902
-105.767
-101.563
-92.099
-90.883

58.085
63.051
82.471
95.888
85.001
128.602
132.756
68.861

199.958
199.288

121.544
-349.439

-33.373
-31.502
-25.261

-35.814

-53.332

-0.50%

17.963
18.088
60.161

16.731

46.945

12.909
22.709
17.759

10.919
7.478
5.708
11.227

14.599
11.876
14.452
14.481

6.947
6.918
28.453

31.523
31.005

23.34
43.046

13.78
11.985
9.818

19.208
17.574

11.883

30.644
26.277

14.931

14.364

56

PHYSICAL PROPERTIES Version 5.6

Users Guide

TABLE 4.3 (CONT.) GROUP CONTRIBUTIONS FOR THE UNIFAC METHOD

GRP ID

FORMULA

65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
93.5
94
95
96
97
98
99
100
101
102
103
104
105
106
107

Br
CH===C
C===C
ME2SO
ACRY
CL<C=C>
ACF
DMF-1
DMF-2
CF3
CF2
CF
COO
SiH3
SiH2
SiH
Si
SiH2O
SiHO
SiO
TERT-N
CCL3F
CCL2F
HCCL2F
HCCLF
CCLF2
HCCLF2
CCLF3
CCL2F2
F (exceptions)
CONH2
CONHCH3
CONHCH2
CON<CH3>2
CONCH3CH2
CON<CH2>2
C2H5O2
C2H4O2
CH3S
CH2S
CHS
MORPH
C4H4S
C4H3S

T
0.056
0.125
0.125
error
error
0.082
0.147
error
error
0.340
0.222
0.103
0.327
0.209
0.205
0.151
0.144
0.245
0.245
0.215
0.148
error
0.314
error
0.209
0.327
error
error
error

0.422
0.557
0.553
0.670
0.666
0.662
0.839
0.609
0.207
0.203
0.149
error
error
0.379

Tb

Hf298

Gf298

Hv298

0.522
0.274
0.274
error
error
0.318
0.340
error
error
0.886
0.638
0.391
0.485
0.398
0.298
0.251
0.269
0.675
0.675
0.645
0.200
error
1.027
error
0.709
0.956
error
error
error

0.372
0.605
0.596
0.946
0.937
0.929
0.658
0.761
0.485
0.476
0.429
error
error
0.960

6
-12
-12
error
error
23
27
error
error
188
127
66
47
-6
41
25
37
108
108
108
-15
error
143
error
104
165
error
error
error

73
114
115
101
102
103
55
109
64
65
49
error
error
125

353
288
288

190
135

141
108
91
338
164
164
164
164
44
44
61
225

569

477
348

17
707
835
833
862
860
858
830
495
473
471
447

1.834
220.803
227.368

-36.097
-161.74

-679.195

-313.545

-258.96

-446.835

-223.398
-203.188
-67.778
-182.005
-189.888
-46.562

-344.125

-2.084
18.022

-1.721
217.003
216.328

-28.148
-144.549

-626.58

-281.495

-209.337

-392.975

212.718
136.742

-65.642

241.373

30.222
38.346

11.423
7.751
11.549

57

4.877

8.901
1.86
8.901

13.322

8.301

51.787

16.921
17.117
13.265

27.966

PHYSICAL PROPERTIES Version 5.6

Users Guide

TABLE 4.3 (CONT.) GROUP CONTRIBUTIONS FOR THE UNIFAC METHOD

GRP ID

FORMULA

108
109

C4H2S
NMP

Tb

Hf298

Gf298

Hv298

0.372
error

0.978
error

137
error

ACENTRIC FACTOR BY THE UNIFAC METHOD

The Unifac method itself does not provide estimations for the acentric factor. When the Unifac method is
selected, CHEMCAD uses the Lee-Kesler method to estimate the acentric factor:

where

= lnPc 5.97214 + 6.09648 -1 + 1.28862ln - 0.169347 6

= 15.2518 - 15.6875 -1 13.4721ln + 0.43577 6

Tb
Tc

Pc [=]atm.
LIQUID VOLUME CONSTANT BY THE UNIFAC METHOD
When the Unifac method is selected, the liquid volume constant is estimated using the following
procedure:

i.

Estimate the Rackett Constant, ZRA:

Z RA = 0.29056 0.08775

ii.

Estimate the Liquid Molar Volume , V, at 77F:

V =

iii.

27
RTc
(Z RA )[1+ (1Tr ) ]
Pc

Calculate the Liquid Volume Constant, LVC:

LVC =

&
1611 #
$ 5.7 +
!
$
Tc !"
%

58

PHYSICAL PROPERTIES Version 5.6

Users Guide

THE SPECIFIC GRAVITY AT 60F BY THE UNIFAC METHOD

The specific gravity at 60F is calculated using the Cavett equation. The Cavett equation has the form:
liquid volume = Vol Con * (5.7 + 3Tr)

where

Liquid volume =
Vol Con
=
Tr
=

is in cc/gmole
Liquid mole volume constant
Reduced temperature

The inverse of this value is divided by the density of water at 60F to get the specific gravity.
SOLUBILITY PARAMETER BY THE UNIFAC METHOD
The solubility parameter is calculated from its definition:

. Hv 298R +
)
VL
*
-

0 .5

= ,

[=]

& cal #
$! !
% C"

0 .5

WATSON FACTOR BY THE UNIFAC METHOD

The Watson Factor, K, is calculated like so:
K =

(NBP )0.333
S.G.

DEFINING A COMBUSTION SOLID

The user may specify element types such as C,H O, S, Si and their weight percent when the actual
formula of a combustion solid is unknown the elemental analysis is available. The combustion solid can
be used to simulate burning reactions in a Gibbs reactor UnitOp. Heating value and heat capacity of the
solid may also be given.

EXAMPLE: PHYSICAL PROPERTIES ESTIMATION FOR 1,1,2-TRIMETHYLCYCLOHEXANE

To illustrate the physical properties estimation procedure, lets estimate the physical properties of the
component 1,1,2-Trimethylcyclohexane using the Joback Method.
We begin by selecting the New Component command from the Databank Menu, which is found on the
ThermoPhysical Menu on the Menu Bar, like so:

59