Appendix

C8

Estimation of HSP from Group Contribution Methods

Table C8-2 Coefcients in Group Contribution Methods (Continued)

Lydersen
Group

Gi (Tc)

Joback
Gi (Pc)

Gi (Vc)

Group

Gi (Tc)

Gi (Pc)

Gi (Vc)

Ring groups
OH (phenol)

0.0310

0.0200

3.0

OH (phenol)

0.0240

0.0184

25.0

O

0.0140

0.1200

8.0

O

0.0098

0.0048

13.0

>CO

0.0330

0.2000

50.0

>CO

0.0284

0.0028

55.0

CH2

0.0130

0.1840

44.5

CH2

0.0100

0.0025

48.0

>C<

0.0070

0.1540

31.0

>C<

0.0042

0.0061

27.0

>NH

0.0240

0.0900

27.0

>-

0.0070

0.1300

32.0

S

0.0080

0.2400

45.0

>CH

0.0120

0.1920

46.0

>CH

0.0122

0.0004

38.0

CH

0.0110

0.1540

37.0

CH

0.0082

0.0011

41.0

C<

0.0110

0.1540

37.0

C<

0.0143

0.0008

32.0

0.0110

0.1540

37.0

Gi refers to one specic value of a group contribution

parameter representing a specic functional group.
This would be obtained from a reference table, such as
Table C8-23 which contains the parameter values for
common structural groups for both the Lyderson and
Joback estimation systems.

Consider acetone as an example. Its atoms, groups, and

structure are shown in Figure C8-1. Acetone has two CH3
(methyl) groups and 1 CO (carbonyl) group. It has a total
of 10 atoms (N 2 x 4 + 1 x 2), its molecular weight (M) is

3
The group identications in Table C8-2 are: C (carbon atom), H
(hydrogen atom), F (uorine atom), Cl (chlorine atom), Br (bromine
atom), I (iodine atom), B (boron atom), S (sulfur atom), N (nitrogen
atom), Si (silicon atom); CN (carbon atom covalently bonded with
nitrogen atom); e (any covalent bond),> or < (any two covalent
bond connections to other atoms not shown), (double or unsaturated
covalent bond); and non-ring (not within an unsaturated or saturated
cyclic solvent).
Where only one bonded connection is shown, such as CH3, CH2,
>N, or hCH, the noted group must be located at one end of the
solvents structure.
The group identied as >CH includes any three other groups
covalently bonded to the noted carbon atom, and one of the four
required covalent bonds attached to the noted hydrogen atom. The
>CH group might be attached within solvents such as isopropanol,
2-bromopropane, isobutane, chloroform, or methyl isopropyl ether.

630

58.1, its normal boiling point is 55.5 C. Its critical properties are calculated in Table C8-3.
The values of critical properties for acetone as calculated by the Lydersen and Joback methods, and reported
in the literature, are: critical temperature, 229.8 C,
237.6 C, and 235 C respectively; critical pressure,
716.9 psig, 696.5 psig, and 681.7 psig respectively; and
critical volume, 210 cc/g-mole, 209.5 cc/g-mole, and 209
cc/g-mole respectively.
These outcomes are typical of the application of group
contribution methods.

C. GROUP CONTRIBUTION
METHODS FOR HANSEN SOLUBILITY
PARAMETERS
There are at least six published methods for the estimation
of HSP via group contribution methods. Probably the best
comparative examination of their use is the computer
program HSPiPG, and the most complete description
of them is by Miller-Chou and KoenigH These authors
include: DunkelI, SmallJ, FedorsK, Hoy (Appendix C10)L,
BeerbowerM, and Van KrevelenN.