Estimation of HSP from Group Contribution Methods

E. APPLICATION OF THE STEFANIS

PANAYIOTOU METHOD
Examples of using the Stefanis and Panayiotou group
contribution method to estimate the three HSP6 for some
common cleaning solvents are shown in Tables C8-7
(disperse), C8-8 (polar), and C8-9 (hydrogen bonding).
Their order in each table is alphabetical.
The HSP values in the column in each of the three tables
headed by the text REF are from Table A-1 in the reference
of Appendix C2, Endnote A. Those in the column headed
by the text SP in each of the three tables are calculated
using Equations C8-3A, C8-3B, and C8-3C.
ddisperse 17:00

dpolar 7:61

Contrii

Contrii

dhydrogen bonding 7:70

Contrii

C8  3A

C8  3B

C8  3C

The values of the three constants in Equations C8-3A,

C8-3B, and C8-3C are taken from Table C8-4.
The ve7 columns headed by the word contri are each
the product of a group contribution value times the
number of times that group is noted as present in the
solvent molecule under consideration.
Note that in Tables C8-8 (polar HSP) and C8-9
(hydrogen bonding HSP) there are two cleaning solvents
with reference values8 less than 3.0 MPa: cyclohexane and
toluene. Using the guidance from the reference of Endnote
O, the polar and hydrogen bonding values were estimated
using polar LOW and hydrogen bonding LOW
constants from Table C8-4. These changes can be recognized at the bottom of these tables by the change in font
color from dark to light. In other words, Equations C8-3B
and C8-3C were used, but with different constants.
In this book, the 50 secondary groups available in
the SP method are neither identiedP nor used. Stefanis
and Panayiotou claim an improvement of a relative

C8

Appendix

amount of 6.8% (disperse), 34.8% (polar), and

14.8% (hydrogen bonding) when their secondary groups
are implemented. This author feels the claimed gain of
precision is not justied by the addition of a second level of
complexity.

E.1 Simplicity from Linearity

Group contribution methods, as practiced with HSP, are
linear. This means that the contribution constants for subgroups such as ethyl, propyl, butyl, or ethoxy, propoxy,
butoxy, etc. can be computed from those of their component groups. For example, one can compute any of the ve
group constants in the SP method for propoxy by adding
those for CH3 to CH2 (added twice), and O to get correct
values. This is shown in Table C8-6 where the combined
groups are referred to as synthetic groups.

F. A SPECIFIC EXAMPLE
Consider, from Tables C8-7 (disperse), C8-8 (polar), and
C8-9 (hydrogen bonding), calculation of the three HSP for
propylene glycol methyl ether acetateQ.
The simple linear atomic structure is shown in Figure
C8-4. It contains, from left to right, the following ve
groups of atoms:

One group
One group
One group
One group
One group

of
of
of
of
of

CH3O
CH2
CH<
CH3
CH3COO

ddisperse 17:00 1   0:4532; for CH3 O

1  0:0089; for CH2 
1  0:5982; for CH <
1   0:9328; for CH3 
1   0:4113; for CH3 COO
15:81fvs 5:6g
dpolar 7:61 1  0:0089; for CH3 O
1   0:3141; for CH2 
1  0:6051; for CH <

Note that the group contribution constants in Tables C8-4, C8-5, and
C8-6 are color-coded, and that this notation is continued where they are
used in Tables C8-7 (disperse), C8-8 (polar), and C8-9 (hydrogen
bonding).
7
The value of ve is simply the largest number of different groups found
in nearly all molecules used as cleaning solvents. More complex
chemicals, such as pharmaceutical intermediates, will necessarily have
more than ve contris.
8
In the case where there is no reference value of either polar or
hydrogen bonding HSP, one should use both the normal and LOW
constants and choose the lowest value of the HSP. This situation does
not occur with the disperse HSP as there are no LOW constants for
this parameter.

1   1:6444; for CH3 

1   0:6075; for CH3 COO
5:66fvs 5:6g
dhydrogen bonding 7:70 1  0:2675; for CH3 O
1   0:3877; for CH2 
1  0:2064; for CH <
1   0:7458; for CH3 
1  1:7051; for CH3 COO
8:33fvs 9:8g

635