Appendix

C4

Estimation of HSP from Solvent Mixtures

Table C4-3 Solvent Combinations Performing Considerably Outside of Expectations

d
Disperse

d
Polar

Dissolution
Time, Min

d
H Bonding

Excess
(RA  RO)

Molar
Volume
cc/mol

Pure
Solvents

Outcome

AC
(Acetone)

GOOD
& OUT

0.50

15.50

10.40

7.00

3.02

73.45

Better

BA (Benzyl
Alcohol)

GOOD
& OUT

0.17

18.40

6.30

13.70

3.58

103.58

Better

CHexanone

BAD
& IN

5.00

17.80

8.40

5.10

2.82

103.56

Poorer

THFA &
CHexanone
@ 50%
THFA

BAD
& IN

2.00

17.80

8.30

7.65

1.22

100.10

Poorer

MPa

separate trials. While their existence indicates that the

HSP technology does not perfectly represent solventsolvent-soil interactions, the level of imperfection (4 out of
80) is perfectly satisfactory for industrial cleaning work.

F. LOCAL

VS.

GLOBAL OPTIMA

When one conducts optimizations of any kind, one must

be careful to select appropriate starting points for the
iterative calculations. Outcomes can be a function of the
starting point for calculations. That occurrence is usually
identied as a local optimum.
A global optimum is an outcome which does not depend
upon the starting point of the iterative calculation. This is
not the case for the calculations about PR1 based on the
data in Table C4-1.
All of the optimized HSP results in Table C4-2, where
various dissolving times were used to differentiate among
performance, were produced from a common starting
point. That was the one noted in Box C1.1: ddisperse 15,
dpolar 5, dhydrogen bonding 5 MPa and RA 5 MPa13
(as per Appendix C1).
Other starting points, such as an outcome previously
found with another level of solution time using the same
data, produced somewhat different values of solubility
parameters to those noted in Table C4-2. The differences
were between 5 and 20% based on RO, but none of these
local optima had DF values closer to 1 than did the one
with the common starting point.

13
These values arent based on science. These trial values were chosen
because they are integer median values of all 210 cleaning solvents listed
in the database of Appendix A1, and they were successfully used in
Appendices C2 and C3.

596

vs. Expectation

This is clearly a result of having several data points in

the data set of 80 experiments which are not similar, or are
based on additional science not found in the results of the
overall experiments.
It must also be remembered that optimizations are trialand-error routines. Even with a common starting point, the
results are not always exactly the same as produced in
a previous or successive optimization routine. The reason is
simple: There is an element of randomness in selection of
the initial steps taken from the starting values. The
randomness is programmed into the optimization routine
because the direction of the nal values from the starting
values is not known. Think of trial-and-error optimizations
as completion of a pizza recipe. While the ingredients are
common, the proportions and procedures each chef uses
and follows are different leading to slightly different
outcomes.

G. WHEN A PICTURE MAY NOT BE

WORTH ANY WORDS
The two-dimensional images of Figures 2.41 and 2.42 can
blind one to the true relationships between solvents and
chemicals (polymers, solvents, oils). This is because the
images are two-dimensionaldthey dont show whats in
the plane of the third dimension. That dimension is normally the value of the disperse solubility parameter. This is
because there is normally smaller variation in this HSP
value. It is convenient to do this because useful threedimensional plots are hard to draw, and perhaps much
harder understand.
The images in Table C4-4 show the cross-sectional view
of the periphery of the three-dimensional sphere. Its a
curved line projected onto the three-dimensional plane of