Appendix

C1

Optimization Method for Determination of Solubility Parameters

Conventionally, complete correctness is taken to be:

All data tabulated (or plotted) in three-dimensional

solubility parameter space are from either the GOOD
and IN or BAD and OUT groups, and
No data tabulated (or plotted) from the GOOD and
OUT, and BAD and IN groups.

One can quantify the lack of complete correctness by

noting how far in three-dimensional space4 a GOOD
point is plotted OUT of the sphere and how far a BAD
point is plotted IN the sphere.
For simplicity, lack of correctness in solubility data is
referred to as an error. So in Equation C1-1, which
denes an error, RO is the distance5 in three-dimensional
space from the center of the solubility sphere to its
boundary. And RA is the distance from the center of the
solubility sphere to the location of the center of the
location of the ith solvent.


Error i R A  R O i   fFACTORgi
C1  1
The parameter FACTOR is articialdit is used algebraically
to produce zero error values when the solubility data are
correctly tabulated (plotted), and non-zero error when they
are not. Such an implementation is noted in Table C1-1.
There can be as many Errori values as there are solvents in
the experimental protocol; the maximum value of i is the
number of solvents tested in the experimental protocol.

the way in which they describe the experimental data

upon which they are based6.
It has been conventional when determining solubility
parameters to use a metric called the desirability functionA. This metric is based on the idea that, for a product or
process that has multiple quality characteristics, it is undesirable to have one of them outside of some desired limit.
The method allows the coordinates of the center of the
solubility sphere (ddisperse, dpolar, dhydrogen bonding), and
radius (RO) parameter values to be determined which
provide the most desirable response valuesdthe best
description of the solubility data points.
While the desirability function can be used with nonbinary solubility data (Appendices C3 and C4), it is also
conventional to use binary data (Appendix C2) for the
optimization. This means that with an experimental solubility experiment, one assigns the number 1 if the solvent
was compatible with or dissolved the soil or polymer
satisfactorily (to a certain low level of residue or within
a goal time, for example), and the number 0 if there was
not complete compatibility or solution in adequate time.
The general format of the desirability function (DF) is
Equation C1-2, where the individual dfi values are those
which result from testing with each solvent, and i is the
number of dissolving tests. In Table C2-1, for example, i is
41 as there are 41 dissolving tests with different solvents,
which may also be called responses.
DF fdf 1  df 2  df 3  df 4  df 5 .  df i g1=i

A.2 MATHEMATICAL CRITERIA

TO DEFINE AN OPTIMUM
One simply needs a metric to do thatda standard of
performance about the optimization scheme. The
purpose of the metric is to allow recognition that the
optimum has been found; that movement of the coordinates of the center of the solubility sphere (ddisperse,
dpolar, dhydrogen bonding), and adjustment of the radius
(RO) of the solubility sphere parameters wont improve

This is extremely difcult to do visually in a two-dimensional graph.

Thats why the invention of the spreadsheet has made the technology
which Dr. Hansen invented 20 years earlier signicantly more easy for
him and others to practice.
Data points often appear within a projection of a sphere onto two
dimensionsda circledwhen in fact they are outside the circle. The
reason for this is that usually the disperse solubility parameter is not
specied in the two-dimensional plot, and that affects the location of the
data point in three-dimensional space.
Data in Table C2-1 shows that actual data arent as simple to
characterize as are the imaginary data shown in Figure 2.42.
Two-dimensional solubility plots, which ignore the disperse solubility
parameter, allow discrimination among solvents only when the disperse
solubility parameter of the polymer/soil/solvent being tested is essentially
constant among all tested solvents. This is seldom the case.
5
This is the radius of the three-dimensional sphere. If RA < RO, the
solvent is within the sphere; if RA > RO, the solvent is outside the sphere.
RA is calculated from Equation 2.8.

566

C1  2
The individual dfi functions can be any function of the
errors (Equation C1-1) which one wants to eliminate or
minimize through the optimization scheme.
Conventionally, again, a simple relationship with
Equation C1-1 is used to formulate the individual dfi
values. They are equal to the exponential function (exp) of
the error values, as shown in Equation C1-3.



df i h exp Error i  exp jR A  R Oi   fFACTORgi
C1  3
Equation C1-3 is simpler than it looks because when
a solvent is noted as being GOOD and IN or BAD
and OUT, the value of Errori is 0, and exp (0) has the
value of 17. Only solvents noted as being GOOD and
OUT, or BAD and IN have non-zero error values and
hence non-unity dfi values.

In curve-tting by linear regression, the metric is the sum of the

squares of the deviations between the experimental data and values
calculated using the curve-t equation.
7
The reason one doesnt use the error values directly in Equation C2-3 is
that when any single solvent is correctly tabulated/plotted relative to
a soil/polymer/solvent, the error is zerodso the overall error function is
zero. When the overall error function is zero, further optimization is
impossible. Only the fact that exp (0) 1 allows the optimization to be
completed.