Estimation of Hansen Solubility Parameters (HSP) from Binary DatadPES

For solvents producing a ducing a GOOD & OUT

response (with a 1 being in column J) enter the
formula in column L.
Prior to the start of the optimization, as in Table
C2-1, no solvent is correctly positioned (because the
values of the ddisperse, dpolar, dhydrogen bonding, and RO
parameters are only guessed at and not yet
determined by optimization).
G. In column M, evaluate the dfi function for each solvent.
 Insert the number 1 if there is a 1 in columns G or H
(as determined in step E above), meaning that the
solvent is properly positioned relative to the
position and size of the solubility sphere.
 Insert the value from column K if there is a 1 in
column I (a BAD & IN response), or insert the
value from column K if there is a 1 in column J (a
GOOD & OUT response). Both are determined
in step F above.
H. Evaluate the overall desirability function (DF) for the
polymer/soil/solvent being tested through use of
Equation C1-4. This is the product of the individual
dfi values taken to the power of the reciprocal of the
number of solvents tested (41 in this example). It is the
number in red above column M.
I. Activate the optimization algorithms in the spreadsheet
to seek a value of 1 for the overall DF. They will do that
by separately and independently modifying the values
of the trial ddisperse, dpolar, dhydrogen bonding, and RO
parameters until the value of 1 for DF is reached, or
until it reaches a value of DF close to 1 which it cannot
improve to be closer to 1. One then takes those nal
trial values as being the outcome of the optimization
based on the provided experimental data.
Optimization details and outcome are shown in Table
C2-2 which should be compared with the starting information in Table C2-1.


Note that in every case, the optimized value of RO

(5.390 MPa) is greater than the value of RA
(column F) for the ve solvents which were shown to
dissolve the PES polymer. This means that these
solvents are correctly positioned inside the solubility
sphere (all GOOD and IN).
And, in every case, the optimized value of RO (5.390
MPa) is less than the value of RA (column F) for the 36
solvents which were shown not to dissolve the PES
polymer. This means that these solvents are correctly
positioned outside the solubility sphere (all BAD and
OUT).

The optimized9 HSP values for PES polymer, which produce

a DF 1, are ddisperse 18.8135752121003, dpolar

9
With the Quattro-Pro spreadsheet optimization function, the author
has found the following settings to provide superior results: Quadratic
estimates of subsequent trial values, central derivatives, and a conjugate
search routine for fertile regions in which to locate an optimum.

C2

Appendix

11.2436835925914, dhydrogen bonding 7.86109904033407,

and RO 5.38982536111856 MPa10.
The progress of the optimization can be seen in Figure
C2-3. Only the rst 20 iterations are shown for simplicity.
Note that the right-most values in Figure C2-3, the nal
optimized values for each parameter, are not those fully
determined at the 21st iteration.
Note also the substantial level of convergence obtained in
this case with eight or so iterations. The entire optimization
takes less than 1 to 5 seconds on a personal computer.
Corresponding to the two-dimensional idealized Figure
C2-1 (or Figure 2.42) is the two-dimensional data-based
Figure C2-411.
Because DF 1, all 41 solvents have been positioned
correctly relative to the three- dimensional solubility sphere12.
The green and orange lines in Figure C2-4 are the calculated
two-dimensional projections of the three- dimensional
periphery of the solubility sphere (columns I and J). They are
calculated from Equation 2.8, which is a quadratic equation
with two roots (the green and orange colored lines).
Occasionally, the starting values recommended here will
not produce an optimum with a DF value at or near 1. Then,
one must select new trial values by trial and error which are
somewhat remote from the starting values recommended
here. In this case the optimization routine has located a local
optimum rather than the desired global optima.

B.1 Spherical Reasoning

The dfi function, as Equation C1-3, is based on an arithmetical
difference of two distances in three-dimensional HSP space.
The difference is point-to-pointda straight line separation.
10

Values reported in Chapter 5 of the reference of Endnote A for

ddisperse, dpolar, dhydrogen bonding, and RO are 19.6, 10.8, 9.2, and 6.2
respectively. The DF value is given as 0.999. The excess of digits reported
for each of the four parameters is not signicant. The values are printed
here to show the power of the optimization algorithms.
11
Figure C2-5 is plotted at the ddisperse value for the center of the
solubility sphere.
12
One might inquire why spherical geometry was chosen to represent
the coherence (or lack of it) between soils/polymers/solvents, and
solvents. Consider these three reasons: (1) There are three different HSP
values and a sphere incorporates three dimensions, (2) it's simple, easily
visualized, and communicated, and (3) the use of spherical geometry
generally works well enough.
Yet, Equation 2.8 is not that of a sphere; the number 4 would not
be present in the three-dimensional equation for the surface of a sphere.
So the actual geometry used in determination of HSP is not spherical, but
it is stated to be such.
Actually, there are numerous literature examples of ellipsoidal
geometry being used to describe the solubility envelope between
soluble/miscible, and not so. Dr. Hansen comments upon this point on
page 161 of Endnote A. Further, US Department of Energy Project
DE-FC26-98FT40323-036 was completed earlier in the last decade to
develop a visualization technique to examine various non-spherical
geometries as effective methods of characterizing solubility data
involving crude oil and derivatives.
Further, there is no a priori reason to assume that the shape of the
solubility envelope must be free of inection points, where some
sectors of composition are more or less effective in incorporating all
materials into a solution.

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