You are on page 1of 1

Optimization Method for Determination of Solubility Parameters

C1

Appendix

Table C1-1 Denition of Solubility Errors


Outcome of
Solubility
Experiment

Position of Solvent Relative


to Solubility Sphere

GOOD Solvent
GOOD Solvent
BAD Solvent
BAD Solvent

Value of
Error
9

Inside

Outside

(RO  RA)
88

Inside

Outside

(RA  RO)

Combining Equations C1-2 and C1-3, one gets the


operating Equation C1-4 (shown only for three terms). This
is the equation which will be used for the optimization.
DF fexp jR A  R O j  fFACTORg1 g
fexp jR A  R O j  fFACTORg2 g .
fexp jR A  R O j  fFACTORgi g1=i
C1  4
When the optimization has been completed, by the
spreadsheet function described in Footnote 10, DF has the
value 1dor just slightly less as is possible. If any dissolving
test is not correct, its dfi value is <1, and so the overall DF is
also <1.

A.3 METHOD OF VARIATION OF


PARAMETERS
The mathematical technique of linear programming is used to
solve multi-variable optimization problems such as identifying the best (when DF 1) location of the solubility
sphere (ddisperse, dpolar, dhydrogen bonding), and radius (RO)
parameter based on a set of solubility experiments.
Developed during World War II to plan expenditures and
returns in order to reduce costs to the army and increase
losses to the enemy, linear programming found postwar
applications in such diverse situations as renery optimization, food blending, inventory management, portfolio
and nance management, resource allocation for human
and machine resources, and design of scientic experiments.
While its mathematical derivation and explanation is
beyond the scope of this book, its power is easily harnessed
by readers. A set of sophisticated linear (and non-linear)
programming algorithms is a part of current spreadsheet
software products8.

Chapter 2, Footnote 69 has a more detailed description.

10

11

Value of
FACTOR

Comments

Correct Placement

False Positive

Correct Placement

False Negative

The word linear in linear programming basically


means no surprises (Box C1.1).

Box C1.1
This optimization technology will nd a global optimum as long
as the relationships among the four parameters and DF are linear.
Mathematically, the word linear does not mean straight line. It
does not mean that there cant be curvature in the relationships
between the four parameters underlying DF. Linear means that
the relationships are continuous, proportional (although the
proportionality constant may change), and additive.
In fact, these conditions of linearity do not have to be strictly
followed with the powerful optimization routines available in
modern spreadsheets. One can apply constraints (limitations
placed on trial values of the four parameters). One can specify the
degree of precision of the answer and the maximum number of
iterations to be made. And one can also specify which of the
linear or non-linear goal-seeking algorithms is to be used.
However, absence of linearity in the relationships between the
four parameters and DF can mean that there are multiple optima.
And only one of which will have the value of DF closest to 1.
Different starting points (parameter values) can produce
different optima, without noticing that there are multiple optima.
This author has experienced this outcome with some sets of
experimental data. Thats why he uses the same initial guesses
for every optimization run. If multiple optima are found, the only
valid one in terms of selection of solubility parameters is one in
which DF equals exactly 1. If an optimum is found by the
optimization routine where DF has any other value than 1, choose
another set of initial guesses. If there are no optima found where
DF has the value of 1, choose the optimum which has the DF value
closest to 1.

9
If a solvent is correctly positioned relative to the solubility sphere, it
matters not what are the relative values of RA and ROdthe error is zero
(and FACTOR 0).
10
The units of all errors are the units of solubility
parametersdconventionally MPa1/2 in this book.
11
By the conventions in place in Table C1-1 for differences in solubility
distance, the values of the desirability function (DF) will be between
0 and 1, and cant exceed 1. Should the opposite conventions be
chosen, DF will be above 1, or exactly 1. In either case, the outcome of
the optimization will be unaffected.

567

You might also like