Appendix

| C7 |

Estimation of HSP from an Equation of State

There has been a revolution in solubility parameter
technology over the decade prior to publication. OneA
revolutionary leader is Costas PanayiotouB.
He and his professorial associates have enumerated
two additional methods by which all three HSP can be
estimateddwithout the need for an optimization routine
as demonstrated in Appendix C1, without the fundamental
solubility experiments described in Appendices C2, C3,
and C4, without the uncertainty inherent in the use of the
Pythagorean Theorem described in Appendix C5, or the
inaccuracy associated with correlation equations shown in
Appendix C6.
One of his two revolutionary works, published from
1996 to 2007C,D,E,F, involves the technology which is the
title of this appendix.

A. TWO FUNDAMENTAL BUILDING

BLOCKS
Panayiotou employed two common mathematical
constructs: a visualization (model) of a liquid (uid), and
an equation of stateG produced by detailed examination of
the intermolecular details of that model.

His liquid model describes a molecular-scale

arrangement (matrix) of molecules of a single
component material (a solvent). He calls this
arrangement a quasi-lattice. One can specify the
nature of any molecule in the quasi-lattice by
breaking it up into specic segments (atoms or
groups of atoms)dthose sharing hydrogen bonds;
those with centers of polarity (dipoles); and those
which display neither, but the intermolecular forces
they display are dispersed throughout the molecules
described by the model. Some spaces in the quasilattice can be empty (voids or holes). And there can
be a prescribed degree of randomness (which can be

zero) in the identity of any molecule with particular

segments, or a void, at any specic location in the
quasi-lattice.
The equation of state (EOS) is a thermodynamic
relationship in which three measurable macro-scale
physical properties of a uid are related1. They are
pressure, temperature, and molar density (volume per
mole) (see Box C7.1). Equations of state have
adjustable parameters which relate the three
measurable properties in some specic way. Given an
equation of state for a uid (or uid mixtures), one can
calculate values of macro-scale measurable properties,
such as the heat of vaporization, dipole moment, vapor
pressure, and the like using the standard equations of
classical thermodynamics.

B. IMPLEMENTATION OF THE
FUNDAMENTALS
The mathematics of Panayiotous work is well beyond the
scope of this book, but his approach is straightforward.

First, Panayiotou proposesH a mathematical model (a

description at the molecular level) of a general liquid.
His model describes the molecules which make up
the chosen quasi-lattice arrangement and the
energy interchanges between their atoms which are
produced by their interaction. The interchanges will
depend upon the chosen nature of the molecules in
the quasi-latticedthe specic segments of which it

1
There are many of these. The simplest, and most well-known is that of
an ideal gas, in which PV nRT. Equations of state for liquids are
considerably more complex, because the molecules of a liquid are closer
together, and the interaction forces between them are more numerous
and more complex (and less well-known). The relationship PV nRT
does not hold for a liquid, and is only an approximation for real gases.

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