Appendix

C7

Estimation of HSP from an Equation of State

Figure C7-5 Prediction of the Polar Solubility Parameter

Figure C7-3 Prediction of the Disperse Solubility Parameter

Figure C7-4 Prediction

Parameter

of

the

Hydrogen

Bonding

EOS results5 and those reported in the reference of Chapter 2,

Endnote I.
The improvement achieved by the equation of state
approach is obvious from a comparison of any of the plots
of a common solubility parameter.

D.

ANALYSIS OF OUTCOMES

There are several reasons for the signicant improvement

in estimation of all four HSP without any solubility
experiments:
1. The algebraic trap of Equation C6-1 is avoided.

Equation C6-1 is perfectly valid, and has been

5

Note that the solvents considered in Figures C7-2 through C7-5 are
not the same as those used in Figures C6-1 to C6-4. The former were
selected by Costa Panayiotou; the latter were selected from this authors
database (Appendix A1). There are 18 solvents in the Panayiotou
database which are not found in Appendix A1 because they have no use
as cleaning solvents.

624

useful, but its use allows estimation of a quantity

(dhydrogen bonding + dpolar) from the algebraic difference
between two quantities which are often similar (dTOTAL
and ddisperse)6; followed by subdivision of the sum
(dhydrogen bonding + dpolar) by subtracting from it dpolar
which is estimated from another value not always well
known (the dipole moment).
2. Panayiotous EOS has been well-veried for each
solvent. Multiple constants in the EOS are determined
from multiple physical properties of each solvent.
Other thermodynamic properties can then be
estimated from the EOS for each solvent, and the
multiple constants can be readjusted (smoothed by
regression analysis).
3. The model is based on experience. The effect of
hydrogen bonding is described less by a difference
between knowns (Equation C6-1) and more by
a specication (the quasi-lattice model) about how
adjacent molecules of one solvent have been shown to
interact in many other solvents.

E.

SUMMARY

Panayiotous EOS approach provides the most accurate

estimates of all three HSP values. This is because the
quality of the information on which all three solubility
parameters are determined is much more secure with the
EOS approach than any other one except one using actual
solubility data.
The effect of that improved accuracy is twofold; it
provides the capability to: (1) Derive the right EOS for
each solvent, and (2) integrate measured thermodynamic
6
They are perfectly similar for many solvents such as parafns
and PFCs which are completely unlike one another.