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.

621

Appendix

C7

Estimation of HSP from an Equation of State

Box C7.1 Equations of State and Phase Changes

Typically in an equation-of-state, so-called reduced values of
pressure (Pr), temperature (Tr), and volume (Vr) are the forms
by which measured pressure, temperature, and volume are
represented.
The concept of reduced temperature was noted in
Appendix C5, and was dened in Equation C5-1 as the ratio
of a specied temperature to the critical temperature for
a specied uid (both temperatures expressed in absolute
units).
Similarly, reduced pressure is dened as the ratio of
a specied pressure to the critical pressure for a specied
uid (both pressures expressed in absolute units).
Critical volume is dened as the ratio of a specied molar
volume (reciprocal of molar density) to the molar volume at
the critical point.
There are no absolute units for reduced pressure,
temperature or volume.
The critical temperature for a uid is one where there is no
phase boundary (or difference) between the liquid and vapor
phases. In other words, at temperatures above the critical

temperature, one cannot produce another distinct phase (a gas)

by any increase of temperature. In the same way, at pressures
above the critical pressure, one cannot produce another distinct
phase (a liquid) by any increase of pressure. Written still
differently, the heat of vaporization is zero at and beyond the
critical point, as there is no distinction between the phases.
There is or can be only one phase. Its usually called a uid.
Nomenclature in this appendix only for reduced pressure,
temperature, and volume is Pred, Tred, and Vred because
those are the terms used by Panayiotou. All are dimensionless.
The law of corresponding states is an empirical law,
formulated by J.D. van der Waals in his 1873 PhD thesis,
that encapsulates the nding that equations of state for
many real gases are remarkably similar when they are
expressed in terms of reduced temperatures, pressures,
and volumes. Since a material in the gas phase is merely
a liquid at low pressure or high temperature, or a material
in the liquid phase is merely a gas at high pressure or low
temperature, the use of reduced parameters in EOS which
apply to both liquids and gases is entirely sensible.

a specic lattice location. If these parameters are

known, any thermodynamic property of a uid,
including all three Hansen Solubility Parameters, can
be calculated (Chapter 2.9.2).
Note that the specic EOS which is Equation C7-1 is an
outcome of the details assumed about the liquid model
proposed in the rst step. For every model, there is
a unique equation of state.

is composed (hydrogen bonding, polar, general

[dispersion], or void).
Second, Panayiotou derives an equation of state (an
algebraic representation of the effects of the model at
the macro-level) based on the micro-level details of his
model.
The EOS used by Panayiotou to describe all the
molecules of his model is Equation C7-1.

 
  

 
1
1
1
 vH


Pred T red  ln 1 
V red
V red
r



 


z
1
q
z
 ln 1 
 lnhG00 i


2
V red
r  V red
2

0
C7  1
2

In this equation, the parameters r, s, vH , z, q, and G00

refer to various numerical descriptors of the nature of
the model representing the collection of molecules.
These descriptors refer to the number of bonds of
various types, the number of void locations in the
model, the size of each molecule, and the probability
of nding a specic molecular characteristic at

2
For example (in Equation C7-1), vH is the volume change upon
hydrogen bond formation, r is the number of segments per molecule, s is
the surface to volume fraction of each molecular segment, and q is the
product of r times s. In addition, G00 is a parameter representing the
chosen degree of randomness. The parameter z is a site identier called
a lattice coordination number. Panayiotou calls his EOS an NRHB
(nonrandom hydrogen bonding) EOS.

622

Third, Panayiotou estimates those numerical

descriptors (adjustable parameters, also referred to as
scaling constants) in the EOS. He derives from the EOS
(Equation C7-1) the thermodynamic equations for the
latent heat of vaporization, vapor pressure, and the
liquid and gas densities (as well as the dipole moment)
for any liquiddbased on the scaling constants and the
equation form. Then he uses measured data3 for those
and other thermodynamic properties to estimate values
of the scaling constants for each solvent of interest4.
Because there are multiple adjustable parameters and
multiple measured properties, there is some statistical
regression analysis necessary to select the best values of
those adjustable parameters.
Fourth, with an equation of state and values of its
adjustable parameters for a variety of solvents,

Panayiotous main source of data was the critical compilation DIPPR

(Design Institute of Physical Properties) for the thermodynamic data and
the dipole moments of the studied uids. Appendix C5, Endnote B has
more information.
4
Every solvent has unique values of the scaling constants in the same
EOS.

Estimation of HSP from an Equation of State

C7

Appendix

Conceptional Diagram of Computation of HSP from Equation of State

Figure C7-1 Conceptional Diagram of Computation of HSP from Equation of State

Panayiotou can use the EOS to calculate the three

solubility parameters for any one of a considerable
variety of solvents. Their dening equations are known
from Equations 2.5 and 2.6. Panayiotou also repeated
the work with pressure-volume-temperature (PVT) data
for high molecular weight polymers.

C. CALCULATED OUTCOMES VS.

ACCEPTED HSP VALUES
As with Figures C6-1 through C6-4 in Appendix C6, for
calculation of the three HSP values with correlations and the
Pythagorean theorem, corresponding gures can be drawn
for calculation of the three HSP via Panayiotous equation of
state method. They show a considerably improved reproduction of the experimentally derived (mostly) values from
the reference of Chapter 2, Endnote I, Dr. Hansen's published database.
The Hildebrand (TOTAL) Solubility Parameter in Figure
C7-2 is calculated from Equation C7-1 using Panayiotous

Figure C7-2 Prediction of the Hildebrand Solubility

Parameter

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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.

Estimation of HSP from an Equation of State

properties (the information) into it so that other thermodynamic properties (the three HSP) can be directly
calculated.
Panayiotous work provides a critical conrmationI. He
has found that an analysis of molecular characteristics
using thermodynamic equations provides the same
outcome as does a measurement of turbidity in a soilsolvent mixture.

Endnotes
A. Others are Dr. Hansen (of course, charles.hansen@get2net.dk),
Professor Steven Abbott of the University of Leeds (steven@
stevenabbott.co.uk), and Dr. Hiroshi Yamamoto (http://pirika.com/
CV.html).
B. Of the Department of Chemical Engineering, University of
Thessaloniki, 54124 Thessaloniki, Greece.
C. Stefanis E, Tsivintzelis I, Panayiotou C. The Partial Solubility
Parameters: An Equation-of-State Approach. Fluid Phase Equilibria.
2006;240:144e154.
D. Panayiotou C, Pantoula M, Stefanis E, Tsivintzelis I, Economou I.
Nonrandom Hydrogen Bonding Model of Fluids and Their
MixturesdPure Fluids. Industrial Engineering Chemical Research.
2004;43:6592e6606.
E. Panayiotou C. Solubility Parameter Revisited: An Equation-of-State
Approach for Its Estimation. Fluid Phase Equilibria.
1997;131:21e35.
F. Chapter 2, Endnote I; Dr. Hansen's published database.
G. Panayiotou C, Sanchez IC. Hydrogen Bonding in Fluids: An
Equation-of-State Approach. Journal of Physical Chemistry.
1991;95:10,090e10,097.
H. Panayiotous work is valuable, but not unique. Others have taken
the same approach with other objectives than prediction of HSP.
A recent reference where a model is proposed and an EOS is based
on it is: Xu X, Liu H, Peng C, Hu Y. A New
Molecular-Thermodynamic Model Based on Lattice Fluid Theory:
Application to Pure Fluids and Their Mixtures. Fluid Phase Equilibria.
2008;265:112e121.
I. In continuing works, Panayiotou has expanded the technology of
solubility theory (and non-solubility theory) to include both past efforts
not well known (Martire DE. Analytical Chemistry, 1961;33:

C7

Appendix

1143e1147) and current efforts only well used and understood by

practitioners of quantum mechanics (Stefanis E, Panayiotou C.
International Journal of Pharmacology, 2012;426:29e43.
Using tools of modern chemical thermodynamics, Panayiotou (and
collaborators) have split the hydrogen bonding solubility parameter,
dhb, into its acidic and basic components, da and db, respectively,
leaving intact the HSPs for dispersion and polarity, dd and dp,
respectively, and preserving their adherence to cohesive energy
density (Equation 2.2). However, all known methods for splitting dhb
into its acidic and basic components are not predictive methods and
have as a prerequisite knowledge of the overall value of dhb itself (C.
Panayiotou, Phys. Chem. Phys. 2012;14:3882e3908).
In subsequent work, Panayiotou (and supporters) have bypassed this
difculty by turning to the tools and principles of quantum mechanics
from which multivariable linear and non-linear quantitative
structureeproperty or structureeactivity relationships can be derived.
Far outside the scope of this book (A. Klamt, COSMO-RS from
Quantum Chemistry to Fluid Phase Thermodynamics and Drug Design,
Elsevier, Amsterdam, 2005), this approach to chemical
thermodynamics allows a restatement of Equation 2.7) with separate
solubility parameters for the acidic and basic components of the
hydrogen bonding solubility parameter (producing four different
solubility parameters, ala the approach related in footnote 43 of
Chapter 2). In this, Panayiotou relies on the formulations of acidic and
basic contributions to hydrogen bonding of Abraham (A.M. Zissimos,
M.H. Abraham, A. Klamt, F. Eckert, J. Wood, J. Chemical Information
Computer Science 2002;42:1320e1331.)
Essentially, the EOS approach described in this appendix is being
surmounted by an approach based on an attempt to quantify the
individual interatomic and intermolecular interactions which are
collectively described in an EOS without adjustable parameters.
As of publication of this book, the most current references
demonstrate progress (C. Panayiotou, Journal of Chemical
Thermodynamics, 2012;51: 172e189) in a priori prediction of the
three solubility parameters devised by Hansen (Equation 2.6 and
beyond) for solvents with a variety of measured hydrogen bonding
solubility parameters, and of a modest variety of polymers
(C. Panayiotou Polymer, 8 march 2013;54(6):1621e1638). In so
doing, it may be possible to resolve the comprehensive difculty
graphically expressed in Figures 2.19 to 2.32. In is interesting to note
that the point of validation or reference for these works is
measurements of solubility upon which the validity of Hansen
Solubility Parameters are derived and conrmed.

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