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.