Appendix

| C8 |

Estimation of HSP from Group Contribution

Methods
Group contribution methods are calculation schemes not
based on the specic atomic composition of a solvent or its
specic physical properties, but totally on how those atoms
are arranged in functional groups.

A. RELATIONSHIP TO OTHER
METHODS

By way of comparison:

The model upon which an equation of state (EOS) is

based, as described in Appendix C7, is an attempt to
characterize a solvent by the atomic elements of which
it composed, and how they are bonded and interact
together. This is an atomic-scale view, which can be
complicated to understand, but it allows those familiar
with this science to test very specic hypotheses about
the way in which atoms interact together in a solvent
molecule, and how the solvent molecules interact with
one another and with soil molecules. Knowledge of
thermodynamics is essential. The adjustable parameters
(constants) in the methods are found by comparing the
model prediction of measurable thermodynamic
properties to the actual measurements for each solvent,
and adjusting the parameters so that the measured
thermodynamic properties are computed for each solvent
or polymer or polymer solution.
Methods based on correlations, discussed in Appendix
C5, are quite different than EOS or group contribution
methods because they are based on the totality of the
characteristics of a entire solvent molecule, such as
acetone (Figure C8-1). Recall that correlation-based
methods are a molecular-scale view of a solvent, dont

require knowledge of thermodynamics or

thermodynamic properties, may be partially derived
from solubility data, and are relatively easy to
understand.
Methods based on solubility measurements, related in
Appendices C2 through C4, are the original basis
for comparing solvents. These methods reect
a users view of the solvent, and are very easy to
understand.
Group contribution methods are an attempt to
characterize a solvent by the specic ways in which the
atoms of which it is composed are present and
interconnected. This is a functional group-scale view that
is fairly easy to understand. No knowledge of
thermodynamics is required. The adjustable parameters
in the methods are found by regression analysis of
many data points of the three solubility parameters
from many different solventsdnot one specic solvent
as is done with an EOS.

These four methods for estimating HSP values dont

share the same history: solubility-based and correlationbased methods evolved chiey in the 1960s through to
the millennium, group contribution methods evolved
chiey in the 1970sA until now (2012), and EOS methods
evolved during the decade of the writing of this book
(2002e2012).

Figure C8-1 Acetone

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