Appendix

C5

Estimation of HSP from Correlations

Note in Figures C5-11 and C5-12 how the orientation

of the solvent differs when a soil is present (Figure
C5-12, n-propyl bromide) compared to when the
solvent is not contaminated with a soil (Figure C5-11,
acetic acid).
All of these effects on the polar (and hydrogen bonding)
solubility parameters are difcult if not impossible to
predict quantitatively, hence estimates of the polar (and
hydrogen bonding) solubility parameters are always going
to be limited by:



Not knowing the environment in which the solvent

molecules reside, and
Knowing that this environment is likely to change as
new materials (such as soils) are added or removed.

Because of this, calculations of the polar (and hydrogen

bonding) HSP values are going to be an inferior representation of the character of a solution relative to measured
HSP values from solubility experiments such as those of
Appendix C9.
Furthermore, the calculated values are likely to differ
depending upon the assumptions made about the nature
of the environment in which the molecules are found
(Box C5.2).

C.3. Calculation of the Polar

Solubility Parameter
Characterization of the effect of point polar sources in
solvent molecules has been done in parallel with solubility
parameters by Professor Hildebrand and others.

Box C5.2 About Values of Dipole Moment

Specic data regarding the way dipole moments of
solvents are related to solvent structure as well as the
environment around the solvent can be found in: Bttcher
CJF. A Method for Calculating the Dipole Moment of
a Free Molecule from Data of the Pure Dipole Liquid.
Physica. 1939;6(1):59e81.
For acetone, values of dipole moment are: In the gas
phase, measured as 3.0; for dilute solution, measured as 2.7
to 2.8; and calculated as 3.0 to 3.1.
For acetonitrile, values of dipole moment are: In the gas
phase, measured as 3.9; for dilute solution, measured as 3.1
to 3.5; and calculated as 3.6.
For ethanol, values of dipole moment are: In the gas
phase, measured as 1.7; for dilute solution, measured as
1.7; and calculated as 2.8 to 3.1.
For water, values of dipole moment are: In the gas phase,
measured as 1.8 to 1.9; for dilute solution, measured as 1.7
to 2.0; and calculated as 3.0 to 3.1.

608

In 1952, Dr. Carl Johan Friedrich Bttcher14 publishedD

an empirical equation for the energy transfer (work) associated with the contribution of permanent dipoles to the
energy of a liquid or a gas.
The equation is shown below as Equation C5-2. The
terms in Equation C5-2 are , the solvent dielectric
constant15 (dimensionless), n, the solvent refractive index
for the sodium D-line (dimensionless), and m, the solvent
dipole moment (in debyes, D). The units of Equation C5-2
are calories.
Work of Energy Transferh

12;108   1  n2 2  m
n2 2
C5  2

If this equation were combined with Equation 2.2 (the

general form of a solubility parameter being the square
root of energy transfer divided by molar volume) or
Equation 2.5 (the same form for each of the three types of
intermolecular force), an equation for the polar solubility
parameter would result, as shown in Equation C5-3.
spolar

s
12;108   1  n2 2  m

n2 2   Vm

C5  3

While useful for the purposes of Dr. Bttcher and other

scientists, Equation C5-316 is nearly useless for those
wanting to know something about cleaning solvents,
because it requires knowledge of three solvent properties
which are seldom known without performing complex
measurements, namely the dielectric constant, refractive
index, and dipole moment. Molar volume is commonly
known via solvent molecular weight and density, and
representative values are listed in Table C5-4.
In 1971, Dr. Hansen and A. Beerbower simplied
Equation C5-3 into Equation C5-417 by recognizing that
several terms in Equation C5-3 could be approximated by
constants for many solvents.
spolar

s r
12;108   1  n2 2
m


n2 2 
Vm
r
m
z37:4 
C5  4
Vm

Frits Bttcher was born in 1915 and received his doctorate in

physical chemistry from the University of Leiden (The Netherlands) in
1932. With some 30 others, he was a founder in 1968 of the club of
Rome whose mission is to act as a global catalyst of change that is
free of any political, ideological or business interest. Frits Bttcher is,
in his country, a well known skeptic about the greenhouse effect.
15
Ref. 1, Chapter 3, Section 2.
16
The units for spolar in Equation C5-3 are (calories/cc)1/2. One converts
to the units of this book (MPa1/2) by multiplying (calories/cc)1/2 by
2.0455.
17
Revised calculations by this author using 633 updated data points,
propose a value of 36.1 to replace the value of 37.4.
14