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Appendix

C8

Estimation of HSP from Group Contribution Methods

Table C8-11 Functional Groups Representing Isopropanol

Hoy

Stefanis Panayiotou

Neural Network

Group 1

CH3 (2X)

CH3 (2X)

iso_Pr

Group 2

>CH

>CH

2_OH

Group 3

pOH

OH

The molecule propane has zero polar HSP (there are no


polar centers) and zero hydrogen bonding HSP (there
are no OH groups); while the molecule isopropanol
has both.
Its the same CH3 group in both chemicals.

So while one might expect the group contribution


constants for polar and hydrogen bonding HSP for the CH3
group to be zero, they are not. Values listed in Table C8-5
for the SP method are 1.6444 and 0.7458 respectively.
Consequently, calculation of the polar and hydrogen
bonding HSP for parafnic hydrocarbons will not produce
the correct value (zero).
Certainly, this aw is also common to the CH2 and CH<
groups, as well as similar functional groups.

Endnotes
A. Table 1.1 of the reference of Chapter 2, Endnote I has more information
which was developed from the following reference: Beerbower A.
Environmental Capability of Liquids, in Interdisciplinary Approach to
Liquid Lubricant Technology. NASA Publication SP-318, 1973:365e431.
B. Choi P, Kavassalis TA, Rudin A. Estimation of the Three-Dimensional
Solubility Parameters of Alkyl Phenol Ethoxylates Using Molecular
Dynamics. Journal of Colloid Interface Science. 1992;150:386.
C. Dr. Hansen describes the use of critical properties in Chapter 1 in the
reference in Chapter 2, Endnote I.
D. Lydersen AL. Estimation of Critical Properties of Organic Compounds.
Univ. Wisconsin Coll. Eng., Engineering Experimental Station Report.
Vol. 3, Madison, WI, April 1955.
E. Ambrose D. Correlation and Estimation of Vapor-Liquid Critical
Properties. I. Critical Temperatures of Organic Compounds. National
Physical Laboratory Report in Chemistry, Report No. 92, 1e35, 1978.
See also. Perrys Handbook of Chemical Engineering. 6th ed. Section
2, Page 340, Equation 2e1.
F. Joback KG, Reid RC. Estimation of Pure-Component Properties from
Group-Contributions. Chemical Engineering Communications.
1987;57:233e243.
G. Hansen CH, Abbott S, Yamamoto H. Hansen Solubility Parameters in
Practice, 2012; available for purchase including an e-handbook at
http://www.hansen-solubility.com.
H. Miller-Chou BA, Koenig JL. A Review of Polymer Dissolution. Progress
in Polymer Science. 2003;28:1223e1270.
I. Dunkel MZ. Calculation of Intermolecular Forces in Organic
Compounds. Journal of Physical Chemistry. 1928;138:42e54.
This reference predates Hildebrands work and considers internal
energy as an additive property for small molecules, but does not derive
a solubility parameter per se. Dunkel considered that the heat of
vaporization (Equation 2.4) could be estimated for a solvent molecule
by a group contribution approach based on the functional groups
within that molecule.

644

J. Small PA. Some Factors Affecting the Solubility of Polymers. Journal of


Applied Chemistry. 1953;3:71e80.
This reference also predates Hansens work and considers
a parameter noted as a molar attraction constant. Smalls
parameter is the square root of the product of (molar cohesive
energy times molar volume). Molar cohesive energy is essentially
the numerator in Equation 2.1, and may be considered to be the
internal energy change on vaporization.
Smalls work was based on that of Scatchard (Scatchard G.
Equilibrium in Nonelectrolyte Mixtures. Chemical Review.
1949;44:7e35.) which had previously shown that the square root
of (molar cohesive energy times molar volume) was additive for
mixtures of compounds (solvents).
Small thus considered that his molar attractive constant might be
additive within compounds on an atomic and constitutive basis.
Small does not propose a solubility parameter per se, but his
results were used by Hoy (and others) as a component of an
independent approach to formulate a total solubility parameter,
as in Equation 2.7.
K. Fedors RF. Method for Estimating Both the Solubility Parameter and
Molar Volume of Liquids. Polymer Engineering Science.
1974;14:147e154. Fedors applies Smalls method to a larger number
of functional groups to achieve estimates of both molar cohesive
energy and molar volume. Fedors does propose a total or overall
solubility parameter, but does not fractionate it as did Hansen.
L. Hoy KL. New Values of the Solubility Parameters from Vapor Pressure
Data. Journal of Paint Technology. 1970;42:76e118 and Hoy KL.
Solubility Parameter as a Design Parameter for Water Borne Polymers
and Coatings. Journal of Coated Fabrics. 1989;19:53e67.
Hoy proposed three solubility parameters similar to but not identical
to that of Hansen (Appendix C10).
Hoy combined vapor pressure data to estimate the heat of
vaporization (see Equation C6-2), and then uses Fedors group
contributions for both heat of vaporization and molar volume to
calculate a solubility parameter.
Use of Hoys three solubility parameters is implemented in
a commercial product which can be found at http://www.
compchemcons.com/products/Hoy/hoy_theory.html. Hoys
parameters can also be computed using the commercial product
noted in Appendix C10, Endnote C.
M. Beerbower A. Environmental Capability of Liquids, in
Interdisciplinary Approach to Liquid Lubricant Technology. NASA
Publication SP-318, 1973: page 374, Table 2. The values from
this reference have been updated by Hansen in Ref. 159 (Table
1.1) and should be used in preference to those from the original
reference.
N. van Krevelen DW, Hoftyzer PJ. Properties of Polymers: Their
Estimation and Correlation with Chemical Structure. Elsevier,
Amsterdam, 2nd Ed. 1976. van Krevelens approach leads to
three individual solubility parameters, as does Hansens and
Hoys; but van Krevelen develops three separate group
contribution parameters, each with a different dening equation
for their use. The equations are for the disperse parameter:
P
Gdi
dd
;
V