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Appendix

| A3 |

Derivation of Blend Rule for


Solubility Parameters
In this authors opinion the most technically correct blend
rule can be derived from Equation 2.3. The derived equation
is based solely on a balance of energy, as will be shown below.
It remains to be seen whether this rule is more useful in
practice.
Using Equation 2.3 for any single solvent, the total
dispersion, polar, or hydrogen bonding energy of a blend
is equal to the sum of these respective energies for each of
the components. That energy balance is stated as Equation
A3-1, for four components in a blend.
X

Equation A3-1 is valid with any number of components.


It represents the energy content associated with the
application of any single type of intermolecular force. The
units used in Equation A3-1 are those of energy.
To use Equation A3-1, one needs to know the amount
(molar quantity) of each component present in the blend,
and the value of the type of energy that is associated with
that component. Energies, of all types, are normally

Total Energyany blend Energyany 1 Energyany 2 Energyany 3 Energyany 4 .

For the three types of solubility parameters (disperse,


polar, and hydrogen bonding), there are three identical
versions of Equation A3-1. The subscript any refers to
any one of the three types of cohesive energy (Box A3.2)d
disperse, polar, and hydrogen bonding. The number subscript refers to the component number. The left-hand term in
Equation A3-1 is any one of the three right-hand terms in
Equation 2.3.
In other words, there is only one blend rule for solubility
parameters. It may be used with any single solubility
parameter1.


with the blend than the sum of that contributed by its


components2.

Equation A3-1 means simply that the total energy (E


in Equation 2.3) from any of the three types of
intermolecular force within the blend is the sum of the
energy associated with that type of intermolecular force
contributed by each blend component. There is no
more and no less cohesive energy of any type associated

1
The word any, used as a subscript, refers to any solubility parameter,
Hansen, Hildebrand, Hoy, etc.; or disperse, polar, or hydrogen bonding.

A3  1

Box A3.1 The Linear Blend Rule


P
dany fvi  di g
Linear Blend rule
The linear blend rule (above) has been used successfully
for the past 40 years. It has the merit of simplicity3 and
perhaps the assumptions behind solubility parameters dont
warrant a more complex formula.

2
It is this authors belief that the linear blend rule was chosen on the
basis of two factors: (1) Simplicity of calculation when personal
computers and spreadsheets hadnt yet been invented, and (2) that the
form of the blend rule wasnt signicant when the values of the solubility
parameters were similar.
3
To combine the three solubility parameters, one uses Equation 2.6.

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Appendix

A3

Derivation of Blend Rule for Solubility Parameters

Box A3.2 About Cohesive Energy


Cohesive energy, normally expressed as a volumetric density
as in Equation 2.5, is the energy needed to:


Totally separate molecules from one another, whether they


be of a single component or of a mixture of components;
Overcome all the intermolecular forces acting over the
distance of separation between molecules of the same or
different types; and
Essentially vaporize all the liquid molecules into the vapor
phase.

Cohesive energy is not the energy (heat) of mixing.


Cohesive energy includes the heat of vaporization, which is
not included in the energy accounting which allows
calculation of the heat of mixing.
Heat of mixing is that energy (enthalpy) which is required
to produce a solution. For most solvent mixtures, as well as

expressed on a molar basis, i.e. BTU per pound mole,


calories per gram-mole, or kilojoules per kilogram-mole:



The amount of each component present is represented


by its mole fraction, mi.
The individual values of any type of cohesive energy are
represented by Eany i.

Equation A3-1, for four components, and energy associated with any type of intermolecular force, can be restated
as Equation A3-2.
X



Total Energyany blend m1  Eany 1 m2



 Eany 2 m3  Eany 3


m4  Eany 4 .
A3  2

dany blend

dany blend

restated for the solvent blend as Equation A3-3, for any


type of cohesive energy (Box A3.2).
The molar volume of a solvent blend is always taken
to be the algebraic sum of the molar volumes of the
individual blend components multiplied by the molar
amount of each present. This means one assumes that
there is no volume change on mixing. The assumption
is stated, for four or more blend components, as
Equation A3-4.
Vmblend v1  Vm1 v2  Vm2 v3  Vm3
v4  Vm4 .
A3  4
Combining Equations A3-4 and A3-2 into
Equation A3-3, one obtains Equation A3-5 (for a four or
more-component blend).

s
 
 
 
 
m1  Eany 1 m2  Eany 2 m3  Eany 3 m4  Eany 4 .
Vmblend 

s
Total Energyany blend
Molar Volumeblend

sP
Eany blend

Vmblend
A3  3

To implement this energy balance, one recalls Equation


2.2dthe denition of a solubility parameter. This is

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polymer-solvent solutions, the heat of mixing is endothermic


(positive)dmeaning that heat is required to produce the
solution. In this case, the total energy of the system has
increased because energy was added.
Heat of mixing is an overall parameter which includes
all three intermolecular forces. When the Total (Hildebrand)
Solubility Parameter of a solvent exactly matches that of
another solvent or of a polymer, the heat of mixing is zero.
For a summary of the interactions between cohesive
energy, heat of mixing, and surface energy, see Gardon JL.
Critical Review of Concepts Common to Cohesive Energy
Surface Tension, Tensile Strength, Heat of Mixing, Interfacial
Tension, and Butt Joint Strength. Journal of Colloid and
Interface Science, 1977;59(3):582e596.

2

Total Energyany i Vmi  dany i

A3  5

A3  6

Equation A3-3 also applies for any type of cohesive energy


for a single component. It can be restated as Equation A3-6
in terms of cohesive energy, and then combined with
Equation A3-5 to produce Equation A3-7.

Derivation of Blend Rule for Solubility Parameters

dany blend

A3

Appendix

s

 
 
 
 
m1  Vm1  fd1 g2 m2  Vm2  fd2 g2 m3  Vm3  fd3 g2 m4  Vm4  fd4 g2 .

Vmblend
A3  7
vi  ri
Mi
mi P v 
ri
i
Mi

A2  6

Next, one can substitute two relationships into Equation


A3-7:



For the mole fraction of the ith component, mi, using


Equation A2-6 from Appendix A2, and
Using the denition of molar volume from Appendix
A2, Table A2-1.
Vm

M
r

The result, for four components, is Equation A3-8.

dany blend

Equation A3-8 can be simplied (fortunately), for a fourcomponent blend, to Equation A3-9, by performing algebraic manipulations (canceling the molecular weights and
densities) in each of the terms in the numerator and
recognizing that the two terms in the denominator are the
inverse of one another (both are the blend molar volume),
and so cancel.
The blend rule for any solubility parameter used in this
book is Equation A3-74.
q
X
A3  7 (or) A3  9

dany
vi  di 2
The point of this Appendix is to recognize that the
HSP blend rule, Equation A3-9, is an energy summation (balance)dfor any of the three types of cohesive




u
v  r
M
v 2  r2
M2
v 3  r3
M3
v 4  r4
M4
1
1
u
1

 d1 2

 d2 2

 d3 2

 d4 2
u
u
M1
r1
M2
r
M3
r3
M4
r4
2


u
t
P v i  ri
P v i  Mi

Mi
ri

A3  8

dany blend

X
 
 


v 1  d1 2 v 2  d2 2 v 3  d3 2


v4  d4 2 or Equation A2-7
for four components

energy associated with the respective intermolecular


forces.

A3  9

4
An answer to the question of whether or not the energy balance as
Equation A3-1 is valid for so-called ideal uids and non-ideal uids is
beyond the scope of this book.

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