Ideal Solubility Parameters

Ideal Solubility Parameters
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Regular Solution Theory
Solubility Parameter
Ability of a liquid to act as a solvent is called solubility parameter.
Advantage
Prediction of excess free energy of mixing
Limitations
Can not predict thermodynamic properties like
1. Heat of solution
2. Volume after mixing
Applications of Solubility Parameters
1. Selection of solvent
2. Preparation of polarity scales
3. Cosolvency Power determination
4. Chemical kinetics determination
5. Determination of mechanism involved in drug action
6. Structural Activity Relationship (SAR)
7. Drug transport through model Membranes
8. Help in designing drug delivery systems of poorly soluble drugs
Types of Solubility Parameter
Solubility parameter is of two types
1. Hildebrand Solubility Parameter and
2. Hansen Solubility Parameter
1.Hildebrand Solubility Parameter
Hildebrand reported that both physical and chemical bonds in any material e.g.,
Van der Waals interactions, covalent bonds, hydrogen bonds, ionic bonds.., etc.,
are a calculative value.
The sufficient energy needed to overcome all these forces and allow a molecule
(or an atom) to be pulled away from the whole assembly is called cohesion
energy.
By dividing this value by molar volume we get the cohesion energy density or
Solubility parameter (δ).
Hildebrand solubility parameter describes the degree of solubility for nonpolar
or slightly polar substances without hydrogen bonding.
It also describes the amount of energy required to evaporate one-unit volume
of a liquid.
When two materials have the same or relatively close solubility parameters, it
means they are miscible in each other.
One of the first attempts to develop a system to describe solvents and the substances they solubilise is the
Hildebrand solubility parameter.
The Hildebrand solubility parameter is defined by the following equation:
δ = (E coh) = ΔHvap – RT /Vm

δ =√ E coh = [ΔHvap – RT /Vm]1/2
Where
Ecoh is the cohesive energy density (the cohesive energy density of a liquid is a numerical value that indicates
the energy of vaporization in calories per cubic centimeter, and is a direct reflection of the degree of van der
Waals forces holding the molecules of the liquid together).
ΔHvap is the heat of vaporization(also known as the enthalpy of vaporization, is the amount of energy that
must be added to a liquid substance, to transform a quantity of that substance into a gas);
R is the universal gas constant;
T is the absolute temperature; and
Vm is the molar volume(the molar mass (M) divided by the mass density (ρ)).
The cohesive energy density is defined as the energy needed to break all attractive interactions in one mole
of a solvent divided by the molar volume.
• Interestingly, this correlation between vaporization and van der Waals
forces also translates into a correlation between vaporization and
solubility behaviour.
• This is because the same intermolecular attractive forces have to be
overcome to vaporize a liquid as to dissolve it.
• This can be understood by considering what happens when two liquids
are mixed: the molecules of each liquid are physically separated by the
molecules of the other liquid, similar to the separations that happen
during vaporization.
• The same intermolecular van der Waals forces must be overcome in both
cases.
• Since the solubility of two materials is only possible when their
intermolecular attractive forces are similar, one might also expect that
materials with similar cohesive energy density values would be miscible.
• This is in fact what happens.
2. Hansen Parameter
• Hansen assumed that total cohesion energy is the sum of dispersion ED,
polar EP, and hydrogen bond energy EH
E T = E D + E P + EH
• Dividing this by the molar volume gives the square of the total (or
Hildebrand) solubility parameter as the sum of the squares of the
Hansen D, P, and H components.
δT2 = δ D2 + δP2 + δH2
• And by dividing both sides of the equation by molar volume V, we will

have the total Hansen solubility parameter
• ET/V = ED/V + EP/V + EH/V
2. Hansen Parameter
• Hansen solubility parameters by Charles M. Hansen 1967 as a way of
predicting if one material will dissolve in another and form a solution.
• They are based on the idea that like dissolves like where one molecule is
defined as being 'like' another if it bonds to itself in a similar way.
• Specifically, each molecule is given three Hansen parameters
1. δ D is the energy from dispersion forces between molecules
2. δ P is the energy from dipolar intermolecular force between molecules
3. δ H is the energy from hydrogen bonds between molecules.
2. Hansen Parameter
These three parameters can be treated as co-ordinates for a point in three
dimensions also known as the Hansen space.
The nearer two molecules are in this three-dimensional space, the more
likely they are to dissolve into each other.
To determine if the parameters of two molecules (usually a solvent and a
polymer) are within range, a value called interaction radius (R0) is given
to the substance being dissolved.
This value determines the radius of the sphere in Hansen space and its
center is the three Hansen parameters.
To calculate the distance (Ra) between Hansen parameters in Hansen
space the following formula is used
2. Hansen Parameter
Combining this with the interaction radius gives the relative

energy difference (RED) of the system:
RED = Ra-R0
RED < 1 the molecules are alike and will dissolve

RED = 1 the system will partially dissolve
RED > 1 the system will not dissolve
Methods to determine Ideal solubility Parameters

Ideal Solubility Parameters

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Ideal Solubility Parameters

δ = (E coh) = ΔHvap – RT /Vm

δT2 = δ D2 + δP2 + δH2

• And by dividing both sides of the equation by molar volume V, we will

Combining this with the interaction radius gives the relative

RED < 1 the molecules are alike and will dissolve

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