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Intermolecular forces
The molecules within a liquid crystal are attracted to one another through
intermolecular forces. The intermolecular forces acting between the molecules
are moderately strong. These forces are not strong enough to give the substance
rigidity, so that this fluid will conform to the shape of its container.
They are of sufficient strength to give a liquid crystal resistance to
increase it surface area (surface tension) and resistance to flow (viscosity).
Surface tension is caused by a balance between cohesive forces between
the molecules within the liquid and adhesive forces between these molecules
and other types of molecules at the liquid's interface, increasing with
the strength of the attractive intermolecular forces. Viscosity also increases
with the strength of the cohesive intermolecular forces. The width, length
and arrangement of the liquid crystal's constituent molecules also affect
viscosity, where large and long molecules can entangle each other.
The discussion above is macroscopic, continuum description of forces
acting within a liquid crystalline substance. At the discrete level, the
intermolecular forces acting between individual molecules, can be subdivided
5 categories. These forces and their relative strength to that of a typical
covalent or ionic chemical bond is listed below:
| Intermolecular Force |
Relative Strength |
| Ion-dipole |
3% to 10% |
| Ion-induced dipole |
0.1% to 1% |
| Hydrogen-bonding |
3% to 10% |
| Dipole-dipole |
0.2% to 0.8% |
| Dipole-induced dipole |
0.0006% to 0.02% |
| London Dispersion |
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Ion-dipole
Ions form within a liquid medium where electrolytic species are
dissolved. In the presence of ions, a polar molecule will attempt
to align itself in the direction of the ion. It will point the
partially charged end that is opposite to that of the ion (i.e.,
partial positive end towards negative ion and partial negative
end towards positive ion). The strength of this interaction depends
on the dipole moment (µ) of the polar molecule, the charge
of the ion (Q), the angle of alignment ( ),
and the distance separating them (R).
Alignment of a polar molecule to a negative ion.
Alignment of a polar molecule to a positive ion.
This interaction is especially important in solutions of ionic substances
in a liquid solvent composed of polar molecules. An example of such a solution
is salt in water.
Ion-induced dipole
The electrostatic field of an ion can also polarize a neighboring neutral atom
or molecule distorting the latter's electron distribution. The
polarized species will be attracted to the ion. The strength of
this interaction depends on the polarizability ( )
of the atom or molecule, the charge of the ion (Q), and the distance
between them (R).
Electron distribution of a neutral
atom polarized by a negative ion.
Electron distribution of a neutral atom polarized
by a positive ion.
This interaction, which varies as 1/R4, is short-ranged.
Dipole-dipole
Certain molecules develop permanent dipole moments either from uneven
distribution of charges within their bonds or due to their shape. Neighboring
polar molecules will attempt to align themselves to each other such that
the ends of one molecule align toward the end of another molecule that
has opposite partial charge to maximize the attractive interaction between
them. In a liquid, the polar molecules are free to move with respect to
one another, sometimes having attractive and at other time repulsive interactions.
The net effect, averaged over time, the interactions are attractive.
Alignment of polar molecules to each other.
Opposite ends attract.
The strength of this interaction depends on the magnitude of
the permanent dipole moments ( A, B),
the angles of alignment ( A, B, A, B),
and the distance (R) between the molecules. This type of
interaction weakens with increasing distance between the polar
molecules and also weaken at high temperatures where random thermal
energy cause bigger fluctuations in their alignment. This
is the strongest type of intermolecular interaction possible between
two neutral molecules. It is at best comparable to ordinary
thermal energies and is much weaker than the energies of covalent
bonds.
Dipole-induced dipole
The electrostatic field emanating from a polar molecule, though weak
compared to an ion, can also polarize another atom or nonpolar molecule.
Electron distribution of a neutral atom polarized
by a polar molecule.
The strength of this interaction depends on the magnitude of
the dipole's permanent moment ( A),
the polarizability of the other atom or molecule ( B),
the angle of alignment ( A)
between the dipole and the polarized species, and the distance
(R) between them. Bigger atoms and molecules are more susceptible
to the polarization of their electron distribution because these
electrons are farther from their atomic nuclei. Because
of the 1/R6 dependence of this interaction is exceeding
weak until the species come into contact with one another.
Hydrogen-bonding
Hydrogen bonds are special dipole-dipole interactions between two molecules.
In these situations a hydrogen atom attached to an electronegative atom,
through a polar covalent bond of one molecule, aligns with the unshared
lone electron pair of an electronegative atom on another neighboring molecule.
The configuration of a hydrogen-bond is:
X - H --- Y
The atom X is covalently bonded to the hydrogen atom through a single
bond. The dashed line represent the interaction of X through the
hydrogen to Y on another molecule.
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Typical electronegative atoms: X or Y
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Nitrogen N
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Oxygen O
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Fluorine F
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Chlorine Cl
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The strength of these interactions varies from 4 Kilojoules (KJ) up
to 25 KJ. Although the strongest hydrogen-bonding interactions are
only about 12% that of a covalent chemical bond, they are significantly
stronger than the typical dipole-dipole and dispersion forces. This
interaction plays a significant role in the varies properties of water
such as its high boiling point and its subtle blue tinge in color.
It is also responsible for holding our genetic material (DNA) together.
London dispersion
This force is very weak but is present between all atoms and molecules
regardless of their nature. This is due to random fluctuation of an atom's
electronic distribution with time, producing an instantaneous, but transient
dipole moment. This moment would induce nearby atoms or molecules to polarize
and become attracted each other. The behavior of this interaction
is rather complex, a reasonable approximation is given by:
The strength of this interaction between species increases with
their size. In general, the larger the molecule, the farther its
electrons are away from their nuclei, and, consequently the greater
its polarizability ( A, B).
The interaction also increases in strength with the frequency
of the electronic fluctuation ( A, B)
and the distance between them (R). The interaction is significant
only at contact distances, due to its 1/R6 dependence.
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