Physical properties
6.1 Polymorphism, crystal structure and melting point
In the solid state, long-chain compounds frequently exist in more than one
crystalline form and consequently have more than one melting point. This
property of polymorphism is of both scientific and technical interest.
6.1.1 Alkanoic and alkenoic acids
The melting points of acids with an even number of carbon atoms
in the molecule and their methyl esters plotted against chain-length fall on
smooth curves lying above similar curves for the odd acids and their methyl
esters. Odd acids melt lower than even acids with one less carbon atom. The
two curves for saturated acids converge at 120 - 125°C.
6.1.2 Glycerol esters
For most technical purposes the melting behaviour of triacylglycerols is more
important than that of fatty acids. It has long been known that fats show
multiple melting points, and as far back as 1853 glycerol tristearate was
reported to have three melting points at 52, 64 and 70ëC. When the melt of a
simple triacylglycerol is cooled quickly it solidifies in its lowest melting form
(α) with perpendicular alkyl chains in its unit cell (the angle of tilt is 90ë).
When heated slowly this melts but, held just above this melting point, it will
re-solidify in the β ' crystalline form. In the same way a more stable β form
can be obtained from the β ' form. The β form has the highest melting point
and is obtained directly by crystallisation from solvent.
6.2 Spectroscopic properties
6.2.1 Ultraviolet spectroscopy
The use of ultraviolet spectroscopy in the study of lipids is confined to
systems containing or generating conjugated unsaturation. It is therefore of
value in the study of natural acids with conjugated unsaturation such as the
dienes, trienes, tetraenes and acetylenic compounds.
Conjugated dienes have a UV maximum around 230-240 nm and
trienes show triple peaks around 261, 271 and 281 nm. Methylene-interrupted
polyenes do not show any interesting UV absorption until double bonds
migrate to form conjugated systems.
6.2.2 Infrared spectroscopy
Infrared spectroscopy has been applied to solid lipids to provide information
about polymorphism, crystal structure, conformation and chain-length but the commonest
use of traditional IR spectroscopy has been the
recognition and quantitation of trans unsaturation in acids and esters where
unsaturation is predominantly cis, using neat liquids or solutions. One trans
double bond absorbs at 968 cm-1. Additional trans centres increase the
intensity but do not change the frequency unless they are conjugated when
small changes are reported.
6.2.3 Electron spin resonance (ESR) spectroscopy
ESR spectroscopy is used for the study of free radicals (odd electron species) but finds only
limited use in lipid studies.
#What is lipid?
Lipid, any of a diverse group of organic compounds including fats, oils, hormones, and
certain components of membranes that are grouped together because they do not interact
appreciably with water. One type of lipid, the triglycerides, is sequestered as fat in adipose
cells, which serve as the energy-storage depot for organisms and also provide thermal
insulation.
Define Smoke point
The smoke point, also referred to as the burning point, is the temperature at which an oil or
fat begins to produce a continuous bluish smoke that becomes clearly visible, dependent upon
specific and defined conditions.
Solubility of gases in oils
When an oil is in contact with air, the dissolved gases will
depend on their individual solubility as well as their concentration in air. The
high solubility of the monatomic argon enhances its concentration so that one
per cent in air becomes three per cent of the gases in the oil.
Koetsier in Gunstone & Padley (1997) has summarised data on the
solubility of hydrogen in vegetable oil. This information is obviously
important for hydrogenation. He cites solubility values (maximum
concentration in oil at a given temperature and pressure) from two sources
at 1 bar and 100-200°C of 2.60-3.36 mol/m3 and 2.76-3.40 mol/m3.
Melting point
The melting point of a fat corresponds to the melting point of the ? form, which is the most
stable polymorphic form and is the temperature at which all the solids melt.
When short chain or unsaturated acids are present, the melting point is reduced.
The melting point is of great importance in the processing of animal fats.
The melting points of pure fats are very precise, but since fats or oils are made up of a
mixture of lipids with different melting points we have to refer to the melting zone, which is
defined as the melting point of the component of fat that melts at a higher temperature.
Viscosity
The viscosity of a fat is due to the internal friction between the lipids that constitute it. It
is generally high due to the high number of molecules that make up a fat.
By increasing the degree of unsaturation the viscosity decreases, and when the length of the
chain increases the fatty acids components also increases the viscosity.
Refractive index
The refractive index of a substance is defined as the ratio between the speed of light in air
and in matter (oil or fat) that is analyzed.
Increasing the degree of unsaturation increases the refractive index, and when the length of
the chain increases the refractive index also increases, that is why it is used to control the
hydrogenation process.
As the temperature increases, the refractive index decreases.
The refractive index is characteristic of each oil and fat, which helps us to perform a quality
control on them.
Density
This physical property is of great importance when it comes to designing equipment to
process grease.
Density decreases when fats dilate when going from solid to liquid
When the fats melt, their volume increases and therefore the density decreases.
For the control of percentages of solid and liquid in commercial fat, dilatometric curves are
used.
Solubility
Solubility has great relevance in the processing of fats.
Fats are fully soluble apolar solvents (benzene, hexane …).
Except for phospholipids, they are completely insoluble in polar solvents (water, acetonitrile).
They are partially soluble in solvents of intermediate polarity (alcohol, acetone)
The solubility of fats in organic solvents decreases with increasing chain length and degree
of saturation.
Phospholipids can interact with water because the phosphoric acid and the alcohols that
compose them have hydrophilic groups.
Generally the surface tension increases with the length of the chain and decreases with
temperature. Surface tension and interfacial tension decrease with ease with the use of
surfactant agents such as monoglycerides and phospholipids.
Plasticity
It is the property that has a body to preserve its shape by resisting a certain pressure.
The plasticity of a fat is caused by the presence of a three-dimensional network of crystals
inside which liquid fat is immobilized.
For a grease to be plastic and extensible there must be a ratio between the solid and liquid
part (20 -40% solid state fat), the nets must not be tight and their crystals must be in ? form.
The plastic fats act as a solid until the deforming forces that are applied break the crystal
lattice and the grease passes to behave like a viscous liquid and therefore can be smeared.
Emulsifying capacity
The emulsifying capacity is the capacity in the water/oil interface allowing the formation of
emulsion.
