What is the advantages and disadvantages of vegetable oils as an alternative lubricant

compared to conventional mineral oil?

Vegetable oils can and have been used as lubricants in their natural forms. It have several
advantages and disadvantages when considered for industrial and machinery lubrication. On
the positive side, vegetable oils can have excellent lubricity, far superior than that of mineral
oil. Lubricity is so potent that in some applications, such as tractor transmissions, friction
materials need to be added to reduce clutch slippage. Some crude vegetable oils tested at UNI-
ABIL have passed hydraulic pump/wear tests, such as ASTM D2882 and ASTM D2271, in
their natural form.
Vegetable oils also have a very high Viscosity Index (VI); for example, 223 for soybean oil vs.
90 to 100 for most petroleum oils. Restated, the viscosity of a high VI oil changes less than
that of a low VI oil for a given temperature change. The oil’s viscosity does not reduce as much
when exposed to high temperatures, and does not increase as much as petroleum oils when
exposed to cool temperatures.
Another important property of vegetable oils is their high flash/fire points; 610°F (326°C) is
the flash point of soybean oil compared to a flash point of approximately 392°F (200°C) for
mineral oils.
Most importantly, vegetable oils are biodegradable, in general are less toxic, are renewable and
reduce dependency on imported petroleum oils. Additionally, using lubricants and greases
made of soybean oil helps reduce soybean surpluses and helps stabilize soy prices for American
farmers. For most industrial machinery users these products offer considerable public relations
benefits and goodwill within the agricultural community.
On the negative side, vegetable oils in their natural form lack sufficient oxidative stability for
lubricant use. Low oxidative stability means, if untreated, the oil will oxidize rather quickly
during use, becoming thick and polymerizing to a plastic-like consistency. Chemical
modification of vegetable oils and/or the use of antioxidants can address this problem, but
increase the cost. Chemical modification could involve partial hydrogenation of the vegetable
oil and a shifting of its fatty acids. The challenge with hydrogenation is to determine at what
point the process is to cease. Full hydrogenation of oil can lead to solid products like margarine.
Depending on the needed liquidity and pour point of the oil, optimum hydrogenation is
determined. Recent advances in biotechnology have led to the development of genetically
enhanced oilseeds that are naturally stable and do not require chemical modification and/or use
of antioxidants. A soybean seed developed through DuPont technology, for example, presents
more than 83 percent oleic acid as compared to only 20 percent oleic acid content in
conventional soybean oil. Originally developed for frying applications, this oil has shown about
30 times more oxidative stability and viscosity stability in hydraulic pump tests conducted at
the UNI-ABIL Research Program. High oleic varieties of canola oil, rapeseed, sunflower and
soybean are now becoming standard base oils for biodegradable lubricants and greases. The
primary advantage of soybean is that it is U.S.-grown and has a well-established infrastructure
to deliver the quality, quantity and economy for these alternative products.
All conventional, chemically modified or genetically modified oils tested at UNI-ABIL have
shown the same levels of biodegradability. Using tests developed by American Standard for
Testing and Materials (ASTM) and Organization for Economic Cooperation and Development
(OECD), the oil is inoculated with bacteria and is kept under controlled conditions for 28 days.
The percentage of oxygen consumption or CO2 evolution is monitored to determine the degree
of biodegradability. Most vegetable oils tested have shown to biodegrade over 70 percent
within that period as compared to petroleum oils biodegrading at about 15 to 35 percent. For a
test to be considered readily biodegradable, there must be more than 60 percent degradation in
28 days. Similarly, using a variety of tests involving fish, daphnia and other organisms, the
toxicity of the vegetable oils are tested. In this case, in their pure form, both mineral oil and
vegetable oils show little toxicity, but when additives are included, toxicity increases.
Another negative to vegetable oils is their high pour point (the temperature at which oil loses
fluidity and does not flow). This problem too can be addressed by winterization, addition of
chemical additives (pour point suppressants) and/or blending with other fluids possessing
lower pour points. Various synthetic oils can be used for this purpose. With a combination of
these techniques, UNI-ABIL has developed hydraulic fluids with pour points of -32.8°F (-
36°C) for use in snow blowers used by the Iowa Department of Transportation. Another
experimental hydraulic fluid using genetically enhanced oils meets military specifications for
pour points of -65.2°F (-54°C). While the use of genetically modified seed oils alleviates the
problem of oxidation stability, the cold temperature properties must be enhanced by the
addition of chemical pour point depressants and/or the addition of other liquids with much
lower pour points.
If a high degree of biodegradability is required, then biodegradable synthetic esters are added
to improve cold temperature properties. On the other hand, if the attempt is to maintain the so-
called biobased property, where at least 51 percent is of natural biomaterials, then a portion of
the blend could be light mineral oil with low pour points. The latter will show a higher degree
of toxicity and a lower degree of biodegradability.
Outline chemical and physical properties of fat and oils?

Physical Properties

1. State. Fats containing saturated fatty acids are solid at ordinary room temperature. The
animal fats belong to this category. Most plant fats, on the contrary, possess unsaturated fatty
acids and are, henceforth, liquid at room temperature.

2. Colour, Odour and Taste. When pure, the fats are colourless, virtually odourless and
possess an extremely bland taste. They are capable of absorbing a variety of odours and hence
flavour during storage. For the same reason, a housewife knows that the flavour of an onion
quickly permeates butter that is stored with it in a refrigerator. In some cases, however, this
absorbing property of fats is of advantage. For example, the perfumes of some flowers can be
isolated by placing their petals in contact with the fat for a certain period, then extracting the
fat with alcohol and concentrating the essence.

3. Solubility. The fats are, however, only sparingly soluble in water. These are, therefore,
described as hydrophobic in contrast to the water-soluble or hydrophilic substances like many
carbohydrates and proteins.

However, these are freely soluble in organic solvents like chloroform, ether, acetone and
benzene. These solvents, as they dissolve fats in them, are also known as ‘fat solvents’. The
solubility of the fatty acids in organic solvents, in fact, decreases with the increase of chain
length. The introduction of hydroxyl groups, however, increases solubility.

4. Melting point. The melting point of fats depends on the chain length of the constituent fatty
acid and the degree of unsaturation. Fats containing saturated fatty acids from C 4 to C 8 are
liquid at room temperature but those containing C 10 or higher saturated fatty acids are solid
and their melting points increase with increasing chain length. With the introduction of double
bond in the fat molecule, the melting point lowers considerably. It may be stated, in general,
that greater the degree of unsaturation (or higher the number of double bonds) of the
constituent fatty acid, the lower is the melting point of the fat. In fact, short chain length and
unsaturation enhance the fluidity of fatty acids and of their derivatives.

5. Specific gravity. The specific gravity of the fats is less than 1 (about 0.86) and, therefore,
they float on water surface. Solid fats are lighter than the liquid fats. Oils spread on water to
form thin monomolecular layers. In general, either unsaturation of the fatty acid chains increase
or increase in chain length of the fatty acid residues tend to increase the specific gravity.

6. Geometric isomerism. As stated earlier, the presence of double bond (s) in the unsaturated
fatty acid part of the fat molecule produces geometric (or cis-trans) isomerism.

7. Insulation. The fats possess high insulating power, i.e., they are bad conductor of heat. A
layer of fat below the skin provides a sort of blanket for warm-blooded animals (or
homoiotherms). This is especially important for whales and seals which have to maintain a
high temperature in cold waters. The fishes are cold-blooded animals (or poikilotherms) and,
therfore, do not require maintenance of high temperature and so have very little subcutaneous
fat.
8. Emulsification. It is the process by which a lipid mass is converted into a number of small
lipid droplets. The fats may be emulsified by shaking either with water or with emulsifying
agents like soaps, gums, proteins etc. An emulsifying agent helps in the production of a finely
divided suspension of a fat in an aqueous medium. The hydrocarbon portions of the two (the
emulsifier and the fat) tend to aggregate. This leaves the water-soluble group of the emulsifier
projecting into the aqueous phase. A fat droplet will associate with a number of molecules of
the emulsifier, thus producing a new water- soluble surface. The process of emulsification is
of great metabolic significance. In fact, the fats have to be emulsified before they can be
absorbed by the intestinal wall. The process is accomplished by the bile juice secreted from
liver.

9. Surface tension. The force with which the surface molecules are held together is called the
surface tension. When liquid fat is poured on water, it spreads uniformly over the surface of
water in the form of a unimolecular layer and thus reduces the surface tension of water.

Chemical Properties

The chemical reactions of the fats reflect the reactivities of the ester linkage and the degree of
unsaturation of the hydrocarbon chain.

REACTIONS INVOLVING COOH GROUP

1. Hydrolysis. The fats are hydrolyzed by the enzymes lipases to yield fatty acids and glycerol.
The lipases catalyze this reaction at a slightly alkaline pH (7.5 – 8.5) in a stepwise manner. The
fats first split to produce diglycerides, part of these are then split to monoglycerides. Finally,
part of the monoglycerides split to yield fatty acid and glycerol. In the intestine, the absorption
of mono-, di- and triglycerides is so rapid that very little free glycerol is formed.

2. Saponification. The hydrolysis of fats by alkali is called saponification. The soap are of two
types: hard and soft. Hard soaps such as the common bar soaps are the sodium salts of the
higher fatty acids. Soft soaps are the potassium salts of higher fatty acids and are marketed as
semisolids or pastes. The fatty acid salts of calcium, magnesium, zinc and lead are, however,
insoluble in water. Calcium soaps are used industrially as lubricating greases. Zinc soaps are
employed in the manufacture of talcum powder and other cosmetics. Lead and magnesium
soaps are used in paints industry to hasten the process of drying.

In this schematic drawing of a soap micelle, the nonpolar tails of the fatty acids are directed
inward, where they interact with the greasy matter to be dissolved. The negatively-charged
heads are located at the surface of the micelle, where they interact with the surrounding water.
Membrane proteins, which also tend to be insoluble in water, can also be solubilized in this
way by extraction of membranes with detergents.

Soaps are important cleansing agents. Their cleansing property is due to their emulsifying
action (i.e., capacity to render more prolonged the mixing of oil and water). This is
accomplished by means of negative charge the soap anion confers on oil droplets. The
electrostatic repulsion then prevents the coalescence of soap and oil droplets into an oil phase.

3. Hydrolytic rancidity. When butter or other fats are stored, they often become rancid and
hence unpalatable. Rancidity is caused by the growth of microorganisms which secrete
enzymes like lipases. These split the fats into glycerol and free fatty acids. The fatty acids
impart unpleasant odour and flavour to the fat. However, butter may be prevented from
becoming rancid by refrigeration or by exclusion of water.

Explain methods for moisture content analysis?

Air Oven Method.

Definition : moisture content of oil and fatis the loss mass of the sample on heating at 105
plus minus under operating condition specific.

Apparatus : Metal dishes 7-8cm diameter and 2-3 cm deep provided with tight fitting slip
on covers.

Procedures : Weight in previously dried and tared dish about 5-10g oil or fat which has
been thoroughly mixed by stirring. Loosen the lid of the dish and heat, in an oven at 105
plus minus 1 degree celcius for 1 hour. Remove the dish from the oven and close the lid.

Cool in a desiccator containing phosphorus pentoxide or equivalent dessicant and weight.

Heat in the oven for a further period of 1 hour, cool and weight. Repeat this process until
change in weight between two successive observations does not exceed 1mg.

Carry out the determination in duplicate:

𝒘𝟏 𝒙 𝟏𝟎𝟎
Moisture and volatile matter, percent by weight = 𝒘

Where,

W1 = Loss in gm of the material on dryinf

W = weight in gm of the material taken for test.
Polymorphism?