GENERAL INTRODUCTION
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have inherent superior overload capacity without suffering insulation damage;
hence can withstand harmonic levels that exceed specific load range. EPA
[Environmental protection agency] of America has approved these
Transformers. The parameters they test for use of any oil as dielectric coolant
are fire and flash point, dissipation factor, dielectric breakdown, neutralization
number, interfacial tension, viscosity, pour point, water content, conductivity,
aquatic biodegradation, aquatic toxicity, fatty acid content, phenolic
antioxidants and metals. So to use any vegetable oil as transformer coolant,
study of dielectric properties and viscosity properties are important.
5. Dielectric studies of oils are also carried out as food oil sensor. The Food Oil
Sensor [FOS] is designed to test the dielectric constant of fat. As oil undergoes
thermal and oxidative breakdown, its dielectric constant increases. Oil should
be replaced when its FOS reaches 5, during frying.
The terms fats and oils are generally considered to refer to substances which
have a similar chemical structure and which have the same metabolism in the animal
body. Fats are those substances which are solids at ordinary temperatures, while oils
are liquids under similar circumstances. Thus what may be considered as a fat in one
locality which is colder may be considered as oil in a warmer climate.
Oil molecules are triglycerides.Structurally, a triglyceride is the reaction
product of one molecule of glycerol with three molecules of fatty acids to yield three
molecules of water and one molecule of triglyceride.
H H
H H
Glycerol Fatty acids Water Triglyceride
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The product is a simple triglyceride, if the three fatty acids are identical and is
a mixed triglyceride if the three fatty acids are dissimilar. Simple triglycerides are
synthesized in the laboratory by the direct esterification of glycerol with a fatty acid,
mixed triglyceride of known structure are obtained by special methods.
Mono glycerides and di- glycerides do not occur naturally in appreciable
quantities except in fats and oils that have undergone partial hydrolysis.
Natural fats and oils vary widely in their physical properties, even though they
are made up of the same or similar fatty acids. Some of the factors that influence the
fatty acid composition and triglyceride structure of natural fats and oil of the
vegetable kingdom are
a) Climatic conditions[hot or cold, wet or dry]
b) Soil type in which parent plants are grown,
c) Geography of the growing location,
d) Maturity of the plant,
e) Health of the plant,
f) Numerous environmental conditions [proximity of certain molds, bacteria and
enzymes etc.
g) Specific location qf the oil seeds within the flower itself,
h) Genetic variations of the plant.
The factors that influence the fat and oil composition in land animal kingdom are
a) Animal species,
b) Diet of the animal,
c) Location of the fat within the animal,
d) Health and well-being of the animal,
e) The environment in which the animal is matured.
In case of marine animal fats and oils, the composition is influenced by
a) Oceanic or fresh water species,
b) Within a particular species, whether it is cold or warm water species etc.
There are very large number and variety of fats and oils in nature. It is the
experience of several agricultural scientists as on today that a slight and imperceptible
change in the environment has a greater effect on the composition and structure of the
fat or oil.
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After knowing that fats and oils contain fatty acids, it is necessary to
understand the influence of fatty acids on the physical and chemical behavior of fats
and oils.
In a triglyceride, the molecular weight of the glycerol portion [C3H5] is 41,
where as the combined molecular weight of fatty acid radicals [R C00-] containing
the remainder of the molecule will vary with different fats ranging from 650 to 970.
Thus, the fatty acids contribute 94-96% of the total weight of the molecule. This is the
reason why the fatty acids greatly influence both the physical and chemical characters
of the glycerides as such the Physio-chemical behavior of the fats and oils. [3].
The Classification of Fatty Acids
Fatty acids are classified in the following way:
a) Saturated fatty acids and
b) Unsaturat d fatty acids.
Saturated Fatty acids
A fatty acid is saturated when all available carbon bonds are occupied by a hydrogen
atom. The empirical formula for saturated fatty acids is CnH2nC>2 .In the case of
natural fats, n is almost an even number in every case. However, some fats consist of
fatty acids with odd carbon atoms. They are highly stable, because all the carbon-
atom linkages are filled-or saturated-with hydrogen. This means that they do not
normally go rancid, even when heated for cooking purposes. They are straight in form
and hence pack together easily, so that they form a solid or semisolid fat at room
temperature. Our body makes saturated fatty acids from carbohydrates and they are
found in animal fats and tropical oils.
Role of Saturated fats in body chemistry
o The much maligned saturated fats-which Americans are trying to avoid-are not
the cause of our modem diseases. In fact, they play many important roles in
the body chemistry:
o Saturated fatty acids constitute at least 50% of the cell membranes.
o They are what give our cells necessary stiffness and integrity.
o They play a vital role in the health of our bones. For calcium to be effectively
incorporated into the skeletal structure, at least 50% of the dietary fats should
be saturated.
o They lower Lp[a], a substance in the blood that indicates proneness to heart
disease.
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o They protect the liver from alcohol and other toxins, such as Tylenol,
o They enhance the immune system.
o They are needed for the proper utilization of essential fatty acids. Elongated
omega-3 fatty acids are better retained in the tissues when the diet is rich in
saturated fats.
o Saturated 18-carbon stearic acid and 16-carbon palmitic acid are the preferred
foods for the heart, which is why the fat around the heart muscle is highly
>♦
saturated. The heart draws on this reserve of fat in times of stress,
o Short- and medium-chain saturated fatty acids have important antimicrobial
properties. They protect us against harmful micro organisms in the digestive
tract.
o The scientific evidence, honestly evaluated, does not support the assertion that
"artery-clogging" saturated fats cause heart disease. Actually, evaluation of the
fat in artery clogs reveals that only about 26% is saturated. The rest is
unsaturated, of which more than half is polyunsaturated.
The fatty acids with carbon atoms less than 10 are liquids at ordinary
temperatures, while those with 10 carbons and more are solids. Like other members of
liquids, they are also insoluble in water and soluble in ethyl alcohol, diethyl ether,
chloroform, benzene, carbon tetrachloride, petroleum ether etc. However, butyric acid
is completely miscible with water in all proportions.
High intake of saturated fats has been linked with increased blood cholesterol
levels [particularly LDL], a major risk factor. Generally, experts agree that these fats
play a major role in the promotion of heart disease, and their intake should be
restricted in any heart-healthy diet. Dietary recommendations for daily intake of
saturated fat range from 7 to 10% of total calories.
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Monounsaturated Fatty Acids
Monounsaturated fr.tty acids have one double bond in the form of two carbon atoms
double-bonded to each other and, therefore, lack two hydrogen atoms and have
empirical formula CJ^n-aOi. Our body makes monounsaturated fatty acids from
saturated fatty acids and use them in a number of ways. Monounsaturated fats have a
kink or bend at the position of the double bond so that they do not pack together as
easily as saturated fats and, therefore, tend to be liquid at room temperature. Like
saturated fats, they are relatively stable. They do not go rancid easily and hence can
be used in cooking. The monounsaturated fatty acid most commonly found in our
food is oleic acid, the main component of olive oil as well as the oils from almonds,
pecans, cashews, peanuts and avocados. The most important monosaturated fatty
acids are oleic and palmitoleic acids.
Monounsaturated Fatty Acids [MUFAs] have one carbon-carbon link free so
that it can take up more hydrogen atoms. In studies in which monounsaturated fats
were substituted for saturated fats in the diet, blood cholesterol levels dropped. It is
thought that monounsaturated fatty acids reduce LDL ["bad" cholesterol] while
maintaining the levels of HDL ["good" cholesterol] in our blood, but research results
have not been consistent.
6
.Acid^'-X, ■Formula)^ nip (*6
REFERENCE: www.chemistry.msu.edu/faculty/reuschA/irtTxtJml/lipids.htm
7
almost exclusively in animal fats. The two essential fatty acids are also long chain, 18
carbons each in length. Another important long-chain fatty acid is gamma-linolenic
acid [OLA] which has 18 carbons and three double bonds. It is found in evening
primrose, borage and black currant oils. Our body makes OLA out of omega-6
linoleic acid and uses it in the production of substances called prostaglandins,
localized tissue hormones that regulate many processes at the cellular level.
Very-Long-Chain Fatty Acids
Very-long-chain fatty acids have 20 to 24 carbon atoms. They tend to be highly
unsaturated, with four, five or six double bonds. Some people can make these fatty
acids from EFA's, but others, particularly those whose ancestors ate a lot of fish, lack
enzymes to produce them. These "obligate carnivores" must obtain them from animal
foods such as organ meats, egg yolks, butter and fish oils. The most important very-
long-chain fatty acids are dihomo-gamma-linolenic acid [DGLA] with 20 carbons and
three double bonds; arachidonic acid [AA] with 20 carbons and four double bonds;
eicosapentaenoic acid [EPA] with 20 carbons and five double bonds; and
docosahexaenoic acid [DHA] with 22 carbons and six double bonds. All of these
except DHA are used in the production of prostaglandins, localized tissue hormones
that direct many processes in the cells. In addition, AA and DHA play important roles
in the function of the nervous system.
Methods that can be used to characterize fats and oils [lipids]:
These include the determination of certain important parameters namely free fatty
acid content, total acidity [acid value], iodine number, saponification number and
unsaponifiable matter. The free fatty acid [FFA] of an oil or fat is half its acid value.
It is the fatty acid piesent in oil following hydrolysis by lipase and which has not been
neutralized. The FFA is a measure of the amount of free fatty acid in a fat or oil. The
acid value of an oil or fat is the number of milligrams of potassium hydroxide [KOH]
required to neutralize the free acid in l.Og of the oil and is a measure of the total
acidity of the oil arising from all the constituent fatty acids that make up the fat or oil.
The acid value measures the extent of decomposition of the glycerides in the oil by
lipase. Rancidity is accompanied by the formation of FFA and so acid value or FFA
determination is employed as a means of knowing the quality and edibility of oil.
The iodine number of oil is the number of grams of iodine which can be
absorbed by lOOg of the oil, and it measures the amount of unsaturated fatty acids
occurring in the oil. Iodine does not react readily with the double bonds of oil/fat
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molecule and the quantity of iodine absorbed by oil is an index of its degree of
unsaturation. Low iodine number implies the presence of few unsaturated bonds and
hence low susceptibility to oxidative rancidity. Therefore, the higher the iodine value
the higher the degree of unsaturation and hence the greater the tendency of the oil/fat
to undergo oxidative rancidity. The latter is a chemically induced autolysis [self
deteriorative process] in which non-conjugated polyunsaturated oils react with oxygen
to give peroxides which abstract proton from the system to produce hydro-peroxides
that build up and consequently breakdown to produce odorous aldehydes, ketones,
alcohols and acids which cause the off-flavor in oxidized fats and oils.
The process is accelerated by high temperature, ultraviolet light and some
divalent metals. Hydrolytic rancidity occurring mainly in oil extracted with water is
an enzyme catalyses reaction in which fats in the presence of water are hydrolyzed to
give glycerol [a trihydric alcohol] and free fatty acids.
I
Hydroperoxides
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the quality and establishing the nature of individual fats and oils before they are
deemed suitable for either domestic or industrial consumption.
Laurie, myristic, palmitic and stearic among saturated and palmitoleic, oleic,
linoleic, and linolenic among unsaturated are the most common fatty acids occurring
in fats and oils.
LAURIC ACID: Laurie acid is one of the most widely distributed naturally occurring
saturated fatty acidic It derives its name from the seed fats of the laurel family. The
richest common sources of lauric acid are coconut oil and palm kernel oil. It is found
in small amounts in milk fats. [2 to 8%].
OLEIC ACID: It is most common one of the monounsaturated acids. This acid is
widely distributed in natural oils. It is found in practically every vegetable and animal
fat and frequently constitutes more than 50% of the total fatty acids. Rich sources of
oleic acid are olive oil [80%], ground nut oil[60%] etc.
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Fig 5, 01 ic acid = C1S:1 (Octadec-cis-9-enoic acid)
LINOLENIC ACID: The best sources of linolenic acid are vegetable fats. Rich
sources are lineseed oil [45 to 50%], hempseed[35%] and eggyolk [17%]. Generally,
when the linolenic acid content of the oil approaches 35%, the oil is less likely to be
an edible oil.
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The ratio of palmitic/stearic acid in many vegetable seed oils varies to a
considerable extent. The oleic/linoleic ratio [O/L] is found to be an excellent indicator
of oil stability.
From above introduction it is obvious that the properties of oils change with
the percentages of saturated and unsaturated acids in the oil. Since BLENDED OILS
are introduced into market claiming good health for consumers by consuming them,
author tried to study the certain physical properties of following blended oils, taking
oils in different weight proportions.
Oils and the blends studied by the author are:
1. Sunflower oil, Ricebran oil and their blends
2. Palmolein oil, Soyabean oil and their blends
SUNFLOWER OIL: Sunflower oil is not only low in saturated fats and high in
unsaturated fats but has also got a good balance of MUFA and PUFA. What's more it
is rich in natural vitamin E and Omega- 6, an essential fatty acid vital for the proper
functioning of our body. Sparkling clear, light colored transparent oil versatility
makes it suitable for multi purpose cooking. Sunflower oil contains predominantly
linoleic acid in triglyceride form.
Sunflower oil contains nearly 50% of polyunsaturated fatty acid Linoleic acid.
It has a melting point of -268K. It contains about 42% of oleic acid whose melting
point is 277K and both are liquids at the minimum temperature of the range i.e at
298K. It also contains the saturated fatty acids 5.7% Palmitic acid [mp 341K], 2.8%
Stearic acid [mp 345K.] and 0.2% Arachidic acid.[mp348.3K and density
0.8240gm/cc].
We used Sundrop-Superlite-Refined Sunflower Oil, Saturatesl2%, Mono and
Poly unsaturates 88% [Values given by company]. Manufactured and packed by
Agrotech foods Ltd., 31 SarojiniDevi Road, Secunderabad.
www.sundrop@.foods.com.
RICE BRAN OIL: Rice bran oil is produced from the rice bran, which is removed
from the grain of rice as it is processed. It is considered to be a very healthy
alternative as cooking oil because it is rich in vitamins, minerals, amino acids,
essential fatty acids, and antioxidants. Bice bran oil has a somewhat nutty flavor that
enhances the taste of foods when used in processing or preparing snack foods, fried
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foods, and crackers. Rice bran makes up about 6% by weight [dry bases] of rough rice
and contains about i5 to 20% of lipids. Rice bran is that part of rice which is richest
in fat. It is a potentially important source of fat because rice is world’s most important
crop. The composition of rice bran oil subjects it to be used as a salad oil and for
cooking and the manufacture of hydrogenated products. Rice bran oil has very good
oxidation stability, which is due to its multi-component system of natural
antioxidants.
‘Rice Bran Oil’ sounds so common to us but surprisingly it boasts of many
health benefits. The oil is called 'Heart Oil' and is consumed extensively in the
western world for its heart-healthy virtues.
Rice Bran Oil is specially extracted from Rice Bran, a by-product in the rice
milling process. Micronutrients, which we miss by consuming polished rice, are
brought back into our diet in the form of Ricebran oil. Modem extraction technology
helps retain the essential nutrients. After extensive research, World Health
Organization [WHO] recommended the ideal ratio of fatty acids in the edible oils as
1:1.5:1, respectively. Priya foods division claims their product ‘Rice Rich' which is
pure Ricebran oil is closest to these WHO recommended values.
Hence the diet should ideally reduce circulating of LDL cholesterol and
simultaneously increase the HDL cholesterol levels in the human body.
Priya food marketing division claims their ricebran oil product contains Gamma
Oryzanol that has the special property; it reduces bad cholesterol and elevates Good
cholesterol that in turn helps in preventing Coronary Heart Diseases.
Rice bran oil has got a high free fatty acid content and also high acidity which
is inherent in this oil as rice bran contains an unusually active lipase. This oil contains
considerable wax and quite high content of unsaponifiable material. The color of the
erode or refined oil varies considerably and poor oils of high acidity may be difficult
to refine and bleach to a color acceptable for edible products.
Heart healthy nutrients in RBO such as tocopherols, tocotrienols and oryzanol
are known for their cholesterol lowering ability. Besides, RBO also has a high
percentage of monounsaturated fatty acids which have been proven to not only reduce
the ‘bad’ LDL cholesterol levels but increase the levels of ‘good’ HDL cholesterol in
blood. Rice bran oil contains about 15 to 20% saturated fatty acids and about 80 to
85% of unsaturated fatty acids .This oil represented a better stability than any of the
other vegetable oils. This is also widely used as edible oil.
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SOYABEAN OIL:
Soybean oil is one the most widely used oils in the manufacture of margarine,
vegetable oil, and shortening. In fact, in the United States, soybean oil is used more
often than any other oil in the production of commercially prepared food items that
contain oil. It has long been one of the top favorites for use in Chinese cooking.
In the United States, soybean oil is highly refined and has a high smoke point,
making it good all-purpose cooking oil. The generic brands of vegetable oil are often
100% soybean oil or they may be a blend of several highly refined oils. Soybean oil is
inexpensive and has several healthy attributes including high levels of
polyunsaturated [including omega-3 fatty acid] and monounsaturated fats and it is
fairly low in saturated fat. Isoflavones, present in soy compounds, act like human
hormones that regulate cholesterol levels.
Soyabean is one of the oldest crops cultivated and was grown in China as far
back as 2338 B.C. Subsequently it has been grown in Asia, Europe and America.
Soyabean oil is used as edible oil in some parts of India. The fat in Soybean is mainly
polyunsaturated and monounsaturated fats. It also contains two essential fatty acids -
linoleic and linolenic acids, which are rare in plant foods.
Soya beans [oil content 18-22%] can be safely stored at 12% moisture without
any noticeable increase in free fatty acids. Crude Soyabean oil can be obtained from
the bean by pressing more normally hexane extraction. Good quality oil is light amber
in color with a free fatty acids and modified lipids and is more difficult to bleach. The
residual meal is a major source of animal feed.
PALMOLEIN OIL;
Palmolein oil is another of the few plant products that is very high in saturated
fat. The oil is obtained from the pulp of the fruit of the African palm. It has a red-
orange color, a strong unique flavor, Palm oil traditionally has been used for baking,
shortenings, margarines and deep fat frying, as it is shelf stable with a high melting
point and does not require hydrogenation. Therefore, it contains no trans fatty acids.
Palmolein Oil has got the natural anti oxidants to preserve our food for longer
time. Palmolein is best suited oil for deep frying & reuse. Saturated and Trans fats
raise blood cholesterol levels. Polyunsaturated fats lower blood cholesterol but also
seem susceptible to oxidation. Over time, oxidation speeds buildup of plaques inside
your arteries. Monounsaturated fats may help lower blood cholesterol and are resistant
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to oxidation. Reducing the amount of saturated fat and cholesterol you eat is a very
important step in reducing your blood cholesterol levels.
The oil contains large quantities [40 to 47 percent] of palmitic acid [C 16:0]
and similar amounts of oleic acid [Cl8:1]. The limited presence of polyunsaturated
fatty acids permits close packing of the component triglycerides which results in a
relatively high slip melting point.
Oils and fats generally are susceptible to attack by atmospheric oxygen,
resulting in rancidity. Virgin Palm Oil contains tocols [Vitamin E] which are powerful
natural antioxidants. Therefore, it has exceptional resistance to rancidity. Virgin Palm
Oil is known for its excellent stability at high temperatures.
REVIEW:
Ultrasonic studies on several oils have been reported by Gouw and Vultger[l].
The ultrasonic attenuation of some vegetable oils has been linked with high frequency
rheology by Mikhailov etal [2]. It is well known that the velocity and attenuation
depend on the frequency of operation and temperature according to Kuo HL etal [3].
The ultrasonic behavior of some vegetable oils has been reported by Gladwell etal
[4], Information on the physical properties of oils and fats can be found in many
reviews and text books [5, 6, 7]. Mohan etal [8] has made a detailed study on the
adiabatic compressibility and velocity of some essential oils. V Armugam etal [9]
measured the ultrasonic velocity, viscosity and density of different oils and estimated
other parameters like internal pressure , free volume and Rao’s constant for these oils.
Gouw and Vlugter [1], Javanaud and Rahalkar [10] related the ultrasonic velocity to
the chemical formulae in a number of liquid triglycerides and fatty acid methyl esters.
Javanaud and Rahalkar[10] also related the ultrasonic velocity to the velocity of their
constituent components. Hussain and Povey [11] Javanaud and Rahalkar [10] studied
the variation of ultrasonic velocity with temperature over a number of animal and
vegetable oils and these studies have been used to detect adulteration in oils. Very
recently McClements and Povey [12, 13, 14, 15] investigated the variation of
ultrasonic velocity with temperature for nine commercially available vegetable oils
and they examined the relationship between the triglyceride composition and
ultrasonic velocities.
Very recently, Subrahmanyam [16] of our department studied the variation of
viscosity with temperature and also the variation of density with temperature over a
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number of oils during his research for fulfillment of Master of philosophy. From his
studies, he obtained the fluidities and the molai values. He fitted his observations to a
number of empirical and semi-empirical relations to find the suitability of one or
several expressions for the oils under consideration. The fatty acid composition for
the same samples investigated by him was also studied using gas liquid
chromatographic studies. In addition to the above he determined a number of
thermoacoustic parameters including Sharma’s constant in all the oils investigated by
him.
In the present studies the author investigated the variation of the ultrasonic
velocity with temperature and variation of dielectric constant and dielectric loss with
temperature and frequency in all the four vegetable oils and their blends of different
concentrations. Using the velocity data and density measurements the author also
estimated
1. Rao’s number,
2. Adiabatic compressibility,
3. Molar compressibility,
4. Vander Waal’s constant,
5. Free volume
6. Inter molecular free length.
7. Acoustic impedance
8. Molar volume
9. Molecular radius
10. Geometric volume
11. Molecular surface area
12. Available volume
13. Surface tension
We also calculated the theoretical values of ultrasonic velocities for binary
mixtures and found the differences from experimental values to access their ideality.
The work presented in this thesis is a preliminary step for the long range program to
be undertaken.
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References:
[ 1 ]. Gouw Ir TH & Vlutger Ir JC , Fette Seifen Anstichm,3 [ 1967] 159.
[2] , Mikhailov IG, Manuteharov Yu S & Khakimov O, Ultrasonics,3[1975]66.
[3] . Kuo H L, Jpn J Appl Phys, 10[ 1971 ] 167.
[4] . Gladwell N, Javanaud C, Peers KE & Rdhalkar RR, J oil Chem
Soc,62[l 985] 1231.
[5] . Formo MW, Bailey’s industrial oil and aft products, ed. D Swem 4th edition,
John Wiley & Sons, NY, 1979,177.
[6] . Timms RE, Prog Lipid Res,23[1984]1.
[7] . Williams WA, Oils ,fats and Fatty foods[JA Churchill Ltd,London],1966
[8] . Mohan V, Indian oil Soap J,28[1963]225.
[9] . V Armugam, R Sanjeevi, Draghunatha Rad, R Balakrishnan, IB Shameem
Banu, IJPAP, 36[October 1998],578-583.
[10] . Velocity of Sound in Vegetable oils, By Clarissa Javanaud & R.R.Radhalkar,
Fat Sci Technology, JahrangNo.2, 1988, pp.73-75.
[11] . Hussain, A. B. B., and Povey, M. J. W. [1984], A Study of Dilation and
Acoustic Propagation in Solidifying Fats and Oils. II - Experiment, J. Am.
Oil. Chem. Soc. 61, 560-564.
[12] . McClements, D. J., and Povey, M. J. W. [1987], Solid Fat Content
Determination Using Ultrasonic Velocity Measurements, Int. J. Food Sci.
Tech. 22,419-428.
[13] . McClements, D. J., and Povey, M. J. W. [1988], Investigation of Phase
Transitions in Glyceride/Paraffm Oil Mixtures Using Ultrasonic Velocity
Measurements, J. Am. Oil. Chem. Soc. 65,1791-1796.
[14] . McClements, D. J., and Povey, M. J. W. [1988], Ultrasonic Velocity
Measurements in Some Triglycerides and Vegetable Oils, J. Am. Oil. Chem.
Soc. 65,1787-1789.
[15] . McClement:, D. J., and Povey, M. J. W. [1992], Ultrasonic Analysis of Edible
Fats and Oils, Ultrasonics 30, 383-388.
[16] . V.S.R.Subrahmanyam, Ultrasonic and Viscosity studies on some pure oils,
Dessertation for Master of Philosophy, Department of Physics, Aeharya
Nagarjuna University, Nagaijuna Nagar, A.P.
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