Unit 3
Unit 3
Structure
3.1    Introduction
3.2    Introduction to Lipids
3.3    Classification and Composition
       3.3.1 Classification of Lipids
       3.3.2 Categories of Fats and Oils
3.4    Functional Properties of Food Lipids
3.5    Deep Fat Frying
       3.5.1 Factors Affecting Process of Deep Fat Frying
       3.5.2 Maintaining the Quality of Frying Oil
3.6    Deteriorative Changes in Fats and Oils
       3.6.1 Autoxidation
       3.6.2 Factors Influencing Lipid Oxidation
       3.6.3 Lipolysis
       3.6.4 Thermal Decomposition
3.7    Antioxidants – Preventing the Deteriorative Changes in Fats and Oils
3.8    Let Us Sum Up
3.9    Glossary
3.10   Answers to Check Your Progress Exercises
3.1 INTRODUCTION
Lipids in food exhibit unique physical and chemical properties. Their composition,
crystalline structure, melting properties and the ability to associate with water and other
non-lipid molecules are especially important to their functional properties in many foods.
We will learn about these properties and the role of lipids in product preparation in this
unit. Further, during the processing, storage and handling of foods, lipids undergo
complex chemical changes and react with other food constituents, producing numerous
compounds, both desirable and deleterious to the food quality. What are these
deteriorative changes in food lipids? Are there any means of controlling such changes?
These are the other issues highlighted in this unit.
You will realize, that like in previous two units, here too we have not dwelt much on the
structural component of lipids. The reason being that the structure, physical/chemical
properties have been discussed in the Nutritional biochemistry course. We do not wish to
duplicate the effort here and make the content bulky. However, we do advise you to look
up the relevant block/unit in the Nutritional Biochemistry course before you start
studying this unit. Best approach would be to have those blocks handy so that you can
refer to them as and when required.
Objectives
After studying this unit, you will be able to:
      •   enumerate the important sources of food lipids,
      •   describe the basic composition of food lipids,
      •   discuss the role of food lipids in product preparation,
      •   debate on the importance of functionality of food lipids with reference to food
          processing and quality of finished products, and
      •   recognize the deteriorative changes in food lipids and means of controlling such
          changes.
In its broadest sense, ‘lipids’ defines substances as oils, fats and waxes which can be only
characterized by a large array of properties. They are in general:
      -   coming from plant and animal origin;
      -   insoluble or immiscible with water but soluble in organic solvents such as
          chloroform, ether, benzene, acetone; and
      -   formed of long-chain hydrocarbon groups (carbon and hydrogen), but may also
          contain oxygen, phosphorous, nitrogen and sulphur.
Glycerol esters of fatty acids, which make up to 99% of the lipids of plant and animal
origin have been traditionally called fats and oils. This distinction, based solely on
whether the material is solid or liquid at room temperature, is of little practical
importance and the two terms are often used interchangeably.
Food lipids are either consumed in the form of “visible” fats, which have been separated
from the original plant or animal sources, such as vegetable oil and butter, or as
constituents of basic foods, such as milk, cheese and meat. This is referred to as ‘invisible
fat’. You already know that dietary lipids play an important role in nutrition. They supply
calories and essential fatty acids, act as vitamin carriers and increase the palatability of
food. The largest supply of vegetable oil comes from the seeds of soy bean, cottonseed,
peanut and the oil-bearing trees of palm, coconut and olive.
Oil–bearing fruits, nuts and seeds have been grown and used for food for many centuries.
More than 100 varieties of plants are known to have oil–bearing seeds, but only a few
have been commercialized. The largest source of vegetable oil at present is the seeds of
annual plants such as soybean, cottonseed, peanut, sunflower, safflower, mustard and
rapeseed. Many of the oil–bearing seeds are not only a source of oil, but also protein, the
protein portion has the most value. A second source of vegetable oils is the oil–bearing
fruits and nuts of trees such as coconut, palm, palm kernel and olive. The oil from the
palm and olive is extracted from the fruit rather than the seed of the fruit. All the oil–
bearing trees require a relatively warm climate, two of which are tropical: coconut and
palm.
Oil contents for vegetable oil–bearing materials vary between 18% and 68% of the total
weight of the seed, nut, kernel or fruit as indicated in Table 3.1.
Meat fats are derived almost entirely from three kinds of domestic animals: hogs, cattle
and sheep. Milk of cow and buffalo is an important source of fat in the form of either
butter or ghee. Bulk of the world’s milk fat production consists of butterfat from cow’s
milk, and in India, butter and ghee have a well-established place in the culinary practices.
Fats and oils are a unique class of agricultural products in that a high degree of
interchangeability among them is possible for many products and uses. Additional
processing and/or blending of one or more source oils may be necessary for a satisfactory
substitution. Knowledge of the physical and chemical properties of each individual raw
material is necessary to successfully duplicate or improve on the functionality of the
original source oil’s functionality. To understand this, we need to first look at the
composition of lipids. The next section is devoted to the classification and composition of
lipids.
3.3 LIPIDS - CLASSIFICATION AND COMPOSITION
The classification and categories of lipids is presented in this section. There may be
different ways of classifying lipids. A general classification is presented herewith.
You may recall reading about the classification of lipids in the Advance Nutrition Course.
Derived lipids   Materials that meet the Examples: fatty acids, carotenoids,
                 definition of a lipid but steroids, fat-soluble vitamins
                 are not simple or
                 compound lipids
It should also be recognized that other classifications may sometimes be more useful. For
example, the sphingomyelins can be classed as phospholipids because of the presence of
phosphate. The cerebrosides and the gangliosides can also be classified as glycolipids
because of the presence of carbohydrate and the sphingomyelins. The glycolipids can be
classed as sphingolipids because of the presence of sphingosine.
The most abundant class of food lipids is the acylglycerols, also known as glycerol esters
of fatty acids, which dominate the composition of depot fats in animals and plants. The
polar lipids are found almost entirely in cellular membranes (phospholipids being the
main component of the bilayer), with only very small amounts in depot fats. In some
plants, glycolipids constitute the major polar lipids in cell membranes. Waxes are found
as protective coatings on skin, leaves and fruits. Major components of lipids are the
acylglycerols. They are the esters of glycerol and fatty acids, having a varying chain
length. Fatty acids are aliphatic monocarboxylic acids that can be liberated by hydrolysis
from naturally-occurring fats. For example, oleic acid, which is a common fatty acid
found in acylglycerols, has 18 carbon atoms in its chain. The carboxyl (COOH) group of
the acids forms the ester by combining with the hydroxyl (OH) group of glycerol. There
are 3 hydroxyl groups in a glycerol molecule. If all the three groups are forming ester
linkage with fatty acids, the resulting compound is called a triacylglycerol or a
triglyceride. Structure of a triacylglycerol is shown:
CH2OOC (CH2)16CH3
CH3 (CH2)16COOHCH
You came across the terms saturated and unsaturated in the above section. Let’s
understand these terms better.
Systematic                                                                  Short-hand
Name                     Common Name                 Formula                Description
Some of the more important saturated fatty acids with their systematic and common
names are listed in table 3.3a, and some of the unsaturated fatty acids in table 3.3b. The
naturally occurring unsaturated fatty acids in fats are almost exclusively in the cis – form,
although trans – acids are abundant in ruminant milk fats and in catalytically
hydrogenated fats. What are cis and trans-acids? You may have learnt about this concept
in the Nutritional Biochemistry Course. We suggest you look up Block 1, Unit 2 of the
Nutritional Biochemistry course for understanding this concept.
Table 3.3 b. Unsaturated Fatty Acids
Systematic                                                                         Short-hand
Name                    Common Name                               Formula
                                                                                   Description
Milk Fats
Fats of this group are derived from the milk of ruminants, particularly cows and
buffaloes. Although the major fatty acids of milk fat are palmitic, oleic and stearic, this
fat is unique among animal fats in that it contains appreciable amounts of the shorter
chain fatty acids (C4 to C12), small amounts of branched and odd numbered acids and
fatty acids with trans-double bonds.
Lauric Fats
Fats of this group are derived from certain species of palm, such as coconut. The fats are
characterized by their high content of lauric acid (40 – 50%), moderate amounts of C6,
C8 and C10 fatty acids, low content of unsaturated acids and low melting points.
Vegetable Butters
Fats of this group are derived from the seeds of various tropical trees and are
distinguished by their narrow melting range, which is due mainly to the arrangement of
fatty acids in the triacylglycerol molecules. In spite of their large ratio of saturated to
unsaturated fatty acids, trisaturated acylglycerol are not present. The vegetable butters are
extensively used in the manufacture of confections, with cocoa butter being the most
important member of the group.
Oleic – Linoleic Fats
Fats in this group are the most abundant. The oils are all of vegetable origin and contain
large amounts of oleic and linoleic acids, and less than 20% saturated fatty acids. The
most important members of this group are cottonseed, corn, peanut, sunflower, safflower,
olive, palm and sesame oils.
Linolenic Acids
Fats in this group contain substantial amounts of linolenic acid (C18 triunsaturated).
Examples are soybean, mustard, rapeseed, flaxseed and wheat germ hempseed and perilla
oils, with soybean being the most important. The abundance of linolenic acid in soybean
oil is responsible for the development of an off-flavour problem known as ‘flavour
reversion’.
Animal Fats
This group consists of depot fats from domestic land animals (e.g., lard and tallow), all
containing large amounts of C16 and C18 fatty acids, medium amounts of unsaturated
acids, mostly oleic and linoleic and small amounts of odd numbered acids. These fats also
contain appreciable amounts of fully saturated triacylglycerols and exhibit relatively high
meting points. Egg lipids are of particular importance because of their emulsifying
properties and their high content of cholesterol.
The lipid content of whole eggs is approximately 12%, almost exclusively present in the
yolk, which contains 32 – 36% lipid. The major fatty acids in egg yolks are 18: 1 (38%),
16: 0 (23%), and 18: 2 (16%). Yolk lipids consist of about 66% triacylglycerols, 28%
phospholipids and 5% cholesterol. The major phospholipids of egg yolk are
phosphatidylcholine (73%) and phosphatidylethanolamine (15%).
Marine oils
These oils typically contain large amounts of long – chain omega-3-polyunsaturated fatty
acids, with up to six double bonds and they are usually rich in vitamins A and D. Because
of their high degree of unsaturation, they are less resistant to oxidation than other animal
or vegetable oils.
With this, we come to the end of first part of this unit i.e., the introduction, classification
and composition of lipids. Look up the points to remember given herewith. They are the
useful hints/tips for remembering the concept on your finger tips. Read them carefully.
                                       Points to Remember
1. Lipids consist of group of compounds that are generally soluble in organic solvents
     but only sparingly soluble in water.
2. Glycerol esters of fatty acids (Acylglycerols) which make up to 99% of the lipids of
     plant and animal origin have been traditionally called fats and oils.
3. Common fatty acid present in acyl glycerols are stearic acid (C-18, saturated), oleic
     acid (C-18, monounsaturated), linoleic (C-18, di unsaturated) and palmitic (C-16,
     saturated).
4.   Major sources of oils and fats are peanut (groundnut), mustard, soybean, sunflower,
     coconut, palm and milk.
5. Fats and oils belonging to oleic-linoleic acid group are the most abundant. They
     contain large amounts of oleic acid (C-18 mono unsaturated) and linoleic acid (C-18
     diunsaturated) and less than 20% saturated fatty acids.
6. Important members of oleic-linoleic acid group are peanut, sunflower, cotton seed
     and sesame oils.
7. Milk fat is unique because it contains appreciable amounts of shorter chain acids (C-4
     to C-12).
8. Animal fats contain appreciable amounts of fully saturated triacylgylcerols and
     exhibit relatively high melting points.
Chemically, fats and oils, as you may already know by now, are a combination of
glycerol and fatty acids. The glycerol molecule has three separate points, where a fatty
acid molecule can be attached. Physically, fats and oils differ in that fats are solid and oils
are liquid at room temperature. You learnt earlier that the different properties are to a
large extent determined by the fatty acid composition and the extent of saturation or
unsaturation present. These aspects are identified by the carbon chain length and the
number and position of double bonds for the individual fatty acids and their position of
the glycerol. Generally, solid fats indicated by a dominance of saturated fatty acids and
liquid oils, are an evidence of a high level of unsaturated fatty acids.
Carbon chain lengths of fatty acds in edible oils and fats vary between 4 and 24 carbon
atoms with up to three double bonds. The most prevalent saturated fatty acids are lauric
(C-12:0), myristic (C-14:0), palmitic (C-16:0), stearic (C-18:0), arachidic (C-20:0),
behenic (C-22:0) and lignoceric (C-24:0). The most important monounsaturated fatty
acids are oleic (C-18:1) and erucic (C-22:1). The polyunsaturated fatty acids are linoleic
(C-18:2) and linolenic (C-18:3).
Natural fats and oils vary widely in their physical properties even though they are
composed of the same or similar fatty acids. These differences result from differences in
the proportion of the fatty acids and the structure of the individual triglycerides. Factors
that affect the properties of vegetable oil are plant maturity, plant health, microbiological,
seed location within the flower and the genetic variation of the plant. Animal fats and oils
composition varies according to the animal species, diet, health and fat location on the
carcass and maturity.
Physical properties of an oil or fat are of critical importance in determining its functional
characteristics or use in food products. One fundamental physical property of importance
is demonstrated by the terms fats and oils, which indicate whether a lipid is a solid or
liquid at ambient temperatures. But this grouping is not rigid because vegetable oils that
are solid at ambient temperatures in a temperate climate are liquid at the tropical ambient
temperatures. How then can one measure the functional properties? Have you come
across the term performance testing? The next section presents a detailed discussion on
this aspect.
Some essential attributes contributed by fats and oils cannot be directly measured with
chemical or physical analytical methods. In these cases, performance testing is the only
means for evaluating the ability of fat or oil to perform the desired functions in a food
product. Actual determinations of the performance qualities of an edible fat and oil
product are made with small scale practical tests that evaluate a finished product.
Performance testing is essential for the development of new products, especially for fats
and oils products designed for a specific food product, a formulation, or a process. After
development, physical or chemical analysis can be related to performance results in most
situations; however, continuation of certain performance evaluations is necessary for
some products to ensure adequate performance or more timely results in some cases.
Initially, most performance testing was designed for bakery products but has now been
expanded to every specialty product situation, i.e., baking, frying, candy, coatings,
formulated foods, nondairy products, and so forth, wherever tailored oils, margarines, oils
and other specialty products are utilized. In many cases the performance tests are
developed to evaluate the fat and oil ingredient as it would be used by a specific food
processor. You would realize, performance evaluation in itself can be a detailed subject
of study. Here, in this unit we shall not dwell on this aspect. Those of you, who are
interested to learn more about performance evaluation, read box 1 for information. It
provides a few examples of performance evaluation.
Cake mix evaluation – Originally, cake mix formulations were very similar to bakery
cakes and utilized standard “Hi-Ratio” cake oils; however, development of improved
cake mixes required rapid aerating oils to minimize mixing times for the house wife,
while at the same time increasing the product’s mixing and baking tolerances. The
competitive nature of the cake mix industry has continued the demands for new and
improved products, of which oil has always been a major contributor. A basic white
mix cake formulation and the make-up procedure can serve to evaluate new or revised
emulsifier systems for aeration, eating qualities and cake shelf-life, as well as the oil
carrier for lubrication and consistency.
Restaurant deep fat frying evaluation – A number of factors are studied when
evaluating frying oils. During deep fat frying, the fat is exposed continuously to
elevated temperatures in the presence of air and moisture. A number of chemical
reactions, including oxidation and hydrolysis, occur during this time, as well as changes
due to thermal decomposition. As these reactions proceed, the functional, sensory and
nutritional quality of the frying fat changes and eventually reaches a point where it is
no longer possible to prepare quality fried products and the fat will have to be
discarded. The rate of frying fat deterioration varies with the food fried, the frying fat
utilized, the fryer design and the operating conditions.
The deep fat frying evaluation consists of controlled heating of the test oils at 360±10°F
(176 to 187°C) continuously until the test is terminated. Fresh French cut potatoes (227
grams) fried three times daily for 7 minutes at 3-hour interval are flavoured once daily.
 Frying observations recorded after each frying includes smoking, odor, clarity, gum
 formation and a determination of foam development. Foam development described as
 none, trace, slight, definite and persistent should also be measured with a foam test
 daily and each time a change in the observed foam is recorded. Samples are taken after
 each 24-hour period for analysis of colour, free fatty acid and iodine value for
 quantitative measurement of darkening, hydrolysis and polymerization. The frying test
 is terminated when persistent foam has been observed and substantiated by foam height
 testing.
We have read about the deep fat frying evaluation method for measurement of functional
properties of fat. Deep fat frying is commonly used as a cooking method in most homes.
What are the issues to be considered while using this method of cooking is the focus of
discussion in the next section.
Deep fat frying, as you may already know, is the method which involves cooking food in
hot fat/oil. The fat immediately surrounds the food and cooks it from all sides, creating an
exterior layer that seals in the food's flavors and juices inside. Deep frying is one of surest
ways of locking in flavor and developing great texture (also known as "crunch") in
cooking. Deep fat frying, in fact, has become one of the more important methods of food
preparation used by the food service, snack and baking industries, as well as the home
kitchen. The deep fat frying process consists most simply of (1) partially or totally
immersing the food prepared for frying into (2) a body of heated frying fat, which is (3)
contained in a metal vessel, and (4) maintaining the food in the fat at the appropriate
frying temperature for (5) the duration required to cook the product. Going into the
cooking utensil are (a) frying fat, (b) heat, and (c) the food prepared for frying. Emerging
from the utensil are (a) steam and steam- entraining frying fat, (b) volatile by-products of
heating and frying, (c) the finished product, and (d) with filtering, the crumbs or foreign
solid by-products of the frying operation.
As you read the next section, you will realize all these factors mentioned above, have a
role to play in the deep fat frying process. Let us get to know them.
As frying continues, the level of oil in the fryer depletes. There are two beneficial frying
fat quality factors affected during the frying operation. These include:
    •   the steam released during frying, and
    •   the addition of fresh oil to replace the fat absorbed by the food fried.
Steam formed from the moisture released from the food mixes intimately with the fat,
and when given off, it carries with it the odor- and flavour-bearing volatile by-products of
frying that would otherwise accumulate in the frying fat to adversely affect the flavour
and odor of the fried food. This steam continually scrubs or purges the frying fat of the
potential off – flavours and odors each time the food is fried, even though it is the same
moisture that causes hydrolysis. Fresh oil must be added to the fryer to compensate for
the fat removed by the fried product. This addition helps to overcome the changes to the
frying fat brought about by the heat and other frying fat enemies. Obviously, the frying
fat will remain in better condition when higher replacement oil quantities are required.
The ratio of the fryer’s capacity to the rate at which the fresh oil is added to replenish the
fryer is referred to as turnover rate, or the number of hours required for the addition of
fresh frying oil equal to the amount of fat maintained in the fryer. Because oxidative
changes occur continuously in heated fats, turnover must be related to the total period
that the fat is heated, rather than only the actual time the product is fried. Obviously, the
quality and, especially, the flavour of the frying fat will be maintained at a more desirable
level with the highest turnover rate. In general, an operation with a turnover less than a
day should never have to discard used frying oil because of breakdown, except in the case
of product abuse or a contaminant. Operations with a slower turnover rates need to
include this product quality and economic factor in their frying oil selection criteria.
Before we move on further, let us recapitulate what we have learnt so far. The salient
points are listed in points to remember given herewith. Read them carefully.
                                POINTS TO REMEMBER
   1. Natural fats and oils vary widely in their physical properties even though they are
       composed of the same or similar fatty acids.
   2. Physical properties of a oil or a fat are of critical importance in determining its
       functional characteristics or use in food products.
   3. Performance testing is the means for evaluating the fat or oil’s ability to perform
       the desired functions in a food product.
   4. Cake batter aeration can be affected by the plasticity, consistency, emulsification
       and other properties of fats and oil.
   5. Deep fat frying has become one of the most important methods of food
       preparation.
   6. Factors affecting the frying process are frying temperature, oxygen from air,
       moisture content of the food, duration of frying and presence of contaminants.
   7. The rate of frying fat deterioration varies with the food fried, the frying fat
       utilized, the fryer design and the operating conditions.
   8. Fresh oil must be added to the fryer to compensate for the fat removed by the
       fried product. This addition helps to overcome the changes in the frying fat.
   9. Quality and flavour of the frying fat will be maintained at a desired level with the
       highest turnover rate.
From our discussion so far it is clear that the food products undergo changes in flavour
due to the chemical changes occurring in fats and oils present in them. The causative
factors responsible for such changes are presence of enzymes, atmospheric oxygen and
application of high temperature. Lipid oxidation is one of the major causes of food
spoilage. It is of great economic concern to the food industry because it leads to the
development of various off-flavours and off odours generally called ‘rancid’ (oxidative
rancidity), in edible oils and fat-containing foods, which render these foods less
acceptable. In addition, oxidative reactions can decrease the nutritional quality of food
and certain oxidation products are potentially toxic. On the other hand, under certain
conditions, a limited degree of lipid oxidation is sometimes desirable, as in aged cheeses
and in some fried foods.
In this section we will look at the oxidative and other changes occurring in fats and oils
causing deterioration. We begin with autoxidation.
3.6.1 Autoxidation
It is generally agreed that “autoxidation”, that is, the reaction with molecular oxygen via
a self – catalytic mechanism, is the main reaction involved in oxidative deterioration of
lipids. Autoxidation reaction can be divided into three parts:
a. initiation,
b. propagation, and
c. termination.
In the initiation part, hydrogen is removed from the fatty acid chain to yield a free radical.
The removal of hydrogen takes place at the carbon atom next to the double bond and can
be brought about by the action of light, metals etc. Let us understand this concept with
the help of an example. For example, in oleic acid, the reaction will proceed by removal
of hydrogen from carbons 8 or 11 resulting in free radical as shown herewith.
                                    8       9   10       11
               COOH (CH2)6 CH2 CH=CH CH2_(CH2)6_CH3
                       _        _       _            _
           8     9    10   11                                 8   9   10   11
       _
           CH_CH=CH_CH2_                                      CH2_CH_CH=CH_
The propagation can be followed by termination, if the free radicals react with
themselves to yield non-active products:
R’ + R’         R _R
R’ + RO2             RO2R
nRO2’           (RO2)n
You must remember that the hydro peroxides (ROOH) formed in the propagation part
of the reaction are the primary oxidation products. They are generally unstable and
decompose into secondary oxidation products which include a variety of compounds.
Among the secondary oxidation products, aldehydes and alcohols form an important
group. The volatile aldehydes are mainly responsible for the oxidized flavour (rancid)
of fats.
A general scheme summarizing the overall picture of lipid autoxidation is given in the
figure 3.1.
        RH
                    O2
                               Dimers, polymers; cyclic
                               peroxides;
                                                  ROO’
                               Hydroperoxy compounds
                               R’
Cleavage
                                                                      Aldehydes,
                                                                      Ketones, hydrocarbons,
                                                          RH          Furans, acids
                                        ROOH
                                                    OH
                   ROOR,
                ROR dimers               RO’              Keto,
                                                          hydroxy
                                                          and epoxy
                                                          compounds
                                            Cleavage
         O2
                     Condensation
                                                                           O2
Hydrocarbons                 Hydrocarbons
Shorter aldehydes
Acids
epoxides
                             Terminal
                             ROOH
                                        Hydrocarbons
                                        Aldehydes,alcohols
              Figure 3.1:Generalised scheme for autoxidation of lipids
There are many factors influencing the lipid autoxidation process you have just learnt
about. Let us get to know them.
At somewhat higher water activities (aw = 0.55 – 0.85), the rate of oxidation
increases again, presumably as a result of increased mobilization of catalysts and
oxygen.
•   Pro-Oxidants
Transition metals, particularly those possessing two or more valency states and a
suitable oxidation – reduction potential between them (e.g., cobalt, copper, iron,
manganese and nickel), are effective pro-oxidants. If present, even at
concentrations as low as 0.1 ppm, they can decrease the induction period and
increase the rate of oxidation. Trace amounts of heavy metals are commonly
encountered in edible oils and they originate from the soil in which the oil –
bearing plant was grown, from the animal, or from metallic equipment used in
processing or storage. Trace metals are also naturally occurring components of all
food tissues and of all fluid foods of biological origin (eggs, milk, and fruit juices)
and are present in both free and bound forms.
After autoxidation, we look at the deteriorative changes caused by lipolysis.
3.6.3 Lipolysis
What do we mean by lipolysis? Hydrolysis of ester bonds in lipids is called lipolysis. This
may occur by enzyme action or by heat and moisture, resulting in the liberation of free
fatty acids. Free fatty acids are virtually absent in the fat of living animal tissue. These
can be formed, however, by enzyme action after the animal is killed. Since animal fats
are not usually refined, prompt rendering is of particular importance. The temperatures
commonly used in the rendering process are capable of inactivating the enzymes
responsible for hydrolysis. In contrast to animal fats, oils in mature oil seeds may have
undergone a substantial hydrolysis by the time they have harvested, giving rise to
significant amounts of free fatty acids. Neutralization with alkali is thus required for most
vegetable oils after they are extracted.
Lipolysis is a major action occurring during deep fat frying due to large amounts of water
introduced from the food and the relatively high temperatures used. Development of high
level free fatty acids during frying is usually associated with foaming and a decrease in
the smoke point of the oil and reduction in the quality of the fried food. The release of
short – chain fatty acids by hydrolysis is responsible for the development of an
undesirable rancid flavour (hydrolytic rancidity) in raw milk. Furthermore, free fatty
acids are more susceptible to oxidation than other fatty acids esterified to glycerol.
Lipolysis, therefore, can cause changes in fats and oils which are best avoidable. On the
other hand, you would be surprised to learn that certain typical cheese flavours are
produced by deliberate action of microbial and milk lipases. Controlled and selective
lipolysis is also used in the manufacture of other food items, such as yogurt and bread.
Besides lipolysis, thermal decomposition too can bring about changes in oils and fats
which are deteriorative. Let us learn about these changes.
The chemistry of lipid oxidation at high temperatures is complicated by the fact that both
thermolytic and oxidative reactions are simultaneously involved. Both saturated and
unsaturated fatty acids undergo chemical decomposition when exposed to heat in the
presence of oxygen. A schematic summary of these mechanisms is shown in figure 3.2.
Saturated Unsaturated
                                       O2                   Thermolytic                  O2
        Thermolytic           (α, β, γ,δ- attack )           Reactions
         Reactions
                                                                                        Volatile and
                               Long-chain alkanes,          Acyclic and                    dimeric
           Acids              aldehydes, ketones and       cyclic dimers                 products of
       hydrocarbons                  lactones                                           autoxidation
        propenediol
          acrolein
          ketones
With thermal decomposition, we complete our study on the deteriorative changes in fats
and oils. Now, the next important issue is how to prevent these deteriorative changes?
The answer lies in one word ‘Antioxidants’. Let us learn about what the antioxidants are
and how they play a protective role in the context of fats and oils.
3.7    ANTIOXIDANTS
Antioxidants are the substances that can delay onset, or slow the rate of oxidation of
autoxidizable materials. By virtue of this property, they provide protection against
oxidative changes in fats and oils. They act by reacting with the free radicals and thereby
terminate the propagation of chain reaction. The antioxidant reacts with the fatty acid free
radical or with the peroxy free radical. Literally hundreds of compounds, both natural
(including vitamins C and E, vitamin A, selenium (a mineral) and a group known as the
carotenoids) and synthesized, have been reported to possess antioxidant properties. Their
use in foods, however, is limited by certain obvious requirements not the least of which is
adequate proof of safety. The main lipid soluble antioxidants currently used in food are
monohydric or polyhydric phenols with various ring substitutions. For maximum
efficiency, primary antioxidants are often used in combination with other phenolic
antioxidants or with various metal sequestering agents.
Although the mechanisms by which many antioxidants impart stability to pure oils are
relatively well known, much remains to be learned about their action in complex foods.
Some commonly used/present antioxidants in fats and oils and their characteristics are
discussed herewith.
                                   POINTS TO REMEMBER
     1. Lipid oxidation is one of the major causes of food spoilage. It leads to the
        development of off flavours and off odours generally called rancid.
     2. Autoxidation is the reaction of fats and oils with molecular oxygen. It consists of
        three steps namely, initiation, propagation and termination.
     3. Volatile aldehydes formed during autoxidation are mainly responsible for the
        rancid flavour of fats and oils.
     4. The number, position and geometry of double bonds in the fatty acid chain affect
        the rate of oxidation. As the number of double bonds increase, there is an increase
        in the rate of oxidation.
     5. Oxygen concentration, temperature, surface area of the lipid exposed to air and
        moisture content influence the lipid oxidation.
     6. Hydrolysis of ester bonds in lipids can occur by enzyme action, heat and
        moisture, resulting in the liberation of free fatty acids.
     7. Development of high level of free fatty acids during frying is associated with a
        decrease in smoke point and reduction in the quality of fried food.
     8. Lipid oxidation at high temperature involves both thermolytic and oxidative
        reactions leading to loss of flavour, appearance and nutritive value.
     9. Antioxidants can delay the onset, or slow the rate of oxidation of fats and oils.
Lipids are the major components of oil bearing materials and adipose tissue. They consist
of broad group of compounds that are generally soluble in organic solvents. Largest
source of vegetable oil is the seeds of plants such as peanut, sunflower, cottonseed,
mustard and safflower. Acylglycerols or glycerol esters of fatty acids which make upto
99% of the lipids of plant and animal origin have been traditionally called fats and oils.
Oils of vegetable origin contain large amounts of oleic and linoleic acid. Physical and
chemical properties of oils and fats are important to their functional properties in many
foods. Many essential attributes contributed by fats and oils can be evaluated by
conducting performance tests. These tests are designed for products such as baked goods,
candy, coating snacks and formulated products. Deep fat frying is an important method of
food preparation. Factors affecting the process of deep fat frying are frying temperature,
exposure to air, moisture content of the food being fried, presence of contaminants such
as trace metals, soap or detergent and duration of heating. Fats and oils undergo changes
in flavour or they develop rancid flavour due to the presence of enzymes, atmospheric
oxygen and application of high temperature. Autoxidation is the main reaction involved
in the oxidative deterioration of lipids. Autoxidation occurs through free radical
mechanism consisting of three steps, namely, initiation, propagation and termination.
Lipid oxidation is influenced by the fatty acid composition, oxygen concentration,
temperature, surface area, moisture and pro-oxidants. Lipolysis is the hydrolysis of the
ester bonds in the lipids resulting in the liberation of free fatty acids which are more
susceptible to oxidation than acylglycerols. Lipids undergo chemical decomposition
when exposed to heat in presence of oxygen. Antioxidants are the substances that can
delay the onset or slow the rate of oxidatioin of lipids. The main antioxidants used in
food are monohydric or polyhydric phenols with various ring substitutes. Tocopherols are
the most widely distributed natural antioxidants in vegetable oils. Tertiary butyl
hydroquinone (TBHQ) is more effective than any other antioxidant in providing
oxidative stability to oils and fats.
3.9     GLOSSARY
Acylglycerols            : Most abundant; these constitute upto 99% of the lipids of
                         plant and animal origin. They are esters of fatty acids with
                         glycerol.
Antioxidants             : Substances that can delay the onset, or slow the rate of
                         oxidative deterioration of oils and fats.
Autoxidation             : Reaction of the molecular oxygen with oils and fats
                         leading to the development of off odour or rancidity.
Cis-trans isomers        : Atoms or groups are called cis or trans to one another
                         when they project respectively on the same or on opposite
                         sides of a reference plane identifiable as common among
                         stereoisomers. The compounds in which such relations
                         occur are termed cis/trans-isomers.
Fatty acids              : Aliphatic monocarboxylic acids that can be liberated by
                         hydrolysis from naturally occurring fats and oils.
Functional property      : Properties of fats and oils which have a marked influence
                         on the preparation and quality of a food product.
Lipids                   : Broad group of compounds that constitute the principal
                         structural components of all living cells, and are generally
                         soluble in organic solvents.
Lipolysis                : Hydrolysis of ester bond in lipid caused by enzyme
                         action, heat and moisture resulting in liberation of free fatty
                         acids.
Oleic – linoleic group   : Most abundant group of fats and oils that contain large
                         amounts of oleic and linoleic acid.
Oxidation-reduction
Potential (ORP)          : ORP is related to the concentration of oxidizers or
                         reducers in a solution, and their activity or strength. It
                         provides an indication of the solution's ability to oxidize or
                         reduce another material. These chemicals have the ability
                         to oxidize (accept electrons) or reduce (donate electrons)
                         molecules.
Performance test              : A method for evaluating the ability of fat or oil to perform
                              the desired functions in a food product.
Pro-oxidants                  : Transition metals, possessing two or more valency states
                              and a suitable oxidation-reduction potential between them.
Rancidity                     : Development of-off flavour in fats and oils caused by
                              autoxidation, lipolysis or thermal decomposition.
Thermal
Decomposition                 : Chemical decomposition of oils and fats when exposed to
                              heat in the presence of oxygen.
2.     The role of food lipids in human diet are follows: lipids supply calories, essential
       fatty acids, act as fat-soluble vitamin carriers and increase the palatability of food.
3.     The major classes of lipids are simple lipids (acylglycerols and waxes);
       Compound lipids (glycerophospholipids); Derived lipids (compounds that are not
       simple or compound lipids) example, Carotenoids and vitamins. Acylglycerols are
       the glycerol esters of fatty acids which make up to 99% of the lipids of plant and
       animal origin.
2.      The important functional properties of fats and oils are discussed as follows.
        Frying oil is an effective heat exchange medium, to help in development of
        texture and flavour of fried foods. Form emulsions in batter and dough.
        Contribute to the texture and flavour of baked products.
3.      The salient features of performance test are that it helps in evaluating the ability
        of fat and oil to perform the desired function in a food product. It is essential
        for the development of specific food products and formulations.
4.      The factors affecting deep fat frying are temperature of frying; presence of
        oxygen; moisture content of food; presence of contaminants such as trace metals
        and duration of frying
5.      Number of hours required for the addition of fresh frying oil equal to the
        amount of oil maintained in the fryer is referred to as the turnover rate of frying
        oil.
6.      The turn over rate affects the quality of frying oil by maintaining the flavour at a
        more desirable level, slowing down oxidative changes occurring in frying fat
        and minimizing discard of used frying oil.
2.   Off flavours caused by the chemical changes occurring in fats and oils is referred
     to as rancidity. The compounds responsible for it are unsaturated aldehydes,
     ketones, alcohols and acids.
3.   The factors influencing lipid oxidation are fatty acid composition, oxygen
     concentration, temperature, surface area of the lipid, moisture and the presence of
     pro-oxidants.
4.   Lipolysis is the hydrolysis of ester bonds in lipids caused by the action of enzyme,
     heat or moisture. Free fatty acids are liberated as a result of lipolysis.
5.   The compounds formed by the thermal decomposition of fats and oils are acyclic
     and cyclic dimers, long-chain alkanes, aldehydes, ketones and lactones and
     hydrocarbons.
6.   Antioxidants delay the onset of rancidity by reacting with the fatty acid free
     radical or with the peroxy free radical and thereby terminate the chain reaction of
     lipid oxidation.