ASSIGNMENT NO.

CHEMICAL CHANGES AND

PROTECTIVE MEASURES
OF FAT DURING DEEP
FRYING
SUBMITTED BY:

SYED ALI AKBAR BUKHARI

2016-ag-6512

SUBMITTED TO: DR.ASIM SHABBIR

SUBJECT
Chemistry of Edible Oils and Fats
FST-714

UNIVERSITY OF AGRICULTURE,
FAISALABAD
  WHAT TYPE OF CHEMICAL CHANGES OCCURE IN RELATION TO FAT
MAINLY INVOLVE DEEP FRYING?
It is well known that deep-fat frying is a prevalent and old food cooking method
which can go back to 1600 BC. Although 180◦ C is usually recommended for frying foods, it is
always higher than 180◦ C in the practical deep-fat frying. Fast food processing, palatable taste
of fried food and considerable economic benefit make the deep-fat frying one of the most
popular food cooking methods used. The fried food is endowed with attractive flavor, golden
pellicle and crisp texture or mouth feel when it is fired under the appropriate conditions.
Under the established conditions of fried material’s natural properties corresponding
sample handling, frying can involve all of the components to participate in a series of physical
and chemical alterations. These changes not only include the decomposition reactions of the
constituents such as the nutrients of raw material and triacylglycerol (TAGs) of frying oil
oxidized TAGs with keto, epoxy, hydroxyl, aldehyde and epoxy groups saturated or unsaturated,
but also include the inter-actions among these constituents. Moreover, deep-fat frying is a
complicated physicochemical processes which simultaneously influenced by many factors such
as the nature of fried material and frying oil, time, temperature, intermittent or continuous
heating, fresh oil complement, fryer model and use of filters. Therefore, many products are
formed due to these complex substrates and chemical conditions.

So, here we discuss chemical reactions and their products taken place during deep frying.
1.HYDROLYSIS
When food is fried in hot oil, moisture forms vapor, which evaporates with bubbling
action and gradually decreases as food is fried. Water, steam and oxygen initiate chemical
reactions in the frying oil and food. Water, a weak nucleophile, attacks the ester bond of
triacylglycerol and produces di and monoacylglycerols, glycerol and free fatty acids. Free fatty
acids frying oil content increases with number of fries. The free fatty acid index is used to
control the quality of the oil for frying. The degree of hydrolysis is a function of various factors,
such as oil temperature, interface area between oil and aqueous phases, and amount of water and
steam because water hydrolyzes oil faster than steam. Free and low fatty acids molecular weight
acid products arising from fat oxidation improve the hydrolysis in the presence of steam during
frying. Hydrolysis products, like all oil breakdown products, decrease the stability of frying oils
and can be used to measure the lifespan of fingerlings, for example free fatty acids.
Oil and fat is a mixture of triacylglycerides (TAG) which are composed of one
glycerol and three saturated or unsaturated fat groups acids with different carbon numbers. Not
just the nature of fatty acids, but also the various combination positions from fatty acids to
glycerol molecule would impact the reaction activity of LABEL. Therefore, the degradation of
TAG products is mainly the result of Breaks occurred in the carbon-carbon (C C) double bond of
aliphatic chains and ester bond. These the compounds have a lower molecular weight compared
to father's TAG and almost have volatility like decomposition compounds of lipid oxidation and
hydrolysis of TAG.

2.OXIDATION
Edible fats containing unsaturated Molecules are susceptible to attack by
molecular oxygen. This process is called lipid oxidation and can lead to an undesirable volatile
taste compounds, potentially toxic oxidation products and a general deterioration in the quality of
the fat. Fat oxidation is influenced by a number of parameters, including exposure to light,
temperature presence of pro-oxidant metals (Cu, Ni Co), presence of antioxidant compounds,
and the degree of fat unsaturation. Oxidation of edible oils are influenced by an energy input as
light or heat, composition of fatty acids, types of oxygen and minor compounds such as metals,
pigments, phospholipids, free fats acids, mono and diacylglycerols, thermally oxidized
compounds, and antioxidants.
On the other hand, oxygen, which is present in new oil and is introduced into the
frying oil at the surface of the oil and by adding food, activates a series of reactions that involve
formation of free radicals, hydroperoxides and conjugates dienoic acids. Chemical reactions that
occur during the oxidation process contribute to the formation of both volatile and non-volatile
decomposition products. For example, ethyl linoleate oxidation leads to the formation of
conjugated hydro-peroxides that can form long chain non-recyclable products or they can cycle
and form peroxide polymers Volatile degradation products are usually saturated and
monounsaturated hydroxyl, aldehyde, keto and dicarboxylic acids; hydrocarbons; alcohols;
aldehydes; ketones; and aromatic compounds are primarily responsible for undesirables rusty
(rancid) flavors. Oxidation oil is very important in terms of palatability, nutritional quality and
edible oil toxicity.
OXIDATAION MECHANISMS:
The mechanism of oxidation in frying oils it is similar to autoxidation at 250 ° C;
however, the unstable primary oxidation products, hydroperoxides, decompose rapidly at 190 ° C
in secondary oxidation products such as aldehydes and ketones. Secondary oxidation products
that are volatile contribute significantly to the smell of the oil and the taste of fried food If
secondary oxidation the products are unsaturated aldehydes, such as 2,4-decadienal, 2,4-
nonadienal, 2,4-octadienal, 2-heptenal or 2- octenal, contribute to the characteristic fried flavor
in oils that are not damaged and can be considered desirable. Different chemical mechanisms are
responsible for the oxidation of edible oils during process, storage and cooking, depending on the
types of oxygen. Two types of oxygen can react with Edible oils. One is called atmospheric
triplet of oxygen, 3O2, and the other is singlet oxygen, 1O 2. Triplet oxygen, 3O2 reacts with lipid
radicals and causes autoxidation, which is a free radical chain reaction. the lipid radical reacts
with a triplet. oxygen very quickly into normal oxygen pressure (2 to 8 × 10 9 / M / s) and forms
peroxy lipid radical. Lipid peroxy radical abstracts hydrogen from others lipid molecules to form
lipids hydroperoxide and another lipid radical. The oxidation rate is Non-radical electrophilic
singlet oxygen does not require radicals to react; reacts directly with double bonds of unsaturated
fats and oils with high electron densities, which is called photosensitized oxidation.
Fats and oils must be in radical forms to react with triplet oxygen in autoxidation.
Lipids are normally found in non-radical singlet state and heat, metals, or light accelerates its
radical training. Allyl hydrogen, especially hydrogen bonded to carbon between 2 double bonds,
it removed due to low bond dissociation energy. Carbon and The hydrogen dissociation energies
are the lower in bis-allyl methylene position. Bis-allyl hydrogen in The C11 of linoleic acid is
removed at 75 ° C. up to 80 kcal / mol. The energy needed to remove allyl hydrogen at C8 or
C14 of linoleic acid is 88 kcal / mol, and 101 kcal / mol is necessary to remove the alkyl The
hydrogen from C17 or C18. After the formation of lipids radicals by elimination of hydrogen,
double bond adjacent to carbon radical in linoleic and linolenic acids switch to the next most
stable carbon, resulting in conjugated diene structures. The displaced double bond above all take
more thermodynamically stable trans form.
It depends on several factors, including temperature, presence of inhibitors or
catalysts and nature of the substrates. Unsaturated fatty acids are more susceptible to oxidation
than saturated fatty acids. A property that is primarily due to the activation energy reduced by the
start of free radical formation for the autoxidation of triplet oxy. Hydroperoxides formed by
singlet oxidation of oxygen are in positions that previously contained double bonds. Conjugated
produced singlet oxygen and unconjugated hydroperoxides of linoleic and linolenic acids, but the
triplet of oxygen produced alone conjugated hydroperoxides of linoleic and linolenic acids. The
singlet oxygen reaction rates and oxygen triplet with linoleic acid are 1.3 × 105 M-1s-1 and 8.9 ×
101 M-1 s-1, respectively.
FREE REDICAL AUTOXIDATION:
Autoxidation is an important degradation reaction which is attributed to rancidity
of oil and fat. Autoxidation depends on free radical’s chain reactions, involving the interaction of
oxygen with free radicals generated in methylene groups adjacent to double bonds, especially in
methylene groups between two doubles bonds. Auto-oxidation access atmospheric to unsaturated
oxygen fatty acids or glycerides leads to oxidation deterioration. Saturated and monounsaturated
fats chains rust very slowly and do not as a rule, cause trouble. Gave - unsaturated chains, as in
18: 2 n-6, oxidize faster and polyunsaturated chains very quickly. The reaction of oxygen wit
unsaturated lipids (RH) implies free radical initiation, propagation and termination processes.
Initiation is produced by loss of a hydrogen radical in the presence of trace elements, light or
heat. The lipid-free result radicals (R) react with oxygen to form peroxy radicals (ROO).
In this propagation process, ROO react with more RH to form lipid
hydroperoxides (ROOH), which are the fundamental Primary Autoxidation Products. The main
lipid products peroxidation are hydroperoxides (ROOH), which can be dissociated into free
radicals. Lipid hydroperoxides are stable at physiological temperatures, and an important role of
transition metals is to catalyze its decomposition. Transition metal ions catalyze lipid
hydroperoxides of homolysis that split into alkylperoxyl radicals (ROO) by metal ions in the
oxidized been as the ferric ion, while reduced metal ions, such as ferrous ion, lead to alkoxy
radicals (RO) The free radicals produced in these The processes are believed to stimulate chain
reaction of lipid peroxidation by abstracting more hydrogen from non-oxidized lipids.
THE THERMAL OXIDATION AND THEIR PRODUCTS:
 Thermal oxidation, which is accelerated at high temperature used for frying,
creates rancid flavors and reduces organoleptic characteristics of fried foods. During frying, the
oils degrade from the temperature oxidation to form volatile and non-volatile decomposition
products. chemical changes in frying oil too result in changes in the quality of the fried food. The
fatty acid composition of oil for frying is an important factor affects the taste of fried foods and
their stability; therefore, it must be low level of polyunsaturated fatty acids such as linoleic or
linolenic acids and high oleic acid level with moderate amounts of saturated fatty acids. As a
result, the quality of the frying oil is important due to oil absorbed from fried products during
frying
Soybean oil has a good profile due to high level of unsaturated fatty acid but
less oxidative stability. The chemistry of lipid oxidation in high temperatures of food processes
how to bake and fry is very complex since both oxidative and thermal reactions are involved
simultaneously. Like temperature increases, the solubility of oxygen decreases dramatically,
though oxidation reactions are accelerated the well-known scheme of the oxidation process.
Proceeds through a free radical chain mechanism Heating in the presence of air causes partial
conversion of fats and oils to volatile chain cleavage products, no volatile oxidized derivatives,
and dimeric, polymeric, or cyclic Substances There is some evidence that hot and highly
oxidized fats can have carcinogenic properties because of potentially toxic substances.
FORMATION OF VOLATILE AND SHORT-CHAIN COMPOUNDS DURING
THERMAL OXIDATION:
An important route for the formation of new compounds is the decomposition
of hydroperoxides giving rise to volatiles and short-chain compounds attached to the glyceride
spinal column that is part of non-volatile molecules. Meanwhile, volatiles are largely removed
from the oil during frying and have implications in the taste of frying oil and fried food. The
non-volatile compounds remain in the frying oil reactions, where RH represents here the
triacylglycerol molecule undergoing oxidation in one of its unsaturated fatty acyl groups and are
absorbed by food modifying the nutritional oil and physiological properties. There is a general
acceptance of the mechanism of short-chain compound formation from the hydroperoxides formed
through autoxidation reactions. They originate from the homolytic β cleavage of alkoxy radicals from
allylic hydroperoxides. Homolytic β cleavage occurs on both sides of carbon alkoxy via path A or B.
Through this mechanism, two types of aldehydes (volatile aldehyde and esterified aldehydes) and alkyl
or alkenyl radicals are produced. Greater interaction of alkyl and alkenyl radicals with other low
molecular weight radicals present in oil (H٠and OH٠) contributes to your stabilization to form alcohols
and hydrocarbons.
POLYMERIZATION:

The most likely decomposition hydroperoxide pathway is the neckline. Many non-
volatile polar compounds and triacylglycerol attenuators and polymers are produced in thermally
oxidized oil reactions. Dimerization and polymerization are the main reactions of in thermal oxidation in
oil. Dimers and polymers are large molecules with a molecular weight range of 692 to1600 Daltons and
made up of a combination of –C - C– –C - O - C–, and links –C - O - O - C– Copolymerization occurs more
easily in oil with a high content of linoleic acid than in high oil content of oleic acid. C – C bonds is
formed between 2 acyl groups to produce acyclic dimers in low oxygen heated oil.

The Diels-Alder reaction produces cyclic dimers by tetra substituted cyclohexene

and radical reactions within or between triacylglycerols as well as produce cyclic polymers. Polymers are
rich in oxygen and highly conjugated diene and produce a brown resin, residue. As polymerized products
increased frying oil, the viscosity of the oil also increases. Peroxide value(mg/kg) primary oxidation
analysis products, such as hydroperoxides, at any point in the frying process, provide little information
because its formation and decomposition fluctuate rapidly and are not easily predicted. During frying,
the oils with polyunsaturated fatty acids, suchlike linoleic acid, have a distinctive hydroperoxide
induction period followed by a rapid increase in peroxide values, then quick destruction of peroxides.
levels of polyunsaturated fatty acids, like linoleic acid, it can help determine the degree of thermal
oxidation (sixteen)reported that oxidative degradation oxidized triglycerides produced containing
hydroperoxide, epoxy, hydroxy and keto and dimeric groups dimeric fatty acids or triglycerides.

FORMATION OF CYCLIC FATTY ACIDS DURING THERMAL OXIDATION:

Cyclization can occur in both fatal chains in TAG and the decomposed fatty
acids, provided that the appearance of C-C. Then epoxy-TAG, Cyclic Fatty Acid Monomers
(CFAM)ring with only carbon atom too present in the fryer system. Despite the low
concentration of these cyclic monomers present in the deep-frying products, the suspect latent
biological hazard to the health of the consumer is an issue worth exploring. Various vegetable
oils have been used to investigate the influence of the same in the amount of formation of CFAM
and the results indicated that high oleic acid frying oil had a good frying effect and lower CFAM
yield. It is well known that C_ C is essential for cyclization; However, the degree of cycling,
content, and composition of CFAMs formed during the frying course be varied according to
unsaturation degree, position, and configuration of C_ C in different unsaturated aliphatic
TRANSISOMERS:
In fact, some of the aforementioned cyclic monomers referred to cis/trans
isomerization belonged to the trans isomers category. Except for the trans cyclic compounds,
there were several chains of frying oil. The mechanism proposed for the formation of cyclic fatty
acids in heated oils involved a free radical reaction. However, if this were indeed to operate, it
would probably produce more isomers than were in fact found. A recent publication by
Distillates endangers, suggested an explanation that is more likely, i.e. thermally induced and
prototrophic migrations. As an illustration, the mechanisms for the formation of two of the
isomers fromα-linolenate are shown in Thus, the reaction of carbon C-10 with C14 results in the
formation of a five-membered ring by a pericyclic rearrangement. The resulting cyclopentenyl
compound may then in turn undergo sigma tropic rearrangement with double bond migration and
structural reorganization to form a six-member ring with a double bond between carbons 12
and13.
The mechanism correctly predicts the stereochemistry of the new double
bonds in each case other types of trans isomers. It's okay it is known that the trans isomers of
fatty acids have many adverse effects on human health like coronary heart disease, sudden, and
systemic cardiac death inflammation. However, isomers are very extensive in terms of both raw
materials and food products. During deep fat fry, all break, change, and formation of C_ C
implies the presence configuration trans. Therefore, it is inevitable that the formation of trans
fatty acid during heating of vegetable oil or fry. Trans, trans-2,4-decadienal which is related to
the induction of low-density lipoprotein oxidation occurred as a by-product in French fries.
Fortunately, an ordinary frying process at the right time using non-hydrogenated Edible oils have
little impact on the intake of trans fatty acids from edible oils. With increasing the frying time,
the number of trans fatty acids increased but decreased when butylated hydroxyanisole (BHA) or
phenolic dried rosemary extracts were added to the frying system
OXYSTEROL FORMATION DURING THERMAL OIXDATION:
Sterol derivatives as minority existing components in oils and fats, sterols,
mainly phytosterols, have many benefits for human health. The known types of sterols are
cholesterol (animal sterol), stigma sterol, sitosterol, camp sterol, brassica sterol, avenasterol, etc.,
which exist widely in various types of foods. As a kind of triterpenoid, 28 or 29 carbons and one
or two C_ C (the first one in the core of sterols and the second one on the alkyl side chain) are
present in most phytosterols. Cholesterol autoxidation and phytosterols are provided by many
factors, for example, temperature, light, oxygen, free radical initiators, metal ions, pro-oxidant
agents, and antioxidant shortage. Oxidation The mechanisms of phytosterols are believed to
follow the same paths as oxidation of cholesterol.
 The formation of different oxysterols by autoxidation, such as documented
by experiments, proceeds through a chain reaction of free radicals. The process is started by
allylic hydrogen abstractionC7 in the cholesterol ring structure and tertiary carbons in the C20
positions C25. Radicals like this formed react with oxygen to produce corresponding peroxyl
radicals, which in turn they stabilize yielding different cholesterol hydroperoxides. Thermal
decomposition of these hydroperoxides produces 7α-hydroxy-,7β-hydroxy-, 7-keto-, 20-
hydroxy-, and 25-hydroxycholesterol. Epimeric Cholesterol 7-hydroperoxides can also attack the
Δ5 double bond of cholesterol, forming secondary cholesterol oxidation products, such as
Epimeric epoxycholestanol. Both of the epoxides, in turn, converted to 5αcolesta-3β, 5,6β-triol,
through epoxy hydration ring-opening. Relating to oxysterols in fats and oils used for frying and
cooking, only six to eight components are generally reported. Formation of the main ring the
oxidation products of the structure are shown in with the example of sitosterol
  EFFECT ON HUMAN HEALTH

Frying makes edibles tasty. Frying edible items includes the use of a
large amount of oil. Increased oil consumption is not considered good for human health.
Although a certain amount of potentially toxic products is produced during frying (such
as polar compounds or polymers), fried foods are generally considered safe. Only when
frying oil is used repeatedly does it become toxic for human consumption. Repeated
heating of the oil accelerates the oxidative breakdown of lipids, forming dangerous
reactive oxygen species and depleting the natural antioxidant content of cooking oil.

Prolonged ingestion of foods prepared with reheated oil could

seriously compromise one's antioxidant defense network, leading to conditions such as
hypertension, diabetes, and vascular inflammation. The oxidation of lipids causes a high
risk of developing coronary heart disease. The human body is constantly subjected to
significant oxidative stress as a result of the imbalance between antioxidant protection
systems and the formation of strong oxidizing substances, including free radicals. This
stress can damage DNA, proteins, lipids, and carbohydrates and could have a negative
effect on intracellular signal transmission.

 PROTECTIVE MEASURE WHICH CAN REDUCE CHANGES DURING DEEP

FRYING OF FAT:
The oil can be made safe for human consumption and the damage
caused by repeated use of heated oil can be minimized in a number of ways. The use of natural
antioxidants in cooking oil as adsorbents can make the oil safe by retarding the formation of oil
spoilage products. Antioxidants add tocopherols, Butylated hydroxyanisole (BHA), butylated
hydroxytoluene (BHT), propyl gallate (PG), and tert-butyl hydroquinone (TBHQ) that slow oil
oxidation at room temperature.
However, they become less effective at frying temperature due to losses due
to volatilization or decomposition (Boskou 1988; Choe and Lee 1998). It has been found that the
addition of different antioxidants such as sugarcane bagasse, rosemary extract, an extract of
turmeric, etc. during frying reduces the harmful effect. of spoilage products. Furthermore, this oil
rancidity can be reduced by taking mixed oil or a mixture of oils of different types with varying
concentrations of the different mixed oils. Turmeric extract as an antioxidant: the addition of
curcumin, a natural antioxidant present in the plant turmeric of the Zingiberaceae family can
reduce the harmful effects of the oil spoilage products. There was a decrease in the content of
trans fatty acids in fried foods with the addition of turmeric extract in concentrations of 0.03%.
This was related to curcumin that inhibits the rate of autoxidation by modifying the lipid radical
in a more stable form, which commonly inhibits the oxidation reaction of fats.
The presence of antioxidants added to repeatedly used cooking oil can slow
the rate of oxidation of the oil during frying and contribute to the sensory acceptance of fried
foods. The findings of this study are supported by the claim by that the addition of antioxidants
in cooking oil determines the stability of oxidation during frying; and according to Tuba and,
curcumin is effective to be used as an antioxidant because it can scavenge free radicals by
donating an H atom from phenolic as its active group. In addition to this, many adsorbents such
as sugarcane bagasse ash, magnesia XL, etc. can also be used. to reduce the formation of
spoilage products produced by repeated frying.

REFERENCES
I. https://www.researchgate.net/publication/270727167_Chemical_Reactions_Taken_Place
_During_deep-fat_Frying_and_Their_Products_A_review
II. https://www.researchgate.net/publication/282701462_OXIDATION_OF_COOKING_OI
LS_DUE_TO_REPEATED_FRYING_AND_HUMAN_HEALTH