FATS AND

OILS
UNIT-3

Dr. Gulshan Kumar

 Fats and oils are the most abundant natural products comes under group referred
as lipids in nature. They provide energy for living organisms, insulate body organs,
and transport fat-soluble vitamins through the blood.
 Fats and oils are called triglycerides/lipids (or triacylcylgerols) because they are
esters composed of three fatty acid units joined to glycerol, a trihydroxy alcohol:
 If all three OH groups on the glycerol molecule are esterified with the same fatty acid,
the resulting ester is called a simple triglyceride
 typical triglyceride obtained from naturally occurring fats and oils contains two or
three different fatty acid components and is thus termed a mixed triglyceride.
 Fat Oil
 Fat are solid at room Fat are Liquid at room
temperature temperature
 Saturated  Unsaturated
 High melting and boiling point  Low melting and boiling point
 Found in animals  Found both in animals and
Fatty acids: Fatty acids are comprised of hydrocarbon
plant chains terminating with carboxylic
acid groups.

Myristic acid

Palmitic acid

Arachidic acid
 14:0 (14 carbons, no double
Myristic Acid
bonds
Palmitic Acid 16:0
Stearic Acid 18:0
Arachidic Acid 20:0
Palmitoleic Acid 16:1
Oleic Acid 18:1
Linoleic Acid 18:2
Arachidonic Acid 2:4
Arachidonic acid

Palmitoleic acid

Linoleic acid
 Chemical Reactions of Fats and
Oils
1. Hydrolysis or if basic hydrolysis
“saponification”

 hydrolyzed in the presence of an acid, a base, or specific enzymes known as lipases.

 hydrolysis of fats and oils in the presence of a base is used to make soap and is called
saponification
 Today most soaps are prepared through the hydrolysis of triglycerides (often from tallow, coconut
oil, or both) using water under high pressure and temperature [700 lb/in 2 (∼50 atm or 5,000 kPa)
and 200°C]. Sodium carbonate or sodium hydroxide is then used to convert the fatty acids to their
sodium salts (soap molecules):
 2. Hydrogenation
 Unsaturated fatty acids may be converted to saturated fatty acids by the relatively simple
hydrogenation reaction
 Vegetable oils are commonly referred to as
"polyunsaturated“
 Vegetable oils may be converted from
liquids to solids by the hydrogenation
reaction.
 A major health concern during the
hydrogenation process is the production of
trans fats
 major negative is that trans fat tends to
raise "bad" LDL- cholesterol and lower
"good" HDL-cholesterol
 Trans fat are found in margarine, baked
goods such as doughnuts and Danish
pastry, deep-fried foods like fried
chicken and French-fried potatoes,
snack chips, imitation cheese, and
confectionery fats.
Rancidification

 Rancidification is the decomposition of fats, oils and other lipids by hydrolysis, oxidation,
light and heat for long time.
 They will develop foul smell and sour taste due to release of free fatty acids
 Could be reduced by refrigeration

Factors causing of Rancidity

Oxidation: Oxidation primarily occurs with

unsaturated fats by a free radical-mediated process.
These chemical processes can generate highly reactive
molecules in rancid foods and oils, which are
responsible for producing unpleasant and noxious
odors and flavors. This process is called auto-oxidation
or oxidative rancidity.
Hydrolytic
rancidity
Triglycerides react with water under appropriate condition to form diglycerides and free fatty
acid residues. Diglycerides later combine with water to form monoglycerides and fatty acids.
Finally the monoglycerides completely hydrolysed to form glycerol and fatty acids.
Microbial rancidity by Lipase

Certain microorganisms can produce the hydrolytic enzyme called lipase, which directly
interferes the hydrolysis of triglcerides and produce glycerols and fatty acid. These fatty acids
undergo auto- oxidation to form rancid. The microbial lipase requires suitable pH and other
conditions for its activity upon fats and oil.

Presence of Unsaturation in Fatty Acid Chain:

When a fatty substance is exposed to air, its unsaturated components are converted into
hydroperoxides, which break down into volatile aldehydes, esters, alcohols, ketones, and
hydrocarbons, some of which have disagreeable odours. Butter becomes rancid by the
foregoing process and by hydrolysis, which liberates volatile and malodorous acids,
particularly butyric acid. Saturated fats such as beef tallow are resistant to oxidation and
become rancid at ordinary temperatures.
Polyunsaturatio
n:
The more polyunsaturated a fat is, the faster it will go rancid. Vegetable oils have to become
several times more rancid than animal fats. Presence of polyunsaturation in oils and fats makes
them more susceptible to rancidity than monosaturated and other types of saturated fatty acids.
Temperature and pH:

Suitable temperature and alkaline pH are required for the hydrolytic action of
microbial lipase. Temperature and pH indirectly influence the auto-oxidation
and hydrolysis.
Heat and Light:

Presence of heat and light accelerate the rate of reaction of fats with oxygen, i.e., heat
accelerates auto-oxidation. Heat and light act as the energy source for the production of free
radical in rancidity and reversion of oils and fats.
Prevention of Rancidity
Addition of Antioxidants

Natural antioxidants include flavonoids, polyphenols, ascorbic acid (vitamin C) and

tocopherols (vitamin E).
Synthetic antioxidants include butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT),
propyl-3, 4, 5-trihydroxybenzoate (also known as propyl gallate) and ethoxyquin. Natural
antioxidants tend to be short-lived, but synthetic antioxidants give longer shelf life and better
action.
Addition of Sequestering
Agents:

Sequestering agents bind metals, thus preventing them from catalyzing auto-oxidation.
Examples of sequestering agents include EDTA (ethylene diamine tetra acetic acid) and
citric acid.

proper Storage of Fats and Oil Food:

Rancidification can be decreased by storing fats and oils in a cool, dark place with little exposure
to oxygen or free radicals, since heat and light accelerate the rate of reaction of fats with
oxygen.
 Drying oil
 An oil harden to a tough, solid film after a period of exposure to air, at room temperature. The oil
hardens through a chemical reaction in which the components crosslink by the action of oxygen.
 Drying oils are a key component of oil paint and some varnishes. Some commonly used
drying oils include linseed oil, tung oil, poppy seed oil, perilla oil, castor oil and
walnut oil.

 Addition of oxygen to an organic compound and

the subsequent crosslinking. This process begins
with an oxygen molecule (O2) in the air inserting
into carbon-hydrogen (C-H) bonds adjacent to
one of the double bonds within the unsaturated
fatty acid. The resulting hydroperoxides are
susceptible to crosslinking reactions.
 Bonds form between neighboring fatty acid
chains, resulting in a polymer network, often
visible by formation of a skin-like film on sample
 accelerated by certain metal salts, especially
derivatives of cobalt, manganese, or iron
 Acid Value
 It is defined as the weight of KOH in mg needed to neutralize the organic acids present in
1g of fat and it is a measure of the free fatty acids (FFA) present in the fat or oil
Significance: determine the free fatty acids present in fat/oil. Oil have higher acid value are
unfit for consumption
Principle of Acid value:

The oil or fat in an alcoholic media is directly titrated against a standard potassium
hydroxide or sodium hydroxide solution to ascertain its acid value.
RCOOH + KOH = RCOO– K+ +
H2O
Reagents
preparation:
1). Dissolve one gram of phenolphthalein in 100mL of ethyl alcohol.
2). Ninety-five percent alcohol or rectified spirit neutral to phenolphthalein
indicator
3). Standard aqueous Potassium hydroxide or sodium hydroxide solution 0.1 or
0.5 N. The
solution should be colourless and stored in a brown glass bottle. For refined oils,
the strength of
the alkali should be fixed to 0.1 N.
PROCEDU •1. Weigh accurately 1–10 gm of ghee and place it in a
250mL conical flask, then add 50mL of ethanol-ether

RE: solution.
•2. Shake it well. If necessary, reflux the mixture gently until
the substance is completely dissolved.
•3. Titrate the solution with sodium hydroxide titrant until
0.1N KOH
pink colouration can be observed which persists for 30
second
•4.Record the reading initial and final reading of burette.
Calculate the difference value (ML) and acid vale.
•5. Measure the volume of sodium hydroxide titrant used
andsample+ethanol:pet.
Oil/fat calculate the acid value according to the following
equation:
Ether (1:1)+1mL
phenophthalein
V = Volume in mL of standard potassium hydroxide or
sodium hydroxide used
N = Normality of the potassium hydroxide solution or
Sodium hydroxide solution; and
W = Weight in gm of the sample
 Saponification
Value
Number of mg of potassium hydroxide (KOH - commonly known as potash) needed to saponify the
esters contained in a gram of material.
It is process by which triglycerides or fat hydrolysed by alkali to give glycerol and potassium salt of fatty
acids
Significanc
e
 Saponification value is a measure of the content of ester linkages
 It is a measure of the average molecular weight (or chain length) of all the fatty acids
present.
 Higher the molecular weight of the fat, the smaller is its saponification value.
 Saponification value also indicates the length of carbon chain of the acid present in that
particular oil or fat
 Higher the saponification value, greater is the percentage of the short chain acids present
in the glycerides of the oil or fats
Saponification is simply the process of making soaps. Soaps are just potassium or sodium salts of
long-chain fatty acids. During saponification, ester reacts with an inorganic base to produce alcohol
and soap. Generally, it occurs when triglycerides are reacted with potassium or sodium hydroxide
(lye) to produce glycerol and fatty acid salt, called ‘soap’.
In a practice a known amount of the oil or fat is refluxed with excess amount of standard
alcoholic potash solution and the unused alkali is treated against a standard acid.
Procedure
1. Take a 2g of the test substance such as given oil or fats, accurately weighed, or the quantity
specified in the monograph, in a conical flask with a capacity of about 200mL.
2. Then add 25mL of potassium hydroxide/ethanol, TS1 attach a reflux condenser, and heat in a
boiling water-bath for 30 minutes, or the time specified in the monograph, frequently rotating the
contents of the flask; immediately add 1 mL of phenolphthalein/ethanol TS and titrate the excess of
alkali with hydrochloric acid (0.5mol/l) VS.
3. Add 25ml of 0.5 N alcoholic KOH and mix well, attach this to a reflux condenser.
4. Set up another reflux condenser as the blank with all other reagents present except the fat.

5. Place both the flasks in a boiling water bath for 30 minutes.

6. Cool the flasks to room temperature.
7. Now add phenolphthalein indicator to both the flasks and titrate with
0.5N HCl.
8. Note down the endpoint of blank and test.
9. The difference between the blank and test reading gives the number of
milliliters of 0.5N KOH required to saponify 1 g of fat.
10. Calculate the saponification value.
Ester value:
 Number of milligram of KOH required to saponify the esters
present in 1.0gm of sample.
 It is determined by titrating the lipid sample in alcoholic media
against 0.1N HCl

 Weigh accurately 1-2g of sample and add 25 mL of 0.5 mL

of alcoholic KOH.
 Reflux the reaction mixture for 1 hours and then add 20 mL
of water
 Titrate the excess of alkali (KOH) with 05 mL of HCl, using
phenolphthalein indicator
 Repeat the procedure without sample (Blank reading).
 56.1lank-test)N
Ester Value =
Weight of sample

Blank = volume of 0.5N HCl used in blank titration

Test = volume of o.5N HCl used in actual test

 Iodine value

 The iodine value (or iodine adsorption value or iodine number or iodine index) in
chemistry is the mass of iodine in grams that is consumed by 100 grams of a fat/oil
or added to C=C bond
 Iodine numbers are often used to determine the amount of unsaturation in fatty
acids
 unsaturation is in the form of double bonds, which react with iodine compounds
Methods for the determination of iodine
 higher the iodine number, the more C=C bonds are present in the fat
value
Hübl method
 The basic principle of iodine value was originally introduced in 1884 by A. V. Hübl as “Jodzahl”.
He used iodine alcoholic solution in presence of mercuric chloride (HgCl2) and carbon
tetrachloride (CCl4) as fat solubilizer.
 Residual iodine is titrated against sodium thiosulfate solution with starch used as endpoint indicator
Wijs/Hanuš method
 In this method iodine monochloride (ICl)/ iodine monobromide (IBr) was used in glacial
acetic acid, which became known as Wijs's solution, dropping the HgCl2 reagent
 fat is dissolved in chloroform and treated with excess ICl/IBr. Some of the halogen reacts
with the double bonds in the unsaturated fat while the rest remains
 Then, saturated solution of potassium iodide (KI) is added to this mixture, which reacts with
remaining free ICl/IBr to form potassium chloride (KCl) and diiodide (I 2).
 Afterward, the liberated I2 is titrated against sodium thiosulfate, in presence of starch, to
indirectly determine the concentration of the reacted iodine.
 Saturated fatty acids will not give the halogenation reaction. If the iodine number is
between 0–70, it will be a fat and if the value exceeds 70 it is an oil. Starch is used as the
indicator for this reaction so that the liberated iodine will react with starch to give
purple coloured product and thus the endpoint can be observed.