Fats and Oils

POC II: Unit III

 Fats and Oils
• Occur in living system – lipids
• Like most organic materials, Oils and fats are
made up of three elements:-
Carbon, Oxygen, Hydrogen
Functions:
• Storage of energy (fats – months),
• Protection of delicate tissues (serve as shock
absorbing pads & heat insulators) and
• fats may be components of cell membrane.
• Elements C, H & O combine together to form
chains known as fatty acids.
• Three of these chains then join together to form a molecule
known as a triglyceride.
• The triglyceride molecule is the basis of all oils and fats.
• Differences in - appearance and functionality due to the types of
fatty acid chain which join together to form the triglyceride
molecule.
• Differ from mineral oils (Kerosene) & essential oils (Clove
oil, Lemon oil, etc.)
• oils containing a greater proportion of unsaturated fatty acids
are liquid at room temperature whereas those with higher
amounts of saturated fatty acids will be solid.
• Saturated fatty acids are extremely stable i.e. Good shelf life
(meat, butter, cheese).
• Can increase blood cholesterol levels (LDL), one of the major
factors in heart disease.
• Unsaturated Fats: Monounsaturated Fatty Acids (MUFA) - the
best type of fat to eat.
• They are relatively stable to oxidation & the development of
rancidity (Olive Oil).
• Polyunsaturated fatty acids - They are least stable fatty acids to
oxidation & as such are best used in cold applications.
• Trans Fatty Acids (TFA)- hydrogenated vegetable oils and
animal fats (Margarine).
 Differentiate between fats and oils
Fats Oils
1.
Fats are solids or semisolids Oils are liquids at room temperature
at room temperature
2.
Fats contains large amount of Oils contains large amount of
saturated fatty unsaturated
acids e.g. stearic and palmitic acids fatty acids e.g. oleic acid
3.
Fats melt at high temperature Melt at low temperature
4.
Fats do not contain double bonds Oils have double bonds
5.
Fats are more stable Oils are less stable
6.
Fats are animal fats Oils are vegetable fats
 Reactions
• Hydrolysis
• Hydrogenation
• Saponification
• Rancidity of oils
• Drying oils
 Hydrolysis
• Hydrolysis: Breaking of triesters with water to form fatty
acids and glycerol.
• Fats are hydrolysed by heating with water alone, or in the
presence of acids to form glycerol and the free organic acids.
Hydrolysis of fats and oils carried out by strong aqueous
bases to form soaps is called saponification.
Strung aqueous base cata1yze•s fat hydrolysis
'I '
'. I

O ‹” I

R C O* Na+
CH2 O C R
O CH2 OH O

CH O C R’ N.aOH R’ C O* Na+
CH OH
H2O
+
O O
CH 2 O C R” R” C O* Na+
A fat or oil CH2 OH
Fatty acid salts

Glycerol
 Hydrogenation or Reduction or Hardening of Oils

• Hydrogenation: Addition of hydrogen to oil in presence of

reducing agents to form fats.
• Unsaturated glycerides to saturated glycerides
• The hydrogenation or 'hardening of oils' is used for the
manufacture of Vegetable ghee or 'margarine‘.
• Hardened oils are also extensively used for making soaps and
candles.
• It is carried by passing hydrogen gas under pressure into the
liquid fat or oil having a fine suspension of nickel which acts
as a catalyst.
• The oleic acid adds a molecule of hydrogen at the double bond and is
thus converted to the stearic acid .
 Drying of Oils
• Drying: Certain fatty oils- (Linseed oil) when exposed to
air in thin layers are slowly converted to hard and elastic
coatings.
• This process is called drying and is the basis of the paint and
varnish industry.
• The chemistry of drying which essentially involves
oxidation and polymerization
• The methylene groups flanked by doubly bonded carbon
atoms present in highly unsaturated glycerides are very
reactive.
• The CH, group present in linoleic acid component of the
unsaturated glyceride is readily attacked by oxygen of the air to
form hydroperoxy group (—O--O-----H) at these sites.
• These hydroperoxy groups then react with unchanged CH,
groups in other glyceride molecules to form peroxide bridges.
• The hydroperoxide formation accompanied by polymerisation
as illustrated below, converts polyunsaturated glycerides into a
vast network of interlinked units. Such a network forms a dry,
tough and durable film when exposed to air
Peroxide bridge
 Rancidity
• Rancidity (Hydrolysis-Oxidation). The term rancid is applied to
any fat or oil that develops a disagreeable odour (very bad
odour or taste) when left exposed to warm, moist air for any a
longer time.

• Rancidity is chiefly caused by hydrolysis of the ester links and

oxidation of double bonds of the triglycerides.

• The lower molecular weight acids that are produced are volatile
and impart an offensive odour to fat or oil.
 Hydrolytic Rancidity
• Due to the liberation of lower fatty acids or original acids by
hydrolysis of ester links of triglycerides.

• Hydrolytic rancidity is particularly applicable to butter. Under

moist and warm conditions, hydrolysis of the glycerides in
butter liberates the odorous butyric acid, caproic acid, caprylic
acid, and capric acid.

• Micro-organisms present in the air provide the enzymes

(lipases) that catalyse the hydrolytic process
 Hydrolytic Rancidity

Butter
 Oxidative Rancidity
• It occurs in triglycerides containing unsaturated acid
components.
• It is believed that first the ester linkages are hydrolysed to
yield unsaturated acids.
• The acids so produced are subject to oxidative cleavage at the
site of the double bonds forming short chain acids and
aldehydes.
• Oxidation leading to rancidity in fats and oils is catalyzed by
the presence of certain metallic salts.
 Oxidative Rancidity
CH3 (CH2)7 - CH=CH - (CH2)7- COOH

Cleavage
O2 Air
Oleic acid

CH3 (CH2)7- COOH + HOOC - (CH2)7 - COOH

Pelargonic acid Azelaic acid

 Analysis of Oils and
•
Fats
Since fats and oils are obtained from natural sources, their
purity and composition is variable.
• They may contain free fatty acids produced by hydrolysis
during storage, and non fatty impurities.
• The suitability of a fat or oil as raw material for the
manufacture of soaps, synthetic detergents, paints etc., depends
on the carbon chain length and the degree of unsaturation of
the acid components.
• Usual: melting point, specific gravity and
refractive index.
 Analysis of Oils and
Fats
The fat is subjected to many analytical tests:
• Acid value
• Saponification value
• Ester value
• Iodine value
• Acetyl value
• Reichert-Meissl (RM) value
 Acid value (number)
• Tells the amount of free fatty acids (FFA) present in the
given sample of fats and oils.

• The acid value (AV) is expressed as the Number of

milligrams of potassium hydroxide required to neutralize 1
gram of fat or oil.

• It is determined by dissolving a weighed quantity of the fat

in ethanol and titrating the solution against standard alkali
using phenolphthalein as indicator.
• The acid number of a fat or oil can give the degree of
hydrolytic rancidity (result of peroxide formation) in a stored
sample.
• More FFA in a sample of oil or fat indicates hydrolysis of
triglycerides.

• By the action of lipase enzyme and it is and indicator of

inadequate processing and storage conditions (i.e., high
temperature and relative humidity, tissue damage).

• The source of the enzyme can be the tissue from which the
oil or fat was extracted or it can be a contaminant from other
cells including microorganisms.

• Besides FFA, hydrolysis of triglycerides produces glycerol.

 Acid value (number)

OIL ACID VALUE

Canola 0.071
Maize Soya 0.223
Olive oil 0.60
Used frying oil 6.6
Bee's wax 31
17-36
 Acetyl value
(number)
• some fatty acids have hydroxyl groups:
 Acetyl value
(number)
• The acetyl number gives the proportion of these
hydroxyl-containing fatty acids in a given sample of
fat or oil

• Oxidative rancidity – formation of hydroxy acid - rise in

acetyl value
• Acetyl number: the acetyl number is the number of
milligrams of KOH needed to neutralize the acetic acid
produced from 1 g of acetylated fat –examples:

Castor Oil 146 - 150

Cod liver Oil 1.1
Cottonseed Oil 21 - 25
Olive Oil 10.5
Peanut Oil 3.5
 Iodine number (value)
• measures the degree of un-saturation in a given amount of fat
or oil
• the iodine number is the number of grams of
iodine absorbed by 100 g of fat or oil
• frequently used to determine adulteration of
commercial fats and oils.
 Iodine number (value)
• Iodine value (I.V.) is directly proportional to the degree of
unsaturation (no of double bond) and inversely proportional
to the melting point of lipid.
• An increase in I.V. indicates high susceptibility of lipid to
oxidative rancidity due to high degree of unsaturation.

• Example reagents:
Wij’s reagent: I2/Cl2 in glacial acetic acid
Hanus reagent: I2/Br2 in glacial acetic acid
• According to I.V. oils can be classified into the following
classes:

Class I.V. The main Examples

unsaturated
acid
Non-drying 80-100 Oleic acid Olive oil,
oils Castor oil,
Almond oil
Semi-drying 100-140 Linoleic acid Cottonseed oil,
oils sesame oil
Drying oils 140-200 Linolienic acid Linseed oil,
Fish oil,
Sunflower oil
 Saponification Number
•
(value)
Tells the approximate molecular weight of a fat or oil
• Types of fatty acids involved in the formation of ester
groups: Lower or higher fatty acids
• Number of milligrams of KOH required to saponify 1 g of a
fat or oil or neutralize the free fatty acids and to saponify the
esters in 1 g of the substance.
• SPV of a fat or oil is inversely proportional to the molecular
weight (or chain length)
 Saponification Number
•
(value)
Lower value of saponification number – high molecular
weight fatty acid residuse (C18) in the given fat.
• High value of saponificaiton number – low molecular
weight fatty acid residues.
• Characteristic of a particular fat or oil
• Use: Identification of fats and oils.
 Fat or Oil Saponification Iodine
Number Number
Coconut Fat 250 - 8-10
260
Butter fat 210-230 26-28
Olive oil 187-196 79-90
Cottonseed Oil 190-198 105-114
Sunflower Oil 188-195 170-185
Linseed oil 187-195 170-185
 Ester value
(Number)
• The ester value is the number of mg of KOH required to
saponify the esters present in 1 g of the substance
• It is calculated from the saponification value and the acid
value
• Ester value: Saponification value – Acid value
• Useful- Identification and classification of fats and oils
 Reichert-Meissl (RM) number
• This value is a measure of volatile water soluble acid contents
of the fat.
• Volatile water soluble acid: Short-chain fatty acids (SCFAs),
also referred to as volatile fatty acids (VFAs), are fatty
acids with two to six carbon atoms examples: acetic acid,
butyric acid and propanoic acid
• Definition: m L of KOH (10N) required to neutralize the
volatile water soluble fatty acids obtained by 5 g of fat.
• Higher content of volatile fatty acids of better responsible for
its higher reichert-meissl (RM) number
• Useful – testing purity/adulteration of butter
References:
1) Textbook of Organic Chemistry by B.S. Bahl & Arun Bahl, S.Chand, New Delhi.,22nd edition, 2016.
2) Organic Chemistry by Morrison and Boyd.
3) Practical Organic Chemistry by Mann and Saunders, Pearson Education India; 4 th edition, 2009.
4) A practical book of Pharmaceutical Organic Chemistry by Dr. K. S. Jain, Dr. P.B. Miniyar and Dr. L. V. G.
Nargund. Nirali Prakashan, Pune. First edition-2018.
5) Johnson S, Saikia N. Fatty acids profile of edible oils and fats in India. Centre for Science and Environment.
New Delhi, India, 2009.
6) Potter NN, Hotchkiss JH. Food Science: Fifth Edition. Springer Science & Business Media, Berlin, Germany,
2012.
7) Gunstone FD. Vegetable oils in food technology: Composition, properties and uses. Blackwell Publishing, New
Jersey, USA, 2002.
8) Srilakshmi B. Food Science. New Age International Publishers. Hyderabad, India, 2003.