CHEMICAL AND

PHYSICAL
PROPERTIES OF
OIL AND FATS
CHAPTER 2
Lipids
Lipids are organic compounds formed mainly from alcohol and fatty
acids combined together by ester linkage.

O
H2O O
R CH2 OH R CH2 O C
+ HO C R R
Fatty alcohol Fatty acid Esterase (lipase) ester (lipid)
Lipids
Lipids are insoluble in water, but soluble in fat or organic solvents (ether,
chloroform, benzene, acetone).
Lipids include fats, oils, waxes and related compounds.
They are widely distributed in nature both in plants and in animals.
Lipids
The four main groups of lipids include:
1. Fatty acids (saturated and unsaturated)
2. Glycerides (glycerol containing lipids)
3. Nonglycerides lipids (sphingolipids, steroids, waxes)
4. Complex lipids (lipoprotein, glycolipids)
Lipids
Types of lipids
1. Lipids with fatty acids
- waxes
- triglycerides
- phospholipids
- sphingolipids
2. Lipids without fatty acids
- steroids
Lipids
Saponifiable lipids Nonsaponifiable lipids

Triglycerides Steroids
Glycolipids Prostaglandins
Sphingolipids Leukotrienes
Waxes (some) Terpenes
Phospholipids
Fatty acids
Definition:
Fatty acids are carbon chains with a methyl group at one end of the
molecule and a carboxyl group at the other end.
It has a long, unbranched monocarboxylic acids containing 10 to 22
carbon atoms.
Typically have an even number of carbon atoms due to their
biosynthesis pathway.
Insoluble in water
Physical Properties of Fatty Acids:
Fatty acids are carboxylic acids and therefore weak acids.
Fatty acids do not dissolve in water
As the fatty acid carbon chain length increases, the melting point and
boiling point increases
Unsaturated fatty acids have lower melting points and boiling points
than saturated fatty acids
Fatty acids
Physical Properties of Fatty Acids:
Longer chains
• more hydrophobic, less soluble

Double bonds increase solubility

Fatty acids
Can be classified based on chain length and on the number of C=C
double bonds present.
Classification of fatty acids:
1. Saturated fatty acids
2.Unsaturated fatty acids
COOH
palmitic acid, a saturated acid
COOH

palmitoleic acid, an unsaturated fatty acid

Fatty acids: Saturated
Fatty Acids
Contain no C=C double bonds with 2 – 24 or more carbons
Saturated means that bonded to the maximum number of hydrogen;
will not accept any more hydrogen.
Most of saturated fatty acids are straight hydrocarbon chains with an
even number of carbon atoms
Have molecular formula CnH2n+1COOH
 Fatty acids: Saturated
Fatty Acids
Common IUPAC Name MP RCOOH Condensed
Name o
C Formula Formula
Capric Decanoic 32 C9H19COOH CH3(CH2)8COOH

Lauric Dodecanoic 44 C11H23COOH CH3(CH2)10COOH

Myristic Tetradecanoic 54 C13H27COOH CH3(CH2)12COOH

Palmitic Hexadecanoic 63 C15H31COOH CH3(CH2)14COOH

Stearic Octadecanoic 70 C17H35COOH CH3(CH2)16COOH

Arachidic Eicosanoic 77 C19H39COOH CH3(CH2)18COOH

Fatty acids: Saturated
Fatty Acids
Structure: fit closely in regular pattern

COOH
COOH
COOH
Fatty acids: Saturated
Fatty Acids
Properties of saturated fatty acids

Contain only single C–C bonds

Closely packed

Strong attractions between chains

High melting points

Solids at room temperature

Fatty acids: Unsaturated
Fatty Acids
Contain C=C bonds with cis configuration
Unsaturated means will accept more hydrogen
The presence of double bond causes restrictions in the mobility of the
acyl chain at that point.
The cis configuration gives a kink in the molecular shape and less stable
than the trans form.
Fatty acids: Unsaturated
Fatty Acids
Common I.U.P.A.C MP RCOOH # of Double
Names Name o
C Formula Double Bond
Bonds Position
Palmitoleic cis-9- 0 C15H29COOH 1 9
Hexadecenoic
Oleic cis-9-Octadecnoic 16 C17H33COOH 1 9

Linoleic cis,cis-9,12- 5 C17H33COOH 2 9, 12

Octadecadienoic
Linolenic All cis-9,12,15- -11 C17H31COOH 3 9, 12, 15
Octadecatrienoic

Arachidonic All cis-5,8,11,14- -50 C19H31COOH 4 5, 8, 11, 14

Octadecatrienoic
Fatty acids: Unsaturated
Fatty Acids
Structure: cis double bond

H H
C C

cis double bond COOH

Fatty acids: Unsaturated
Fatty Acids
Properties of unsaturated fatty acid
Contain one or more double C=C bonds
Nonlinear chains do not allow molecules to pack closely
Few interactions between chains
Low melting points
Liquids at room temperature
Fatty acids: Unsaturated
Fatty Acids
Monounsaturated
- Contain one double bond
- Molecular formula CnH2n-1COOH
Polyunsaturated (essential fatty acid)
- Essential fatty acids that can not be synthesized
in the human body and must be taken in
adequate amounts in the diet
- Required for normal growth and metabolism
Fat and Oils
Simple lipids and neutral because they are uncharged due to absence of
ionizable groups in it.
Most abundant lipids in nature.
They are esters of glycerol with various fatty acids.
Fat and Oils
The commonest fatty acids in animal fats are palmitic, stearic and oleic
acids.
The main difference between fats and oils is for oils being liquid at room
temperature, wheares fats are solids
This is due to presence of larger percentage of unsaturated fatty acids in
oils than fats that has mostly saturated fatty acids
Types of Triglycerides
1. Simple triglycerides
If the 3 fatty acids connected to glycerol are of the same type
2.Mixed triglycerides
If they are of different types of triglycerides
Natural fats are mixtures of mixed triglycerides with small amount of
simple triglycerides.
Physical Properties of
Fat and Oils
Freshly prepared fats and oils are colorless, odorless and tasteless. Any
color or taste is due to association with foreign substances.
Fats have specific gravity less than 1 and therefore they float on water.
Fats are insoluble in water but soluble in organic solvents as ether and
benzene.
Melting points of fats are usually low but higher that solidification point.
Chemical Properties of
Fat and Oils
1.Hydrolysis
They are hydrolyzed into their constituents (fatty acids and glycerol) by
the action of superheated steam, acid, alkali or enzyme
During enzymatic and acid hydrolysis, glycerol and free fatty acids are
produced
 Chemical Properties of
Fat and Oils

O O
CH2 O C R1 H2C OH R1 C OH
O Lipase or Acid O
R2 C O C H HO C H + R C OH
2
O
O
CH2 O C R3 3 H2O H2C OH
R3 C OH
Triacylglycerol Glycerol Free fatty acids
 Chemical Properties of
Fat and Oils
2.Saponification
Alkaline hydrolysis produces glycerol and salts of fatty acids
Soap cause emulsification of oily material this help easy washing of fatty
materials

O O
CH2 O C R1 H2C OH R1 C ONa
O O
R2 C O C H HO C H + R C ONa
2
O
O
CH2 O C R3 3 NaOH H2C OH
R3 C ONa
Triacylglycerol Glycerol Sodium salts of
fatty acids (soap)
Chemical Properties of
Fat and Oils
3.Halogenation
Neutral fats containing unsaturated fatty acids have the ability of adding
halogens at the double bonds
It is a very important property to determine the degree of unsaturation
of the fat or oil that determines its biological value.
Chemical Properties of
Fat and Oils

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

Linoleic acid
2 I2

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

I I I I
Stearate-tetra-iodinate
Chemical Properties of
Fat and Oils
4.Hydrogenation or hardening of oils
It is a type of addition reactions accepting hydrogen at the double
bonds of unsaturated fatty acids.
The hydrogenation is done under high pressure of hydrogen and is
catalyzed by finely divided nickel or copper and heat.
Chemical Properties of
Fat and Oils
It is the base of hardening of oils (margarine manufacturing), e.g.,
change of oleic acid of fats (liquid) into stearic acid (solid).
It is advisable not to saturate all double bonds; otherwise margarine
produced will be very hard, of very low biological value and difficult to
digest.

Oils Hydrogen, high pressure, nickel Hard fat

(liquid) (margarine, solid)
(with unsaturated (with saturated
fatty acids, e.g., oleic) fatty acids, e.g., stearic)
Chemical Properties of
Fat and Oils
Advantages of hydrogenated:
It is more pleasant as cooking fat.
It is digestible and utilizable as normal animal fats and oils.
It is less liable to cause gastric or intestinal irritation.
It is easily stored and transported and less liable to rancidity.
Disadvantages of hydrogenated:
fats include lack of fat-soluble vitamins (A, D, E and K) and essential
fatty acids
Chemical Properties of
Fat and Oils
5.Oxidation (Rancidity)
This toxic reaction of triglycerides leads to unpleasant odour or taste of
oils and fats developing after oxidation by oxygen of air, bacteria, or
moisture.
Also this is the base of the drying oils after exposure to atmospheric
oxygen.
Example is linseed oil, which is used in paints and varnishes
manufacturing
Rancidity
Definition:
It is a physico-chemical change in the natural properties of the fat
leading to the development of unpleasant odor or taste or abnormal
color particularly on aging after exposure to atmospheric oxygen, light,
moisture, bacterial or fungal contamination and/or heat.
Saturated fats resist rancidity more than unsaturated fats that have
unsaturated double bonds.
Types and Causes of
Rancidity
1. Hydrolytic rancidity
2. Oxidative rancidity
3. Ketonic rancidity
1. Hydrolytic rancidity
It results from slight hydrolysis of the fat by lipase from bacterial
contamination leading to the liberation of free fatty acids and
glycerol at high temperature and moisture.
Volatile short-chain fatty acids have unpleasant odor.
2. Oxidative rancidity
It is oxidation of fat or oil catalyzed by exposure to oxygen, light and/or
heat producing peroxide derivatives which on decomposition give
substances, e.g., peroxides, aldehydes, ketones and dicarboxylic acids
that are toxic and have bad odor.
This occurs due to oxidative addition of oxygen at the unsaturated
double bond of unsaturated fatty acid of oils.
3. Ketonic rancidity
It is due to the contamination with certain fungi such as Asperigillus
Niger on fats such as coconut oil.
Ketones, fatty aldehydes, short chain fatty acids and fatty alcohols are
formed.
Moisture accelerates ketonic rancidity.
Prevention of Rancidity
1. Avoidance of the causes (exposure to light, oxygen, moisture, high
temperature and bacteria or fungal contamination). By keeping fats
or oils in well-closed containers in cold, dark and dry place (i.e.,
good storage conditions).
2. Removal of catalysts such as lead and copper that catalyze rancidity.
3. Addition of anti-oxidants to prevent peroxidation in fat (i.e.,
rancidity). They include phenols, naphthols, tannins and
hydroquinones. The most common natural antioxidant is vitamin E
that is important in vitro and in vivo.
Hazards of Rancid Fats
1. The products of rancidity are toxic, i.e., causes food poisoning and
cancer.
2. Rancidity destroys the fat-soluble vitamins (vitamins A, D, K and E).
3. Rancidity destroys the polyunsaturated essential fatty acids.
4. Rancidity causes economical loss because rancid fat is inedible.