CHEMISTRY OF OILS AND FATS

Definition
A group of substances that in general are soluble in organic solvents, but are not soluble in water are called lipids. Oils & Fats are one class of lipid. They can be used for edible as well as non-edible purposes.

Roles of Food Lipids

Energy Source Source of essential

fatty acids Carrier of Fat Soluble Vitamins Main Flavor Source of Foods Regulates Hormone and Cell Structure Help to Develop Nervous System Build adipose tissues which cause Thermal Insulation of Body Mouth Feeling Texture of Foods Emulsifying Agents Mold Releasing and Anti-spattering Agent

 Plant

source seeds, grains, fruits, brans etc. Animal source milk, egg, tallow, lard, microbial etc. Marine source fish and other animals. World Supply Vegetable oil 68% Animal fat 28% Marine oil 4%

Source of Food Lipids

Types of Lipids
1. Fatty acids 2. Neutral fats and oils or triglycerides 3. Monoglycerides and diglycerides 4. Waxes 5. Phospholipids 6. Sterols

Composition of fats and oils

Fatty

acid esters of glycerol i.e. triglycerides room temperature are termed as oils and those solids are termed as fats

Triglycerides which is liquid at

Triglycerides

O H2C OH HC OH H2C OH + HO C R O HO C R O HO C R

O H2C O C R O HC O C R O H2C O C R + 3 H2O

Glycerol

3 Fatty Acids

Saturated and Unsaturated Fatty Acids

Cis And Trans Fatty Acids

H CH3 (CH2 )7 C C (CH2 )7 10 9 H O C OH

Cis 9 - Octadecenoic Acid (oleic)

H CH3 (CH2 )7 C C H (CH2 )7

O C OH

Trans 9 - Octadecenoic Acid (elaidic acid)

Polyunsaturated Fatty Acids

Linoleic acid: Linolenic acid: acid Cis, cis, 9, 12 - Octadecadienoic acid Cis, cis, cis 9, 12, 15 - Octadecatrienoic

Arachidonic acid: Cis, cis, cis, cis 5, 8, 11, 14 Eicosatetraenoic acid Linoleic Acid Linolenic Acid Arachidonic Acid

Naturally-occurring Fatty Acids

1. 2.

Cis form Not conjugated (isolated) and conjugated (not very

common) double bonds. 3. Even numbered fatty acids.

Fatty Acids Melting Points and Solubility in Water

x
Melting Point

Melting Point

x x x x x z

x
Solubility in H O 2

Fatty Acid Chain Length

Effects of Double Bonds on the Melting Points

M.P.

# Double bonds

DIFFERENT TYPES OF GLYCERIDES

H2 C OH HC OH O H2 C O C (CH2 )16 CH3 Monoglyceride ( - monostearin)
O H2 C O C (CH2 )16 CH3 HC OH O H2 C O C (CH2 )16 CH3

Diglyceride (, ' - distearin)

( C18 ) (C16 ) (C18 )

O H2 C O C (CH2 )16 CH3 O HC O C (CH2 )14 CH3 O H2 C O C (CH2 )16 CH3

Triglyceride ( - palmityl distearin)

Fatty Acids (%) of Fats and Oils

Fatty Acids C4 6 8 10 12 14 16 16:1 18:0 18:1 18:2 18:3 Butter 3 3 2 3 3 10 26 7 15 29 2 2 Coconut Cottonseed 6 6 44 18 11 6 7 2 1 4 1 3 18 53 Soybean 12 2 24 54 8

Phospholipid
Lecithin (phosphatidyl choline)
O O H2 C O C R CH 3 CH 2 N CH 3 CH 3 Choline
+

R C O CH O H 2 C O P O CH 2 O_ Phosphatidic Acid

Other phospholipids are :

Phophatidyl

ethanol amine serine inositol

Phosphatidyl Phosphatidyl Cardiolipin

WAXES
Esters of Fatty acid and Long chain alcohol
O O C C15 H 31
O C16 H 33 O C C15 H 31

C30 H61

Sterols
Plant

sterols or PHYTOSTEROLS

Animal Sterols or CHOLESTEROLS

Phytosterol

Cholesterol
21 H3C 18 22 20 16 15

CH 3 CH 3

H3C

HO

12 19 17 H3C 11 13 14 10 1 9 2 8 3 6 7 4 5

Characteristic Components Present on Some Special Oil

Lignans

in sesame oil; Oryzanol in rice bran oil; Gossypol in cottonseed oil; Cholesterol in butter as well as in animal fat; Hydroxy fatty acid in Castor oil; Cyclic acid in Sal fat; Trans fatty acid in Vanaspati

Non-lipid component present in Oils & Fats

Fat soluble vitamins Pigments

Some important parameters to Characterize Fats and Oils

Analytical Methods
1. Acid Value 2. Saponification Value 3. Iodine Value 4. Peroxide Value 5. Gas Chromatographic Analysis for Fatty Acid composition 6. Liquid Chromatography for triglyceride composition

Acid Value
Number of mgs of KOH required to neutralize the Free Fatty Acid present in 1 g of oil/fat. Fatty acid generate due to hydrolytic rancidity Triglyceride
Moisture/ Lipase

Fatty acids

RCOOH + KOH

ROO K + H2O
+

AV = (56.1 x N x V)/ wt. of sample

Saponification Value
Definition : mgs of KOH required to saponify 1 g of fat Saponification - Hydrolysis of ester (triglyceride) under alkaline condition. It gives the idea about the average molecular weight of fatty acid present in particular oil/fat.
O H2 C O HC O H2 C O C R O C R O C R + 3 KOH H 2 C OH

Heat

O +
- + 3R C OK

HC O H H 2 C OH

S #= P

5 .1 -S x No H l 6 (B ) f C G a o S m le r m f a p

Iodine Value
gms of iodine absorbed by 100 g of oil. Iodine number indicates the amount of unsaturation in fats and oils.

Iodine Value = (ml of Na2S2O3 volume for blank ml of Na2S2O3 volume for sample) N of Na2S2O3 0.127g/meq 100 Weight of Sample (g)

Peroxide Value
It indicates about the amount of primary oxidation products present in Oil/Fat.
Peroxide Value = ml of Na2S2O3 Normality 1000 Grams of Oil Unit : (mill equivalent /kg)

GC Analysis for Fatty Acids

1. 2. 3. 4. 5. Extract fat. Saponify (hydrolysis under basic condition). Prepare methyl ester (by BF3-methanol/CH3ONa). Inject methyl ester in GC Determine peak areas of fatty acids. (Fatty acids are identified by relative retention time) 6. Compare with response curve of standard.

Chromatogram of Fatty Acids Methyl Esters

18:1
Response

14 18:3 22

16

18

18:2

20

21:1

24

Time

GC condition: 10% DEGS Column (from supelco) Column temperature 200C.

TAG Composition
Triglyceride

composition (e.g. S3, S2U, SU2 or

U3) of oil/fat can be determined by High Performance Liquid Chromatography (HPLC)

In

this chromatography, oil samples can be

injected directly.

LIPID CONTENT ANALYSES

(1) Wet extraction For liquid samples (Milk, curd etc.)

(2) Dry extraction (Soxhlet Method) for solid samples (seed, grain, bran etc.)

Soxhlet Method

Fat Soluble Vitamins

Vitamin A

H3 C

CH3
9 8

CH3
7 6

5 4

CH3
3

CH2OH
2 1

CH3

C H H 3C H 3C

C H C H
3

Vitamin D2
H H C H H O
2

Vitamin E
R1 R2 HO R3 CH3 CH3 O (CH2 CH2 CH2 CH2 )2 CH2 CH2CH2 CH(CH3 )2

Pigments
-Carotene and Chlorophyll (green)

Chlorophyll