FATS & OILS

S.Y.B.Pharm- Sem III

Dr Prerna Ganwir
 UNIT III - Fats and Oils (10)

3.1 Fatty acids – reactions. 4

3.2 Hydrolysis, Hydrogenation, Saponification and Rancidity of oils, Drying oils

3

3.3 Analytical constants – Acid value, Saponification value, Ester value, Iodine
3
value, Acetyl value, Reichert Meissl (RM) value – significance and principle
involved in their determination.
 Biological importance of fatty acids
Fatty acid are long chain of monocarboxylic acid

Long chain of carbon + Carboxylic acid

Fatty acids are the building blocks of dietary fats. The human body stores such fats in the
form of triglycerides.
• Fatty acids are also required for the formation of membrane lipids such as phospholipids
and glycolipids.
• They are required for the esterification of cholesterol to form cholesteryl esters.
FATTY ACIDS
 Types of Fatty acid

Fatty acid

Saturated Fatty Monounsaturated Polyunsaturated

acid fatty acid (MUFA) fatty acid (PUFA)
MUFA and PUFA
 MUFA and PUFA
• cis configuration in nature
• Generally unsaturated fatty acids are confined to the sn-2 position of
phospholipids and are 18-20 carbons long.

- 9 - MUFA

- 3,6 - PUFA
Structure of Fatty acids
 Physical Properties of Saturated Fatty acids
Saturated fatty acids have:
• Molecules that fit closely together in a regular pattern
• Strong attractions (dispersion forces) between fatty acid chains
• High melting points that make them solids at room temperature
 Physical Properties of Fatty acids
Unsaturated fatty acids have:
• Nonlinear chains that do not allow molecules to pack closely
• Weak attractions (dispersion forces) between fatty acid chains
• Low melting points and so are liquids at room temperature
 cis and trans Unsaturated Fatty Acids
• Natural unsaturated fatty acids have cis double bonds
• When unsaturated vegetable oils are hydrogenated to form more saturated
oils (as in margarine), some of the cis fatty acids are isomerized to trans
fatty acids.
• Trans fatty acids are much more linear than cis fatty acids, so their melting
points are higher and studies have shown that trans fats may act similarly
to saturated fats and could contribute to heart disease and some cancers
 cis and trans-
Unsaturated Fatty Acids Fatty Acids and its sources
FATS & OILS
 INTRODUCTION
Fats and oil belong to the naturally occurring group of compounds called
lipids.
All fats and oils belong to lipids but all lipids are not fat and oil.
Lipid: Long-chain of fatty acid with glycerol also, various organic compounds
that are insoluble in water. Eg. Fats, oils, waxes, and hormones.
 INTRODUCTION
Fats Oil

Solid at Room temperature Liquid at room temperature

Saturated fatty acids Unsaturated fatty acids

High melting point Low melting point

Mostly found in animals Found in both animal and plants

 Simple Definition
• Fatty acids; Long chain of carboxylic acid.
• Fats: Triesters of a long chain of fatty acid and glycerol
• Lipids: Triesters of a long chain of fatty acid and glycerol
• Glycerol:

• Triglycerides have also known triesters.

 ‘Simple’ & ‘Mixed’ Glycerides
• Simple glycerides

• Mixed glycerides

• Typical triglyceride obtained from naturally occurring fats and oils contains two

or three different fatty acid components and is thus termed a mixed

triglyceride.
TRIGLYCERIDES
 FATS

No single formula can be written to represent the naturally occurring fats

and oils because they are highly complex mixtures of triglycerides in which
many different fatty acids are represented
Palmitic acid is the most abundant of the saturated fatty acids, while oleic
acid is the most abundant unsaturated fatty acid.
FATS- Composition
 FATS & OILS: Uses

• Main constituents of the storage fat cells in animals and plants, and are one of

the important food reserves of the organism

• Play important roles in many industrial processes

• Used as such in foodstuffs, paints, varnishes, polishes, cosmetics, lubricants, etc.

• Used for the manufacture of soaps, candles, explosives, plastics and a host of

other useful products

 FATS & OILS: Physical and Chemical Poperties
Q. Which of these triglycerides would you expect to find in higher amounts in oils? (In fats?)

Justify your choice.

The triglyceride ‘a’ is expected to be present in higher

amounts in fats because it is composed of a greater

number of saturated fatty acids.

The triglyceride ‘b’ is expected to be present in higher

amounts in oils because it is composed of a greater

number of unsaturated fatty acids.

 FATS & OILS: Physical and Chemical Properties
Draw the structure for each compound.

Trimyristin

Tripalmitin
CHEMICAL REACTIONS
of
FATS & OILS
 FORMATION of HALIDES
Fatty acids react with phosphorous halides to form acyl halides
 HALOGENATION
• Unsaturated Fats or oil have capability to adding halogen

• Degree of unsaturation is determined by this halogenation reactions. E.g. Iodine value

 FORMATION of ESTERS
Fatty acids react with alcohols in presence of a strong acid to form ester (triglycerides)
 HYDROGENATION or REDUCTION
Unsaturated fatty acid undergoes reduction or hydrogenation in presence of reducing

agents to form saturated fatty acid

Hydrogen gas adsorbed on the surface of metal catalyst such as platinum, palladium or

nickel
HYDROGENATION or REDUCTION
HYDROGENATION or REDUCTION
 HYDROGENATION or REDUCTION

Mixture of oleic acid (partially saturated acid )and stearic acid (full saturated acid ) is obtained
 Conversion of cis-oleic acid to stearic acid

During conversion of oleic acid to stearic acid some amount of trans oleic acid is obtained
HYDROGENATION- Trans Fatty acids
HYDROGENATION of FATS/ GLYCERIDES
 HYDROGENATION of FATS/ GLYCERIDES
• Reaction with hydrogen in the presence of a metal catalyst (usually nickel) to give

saturated glycerides

• In similar to the catalytic hydrogenation of alkenes; Partial and complete

 HYDROLYSIS
• Triglycerides are esters

• Hydrolysis in presence of an acid, a base, or specific enzymes known as lipases

• In presence of an acid (H2SO4 or HCl)/heat hydrolysis results in fatty acids and glycerol

• In presence of a base– used to make soap and is called saponification

In presence of acid
In presence of base
 HYDROLYSIS

H
H+ or lipase

+ H

2018
 HYDROLYSIS
• When triglycerides are hydrolysed (saponified) by alkalis, glycerol plus the salts of fatty

acids are produced. Generally the sodium or potassium salts are obtained which are

termed soaps.
 SALT FORMATION
Fatty acids react with bases to form salt or soap

https://youtube.com/clip/UgkxWUI2NFJNCAag-ym9f5yq_YzE0bmBOaDA
 SOAPS

Soap solution – carboxylate salts

 SOAPS
Soap solution – micelle formation
Reactions of Fats
 HYDROLYSIS

Write the equation for the reaction catalyzed by the enzyme lipase that hydrolyzes
glyceryl trilaurate (trilaurin) during the digestion process.
Question
Question
Question
 RANCIDITY OF OILS
• Tend to spoil on storage

• Often develop unpleasant smell and taste in contact with air and moisture

• Complete or incomplete oxidation or hydrolysis of fats and oils when exposed to air or

moisture or micro-oganisms

• Pure fats can be stored for long periods by exclusion of air and moisture.
 RANCIDITY OF OILS

• Hydrolytic rancidification

• Oxidative rancidification

• Microbial rancidification
 HYDROLYSIS
• Produces fatty acids and glycerol from fats

• Lower molecular weight acids that are produced are volatile

• Impart an unpleasant odour to fat or oil

• In particular, short-chain fatty acids, such as butyric acid, are malodorous

• Short-chain fatty acids themselves serve as catalysts; further accelerating the reaction–

Autocatalysis
 OXIDATIVE
• Degradation by oxygen in air

• Double bonds are cleaved by free-radical reactions

• Involves molecular oxygen resulting in superoxide radicals  aldehydes

• Autooxidation causes the release of malodorous and highly volatile aldehydes and

ketones

• Reaction is catalyzed by sunlight; Primarily occurs with unsaturated fats. E.g. Meat, PUFA

• Can be prevented by light-proof packaging, oxygen-free atmosphere (air-tight

containers) and by the addition of antioxidants

 OXIDATIVE

Harmful effects of lipid perioxidation: 1. Damage to cell membrane 2. Cardiovascular diseases 3. Joint disease 4. Aging 5. Cancer
 MICROBIAL

• Water-dependent process

• Microorganisms, such as bacteria or molds, use their enzymes such as

lipases

• Break down fat

• Reduce the process by-

• Pasteurization and/or addition of antioxidant ingredients such as vitamin E

• Adding antimicrobial agents

PREENTION METHODS
DRYING OF OILS
 DRYING OF OILS
• Certain highly unsaturated fatty oils- (Linseed oil) when exposed to air in thin layers are

slowly converted to hard and elastic waterproof films or coatings by undergoing

oxidation and polymerization. This process is called drying

• Drying process is the basis of the paint and varnish industry

• Paints:- They are made by suspending a suitable pigment in linseed oil and adding

turpentine oil to thin it and thus permit an even and easy coating

• In drying, turpentine evaporates immediately and linseed oil dries in a couple of days

leaving a hard water-insoluble coating

 DRYING OF OILS
• Varnishes:- Best type of varnishes contain both linseed oil and a resin dissolved in a

suitable solvent.

• The drying of the oil gives a tough film to which the resin adds gloss. "Spirit Varnishes"

contain only resin e.g., shellac, dissolved in alcohol. They dry quickly but the film lacks

toughness and tends to crack

• Varnishes coloured by dye or pigment

are known as lacquers.

 DRYING OILS- MECHANISMS
• The methylene groups flanked by doubly bonded carbon atoms present in highly unsaturated glycerides

are very reactive

• Linseed oil, the most widely used drying oil, contains about 63% of its fatty acids as linoleates.

• The CH2, 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 CH2, groups in other glyceride molecules to form

peroxide bridges.

• The hydroperoxide formation accompanied by polymerisation converts polyunsaturated glycerides into a

vast network of interlinked units.

• Such a network forms a dry, tough and durable film when exposed to air
DRYING OILS- MECHANISMS
 ANALYSIS METHODS
• Determination of Moisture Content

• Determination of Specific Gravity

• Determination of Refractive Index

• Determination of Saponification Value

• Determination of Acid Value

• Determination of Iodine Value

• Determination of Reichert Meissl and Polenske value

• Determination of Acetyl value

 QUALITATIVE ANALYSIS OF FATS AND OILS
Lipid Index / Parameter Definition Significance

Acid value The number of milligrams of Potassium Indicates the

hydroxide required to completely degree to rancidity
neutralize the free fatty acids present in of a fat
one gram of fat or oil

Saponification value The number of milligrams of potassium Indicated molecular

hydroxide necessary to weight and is
neutralise the free acids and to saponify inversely
the esters present in 1 g of the fat or oil proportional to it

Ester value The number of milligrams of potassium The amount of

hydroxide required to saponify the alkai required for
esters present in 1 g of the fat or oil saponification
 QUALITATIVE ANALYSIS OF FATS AND OILS
Lipid Index / Definition Significance
Parameter

Iodine value The number of parts by weight of iodine It is a measure of

absorbed by 100 parts by weight of oil or fat degree of
sample unsaturation of a fat

Reichert Meissl Number of mls. of 0.1N potassium hydroxide Measure the amount
value solution required to neutralize the volatile of volatile soluble
acids obtained by the distillation of 5 grams fatty acids
of fat or oil.

Acetyl value The number which expresses in milligrams Measure the

the amount of potassium hydroxide required number of
to neutralise the acetic acid liberated by the –OH groups present
hydrolysis of 1 g of the acetylated substance in a fatty acid
 ACID VALUE
• Synonym: Neutralization number, Acid number

• The acid value is defined as the number of milligrams of Potassium hydroxide required to

completely neutralize the free fatty acids present in one gram of fat or oil

• The value is also expressed as per cent of free fatty acids calculated as oleic acid, lauric,

ricinoleic and palmitic acids.

 ACID VALUE- SIGNIFICANCE
• Indication about the age and extent of deterioration or decomposition
• Acid value is a relative measure of rancidity; FFA formed during decomposition

• Rancidity– increase in acid value; Measure of FFA liberated by hydrolysis

• 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.

• FFA are a source of flavors and aromas; (water soluble, volatile with characteristic smell)

• Some instances where hydrolysis of triglycerides and oxidation of FFA are key in the
development of desirable flavor and aroma in foods. This is the case of aged cheeses and
some processed meats.
ACID VALUE- PROTOCOL
ACID VALUE- PROTOCOL
 SAPONIFICATION VALUE
• Synonym: Saponification Number,
• The saponification value is the number of milligrams of potassium hydroxide necessary
to neutralise the free acids and to saponify the esters present in 1 g of the fat or oil .

• Human fat : 195-200

• Butter :230-240
• Coconut oil : 250-260
1. SAP
value
SAPONIFICATION VALUE- PROTOCOL

Et
ha
n ol
 SAPONIFICATION VALUE- SIGNIFICANCE
• Amount of alkali required for conversion of fats to soap
• Indicates the length of carbon chain of the acid present
• Higher the saponification value greater is the percentage of the short chain
acids present in the glycerides of the oil or fats
• Measure of the average molecular weight of the fatty acids present.
• Higher the molecular weight of the fat, the smaller is its saponification value
 IODINE VALUE
• Synonym: Iodine number
• Iodine value is defined as the number of parts by weight of iodine absorbed by
100 parts by weight of oil or fat sample.
IODINE VALUE- PROCEDURE
IODINE VALUE- METHOD A Principle
IODINE VALUE- PROCEDURE
IODINE VALUE- METHOD B Principle
IODINE VALUE- PROCEDURE
IODINE VALUE- METHOD C Principle
 IODINE VALUE- SIGNIFICANCE
• Measure of unsaturation (number of double bonds) or unsaturated fatty acids in a fat
• High is the iodine value, greater the number of double bonds, more is the unsaturation
in lipids
• Unsaturated lipids are more susceptible to rancidity
• It is of great importance in characterizing individual fats and also for finding their
suitability as soap materials.
IODINE VALUE- EXAMPLES
 IODINE VALUE- SIGNIFICANCE
• Measure of unsaturation (number of double bonds) or unsaturated fatty acids in a fat
• High is the iodine value, greater the number of double bonds, more is the unsaturation
in lipids
• Unsaturated lipids are more susceptible to rancidity
• It is of great importance in characterizing individual fats and also for finding their
suitability as soap materials.
 ESTER NUMBER
• The ester value is the number of milligrams of potassium hydroxide required to saponify
the esters present in 1 g of the fat or oil
• Ester value = Saponification value - Acid value.

• Significance: possible to identify and differentiate the fats with this value.
 REICHERT-MEISSL VALUE
• It is the number of mls. of 0.1N potassium hydroxide solution required to neutralize the
volatile acids obtained by the distillation of 5 grams of fat or oil.
• RM number is useful in testing the purity of butter since it contains a good concentration
of volatile fatty acids (butyric acid, caproic acid and caprylic acid).
• Butter has a RM number in the range 25-30, while it is less than 1 for most other edible
oils. Thus any adulteration of butter can be easily tested by its RM number
 REICHERT-MEISSL VALUE- PRINCIPLE
• Fat is saponified using glycerol-alkali solution & acidified by sulphuric acid to liberate free
fatty acids.
• The liberated fatty acids are steam distilled and the steam volatile fatty acids are
collected (as condensate).
• The cooled condensate filtered for separation of water soluble and water insoluble fatty
acids.
• The water soluble fatty acids which pass through the filter paper are estimated by
titration with alkali to give RM value.
• Water - insoluble fatty acids is titrated to give the polenske value.
• The Reichert-Meissl Value gives an estimate of the lower steam· volatile fatty acids
 ACETYL VALUE
• The acetyl value is the number which expresses in milligrams the amount of potassium
hydroxide required to neutralise the acetic acid liberated by the hydrolysis of 1 g of the
acetylated substance
• Principle: Natural or rancid fat that contains fatty acids with free hydroxyl groups are converted into
acetylated fat by reaction with acetic anhydride.
ACETYL VALUE
ACETYL VALUE
ACETYL VALUE
 ACETYL VALUE- SIGNIFICANCE
• Acetyl number is a measure of number of hydroxyl groups present and thus hydroxyl
acids in lipids
• Used for studying the natural properties of the fat
• Detect adulteration and rancidity.
• Increased number of acetyl value indicates more amount of free hydroxy fatty acids.
 INDIAN STANDARDS

The Bureau of Indian Standards is the national Standards Body of India working under the aegis
of Ministry of Consumer Affairs, Food & Public Distribution, Government of India.
 STANDARDS

• AOAC International (Association of Official Agricultural Chemists)

• ASTM (American Society for Testing and Materials)
 Some important questions asked
• Describe the drying of fats and oils.
• Write the definition, significance and determination of following analytical
constants: iodine value & saponification value.
• Explain about oxidation & hydrogenation of fats and oils.
• Define acid value. Describe its significance and determination.
• Write the significance of Iodine value.
• Write the significance & principle involved in the determination of Acid value.
• Write the significance and principle involved in the determination of RM value.
• Define and differentiate fats & oils with examples.
• Explain rancidity of oil
• . Explain Reichert – Meissel value.
• Explain the hydrolysis reaction of fatty acids
FATTY ACIDS