FATS AND OILS

NAEMAA MOHAMAD
Faculty of Applied Sciences
Universiti Teknologi MARA
 LESSON OUTCOMES
At the end of this chapter, students should be
able to:-
a) Classify between different groups of fats and
oils.
b) Differentiate the sources of fats and oils.

c) Draw the basic structure of fats and oils.

d) Differentiate between physical and chemical
properties of fats and oils.
e) Explain rancidity in fats and oils.
 Classification of lipids

 Source

 Structures of triglycerides (TG) and

fatty acids (FA)

 Physical and chemical properties of

oils

 Rancidity
INTRODUCTION
 Lipids-Broad group of chemically diverse compounds that are
soluble in organic solvents such as chloroform and alcohol

 Food lipids: Generally referred to as fats (solid) and oils (liquid)

indicating their physical state at ambient temperatures.

 Also classified as nonpolar (eg: triacylglycerol and cholesterol) or

polar (eg: phospholipids) to indicate their differences in the
solubility and functional properties)
◦ Polar lipids contain hydrophilic head group that has high affinity for water,
attached to a lipophilic tail group that has high affinity for oil.

 Food lipids play an important role in food quality by contributing

to attributes such as texture, flavour, nutrition, and caloric density.

 General term used to describe a large group of naturally occuring

fat-like substances
 PHOSPHOLIPIDS
◦ important compound concerned with the transport of lipids in
the blood stream
◦ Eg. Lecithin play a major part in the digestion of fats
◦ Similar to fats structure based on glycerol but instead of 3
hydroxyl group being combined with fatty acid only two are
being combined, the third being combined with phosphate linked
to choline
 STEROIDS
◦ Classified as lipids but not fatty acid derivatives and dissimilar in
structure (eg: cholesterol, hormones)
 CHOLESTEROLS
◦ A white fat substances which present in body tissue and is found in
variety of animal foods notably brain, kidney, liver and egg yolk.
 WAXES
◦ Made from fatty acid combined with any of alcohol except glycerol
 SOURCES

ANIMAL NATURALLY VEGETABLE

ORIGIN OCCURING ORIGIN
1) Mammal 1)Seed oils
depot fat (eg: soybean oil,
([Link] and canola oil)
tallow) 2) Fruit coat fats
2) Milk fat (eg: palm and olive
3)Marine oils oils)
(eg. Code liver 3) Kernel oils
oil and whale oil) (eg:Coconut oil and
palm kernel)
BASIC CHEMICAL STRUCTURE OF
FATS AND OILS

Triglyceride (TG) and Fatty acids(FA)

 Triglycerides: Esters of glycerol with 3 fatty acids
 Basically fats and oils may be consider as mixtures of
triglycerides (TG)
 Comprised solely of Carbon, Hydrogen and Oxygen.
 They make up 40% of the calories in the average diet.
 Diglyceride/ diacylglycerol= glycerol attached to 2 fatty acids.
 Monoglyceride/ monoacylglycerol = glycerol attached to 1
fatty acid.
Fig: Triglyceride structure
 Glycerol or sometimes referred as glycerin is a simple organic
compound of 3-carbon molecule containing three alcohol groups.
 Fatty acid : organic molecule contains chain of carbon bound to
hydrogen, plus an acid group (COOH) at one end and a methyl
group (CH3) at the other.
 Ester bonds hold fatty acid to glycerol, joining OH groups of
glycerol to the COOH groups of FA, with the loss of water.
 Any fatty acid not linked to glycerol molecule in a fat or oil
is referred to as free fatty acid
 The major component of all fats and oils is made up of TG
which represent 95% of the weight of most food fats in the
form in which they are consumed.
Fatty acid (FA)
 Fatty acid : organic molecule contains chain of carbon bound to hydrogen, plus a
carboxylic acid group (COOH) at one end and a methyl group (CH3) at the other.

 Most natural fatty acids have even number of carbons in a straight chain because of
the biological process of fatty acid elongation where two carbons are added at a time.

 Majority range from 14 to 24 carbons in nature.

 Some fats contain FA with <14 carbons –significant levels of short chain FA mainly
found in tropical oil and dairy fats.
 Odd carbon number and branched chain of fatty acids can be found in
microorganism and dairy fats.

 FA generally classsified as either saturated or unsaturated (containing double bonds).

 Unsaturated FA can be either monounsaturated (1 double bond) or polyunsaturated (
2 or more double bonds).

 FA can be described by systematic , common and abbreviated names.

 Sources of FA
1. Saturated FA;
▪ Primarily animal sources: meat, poultry, milk, butter cheese, egg yol
and lard
▪ Plant sources: chocolate, coconut, coconut oil, palm oil, vegetable
shortening.

2. Monounsaturated FA;
▪ Avocado, peanuts, peanut butter, olives/olive oil

3. Polyunsaturated FA (PUFA);
▪ Primarily plant sources: vegetable oils (corn, safflower, soybean,
canole, etc), margarine, certain nuts (almond, walnut, pecan)
▪ Animal sources: fish
Nomenclature of saturated fatty acid
 IUPAC system names the parent hydrocarbon (HC) of the FA
on the basis of the number of carbons (eg. Ten carbons would
be decane).

 Since FA contains carboxylic acid group, the terminal e in the

HC is replace by oic (eg. Decanoic).

 Normally start the numbering from the carboxyl end

 Many common names originate from the source that the FA

was commonly or traditionally isolated (eg. Palmitic acids and
palm oil).

 A numerical system use for abbreviated names. The first

number in the system designates the number of carbons in
the FA, while the second number designates the number of
double bonds.
◦ Eg. Hexadecanoic=palmitic= 16:0
◦ ☺ second number will always be zero for the saturated fatty acids
Nomenclature of unsaturated fatty acid
 In IUPAC system, anoic designation is changed to enoic (for
the presence of double bond).

 On the basis of the number of double bonds, the terms di-,

tri-, terta- and so on are added.
 Common name exist except for the long chain polyunsaturated
fatty acids

 Numerical abbreviation is similar with the previous with the

second number indicating the number of double bonds (eg.
Octadecadieonic = 18:2).

 The position of double bonds in IUPAC system numbered by

the delta (Δ), indicating the position of double bond from the
carboxylic acid end of FA.
◦ Eg. Oleic acid (18 carbons and 1 double bond)= 9-octadecenoic acid = 18:1
Δ9
Linoleoc acid (18 carbons and 2 double bonds) = 9,12-octadecenoic
acid = 18 :2 Δ 9,12
 Cont.
 Alternative numbering system indicates position of
the double bond from methyl end of FA known as
the omega (ω) system.
 For omega-3 or omega- 6 FA, the numbering start
at methyl end.
 Useful as it can group FA on the basis of their
biological activity and biosynthetic origin.
 Eg. The ω-3 fatty acids able to decrease blood
triacylglycerol levels.
 The omega-3 and omega-6 are considered as
essential fatty acid (EFAs).
Essential fatty acid (EFAs)
 EFAs are essential to human health and cannot be made
by the body
 All EFAs are unsaturated and must be provided from food.
 Occur in fish oil and variety of seed oil.
 The two omega-3 essential FA are:
◦ Eicopentaenoic acid (EPA) and docosahexaenoic acid (DHA)
 Coldwater fish are the best sources of omega-3 EFAs.
 Plant sources contain precursor to EPA and DHA called
alpha-linoleic acid (ALA).
 ALA can be converted into EPA, and EPA into DHA.
 Several function of EFAs;
◦ Required as cell membrane components.
◦ Strengthen immune cells.
◦ Lubricate body joins
◦ Insulation of body again heat loss
◦ Prevention in skin drying
◦ Provide energy
 The omega 6 essential FA include linoleic
acid (LA) and gamma-linoleic acid (GLA)
 Found in seeds; evening primrose,
sunflower and black currant.
 Unsaturated FA comes in 2 configurations.
◦ Cis- and trans- configurations

 Natural configuration of double bonds in unsaturated FA

is the cis- configuration, the hydrogen atoms bonding
to the C=C located on the same side of the double
bond.

 Trans- configuration; the hydrogen atoms attached to

the carbon atoms of the double bond are opposite
each other (eg. in meat, poultry and processed diary
product)

 These structural differences affect properties such as

melting point.
HOW?????
Cont
 Double bond in cis- configuration will cause the FA in
bent configuration, thus are not linear making it
difficult for them to orient themselves in tight packing
configurations.

 Relatively weak van der Waals interactions

between unsaturated FA, their melting point is low.

 Therefore , exist mainly in liquid state.

 FA with double bond in trans configuration are more

linear than unsaturated FA in the cis- configuration.

 Resulting tighter packing and high melting point.

 Eg. Melting point of;
◦ stearic acid (octadecanoic) is 70°C
◦ Oleic acid (cis-9-octadecanoic ) is 5°C
◦ Elaidic acid (trans-9-octadecanoic) is 44°C
Table: Structure and melting point of some
common fatty acids
Chemical reaction of lipids
 Hydrogenation
 Interesterification (IE)
 Fractionation
 Hydrolysis
 Polymerization
 Deep fat frying
 Oxidation
 Hydrogenation

This is a chemical reaction that decreases the

amount of unsaturation in a fat or oil by the
addition of H2 in the presence of a metal catalyst.
 Converting oil to fat
Fat free
Hydrogen milk

Oil
mixture
Refiner Hydrogenation Blender Emulsifier Margarine

Flavourings
Catalyst etc

Processes involved

Chemicals involved

• Most natural oils need processing to make them fit for use.
• Hydrogenation of unsaturated oils – make margarine
• Controlled hydrogenation makes oils more solid.
• Pass H2 through heated oil – nickel catalyst.
• Add flavourings, salt, vitamins etc.
Cont’
 Used in food industry to harden liquid oils
into semisolid fats.
 This process raise the melting point of a fats.
 Have tendency to change the percentage of
cis- unsaturated FA to trans-unsaturated FA.
 Product produced from hydrogenation such
as margarines, shortenings, and partially
hydrogenated oils that improved oxidative
stability.
 Interesterification
 Removal of FAs from glycerol and their subsequent
arrangements, which differ from the original fat
molecule.

 Commercially important to produce monoglyceride

and diglyceride from TG that function as emulsifying
agent especially in food industry.

 Emulsifier tend to hold fat and water together. Eg. In

mixing of cake batter.

 Could improve melting point, plastic range, crystal

structure and flavour stability but does not change the
degree of unsaturation.
 Fractionation
 The process to splits an oil into its higher melting point
components (eg. Stearic acid) and lower melting point
component (eg. Oleic acid).

 Crystallization is accomplished, so the crystal portion (more

saturated or long chain) can be separated from the liquid
portion (more unsaturated and short chain).

 Commonly done to vegetable oil in a process called

winterization.
◦ The oil is simply cooled to about chilled temperature and
the crystallized material removed by filtration
◦ Useful in preparation of salad dressings
◦ Oil in salad dressing will not crystallize and disrupt the
emulsion when stored at a refrigerator temperature
 Hydrolysis
 The reaction requiring heat plus the addition of
water molecules to separate the FA from the
glycerol portion of a lipid molecule.
 Glycerol can further changed to acrolein, which
produces irritating and odorous fumes in the
smoke of an overheated fats.
heat heat
TG + 3H2O 3 FA+ glycerol 3 FA + acrolein +
2H2O
 Polymerization
 Reaction of fat itself, whereby a relatively small molecules of fat or oil
combine to form much longer molecules.

 Occur either at the point of unsaturation or at the juncture of the FA and the
glycerol molecule.

 May be 100 or 1000 times the molecular weight of the original molecules.

 Can occur in deep frying of food (temp; 325-375F).

 Reaction accelerated by frying at a high temperature (350F),presence of

O2, usage of poor quality fat and poor frying practice by heating for long
periods of time.

 Cause physical changes

◦ Gumlike material around the sides of the frying utensils
◦ Increase viscosity of the frying oil
◦ Foaming
◦ Darker colour of frying oil
 Deep fat frying
Requirements:
• Flavorless fat
• High smoke point
- fats last longer
- prevents excessive fat absorption

Deep frying
Fig: Summary of chemical reaction in deep fat frying
• The smoke point generally refers to the temperature at
which a cooking fat or oil begins to break down to
glycerol and Free Fatty Acids.

• The glycerol is then further broken down to acrolein

which is a component of the bluish smoke.

• It is the presence of the acrolein that causes the smoke

to be extremely irritating to the eyes and throat.

• The smoke point also marks the beginning of both

flavour and nutritional degradation.
• When fats and oils heated at the high temperature, fats and
oils began to degrade.

• With the uptake of a molecule water, lipolysis occurs, releasing

a free fatty acid.

• Continue heating cause the removal of two molecules of water

from glycerol which results in the formation of an unusual
aldehyde called acrolein.

• Acrolein immediately vaporised causing the fat to smoke.

Glycerol Acrolein
 Smoke points
Oil/fat Smoke points (F˚)
Corn oil 450
Cottonseed 450
Peanut 450
Lard 360-400
Shortening 450
Shortening + emulsifiers 319-376
 Smoke point and flash point

Flash point!!
Temperature
increasing

Smoke point

Typical operating range

Considerably above the temperature

of the smoke point is the flash point;
the point at which combustion occurs.
 PHYSICAL PROPERTIES
• Melting point
• Polymorphism
• Softening point
• Slipping point
• Shot melting point
• Specific gravity
• Reflective index
• Smoke, flash and fire points
 Melting point
• Fats do not melt sharply but soften over
a range of temperatures

• Not suitable to use in the identification

of pure organic compounds
 Polymorphism
• Fat or fatty acids are heated very slowly, they will melt and
turn into liquid.
• IF we solidify it, a second melting will occur at a higher
temperature.
• IF the material is then chilled rapidly, it will melt at a lower
temperature when it is warmed again.
• It found in many long-chain carbon compounds
• The occurance of more than one crystalline form explains this
phenomenan
• It plays a significant role in solidification of fats
• Example:
 Softening Point
• Capillary tubes are filled with oil and packed in ice
over night

• The capillary tubes are clamped to thermometer

and submerged in a beaker of water with a rising
temperature until the fat rises in the capillary tube.

• Reproducible for some fats, poor with others, cannot

be used with lard.
 Slipping Point
• Small brass cylinders, filled with solid fat.

• Suspended in a bath close to the thermometer.

• As the bath is stirred the temperature is slowly

raised, the point at which the fat rises in the
cylinder or slips is the slipping point.
 Shot Melting Point
• Is the temperature at which a small lead
shot will fall through a sample
 Specific Gravity
• The temperature is carefully controlled since
significant changes in this compounds occur in
short ranges of temperature.

• Usually at 25°C, some use 40°C or even 60°C.

• Variation of SG is not great. However increase

of unsaturation and chain length will tends to
increase the SG.
 Refractive Index
• The index of refraction is the degree of deflection
of a beam light that occurs when it passes from one
transparent medium to another.

• The index decrease as the temperature rises.

• Increases with increase in the length of the carbon

chain and number of double bonds present.
 CHEMICAL PROPERTIES OF
FATS AND OILS

• Saponification number
• Iodine value or iodine number
• Acetyl value
 Saponification Number
• Is defined as the number of milligrams of potassium hydroxide required to
saponify 1g of fat and oil

• When KOH reacts with tryglyceride, three moles of KOH react with one
mole of fat

• If the triglyceride contains low molecular weight fatty acids, the number of
molecules present in a 1g sample of the fat will be greater than of the fatty
acids have long carbon chains and high molecular weights.

• The fat with the low molecular weight fatty acids will consequently have a
high saponification number. By back titration.

• Example: Butter with high butyric acid has high SN.

 Iodine Value
• Number of gram of iodine or iodine compound absorbed
by 100g of fat. The double bonds present in the
unsaturated fatty acids react readily with iodine to form an
addition compound.

• The iodine number is therefore a measure of the extent of

unsaturation of the fatty acids present in a fat

• Higher iodine value means higher unsaturation fats present

in the sample.

• Useful indicator of fat form;

- High IV fats are liquid, low IV fats are solid.
OTHER CHEMICAL PROPERTIES
• Reichert Meissl Number
- Determine the butyric and caproic acids
• Hehner Value
- Measures the amount of fatty acids which
are insoluble in water
• Acetyl Number
- Measures amount of hydroxyl fatty acids
present in a fat
RANCIDITY IN FATS AND OILS
 OXIDATIVE REACTION
 Like hydrogenation, the reactions also occur at the point of
unsaturation.

R – CH = CH – CH3 + O2 R – COH –
COH- CH3

 Oxidation changes in a three stages series of reaction;

1. Initiation
2. Propagation/ elongation
3. Termination
1) Initiation

 The hydrogen is abstracted from the fat/oil to

yield a free radical in the presence of the
initiators such as UV light, heat and heavy metal
such as copper.

Initiators
RH R• + H
Unsaturated fat free radical
2) Propagation

 Once the free radical formed, it will combine with

oxygen to form a peroxy free radical, which in
turn abstract hydrogen from another unsaturated
molecule to yield a peroxide and a new radical.
 The propagation reaction has started.

R • + O2 ROO• (peroxy free

radical)

ROO• + R H R O O H + R•
hydroperoxide

* The hydroperoxide formed in the propagation part of the

reactions are the primarily oxidation products.
3) Termination of the oxidation
 If the free radicals react with themselves to yield
non- active products
ROO•+ R• ROOR
R• + R• R- R
R O O • + R O O• ROOR + O2

 Fat and oil antioxidant such as tocopherol, BHA,

BHT, gallic acid can react with initiating and
propagating radicals to produce harmless
products.
◦ Antioxidants are substances that can delay, or slow the
rate of oxidation.
Oxidative Rancidity
• Oxidative rancidity begins when a free
radical forms, normally in
polyunsaturated fatty acid.

• The free radical then combines with two

oxygen oxygen atoms to form peroxide.

• Subsequently, a hydrogen is removed

from another unsaturated fatty acid, and
that hydrogen atom to finish formation
of the second hydroperoxide, leaving
yet another free radical.

• This process is autocatalytic or self

perpetuating.
 Oxidative Rancidity

A hydroperoxide

Degradation to form smelly compounds

• Unsaturated fatty acids showing double bonds within the molecule are susceptible to
peroxidation.

• The availability or presence of oxygen, increased temperatures, the impact of light

and the presence of pro oxidants speed up autoxidation (oxidative rancidity) over
a period of time.

• Once triggered, takes place at a fast rate.

• The presence of pro oxidants such as iron and copper ions accelerates the onset of
autoxidation as does the presence of oxygen and exposure to light, especially
direct sunlight or light from fluorescent tubes.

• Iron and copper ions can be deactivated by the addition of chelating agents such as
citric acid.

• The oxidation of fat occurs at a faster rate at a reduced water content, because
water acts as a barrier against the reaction of fatty acids with oxygen. The smaller
the quantity of water within food, the more ‘effective’ the oxygen is towards
oxidation.
• Hydroperoxides are also neutral from a sensorial point of view but
demonstrate an extremely high potential for oxidation.

• They ultimately fall apart in the termination phase into countless

relatively unreactive components including aldehydes, hydrocarbons
and ketones.

• Some of the aldehydes obtained from hydroperoxides are

malondialdehyde and its isomeric combinations hydroxyacrolein and
ephedrine aldehyde.

• Aldehydes and ketones, originating from hydroperoxides, are

primarily responsible for the rancid smell of fat.
 Promoters of oxidative rancidity
PROMOTER PREVENTION
Heat Keep cool
Light Keep covered
Oxygen Keep covered
Metal ions Strain after use
Already rancid fats Don’t combine new and old fats

Unsaturated fats ---

• Hydrolytic rancidity is which free fatty acids are split
from the glycerol in fat molecule or lipolysis.

• The uptake of a molecule of water usually is promoted

either by the action of lipase or by heat and yield three
free fatty acid molecules and one molecule of glycerol.
 Rancidity measurements
1. Number of peroxides / Peroxide Value (PV) / Oxidative Rancidity
– measures the number of peroxides present in fat

• Measuring the number of peroxides is also commonly performed on pure

fats and oils and shows the stage of oxidation, or how far oxidation has
progressed already as peroxides are the first components formed during
the oxidation of fat. The peroxide value is helpful in order to determine
the quality of saturated fat but is not that helpful in assessing
unsaturated fats.

• PVs from 0 to 6 are generally seen when fat is not rancid whilst PVs from
7 to 10 are seen when fat is slightly rancid. PVs greater than 10 clearly
indicate rancidity but it should be kept in mind that the PV does not
always directly relate to the state of rancidity.
 2. Determination of the thiobarbituric acid (TBA) value

• The amount of malonaldehyde is determined in a photometric

way and rancidity starts at 0.4-0.6mg of malonaldehyde per
kilogram of sample.

• Within this test, saturated aldehydes obtained during the

termination phase of fat oxidation react with 2-thiobarbituric
acid. TBA-value analysis is performed on the food overall and
not on fat only, in contrast with the peroxide number or free
fatty acid (FFA) tests.

• TBA values generally correlate with the state of rancidity and

increased values indicate an advanced state of rancidity.
 3. Analysis of the FFA content.
Analysing the FFA content is based on measuring
hydrolytic rancidity in fat or oil.

• This type of analysis is performed on fat only, and hydrolytic

rancidity originates from the hydrolysis of triglycerides in the
presence of moisture.

• Enzymes such as lipase generally speed up this process and the

hydrolysis results in FFA.

• FFA values in meat and meat products above 1.2 indicate

rancidity.