Chapter 1

Oils and Fats

Chemical reaction of lipids

• Hydrogenation
• Interesterification (IE)
• Fractionation
• Hydrolysis
• Polymerization
• Deep fat frying
 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
Hydrogen Fat free milk

Oil mixture Refiner Hydrogenation Blender Emulsifier Margarine

Catalyst Flavourings 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.

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 + 319-376
 emulsifiers

Smoke point and flash point

Flash point!!

Temperature Smoke point

increasing

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
 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• R O O R + 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
1. Numbermeasurements
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.
 1. 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.
Thank you