Fats and Oils

Fats & Oils

Content

• Introduction to fats and Oils

• Uses
• Structure and composition
• Physical properties
• Reactions involving fats and oils
• Extractions
• Analysis
• Industrial applications

2
Introduction
• Fats and oils are naturally occurring lipids found in plants and
animals.
• They are triesters of glycerol or glycerin, i.e. triglycerides or
triacylglycerols (TAG)
• The name lipid is derived from the Greek word lipos, means fat.
• Lipids are not soluble in polar solvents, but they are soluble in
non-polar solvents.
• Waxes, steroids and prostaglandins are also considered as lipids.
• At room temperature a fat is solid and an oil is liquid.
• Most TAGs in animals are fats
• TAGs in plants tend to be oils
• Hence the terms animal fats (butterfat) and vegetable oils
(coconut oil, corn oil) are used.
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• Triglycerides have lower densities than water.
• Glycerol is a trihydric alcohol (containing three hydroxyl
groups) and it can combine with three fatty acids to form
triglycerides while releasing three water molecules.
• In TAGs all three acyl groups can be the same or different.
• More commonly, however, the triacylglycerol is a mixed
triacylglycerol in which the acyl groups are different.

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Structure
• There are two major kinds of TAGs.
1. Saturated fats
(no C=C double bonds in fatty acid chains)
2. Unsaturated fats
(contains C=C double bonds in fatty acid chains)
• Unsaturated fatty acids can be monounsaturated fatty acids
(MUFA) or polyunsaturated fatty acids (PUFA).
• Animal fats usually contain more saturated fatty acids
(chicken, beef, pork, milk, butter, etc.).
Exception: Fish oils usually contains unsaturated fats
• Vegetable fats usually contain more unsaturated fats (corn
oil, olive oil, canola oil, avacados, nuts, etc.)
Exception: tropical oils like coconut oils, palm oils. 5
 Some Common Fatty Acids
# of # of Name of the Formula Melting Source
Carbon Double acid Point
Atoms Bonds (oC)

12 0 Lauric CH3(CH2)10COOH 43 Coconut

14 0 Myristic CH3(CH2)12COOH 54 Nutmeg
16 0 Palmitic CH3(CH2)14COOH 62 Palm
16 1 Palmitoleic CH3(CH2)5CH=CH(CH2)7COOH -0.5 Macadamia
nuts
18 0 Stearic CH3(CH2)16COOH 69 Lard
18 1 Oleic CH3(CH2)7CH=CH(CH2)7COOH 13 Olives
18 2 Linoleic CH3(CH2)4(CH=CHCH2)2(CH2)6COOH -9 Safflower
18 3 Linolenic CH3CH2(CH=CHCH2)3(CH2)6COOH -17 Flax

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Naming Fatty Acids

01. IUPAC Nomenclature:

• Carboxylic carbon is taken as carbon-1
• Prefixes such as tetra (4), penta (5),..........deca
(10),.....dodeca (12), ......icosa (20),......doicosa (22) are
used as to describe the length of the carbon chain
• Endings such as enoic, dienoic, trienoic, and tetraenoic
are used to indicate the number of double bonds.
• The number(s) given at the beginning of the IUPAC name
indicates the location(s) of the double bond(s)

Example:
The IUPAC name of the unsaturated fatty acid, oleic acid
CH3(CH2)7CH=CH(CH2)7COOH is cis-9-octadecaenoic acid.
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Naming Fatty Acids

2. Shorthand notation:
Examples:
• Shorthand notation of stearic acid (C18H36O2 or
CH3(CH2)16CO2H) is (18:0)

• This gives the total number of carbon present in the molecule

and the number of double bonds present in the chain.

• The shorthand notation of linoleic acid is (18:2)9,12 indicating

that it has a total number of 18 carbons and 2 double bonds
and the positions of them are C-9 and C-12.
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Naming Fatty Acids
3. Omega notation
• Greek letter omega (ω) is used to identify the location of the
double bonds.
• The "alpha" carbon (α-carbon) is the carbon closest to the
carboxyl group, and the last carbon of the polymer chain is
called the “ω carbon" going by the letter omega as it is the
last letter of the Greek Alphabet.

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• Physically, saturated fats are solids while unsaturated fats are
liquids.
• Unsaturated fats can be chemically changed to saturated fats by
hydrogenation.
Benefits:
• gives the oils a longer shelf-life
•makes them easier to spread!
•keeps oils from separating
•plant-based oils are cheaper

• Most processed foods contain partially hydrogenated fats

• Partial hydrogenation can produce trans fats which has been
linked to heart diseases and breast cancer.
• All natural fats contain cis fatty acids
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Trans Fats
• It is estimated that at least 30,000
deaths due to coronary disease
could be prevented by eliminating
trans fats.
• Rather than banning trans fats
outright, in some countries a law
was passed requiring the amount
of trans fat to be listed on the
nutritional label.
Which fats are good for you?
• monounsaturated fats
• polyunsaturated fats (especially
omega-3 fats)
Which fats are bad for you?
• saturated fats, trans fats
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What are trans fats?

• There are two broad types of trans fats found in foods:

naturally-occurring and artificial trans fats.

• Naturally-occurring trans fats are produced in the gut of some

animals and foods made from these animals (e.g., milk and
meat products) may contain small quantities of these fats.

• Artificial trans fats are created in an industrial process,

Hydrogenation
• The primary dietary source for trans fats in processed food is
“partially hydrogenated oils.”

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Why do some companies use trans fats?

• Trans fats are easy to use, inexpensive to produce and last a

long time.
• Trans fats give foods a desirable taste and texture.

• Many restaurants and fast-food outlets use trans fats to deep-

fry foods because oils with trans fats can be used many times
in commercial fryers.

• Several countries (e.g., Denmark, Switzerland, and Canada)

and jurisdictions (California, New York City, Baltimore, and
Montgomery County) have reduced or restricted the use of
trans fats in food service establishments.
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How do trans fats affect my health?

• Trans fats raise bad (LDL) cholesterol levels and lower

good (HDL) cholesterol levels.

• Eating trans fats increases your risk of developing heart

disease and stroke.

• It’s also associated with a higher risk of developing type 2

diabetes.

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Which foods contain trans fats?

• Fried foods like doughnuts, and baked goods including cakes,

pie crusts, biscuits, frozen pizza, cookies, crackers, and stick
margarines and other spreads.

• You can determine the amount of trans fats in a particular

packaged food by looking at the Nutrition Facts panel.

• However, products can be listed as “0 grams of trans fats” if

they contain 0 grams to less than 0.5 grams of trans fat per
serving.
• You can also spot trans fats by reading ingredient lists and
looking for the ingredients referred to as “partially
hydrogenated oils.” 15
Are there naturally occurring trans fats?

• Small amounts of trans fats occur naturally in some meat and

dairy products, including beef, lamb and butterfat.

• There have not been sufficient studies to determine whether

these naturally occurring trans fats have the same bad effects
on cholesterol levels as trans fats that have been industrially
manufactured.

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Some ways to achieve healthy diet:

• Eat a dietary pattern that emphasizes fruits, vegetables, whole grains,

low-fat dairy products, poultry, fish and nuts.
• Also limit red meat and sugary foods and beverages.
• Use naturally occurring, unhydrogenated vegetable oils such as canola,
safflower, sunflower or olive oil most often.
• Look for processed foods made with unhydrogenated oil rather than
partially hydrogenated or hydrogenated vegetable oils or saturated fat.
• Use soft margarine as a substitute over harder stick forms. Look for “0
g trans fat” on the Nutrition Facts label and no hydrogenated oils in the
ingredients list.
• Doughnuts, cookies, crackers, muffins, pies and cakes are examples of
foods that may contain trans fat. Limit how frequently you eat them.
• Limit commercially fried foods and baked goods made with shortening
or partially hydrogenated vegetable oils
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 Lipids modification
Why modified lipids?

1. Improves Oxidative Stability

2. Alter the Melting Properties

3. Alter the Crystallization Properties

4. Economic Advantages:
Less Expensive Oil  More Expensive Oil

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 Lipids modification

Modification methods.

1. Hydrogenation

2. Interesterification

3. Fractionation

4. Physical blending

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 Lipids modification

1. Hydrogenation

• Treatment of Fats and Oils with Hydrogen in the presence

of a catalyst and Heat to convert liquid oils into solid or
semisolid.

• This process improves Oxidative Stability and imparts

desired Physical Properties such as melting point and SFC.

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 Lipids modification (Hydrogenation)
Possible reactions during hydrogenation

 Complete Saturation:
18:3  18:2  18:1  18:0

 Partial Hydrogenation

 Geometric Isomerization: cis  trans

 Positional Isomerization

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 Lipids modification (Hydrogenation)

How it is done:

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 Lipids modification (Hydrogenation)
How it is done:
• The oils are exposed to hydrogen gas at high pressure and
temperatures (2-10 atm, 140-225°C) in the presence of
0.01-0.2% finely divided nickel, and agitated.

• The reduction of double bonds is “selective”.

• The ones furthest from ester links of triglycerides and those
belonging to the more unsaturated fatty acids are most
reactive.

• First trienoic acids (with 3 double bonds) are converted to

dienoic acids; and then dienoic acids(2 double bonds) to
enoic (1 double bond) acids.
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 Lipids modification (Hydrogenation)

• The objectives of hdyrogenation are:

 To impart oxidative stability to the oil

 To convert a liquid vegetable or fish oil to a fat with

“butter – like” consistency by reducing the degree of
unsaturation

• Hydrogenated oils or fats have a consistency that is ideal for

use as margarine or shortening components.

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 Lipids modification (Hydrogenation)

Definitions of “Hydrogenation Selectivity”:

1. “Preferential hydrogenation of more unsaturated acids with

minimum formation of completely saturated fatty acids”

2. “The ratio of the rate of hydrogenation of linoleic acid to

that of oleic acid”

• Commonly observed selectivities range from 4:1 to 50:1.

• In Very selective hydrogenation: Linoleic acid : Oleic acid
ratio is (50 : 1)
• Highly selective catalysts are more desirable in the industry.
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 Lipids modification (Hydrogenation)
Hydrogenation process requires the following:

1. High temperatures
2. A metal catalyst such as nickel, zinc, copper, or other
reactive metals
3. Hydrogen gas

• The hydrogen gas is bubbled up through the oil

• The catalyst mixture converts unsaturated fatty acids into

saturated fatty acids by flipping one of the attached hydrogen
molecules and rotating it half the diameter of the carbon
chain. 26
 Lipids modification (Hydrogenation)

• This effectively creates a new molecular shape resulting in a

stiffer or more rigid material, hence the change from a liquid
to a semi-solid or solid substance.

• This new shape stiffens with the hydrogenation process

making the oil behave more like a fully saturated fat (such as
coconut fat which is 92% saturation and solid at room
temperature).

SUMMARY:
• The effects of hydrogenation:
Increased Oxidative Stability , Decreased Color; Decreased
Vitamin A; Isomerization (trans fatty acids) 27
 Lipids modification (Hydrogenation)
Trans fats are formed as a result of hydrogenation reaction
• Hydrogenation raises the melting point of the fat and
retards rancidity.
• But as recent health studies have found, other problems can
ensue when consuming large amounts of trans fats from
hydrogenated products.

• Trans Fatty Acid

The hydrogen molecules attached at the center of the fatty
acid carbon chain flips 180 degrees, which straightens the
natural curve or kink in the typical cis-configured fat.

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 Lipids modification (Hydrogenation)

• When hydrogenated, the cis- shape chemically alters to a

trans configuration and hence is called a “trans” fat.
• Most margarine and vegetable shortening have been trans
fat converted through full or partial hydrogenation process.

• Trans fats interfere with metabolic absorption efficiencies

and tend to congregate at adipose tissue sites.

• In some countries, there is a law to label the trans-fat

content of foods on all nutritional fact labels.

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SFI = Solid Fat Index
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Production of Margarine

• Margarine is a“water in oil”emulsion prepared from suitable

“margarine oil” stocks and a “milk phase”.
• The emulsion is modified by the addition of suitable surface
active agents (emulsifiers) including mono or diglycerides
and/or lecithin.

• Salt and other additives such as anti-oxidants, vitamins, color,

flavor, etc. are included.

• Margarine processing involves basically premixing of

ingredients followed by rapid chilling (solidification) and
homogenization.
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 Margarine production

NBD Oils Milk phase

milk
starter culture
Hydrogenation (Streptococcus lactis
Emulsification
Streptococcus
Mixing the oils and cremoris- producing
fats for fat phase. aroma)
Oil soluble Emulsification NaCl
additives(β- Preservatives
carotene, vit A, D,
emulsifiers lecithin, Cooling +
MDG) crystallization
(votator)

Kneading Packaging

(NBD = Neutralized, bleached, deoderized), MDG = Mono- and Di- glycerides 36

Rancidity
What is Rancidity?
The condition reached in certain foods as the lipids material (fat)
undergoes oxidation reactions producing aldehydes, hydroxyl
acids, keto acids, and other compounds which are responsible
for the odour and off-flavour producing stale foods.
What Factors are Favourable for Rancidity?
 Light
 oxygen
 trace elements like iron, and zinc,
 water,
 bacteria,
 Mold
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Rancidity

Two main types of Rancidity:

1. Hydrolytic Rancidity: caused by a breakdown of the fats into

glycerol and fatty acid.
2. Oxidative Rancidity: results from oxidation of unsaturated
and polyunsaturated fatty acids producing undesirable
flavors and odors.

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Rancidity

• Rancidity in foods may be very slight (indicated by a loss of freshness)

or very severe (indicated by objectionable odors and/or flavors)

• Slight degrees of rancidity are more common in foods than severe

rancidity

• A slight degree of rancidity may not be objectionable to consumers,

but products which do not seem fresh will not attract repeat
purchases.

• Even though meat is held under refrigeration or in a frozen state, the

poly-unsaturated fat will continue to oxidize and slowly become
rancid.
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What methods can be employed to control the rancidity?

1. Adding antioxidants—Antioxidants are substances that are added to

some foods to slow down oxidative deterioration.
I. BHA—butylated hydroxyanisole
II. BHT—butylated hydroxytoluane
2. Protected from light (Package food): because light accelerates
oxidation.
3. Vacuum packaging to keep oxygen out: because oxygen accelerates
oxidation.
4. Adding nitrogen to the bag to replace oxygen.
5. Speed up distribution to shorten the time from processing to
consumption.
6. Shelf dating products allows for consumers to know when to use
food products.
7. Vitamin E and Vitamin C also slow oxidative rancidity. 40
Analysis of Fats and Oils

Reasons to analyze fats and oils:

• Shelf life study (how long the item will remain without deterioration in
quality under a given set of conditions)
• Functional quality (e.g., suitability for use in biscuits, bakery,
hydrogenation, etc.)
• Sensory quality (e.g., rancidity)
• Nutritional quality (e.g., melting point, polyunsaturated fatty acids)
• As an aid in controlling production operation (e.g., control of
hydrogenation, recovery of oil in mills)
• Conformance to regulatory standards (e.g., with respect to free fatty
acids, saponification value, peroxide value, moisture)
• Detection of adulteration (e.g., contamination with mineral oil and
argemone oil, adulteration of dairy ghee with vegetable ghee)
• Advanced research (e.g., determination of fatty acid profile)
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Some of the routine tests carried out on fats and oils are as
follows:
 Acid value/Free fatty acid (FFA)
 Saponification value, SV (also termed Saponification number)
 Iodine value, IV (Also termed Iodine number)
 Unsaponifiable matter
 Refractive index
 Melting point (for solid and semisolid items)
 Moisture content
 General tests for adulteration;
• Hexabromide test for the presence of linseed oil
• Halphen test for the presence of cottonseed oil
• Baudouin test for the presence of vegetable ghee in dairy
ghee
Analysis of Fats and Oils

1. Acid Value
• The acid value is defined as the number of milligrams of potassium
hydroxide required to neutralize the free fatty acids present in one
gram of fat.
• It is a relative measure of rancidity as free fatty acids are normally
formed during decomposition of TAGs.
• The value is also expressed as per cent of free fatty acids
calculated as oleic acid.

• The acid value is determined by directly titrating the oil/fat in an

alcoholic medium against standard potassium hydroxide/sodium
hydroxide solution
Analysis of Fats and Oils

02. Iodine Value

• The iodine value of an oil/fat is the number of grams of iodine

absorbed by 100 g of the oil/fat, when determined by using Wijs
solution.
• The oil/fat sample taken in carbon-tetrachloride is treated with a
known excess of iodine monochloride solution in glacial acetic acid
(Wijs solution).
• The excess of iodine monochloride is treated with potassium
iodide and the liberated iodine estimated by titration with sodium
thiosulfate solution.
• The iodine value is a measure of the amount of unsaturation
(number of double bonds) in a fat.
Analysis of Fats and Oils

03. Test for presence of Sesame Oil (Baudouin Test)

• The development of pink colour with furfural solution in the

presence of hydrochloric acid indicates the presence of sesame oil.
• The color is produced on account of reaction with sesamolin
present in sesame oil.
Analysis of Fats and Oils

04. Test for Presence of Cottonseed Oil (Halphen's Test)

• The development of red colour on heating the oil with a solution

of sulphur in carbon disulphide indicates the presence of
cottonseed oil.
• The test is also given by Hempseed oil, Kapokseed oil / oils and
fats containing cyclopropenoid fatty acids (such as sterculic and
malvalic acid).
Analysis of Fats and Oils

05. Saponification Value

• The saponification value is the number of mg of KOH required to

saponify 1 gram of oil/fat.
• The oil sample is saponified by refluxing with a known excess of
alcoholic potassium hydroxide solution.
• The alkali required for saponification is determined by titration of
the excess potassium hydroxide with standard hydrochloric acid.
• The saponification value is an index of mean molecular weight of
the fatty acids of glycerides comprising a fat.
• Lower the saponification value, larger the molecular weight of
fatty acids in the glycerides and vice-versa.
Analysis of Fats and Oils

06. Unsaponifiable Matter Content

• The unsaponifiable matter is defined as the substances soluble in an

oil which after saponification are insoluble in water but soluble in
the solvent used for the determination.

• It includes lipids of natural origin such as sterols, higher aliphatic

alcohols, pigments, vitamins and hydrocarbons as well as any
foreign organic matter non volatile at 100°C e.g (mineral oil) which
may be present.

• Light Petroleum or diethyl ether is used as a solvent but in most

cases results will differ according to the solvent selected and
generally the use of diethyl ether will give a higher result.
Factors affecting Physical Characteristics of Fats and Oils

• The physical characteristics of a fat or oil are dependent upon:

1. Degree of Unsaturation of Fats and Oils

2. Length of Carbon Chains in Fatty Acids

3. Isomeric Forms of Fatty Acids

4. Molecular Configuration of Triglycerides

5. Polymorphism of Fats
Factors affecting Physical Characteristics of Fats and Oils

1. Degree of Unsaturation of Fats and Oils

• Triglycerides can be classified as mono-, di- or tri-saturated
and tri-unsaturated
• Fats that are liquid at room temperature tend to be more
unsaturated than those that appear to be solid, but there are
exceptions.
• For example, coconut oil has a high level of saturates, but
many are of low molecular weight, hence this oil melts at or
near room temperature.
• Thus, the physical state of the fat does not necessarily
indicate the amount of unsaturation
Factors affecting Physical Characteristics of Fats and Oils…..

2. Length of Carbon Chains in Fatty Acids

• As the chain length of a saturated fatty acid increases, the

melting point also increases.

• A short chain saturated fatty acid has a lower melting point

than saturated fatty acids with longer chains.
Factors affecting Physical Characteristics of Fats and Oils …..

3. Isomeric Forms of Fatty Acids

• The melting points of unsaturated fatty acids are profoundly
affected by the position and conformation of double bonds.
• For example, the monounsaturated fatty acid oleic acid and
its geometric isomer elaidic acid have different melting points

• Oleic acid is liquid at temperatures considerably below room

temperature, whereas elaidic acid is solid even at
temperatures above room temperature
Factors affecting Physical Characteristics of Fats and Oils…..

4. Molecular Configuration of Triglycerides

• Melting points vary in sharpness depending on the number
of different chemical entities present.

• Simple triglycerides have sharp melting points while

triglyceride mixtures like lard and most vegetable shortenings
have broad melting ranges.

• Monoglycerides and diglycerides have higher melting points

than triglycerides with a similar fatty acid composition.
Factors affecting Physical Characteristics of Fats and Oils…....

5. Polymorphism of Fats
• Solidified fats often exhibit polymorphism, i.e., they can exist
in several different crystalline forms, depending on the
manner in which the molecules orient themselves in the solid
state.

• The crystal form of the fat has a marked effect on the melting
point and the performance of the fat in the various
applications in which it is utilized.
 Tutorial
Fats & Oils
01. Briefly explain the Margarine Production process.
02. Briefly explain following processes.
(i) Inter-esterification
(ii) Hydrogenation
(iii)Physical Blending
(iv)Fractionation
03. What are trans-fats? Explain how do trans-fats effect human health.
04. Explain following terms briefly.
(i) Acid Value
(ii) Saponification Value
(iii) Iodine Number
(iv) Unsaponifiable Matter Content
5.Write a short account on rancidity of fats and oils. 55