LESSON 7: INTRODUCTION AND STRUCTURE OF LIPIDS

LIPIDS (3) DERIVED LIPIDS

• Comes from Greek word “lipos” which means fat • materials that meet the definition of lipid but neither
• Insoluble in water because of the polarity neutral nor compound
• polar • no FA in their structure
• soluble in hexane, organic solvents such as chloroform, • carotenoids (orange or yellow) found in plants such as
ether (diethyl ether) carrots and squash
• fat soluble vitamins (no FA in their structure)
Classification of Lipids ‣ Vitamins A, D, E, K
(1) SIMPLE LIPIDS • steroids
• esters of fatty acids with alcohol ‣ cholesterol, hormones
• neutral lipids ‣ steroid nucleus (3 cyclohexane and 1 cyclopentane)
• fats • cholesterol
‣ triglycerides or triacyl glycerides ‣ same with steroids but contains methyl groups
‣ glycerol + FA ‣ obtained from animal sources like eggs meat and
• waxes milk
‣ long carbon chain alcohol + long carbon chain fatty ‣ no cholesterols in plants and vegetables
‣ found in many plants and animals • lipoproteins
‣ Spermaceti wax (in sperm whales) cosmetics ‣ transport proteins
‣ Beeswax or carnauba wax in foods for protect and ‣ HDL (High Density Lipoproteins), good, happy
improve quality of the food (coating, postharvest cholesterol which helps keep the arteries clean and
principles) free of plaques
‣ LDL (Low Density Lipoproteins), bad, lethal
(2) COMPOUND LIPIDS cholesterol that forms plaques which hardens and
• contains other groups in addition to fatty acids and narrows the arteries
alcohols • steroid hormones
• phospholipids ‣ hormones are chemical messengers that serves as
‣ glycerol + fatty acids + phosphate + nitrogen group a kind of communication system from one part of the
‣ has amino alcohol body to another
‣ contains polar and non-polar region (flexible) ‣ testosterone, androgen
‣ allows food industry to use it as emulsifier
‣ abundant in cell membrane Classifications
‣ glycerophospholipids (1) SOURCE
‣ Can be used as an emulsifier since it can hold both a. Vegetable
sides (hydrophobic and hydrophilic ends) • palm oil
‣ can stabilize the emulsion • soya oil
‣ reduces the interfacial tension • olive oil
‣ Similar structure to triglycerides but triglyciders have
3 FA attached while phospholipids have 2 FA attached b. Animals
‣ Ex. Lecithin and Cephalin – abundant in egg yolks • pork/pig = lard
(mayonnaise), wheat germ, and yeasts • beef/cow = tallow
• glycolipids/cerebrosides • marine animals (fish or cod liver oils) for supplements
‣ Important components in animal tissue
‣ animal muscles in meat (2) FATTY ACID ATTACHMENT
‣ Glycolipids due to a sugar unit (glucose or galactose) • do not contain fatty acids and cannot by hydrolyzed
and a FA unit • esters that can be hydrolyzed to give fatty acids along
• sphingolipids with other products to give alcohol
‣ sphingosine + fatty acids + phosphate + choline • triacylglycerol or triglyceride broken down you get 3 FA
‣ a basic, • glycerophospholipids broken down you get glycerol, 2
‣ long-chain FA, phosphate group, amino alcohol
‣ unsaturated amino alcohol,
‣ C18H37NO2
‣ Found combined with lipids in brain and nerves

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LESSON 7: INTRODUCTION AND STRUCTURE OF LIPIDS
Cis and Trans Isomers of Unsaturated Fatty Acids
• stereoisomers that differ on the location of the carbons
in the double bonds
• Unsaturated fatty acids can be drawn as cis trans
isomers
‣ Oleic acid, a MUFA found in olives and corn has
double bond of carbon 9
• cis and trans structural formulas can be written using
the line-bind notation
• cis = same side; trans = opposite/adjacent sides

Fatty Acids Cis Structure

• Simplest type of lipids and are found as components in
more complex lipids
• Carboxyl group + hydrocarbon chain
• The cis structure is the most prevalent isomer found in
naturally occurring unsaturated fatty acids
• In the cis isomer, the carbon chain has a “kink” (yung
kulot daw) at the double bond site
• bending (imagine a weight on a stick, the stick will bend
because of the weight)

• C=O (carbonyl); O-C=O (carboxyl)

• Contain a long unbranched carbon chain attached to a
carboxylic acid group at one end
• Naturally occurring fatty acids have an even number of
carbon atoms, usually between 10 and 24
‣ Lauric acid, a 12-carbon atom (in coconut oil)
• In skeletal formula (or condensed structural formula) of
fatty acid, the ends and bends of the line are the carbon
atoms Trans Structure
• methyl ends or acid group for naming • In trans conformation, Hydrogen next to the double bond
• The long chain (14-24 carbons fatty acids of meats, fish , is in the opposite sides of the carbon chain
and vegetable oils are most common in the diet • no bending observed
‣ Myristic onwards • Only a few fatty acids (notably a small percentage of
• Medium chain (8-12 carbon chains) those found in milk and meat products) naturally occur
‣ Caprylic to lauric as trans fat
• Short chain (fewer than 6 carbons) fatty acids also occur, • mainly animal derived but selective vegetable product
primarily in dairy products • Trans-fat remains in the blood stream for a much longer
‣ caproic acid, butyric acid period of time
• Leads to arterial deposition and subsequent plaque
Table 1. Classification of Fatty Acids Based on the Degree of formation
Unsaturation • more stable, more difficult to remove in the blood stream
Double • Increased risk for CVD (cardiovascular diseases)!!!
Type of FA Diagram
Bonds • important factor in analyzing fats and oils (more on
health-wise)
Long carbon
Saturated None chain is an
alkane Location of Double Bond
• Fatty acids differ in the location of double bonds
Long carbon • Chemists identify PUFA by the position of double bond
chain has nearest the methyl end (CH3) of carbon chain, which is
Monounsaturated One
one double described by an omega number
bond
There are at
least two
Multiple
Polyunsaturated carbon-
(>1)
carbon
double bond
FT748: Food Chemistry (Lecture) ↮ PAGE 25
LESSON 7: INTRODUCTION AND STRUCTURE OF LIPIDS
• saturated fatty acids are usually solids at room
temperature
• In unsaturated fatty acids, the cis double bonds cause
the carbon chain to bend or kink, giving the molecules an
irregular shape (fewer interactions between carbon chain)
• kinking is present, lesser chance that the connected
structure is not kinked
• Most unsaturated fats (vegetable derived) are liquid oils
at room temperature.
• higher melting point = longer change

*Sample Problems*
(top) Omega-3-FA; (bottom) Omega-6-FA Consider the condensed structural formula of oleic acid:
Groups of Fatty Acids: Configuration of the Double Bond
a. non-conjugated
b. conjugated

(1) Why is the substance an acid?

- carboxylic end of the structure
(2) How many carbon atoms are in oleic acid?
- 18 carbons
(3) Is it a saturated or unsaturated fatty acid?
- unsaturated due to the double bond
(4) Would it be soluble in water?
- insoluble because it is a fatty acid

Palmitoleic acid is a fatty acid with the following

Cis and Trans Isomers of Unsaturated Fatty Acids condensed structural formula:
• The human body is capable of synthesizing most fatty
acids from carbohydrates or other fatty acids
• However, humans do not synthesize sufficient amounts
of PUFA such as linoleic, linolenic and arachidonic acid
• Essential fatty acids (cannot be synthesized) (1) How many carbon atoms are in palmitoleic acid?
- 16 carbons
Table 1. Essential Fatty Acids with Numerical Formula (2) Is it a saturated or unsaturated fatty acid?
Common Name Numeric Location of - unsaturated (mono)
(Abbreviation) Formula First Double (3) Is it most likely to be solid or liquid at room
(Chain length Bond
double bonds)
temperature?
(Relative to
omega end of - cis structure, kinking, liquid at RT
chain)
Linoleic Acid (LA) 18:2 Omega-6 Fats and Oils: Triacylglycerol
• In the body, fatty acids are stored as fats and oils known
Alpha-linolenic acid (ALA) 18:3 Omega-3
as triacylglycerol
Arachidonic acid (AA) 20:4 Omega-6
• Also called triglycerides are triesters of glycerol (a
Eicosapentaenoic acid (EPA) 20:5 Omega-3 trihydroxyalcohol) and fatty acids
Docosahexaenoic acid (DHA) 22:6 Omega-3 • 3 water molecules are removed
• In triacylglycerol, three hydroxyl group on glycerol form
Physical Properties of Fatty Acids ester bonds with carboxylic groups of three fatty acids
• common in animal derived, ‣ Ex. Glycerol and three molecules of stearic acid form
• The saturated fatty acids fit closely together in a regular glyceryl tristearate which is commonly named as
pattern, which allows strong attraction to occur between tristearin
carbon chains.
• As length of carbon chain increases, more interaction
occurs between the carbon chains requiring higher
melting points

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LESSON 7: INTRODUCTION AND STRUCTURE OF LIPIDS
Melting Points of Fats and Oils
• Saturated fatty acids have higher melting points than
unsaturated fatty acids because they pack together more
tightly
• Animal fats contain more saturated fatty acids than do
vegetable oil
• Therefore, the melting points of animal fats are higher
than those of vegetable oils
• Generally, the shorter the carbon chain, the softer the
fat is at room temperature
• greater saturation, longer FAC = greater degree of
solidity, higher MP
Chemical Properties of Triacylglycerols
(1) STABILITY
• Saturation influences the stability. All fats become
spoiled when exposed to oxygen
• polyunsaturated and monosaturated tends to be rancid
(maanta) faster or oxidation of oils
• Oxidation – rancid
• Polyunsaturated fats spoil most readily because their
double bond are unstable
• Saturated fats are most resistant to oxidation
• 3 ways to protect from rancidity:
(1) sealed airtight, non-metallic container, protected
from light,
(2) use antioxidants
(3) hydrogenation
(2) HYDROGENATION
• to reduce double bonds
• important in the food industry since it can lead to a
series of new products
• increase the degree of saturation
• In the hydrogenation of unsaturated fat, hydrogen is
added to one or more carbon-carbon double bonds to
form carbon-carbon single bonds
• The hydrogen gas is bubbles through the heated oil
typically in the presence of a nickel catalyst
• In commercial hydrogenation, the addition of hydrogen
is stopped before all double bonds in liquid vegetable oil
become completely saturated
• Complete hydrogenation gives a very brittle product
(margarine)
• Partial hydrogenation of vegetable fat changes it to soft,
semi-solid fat (shortening)
• Although these products now contain more saturated
fatty acids than the original oils, they contain NO
cholesterol, unlike similar products from animal sources,
such as butter and lard
• liquid oil becomes solid
(3) HYDROLYSIS
• Triacylglycerols are hydrolyzed (split by water) in the
presence of strong acids or digestive enzymes called
lipases
• water molecules are added
• high fatty acid = oil degradation
• Products: glycerol and three fatty acids
• The polar glycerol is soluble in water, but the fatty acid
with their long hydrocarbon chains are not
(4) SAPONIFICATION
• Saponification occurs when fat is heated with a strong
base as sodium hydroxide to give glycerol and the sodium
salts of the fatty acids which are soaps
• NaOH used – produce solid soap
• KOH used – produce softer, liquid soap
• Oils that are polyunsaturated produce softer soap
• end products differ in the base used
• solidity varies on the degree of unsaturation
FT748: Food Chemistry (Lecture) ↮ PAGE 27
LESSON 7: INTRODUCTION AND STRUCTURE OF LIPIDS
Nomenclature If C1 and C3 are the same triglyceride
Number of Saturated Fatty Acids Unsaturated Fatty Pag ganitong instance, di natin need gumamit ng di kasi
Carbons and (single bond) Acid (double bond) ang rule kapag gagamit ng di sa naming ng triglycerides,
Prefix -anoic acid -enoic/-aenoic acid dapat consecutive.
4 but- butanoic acid butanoic acid
6 hex- hexanoic acid hexenoic acid So example
8 oct- octanoic acid octanoic acid
C1 - myristic
C2 - palmitic
10 dec- decanoic acid decaenoic acid
C3 - myristic
12 dodec- dodecanoic acid dodecaenoic acid a-myristo-b-palmitomyristin
Assign alpha sa C1 lang para meron tayo magagamit to
distinguish C1. Then beta sa C2, then attach lang ulit si C3,
but change the suffix to -in..

Naming Triglycerides

If for instance, 2 consecutive fatty acids (C1 & C2 or C2 &

C3) are the same, the prefix di- can be used
C1 - Palmitic
C2 - Oleic
C3 - Oleic
Name: 𝛼 – Palmitodiolein

Name the triglyceride with 3 palmitoleic acids attached to

glycerol
Name: tripalmitolein

Name the triglyceride if

C1 - Lauric
C2 - Caprylic
C3 - Stearic
Name: α-lauro-β-caprylostearin

Name the triglyceride if

C1 - Stearic
C2 - Stearic
C3 - Lauric
Name: distearolaurin

FT748: Food Chemistry (Lecture) ↮ PAGE 28

LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
Physical Properties of Fats and Oils d. Number of double bonds present
• Melting Point • Smoke Point
• Specific Gravity • Fire Point
• Viscosity • Flash Point
• Density • Shot Melting Point
• Turbidity • Softening Point
• Specific Heat • Slipping Point
e. Configuration of the fatty acid stereo isomers (cis
• Solubility • Congeal Point
or trans)
• Refractive Index • Polymorphism
• more cis = more liquid
• more trans = more solid
The melting point, specific gravity, viscosity, density,
• different oil and fat material is constituted by different
and refractive index depends on the
fatty acids, and ration
(a) type of fatty acid,
• dominance in the composition = characteristic of the
(b) chain length
fat or oil
(c) number and location of cis/trans double bonds on the
fatty acid chain.
*kinking is due to the double bond of the structure, results
toa more liquid state of the oil
*solid fat because of the fitting (compactness) of fatty
acids (saturated fats)

(1) MELTING POINT

• Measures the strength of binding forces between fatty
acid radicals
• Dependent on the properties of the component fatty
acids
• Factors which influence melting point:
a. Molecular weight
• longer chain length, larger molecular weight

b. Length of carbon chain

• longer chain length higher melting point, more
difficult to break the bonds
• shorter chain, lower melting point, easier to break the
bonds or melt
• longer chains meaning it has a greater ability or and
stronger network between fatty acids
• denser molecules more difficult to break the bonds,
higher melting point • non-conjugated structures can decrease the melting
• longer chain, larger molecular weight (and vice versa) point while conjugated structures can increase the melting
Saturated Fatty Acids point
Formula Common Name Melting Point
CH3(CH2)10CO2H lauric acid 45C Measurement of Melting Point – Wiley Melting Point
CH3(CH2)12CO2H myristic acid 55C • In this method (AOCS Cc 2-38), a disc of chilled fat is
CH3(CH2)14CO2H palmitic acid 63C
heated in a bath of alcohol and water.
• The Wiley melting point is the temperature at which the
CH3(CH2)16CO2H stearic acid 69C
disc assumes a spherical shape.
CH3(CH2)18CO2H arachidic acid 76C • the point wherein the oil or fat is melted
• accepted American Oil Chemists Society (AOCS) method
c. Degree of saturation or unsaturation of fatty acid
components
• saturated when the ration on the right side is 0
• unsaturated both rations have values
• saturated fatty acids have a greater melting point

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LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
(2) SOLUBILITY (in water) Measurement of Viscosity – Viscometer
• Long chain triglycerides are essentially water insoluble, • Saybolt Viscometer
slightly soluble in alcohol and readily soluble in organic • Ostwald Viscometer
solvents • Falling Ball Viscometer
• more carbons or increased chain length of the fatty acid,
more forces resist or repel the charges of water =
insoluble
• organic solvents = soluble

(4) DENSITY
• The density of fats and oils is an index of the weight of
a measured volume of the material (g/cm3)
• All fatty acids found in food fats have specific gravities
less than 1.0
Table 2. Characteristics of Fatty Acids • The density of both fatty acids and glycerides increases
Fatty Acids M P (C) mg/100mL soluble in H2O with increasing saturation (compactness of the structure)
C4 -8 970 • The solid fat index (SFI) is related approximately to the
C6 -4 970
percentage of solids in a fat at a given temperature.
C8 16 75
(5) SPECIFIC GRAVITY
C10 31 6 • simply the ration of the density of a substance to the
C12 44 0.55 density of water
C14 54 0.18 • is unitless
C16 63 0.08 • formula
dsample
C18 70 0.04 Specific Gravity (SG) =
dwater
(3) VISCOSITY
• Measure of internal friction between molecules • A dense material will have a higher specific gravity
• Viscosity of the fatty acids increases with chain length • A specific gravity value of <1.00 will float in water
and decreases with increasing unsaturation. • Relevance of this property in the oil industry?
• Oils with lower molecular weight fatty acids are slightly ‣ decreasing specific gravity, increasing plasticity
less viscous than those with higher molecular weight ‣ important in choosing which fat to use in preparing
components with the same degree of saturation. confectionary, icing, pastry (mainly for texture or
• There is an approximately linear relationship between softness)
log viscosity and temperature ‣ more plastic the fat is, more air can the fat hold, low
• viscosity of a fat decreases by about 30% for each specific gravity (more unsaturated a fat is, the more
10C rise in temperature plastic it will be – ex. Vegetable shortening)
• The viscosity of oils usually increases in prolonged ‣ plasticity is the ability of fats or oils to be spread and
heating due to polymerization (gum formation). shaped or molded
• packed molecules = higher internal friction = higher
Table 3. Specific Gravity of Fats
overall viscosity
• less viscous unsaturated fatty acids Fat Specific Gravity Plasticity
• higher or longer chain length increases viscosity Butter 0.86 high
• temperature is a factor in identifying viscosity Shortening 0.90 stable
• repeated use of oils leads to a more chemical reactions Margarine 0.93
and a higher viscosity due to the constant exposure to Lard 0.96
heat, which results to polymerization (complexity of
compound) Measurement of Specific Gravity
• reusing of oil can be toxic • Pycnometer
• Hydrometer
• Hydrostatic Balance

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LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
(8) SHOT MELTING POINT
• Temperature at which a small lead (Pb) shot will fall
through a sample
• Determines viscosity of fat or oil
• The higher the degree of unsaturation, the lower the shot
melting point
• Lower temperature for the lead shot to fall through the
sample
• relative with the concept of melting point

(9) SMOKE POINT

(6) SPECIFIC HEAT • Temperature at which fat gives a thin bluish smoke
• The specific heat of fats is defined as the ratio of the • Results from formation of acrolein (break down product
heat capacity of a fat to the heat capacity of water of glycerol)
‣ The quantity of heat required for a one-degree
temperature change in a unit weight of fats.
• Specific heat does increase with increasing
unsaturation of fatty acids in both the liquid and solid
states of a fat.
• Liquid fats have almost twice the specific heat values
• acrolein is an eye irritant
than those of solid fats.
• Smoke point depends on the amount of free fatty acids
• Liquid fats > solid fats (specific heat)
• Smoke point decreases as the amount of free fatty acids
• due to the specific heat, vegetable oils take time to heat
increases
up to reach the higher temperature point
• higher smoke point better for cooking, indicates that it
has high fatty acids
(7) REFRACTIVE INDEX
• Repeated use of oil decreases the smoke point, indicates
• The degree of deflection of a beam of light that occurs
that quality has deteriorated
when it passes from one transparent medium to another.
• Low molecular weight fatty acids decrease smoke point
• Usually measured at 25C
of oils
• Refractive index decreases as the temperature rises
• Number of double bonds present has little effect on
(loosening of the molecules)
smoke point
• Refractive index increases with increase in chain length
of the carbon chains (concentrated substance, higher RI)
(10) FIRE POINT
• Refractive index increases with the number of double
• Temperature at which the substance will sustain
bonds present
continued combustion
• The refractive index can be utilized as a control
• Low molecular weight fatty acids have low fire point
procedure during hydrogenation processes.
• long chain is ideal
• can be used as a parameter for the quality assurance
protocol for oils and fats
(11) FLASH POINT
• due to fats is constituted by more complex substances,
• Temperature at which the mixtures of vapor with air
leads to more deflection
ignites
• Full hydrogenated = solid, removal of all double bonds
• Low molecular weight fatty acids have low flash point
• Partial hydrogenate = semi-solid
• fast combustion
• has a higher RI
• flash point occurs first before the fire point of oils

Measurement of Refractive Index – Refractometer

• Abbe Refractometer
• Hand Refractometer
Sisilip ka lang daw sa prism to get the RI

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LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
(12) TURBIDITY
• The point where turbidity occurs when a cooling
mixture of oil with solvent and the oil separates from the
solvent
• Affected by the presence of moisture in the oil and
free fatty acid (minimal levels) -> lowers turbidity
temperature,
• increasing solubility of oils, raises turbidity
temperature
• determines contaminants
• Valenta number. The determination is made by heating
equal volumes of the dry filtered fat and glacial acetic
acid (usually 3 cc.) in a test tube until clear, stirring with
a thermometer meanwhile. The mixture is then allowed to
cool, continuing the stirring, and the temperature is noted
at which turbidity first appears.
• Crismer Value. Measures the miscibility of an oil in a
standard solvent mixture, composed of t-amyl alcohol,
ethyl alcohol and water in the volume proportion 5:5:0.27.
Crismer value (CV) is one of the specification criteria used
for international trade, mostly in Europe. Characteristic
values are usually within a narrow limit (AOCS, 1992).
(13) SOFTNENING POINT
• Temperature at which a column of fat rises in a capillary
tube
• the point in which it softens
• Method:
• Capillary tubes are filled with oil and packed in ice
overnight so that the oil can solidify and come to
equilibrium.
• The capillary tubes are clamped to a thermometer
and submerged in a beaker of water.
• The temperature is slowly raised and the temperature
at which the column of fat rises in the capillary tube is
called the softening point.
• Relevance to oil industry?
(14) SLIPPING POINT
• Synonymous to softening point
‣ Temperature at which packed, solid fat slips
Method:
‣ Small brass cylinders, filled with the solid fat are
suspended in a bath close to the thermometer.
‣ As the water bath is stirred, the temperature is slowly
raised.
‣ The point at which the fat rises in the cylinder, or
slips, is recorded as the slipping point
• Depends on the following:
‣ Composition of fat
‣ Amount of air
‣ Amount of water beaten into the fat during
manufacture
(15) CONGEAL POINT
• Highest temperature at which a substance solidifies
• opposite of the softening point
• Method of determination
‣ A liquid (could be melted) sample is cooled and
stirred and at standardized conditions.
‣ When solidification starts, stirring & cooling are
discontinued, and the rise in temperature that occurs
is measured.
‣ The maximum temperature reached is the congeal
point.
(16) POLYMORPHISM
• existence of more than one crystal form which are
significantly different in physical or chemical properties
• results from the different patterns of molecular packing
in fat crystals
Crystal Habits of Fat
Crystallization of fats determines important properties of
food:
1. Consistency and plasticity of fat rich products (ex.
Butter, margarine, chocolate) during stages of
production and storage
2. Sensory properties such as melting sensation in
mouth
3. Physical stability with respect to the formation
and settling of crystals, oil exudation, and
coalescence of particles and emulsions
4. Visual appearance (ex. shininess of chocolates
and icings)
FT748: Food Chemistry (Lecture) ↮ PAGE 32
LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
• different on compactness of structure
• determines the certain properties of fat foods such as
consistency and plasticity of fats – sensorial properties
Facts about the Polymorphism of Solid Fats
• Polymorphic behavior is greatly influenced by 3 factors
(1) FA make up & their position in the fat molecule
(2) Temperature history (temperature abuse during
transport)
(3) Agitation during cooling
• The more heterogeneous is the FA make up of a fat
molecule, the greater the chance to form B’
• Polymorphic behavior is MONOTROPIC (change
proceeds from lower to higher stability )
• The courser the crystal, the higher is the melting point
• Agitation during cooling of processed fat is the key to
achieving the necessary control of crystal formation:
Rapid cooling with agitation → fine crystals
Slow cooling without agitation → coarse crystals
Chemical Properties of Fats and Oils
• Reichert Meissl Number
• Polenske Number
• Kirschner Number
• Hehner Value
• Acetyl Value
• Saponification Number
• Iodine Number
(1) REICHERT MEISSL NUMBER
• test for purity of butter
• Volume of 0.1 N hydroxide solution necessary for the
neutralization of the water-soluble volatile fatty acids
distilled and filtered from 5g of a given saponified fat
• An indicator of how much volatile fatty acid can be
extracted from fat through saponification
• Volatile fatty acids are considered 4:0 to 14:0
• Butyric, caproic, caprylic, capric, lauric, myristic
• Increasing chain length makes the molecule nonpolar,
therefore decreasing solubility in water
• focuses on smaller chain length fatty acids
(2) POLENSKE NUMBER
• Volume of 0.1 N hydroxide solution necessary for the
neutralization of the water insoluble volatile fatty acids
distilled and filtered from 5 grams of a given saponified
fat
• Used to determine whether oils are added to butter
• Volatile fatty acids are considered 8:0 to 14:0
‣ caprylic, capric, lauric, myristic
• longer chain length
• higher Polenske Number = adulterated
(3) KIRSCHNER VALUE
• Volume of 0.1 N sodium hydroxide solution necessary
for the neutralization of the water-soluble silver salts
made from the water-soluble volatile fatty acids distilled
and filtered from 5 grams of a given fat
• Volume of 0.1 N alkali required to neutralization 100 mL
distillate from Reichert Meissl determination
• Describes the amount of butyric acid present in a 5-
gram sample of fat
(4) HEHNER VALUE
• Measures actual amount of fatty acid that is insoluble in
water
• Polenske number is therefore directly proportional with
Hehner value
• Reichert Meissl number is inversely related to Hehner
value
• Fatty acids present in natural fats are insoluble in water,
therefore they have relatively high Hehner value
• all insoluble fatty acids can be measured with the Hehner
value.
(5) SAPONIFICATION NUMBER (KOETTSTORFER)
• Also known as Koettstorfer number
• Number of mg of KOH required to saponify 1g of fat or
oil
• Fats with low MW, have high saponification
• ↓ Molecular Weight ↑ Saponification value
Method of Determination – Titrimetric Method
(mL • N of KOH) - (mL • N of HCl) • 56.1
SN =
g of sample
SN = Saponification number
(mL • N of KOH) = miliequivalence of KOH used for
saponification
(mL • N of HCl) = miliequivalence of HCl used for back
titration to determine unreacted KOH base
FT748: Food Chemistry (Lecture) ↮ PAGE 33
LESSON 8: PHYSICAL AND CHEMICAL PROPERTIES OF LIPIDS
(6) IODINE NUMBER
• Number of grams of iodine compound absorbed by 100g
of fat
• A measure of the extent of unsaturation of fatty acids
present in fat
• Double bonds present in unsaturated FA react readily
with iodine to form an addition compound even while the
FA is attached to glycerol of the fat
• The more iodine is attached, the higher is the iodine
value, and the more reactive, less stable, softer and more
susceptible to oxidation and rancidification
• The reaction is also called halogenation and is also an
addition reaction
• unsaturated fats can be reactive

Method of Determination – Titrimetric Method

(Vb - Vs ) (N of Na2 S2 O3 ) • 126.9

IN =
g of sample

IN = iodine number
Vb = volume of Na2S2O3 (Sodium thiosulfate) used for
titrating control blank
Vs = volume of Na2S2O3 used for titrating liberated iodine
N = exact normality of Na2S2O3

*Test Your Understanding*

Fat with Saturated : Unsaturated (%)
A. 80:20
B. 60:40
C. 10:90
A 1. Which fat has highest melting point?
A 2. Which is the most viscous?
A 3. Which fat is the densest?
C 4. If all fats are heated at the same time, which will
totally melt first?

Oleic = 18:1; Palmitic = 16:0; Lauric = 12:0

A. Triolein
B. β-lauryldiolein
C. β -oleodipalmitin
C 5. Which fat is most probably solid at room temp?
C 6. Which is the most viscous?
C 7. Which fat is the densest?
A 8. If all fats are heated at the same time, which will
totally melt first?
C 9. Which fat is most insoluble in water?
A 10. Which fat is most probably liquid at room temp?

FT748: Food Chemistry (Lecture) ↮ PAGE 34

LESSON 9: DETERIORATION OF FATS AND OILS
Deterioration of Fats
(1) REVERSION
• revert back
• A deteriorative process which results to development of
off-flavors (flavor reversion)
• Flavor of refined oil “reverts” back that of crude oil
• Reversion occurs before onset of rancidity
• Changes in flavor during reversion:
‣ Buttery, beany, grassy, weedy, melon, hay, fishy,
painty (we don’t want this, we want to prevent this)
• Crude oil contains tocopherols, water, phospholipids,
monoglycerides, diglycerides, triglycerides, squalene,
sterols, proteins or peptids, polyphenols and carotenoids
or pigments.
• To refine crude oil, processes should be done:
degumming, neutralization, bleaching, deodorization
Hypothesis behind Flavor Reversion
(1) OXIDATION OF LINOLENIC ACID
• Linolenic acid carries reversion
• Oils with low linolenic acid develops less
reversion flavor
• High linolenic acid has a greater chance of flavor
reversion
• Oils extremely susceptible to reversion
‣ Soybean oil
‣ Fish oil
‣ Rapeseed oil
‣ Linseed oil
(2) PHOSPHATIDE REACTION
• Nitrogen is part of the molecules found in the
flavor extracts of reverted oil
• presence of nitrogenous compounds
• Lecithin provides the trimethylamine oxide,
which in the presence of linolenic acid and
hydroperoxides (produced from oxidative
rancidity), releases formaldehyde and
dimethylamine (results to formation of fishy odor)
(3) UNSAPONIFIABLES
• Induce reversion when added to other oils
• Flavor reversion is improved by removing
unsaponifiables with adsorbents or by drastic
steam deodorization
• If there is a failure in the process of
deodorization, more likely it will revert to its
original crude oil flavor
(4) OXIDIZED POLYMERS
• Oxidized ethyl linolenic polymers could
decompose under nitrogen
• These yields flavor components identical to
those isolated from reverted soybean oil
Flavor Reversion in Oils
• Flavor reversion is an oxidation process involving:
‣ Polyunsaturated fatty acids:
Linolenic > Linoleic > Oleic
- Linoleic Acid and Oleic Acid can also cause flavor
reversion but to a lesser extent as that of the
Linolenic Acid
‣ Unsaponifiables components (if they are effectively
removed by deodorization)
‣ Nitrogenous materials: phosphatides; others
• Some oils are found to be susceptible to rancidity but
are reversion resistant
(2) RANCIDITY
• A deteriorative process leading to unpleasant odor and
flavor
• Characterized by:
‣ Soapy or tallowy flavor
‣ Release foul smelling aldehydes and fatty acids
• 2 types of rancidity:
a. Hydrolytic Rancidity
• lipase induced chemical reaction
• Also called lipolytic rancidity
• Results to the hydrolysis of the triglycerides to its
glycerol and fatty acids in the presence catalysts
• Lipase, heat, and water are catalysts of hydrolytic
rancidity
Off odors and off flavor development
• Individual fatty acids can be more easily detected
compared to an intact triglyceride
• off odors or flavors indicates the level of fatty acids
• more odorous indicated that free fatty acids have formed
• In dairy products that naturally contain lipase, it happens
that short chain fatty acids are major hydrolytic products
• Can also occur in oil-based product
‣ Lipases can be produced by microorganisms
‣ Short fatty acids like butyric acid are particularly able
to be perceived by the taste buds
FT748: Food Chemistry (Lecture) ↮ PAGE 35
LESSON 9: DETERIORATION OF FATS AND OILS
b. Oxidative Rancidity
• Also known as autoxidation
• A radical-driven oxidation reaction
• Development of off-flavors and odors in fat because
of uptake of oxygen and the formation of peroxide,
hydroperoxides and numerous other compounds
• keen to measure peroxides and hydroperoxides
because it is a good indicator for oil freshness

Stages of Oxidative Rancidity

(1) INITIATION (radical formation)
• Involves the removal of H+ atom from the carbon
adjacent to the carbon involved in the double bond
• Gives rise to highly reactive FA molecule with an
unpaired electron – free radical (R●)
• it is a continuous process so as much as possible
prevent it while in the earlier stages
How to stop lipid oxidation?
• Identify the trigger and add metal chelators such as
copper, iron, and light
• Addition of antioxidant to donate electrons which
increases stability

(2) PROPAGATION (peroxides are produced)

• O2 reacts with free radicals (R●) to generate peroxy
free radicals of peroxides (ROO●)
• Peroxides are highly reactive and go on to react with
other unsaturated FA by taking a H+ atom generating
hydroperoxides (ROOH or RCOOH), and another free
radical (R●)

Types of Antioxidants
• Metal chelators
‣ Citric acid
‣ Phosphoric acid
• Oxygen scavenger
‣ Ascorbic acid
• Radical scavenger
‣ Synthetic antioxidants: BHA (butylated
hydroxyanisole), BHT (butylated hydroxytoluene)
(3) TERMINATION
‣ Semi-natural antioxidants: gallic acid, propyl gallate
• Accumulated free radicals (R●) comes to a point when
‣ Natural antioxidants: tocopherols, rosemary extract
they start to react with each other producing stable end
products
Relative Oxidation Rate of Polyunsaturated FA at 37C
• These end products contribute to off flavors of rancid
• higher degree of unsaturation, the more prone it is to
fats
oxidation

FT748: Food Chemistry (Lecture) ↮ PAGE 36

LESSON 9: DETERIORATION OF FATS AND OILS
Factors Contributing to the Oxidative Deterioration of (4) LIGHT
Finished Oil • Protect oil from exposure to light
• Oxygen or Air • Add antioxidants such as:
• Heat ‣ Beta carotene
• Trace Metals ‣ Tocopherol (VitE)
• Light • Initiator of reversion is at blue-violet region of spectrum
• Time (innate) 325 – 460 μm

As much as possible prioritize control in oxygen, heat, (5) TIME

trace metals and light since time is innate. • When given sufficient time, any fat or oil will deteriorate
even if handled under ideal conditions
(1) OXYGEN OR AIR
• Solubility of O2 in oil is high: 3.2ml / 100mL Test for Rancidity
‣ But oxidation can be initiated at much lower O2 • A variety of tests for lipid oxidation have been developed
concentration to measure either:
• Avoid exposure to air during processing 1. Products of hydrolytic rancidity (FFA)
• Avoid spraying in the air during filling and emptying of 2. Products of the initiation and propagation phases
storage or holding tanks Aldehydes, malonaldehydes, free radicals, peroxide,
• Use proper agitation systems in holding or storage tanks. hydroperoxide
• Avoid leakage at joint, fittings or faulty pump seals 3. Products of the termination phase
• Maintain vacuum where possible Hydrocarbons, aldehydes, ketones
• Avoid / eliminate the blowing of lines with air using 4. Depletion of oxygen or substrate
Nitrogen (N2)
• Use antioxidants LIPID OXIDATION TESTS
• “de-gripo” method, lesser exposure to air Predictive Indicator
• checking of the machines • Use accelerated • Are intended to quantify
conditions to measure the degree of rancidity that
(2) HEAT (TEMPERATURE) stability of the fat sample occurred in the fat sample
• Chemical reactions, including oxidation, accelerate with • Measures susceptibility • Measurement of the
DESCRIPTION

increasing temperature of fats to oxidation extent to which rancidity

• Keep the oil no warmer than needed • These tests may be used reactions have occurred
• Avoid localized overheating by agitating the oil when it is to determine ingredient during storage.
quality, measure • Fat sample for analysis is
heated
effectiveness of already rancid
• Keep the storage temperature as low as possible preservatives, or estimate
(temperature regulators) product shelf life
• do not subject the oil to higher temperature
• Active Oxygen Method • Peroxide Value
• Oxidative Stability Index • Thiobarbituric Acid Test
(3) TRACE METALS
TESTS

• Iodine Number • Anisidine Value

• Trace metals act as pro-oxidants accelerating oxidation • Oxygen Bomb Test • Hexanal Value
reactions • Schaal Oven Test • Headspace Profile
• Copper (Cu), the most potent oxidation catalyst and Iron • Free Fatty Acid (FFA)
(Fe) should be kept as low as possible
‣ Cu <5 ppb *Guide Questions*
‣ Fe < 150 ppb Is frying considered a dehydration method? Yes.
• Avoid using iron or copper (bronze) in systems Frying a tempura in high temperature?
(packaging material, machine, container)) in coming into • Water is released from the food
contact with finished oil • Frying oil is hydrolyzed
• Use a chelating agent such as citric acid and phosphoric • Formation of free fatty acids
acid
• Use metal scavenger to render metals unreactive like
EDTA (ethylene diamine tetra acetic acid)
• in meat, metals such as iron is present, prone to
oxidation

FT748: Food Chemistry (Lecture) ↮ PAGE 37