Reactions of Oils and Fats

HYDROLYSIS AND OXIDATION

 Reactions of Oils and Fats

Hydrolysis

Oxidation

Hydrogenation

Esterification
 Hydrolysis
Chemical (Autocatalytic)
Enzymatical (Lipase)

O
H2C OH 3 fatty acids O
H2C O C - R1
O HO - C - R1 O
HC OH +
= HC O C- R2 +3H20
H2C OH HO - C - R2 O O
glycerol H2C O C - R3
HO - C - R3
triacylglycerol
 Acid Value

Number of mgs of KOH required to neutralize the

Free Fatty Acids in 1 g of fat.

ml of KOH x N x 56
AV = = mg of KOH
Weight of Sample
 Oxidation of Oils and Fats
The reaction of molecular oxygen with
organic molecules has for long been a
process of considerable interest.
Although a wide variety of organic
molecules are susceptible to chemical
attack by oxygen, a great deal of attention
has recently been focused on lipids
because of the remarkable implications of
their oxidative damage.
 Oxidation of Oils and Fats
The results of the oxidation of fats and oils is the
development of objectionable flavors and odors
characteristic of the condition known as
oxidative rancidity.

Loss of shelf-life, functionality and nutritional

value.

Adverse health effects (carcinogenic)

 Oxidation of Lipids
Autoxidation of Lipids is the oxidative
deterioration of unsaturated fatty acids via
an autocatalytic process consisting of a
free radical chain mechanism.

The chain of reaction includes

Initiation
Propagation
Termination
 What is Free radical?
A free radical is a group with an odd
number of unpaired electrons.

They are extremely unstable and

immediately react with another molecule to
form stable substances.
 Initiation
The initiation of lipid oxidation starts with the
removal of an hydrogen atom from unsaturated
TGs or FFAs (RH) to form a free radical (R)
(Eq.1).
H H
O C
-O- C

H + H
O
C
-O- C

Represent as RH R + H (Eq.1)
 Initiation
The removal of hydrogen takes place at the
carbon atom next to the double bond.

H H
O C
-O- C

H + H
O
C
-O- C

Represent as RH R + H (Eq.1)
 Formation of Lipid Radical
Hydrogens on carbons next to double bonds most
easily removed (-carbon)
Energy for H removal
(kcal/mole)

H - CH2 - CH2 - CH3 100

H - CH = CH2 103

H - CH2 - CH = CH2 85

CH2 = CH - CH - CH = CH2 65
H
H on carbon next to double bond easier to remove
 Initiation mechanisms

Photosynthesized Oxidation (Photooxdation)

Metal Catalysis

Thermal Oxidation

Enzymatic Oxidation
 Initiation mechanisms-PO
Light, in the presence of oxygen, promotes oxidation of
unsaturated fatty acids.

Photooxidation energy from light is captured aided by

sensitizer molecules (pigments: chlorophile)

Light excites these sensitizers to the triplet state that

promotes oxidation by type I and type II mechanisms.
 Initiation mechanisms-PO
In type I photosensitized oxidation, the triplet state
sensitizer abstracts a hydrogen or electron from the
unsaturated oil, producing radicals that initiate chain
propagation
sens light sens*
sens* + RH R + H

In type II photooxidation, the energy of the triplet sensitizer

is transferred to molecular oxygen, converting it to its
excited singlet state.

3O
light
sens* + 2 sens + 1O2
 Initiation mechanisms-PO
Singlet oxygen more reactive than triplet oxygen

RH + 1O2 ROOH RO + OH
RO provides free radical to start propagation

Initiated by singlet oxygen (1O2)

metastable, excited energy state of O2
two unpaired electrons in same orbital

triplet oxygen singlet oxygen

ground state excited state
2 electrons w/ same 2 electrons w/ different
spin in 2 orbitals spin in 1 orbital
 Initiation mechanisms-Metal Catalysis

Metal ions (e.g. Fe, Co, Cu) can also initiate reaction
found naturally in foods, from metal equipment

RH + M+2 R + H+ + M+
Initiation mechanisms-Thermal Oxidation
The energy requirements for the abstraction of H to
form a lipid radikal can be supplied in the form of
thermal energy.
High temperatures (like frying) facilitate the all stages
of the chain reaction

Initiation mechanisms-Enzymatic Oxidation

Enzyme-catalysed oxidation is initiated even in the
absence of hydroperoxides. This means the enzyme alone
is able to overcome the energy barrier of this reaction
 Propagation
This highly reactive lipid (alkyl) radical (R) can
then react with oxygen to form a peroxy radical
(ROO) in a propagation reaction (Eq.2)

R + O2 ROO (Eq.2)

During propagation, peroxy radicals can react

with lipids (others R1H or same RH) to form
Hydoperoxide (ROOH) and a new unstable lipid
radical (Eq.3)

ROO + R1H ROOH+ R1 (Eq.3)

 Propagation
This lipid radical (R1) will then react with oxygen
to produce another peroxy radical (R1OO)
resulting in a cyclical, self-catalyzing oxidative
mechanism (Eq.4)

R1 + O2 R1OO (Eq.4)
Hydroperoxides (Eq.3) are unstable and can
degrade to produce radicals that further accelerate
propagation reactions (Eq.5) and (Eq.6)
ROOH RO + OH (Eq.5)
2ROOH ROO + RO + H2O (Eq.6)
 Propagation
Hydroperoxides are readily decomposed by
high-energy radiation,
thermal energy,
metal catalysis, or enzyme activity.

Transion metals such as Fe and Cu

ROOH + M+ RO + OH + M+ (Eq.7)
ROOH + M2+ ROO + H+ + M+ (Eq.8)

2ROOH ROO + RO + H2O (Eq.6)

 Termination
The propagation can be followed by
termination if the free radicals react with
themselves to yield non-reactive (stable)
products, as shown here:

R + R RR
RO + R ROR
ROO + R ROOR
ROO + ROO ROOR + O2
Carbonyl compounds (aldehydes and
ketones)and hydrocarbons
Pentane Formation from Linolenic Acid
14 13 12 11 10 9
CH3 (CH2 )3 CH2 CH CH CH2 CH CH CH2 COOH
n
Initiation (metal)
- H.

12 11 10 9
CH3 (CH2 )3 CH2 .
CH CH CH CH CH CH2 n COOH
Propagation + O2
12 11 10 9
CH3 (CH2 )3 CH2 CH CH CH CH CH CH2 nCOOH
O
Propagation
+ H.
.
O

12 11 10 9
CH3 (CH2 )3 CH2 CH CH CH CH CH- CH2 n COOH
O
Hydroperoxide
Decomposition O
H
_ .OH
12 11 10 9
CH3 (CH2 )3 CH2 CH CH CH CH CH CH2 n COOH
.
O

O
12 11 10 9
CH3 (CH2 )3 CH.
2 + H C CH CH CH CH CH
2 n COOH

Termination + H .
CH3 (CH2 )3 CH3
Pentane
 Oxidation Product
Primary Oxidation Products
Hydroperoxides

Secondary Oxidation Products

Aldehydes and ketones
 Factors Affecting Autoxidation
1. Energy in the form of heat and light
2. Catalysts (Metal)
3. Double bonds
4. Enzymes
5. Chemical oxidants
6. Oxygen content and types of oxygen
7. Natural antioxidants
8. Phospholipids
9. Free Fatty acids
 Oxidation Rates: Types of Fatty Acids
As # of double bonds increases
# and stability of radicals increases
Rate increases
Rate of Reaction
Type of Fatty Acid Relative to Stearic Acid
18:0 1
18:1D9 100
18:2D9,12 1200
18:3D9,12,15 2500
Kinetics of Autoxidation
 ANALYSIS OF OIL OXIDATION

1. Peroxide Value

O O
A. KI + CH 3 C OH HI + CH 3 C OK

B. ROOH + 2 HI I2 + H2O + ROH

C. I2 + 2 Na2 S 2 O3 2 NaI + Na2 S4 O6

Peroxide Value = ml of Na2S2O3 N 1000

(milliequivalent peroxide/kg of sample) Grams of Oil
2. p-Anisidine Value.
p-AnV is defined as 100 times the optical density
measured at 350 nm in a 1.0 cm cell of a solution
containing 1.0 g oil in 100 ml of a mixture of solvent and
reagent.
This method determines the amount of aldehyde
(principally 2-alkenals and 2,4-alkadienals ) in animal
fats and vegetable oils.
Aldehyde + p-AnV Yellowish Products
(Under acidic conditions)

3. Totox Value = 2* PV + p-AnV

 K232 and K270
Oxidation of PUF is accompanied by an increase
in the UV absorption of the products.
Lipids containing methylene-interrupted dienes
and trienes show a shift in their double-bond
position during oxidation due to isomerization
and conjugate formation.
The resulting conjugated dienes exhibite an
intense absorption at 232 nm; similarly
conjugated trienes absorb 268 nm.
K232 and P.V correlate well in the early stages
of oxidation.
 Oxidative Stability of Oils and Fats
Active Oxygen Method (AOM)

Determined the time required to obtain certain peroxide

value under specific experimental conditions.
The larger the AOM value, the better the flavor stability
of the oil.

Oil Stability Index / Rancimat Methods

OSI and Rancimat measure the change in conductivity

caused by ionic volatile organic acids, mainly formic acid,
automatically and continuously.
 Antioxidants
Primary Antioxidants
Chain-breaking antioxidants are free radical
acceptors that delay or inhibite the initiation
step or interrupt the propagation step of
autoxidation.

Secondary Antioxidants
Act through numerous possible mechanisms,
but they do not convert free radicals to more
stable products.
 Primary Antioxidants

R + AH RH + A
RO + A ROA
ROO + AH ROOH + RH
Natural and Synthetic Antioxidants
 Secondary Antioxidants
Chelators: citric acid, EDTA
Oxygen Scavengers and Reducing
Agents: Ascorbic acid, ascorbyl palmitate,
Singlet Oxygen Quenchers: Caretenoids
(beta-carotene, lycopene, lutein)
Deplete singlet oxygens excess energy and
dissipate the the energy in the form of heat.