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Hydrogenation
Esterification
Hydrolysis
Chemical (Autocatalytic) Enzymatical (Lipase)
H2C
OH
3 fatty acids
O O
Acid Value
Number of mgs of KOH required to neutralize the Free Fatty Acids in 1 g of fat.
AV =
= mg of KOH
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
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).
O -O- C
O -O- C H
+ H
Represent as
RH
R + H (Eq.1)
Initiation
The removal of hydrogen takes place at the carbon atom next to the double bond.
H
C
O -O- C
O -O- C
+ H
Represent as
RH
R + H
(Eq.1)
Initiation mechanisms
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. sens* +
3O
light
2
sens + 1O2
Initiation mechanisms-PO
Singlet oxygen more reactive than triplet oxygen RH + 1O2 ROOH RO + OH
RH + M+2
R + H+ + M+
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)
R 1 + O 2
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 2ROOH
RO + OH ROO + RO + H2O
(Eq.5) (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+ ROOH + M2+ RO + OH + M+ ROO + H+ + M+ (Eq.7) (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
RO + R ROO + R
RR
ROR ROOR
CH3
(CH2 )3
CH2
CH CH
CH 2 - H.
CH CH
CH 2
COOH
Initiation (metal)
12
11
10
CH3
(CH2 )3
CH2
CH CH + O2
12 11
CH
10
CH
9
CH
CH 2 n COOH
CH + H.
11
CH
CH
CH 2 nCOOH
Propagation
10
CH3
(CH2 )3
CH2
CH CH
CH _
CH
CH -
CH 2 n COOH
Hydroperoxide Decomposition
O O H
12
.OH
11 10 9
CH3
(CH2 )3
CH2
CH CH
CH
CH
CH
CH 2 n COOH
.
CH3 (CH2 )3 CH2
O + H C
12
11
10
CH CH
+ H
CH
CH
CH 2 n COOH
Termination CH3
(CH2 )3 Pentane
CH3
Oxidation Product
Primary Oxidation Products
Hydroperoxides
2500
Kinetics of Autoxidation
1.
Peroxide Value
O A. KI + CH 3 C OH HI + CH 3 O C OK
B.
ROOH + 2 HI
I2 +
H2 O +
ROH
C.
I2 + 2 Na2 S 2 O3
2 NaI +
Na2 S4 O6
Peroxide Value =
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)
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.
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 RO + A ROO + AH RH + A ROA ROOH + RH
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.