Chemical Changes of Olive Oil

FST 5101 Macro-components of Foods

Law Boon Pin Suraya Hashim Devathaa Nadarajan Nur Zahidah Syahirah Marzuki Rumaizah Muhammad
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Chemistry of Olive Oil

Factors that affect the composition of olive oil: Olive variety Edaphoclimatic condition (different soil & climatic conditions) Harvesting period and technique Fruit ripening degree Leaf removal, extraction system Best olive producing area: cool region - Tuscany
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Chemistry of Olive Oil

Composition of olive oil

Source: http://www.fao.org/docrep/003/x6545e/X6545E01.htm MoFT 2013/14 3

Composition of Olive Oil

Major
Triacylglycerols : Myristic acid (C14:0) Oleic Acid (C18:1) Linoleic Acid (C18:2) Palmitic Acid (C16:0) Stearic Acid (C18:0) Linolenic Acid (C18:3) Arachidic acid (C20:0)

Minor
Glycerol, FFA Phenolic Compound Tocopherol (Vitamin E), Vitamin K Pigments: e.g. chlorophyll , carotenoid Phospholipids Sterols

Mono- & Diglycerides

Fatty alcohols, waxes, and diverse aroma compounds
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Fatty Acids in Olive Oil

Fatty acid Oleic acid (C18:1) Linoleic acid (C18:2) Type Monounsaturated (Omega-9) Polyunsaturated (Omega-6) Percentage (%) 55.0 83.0 3.5 21.0

Palmitic acid (C16:0)

Stearic acid (C18:0) Myristic acid (C14:0) Arachidic acid (C20:0) Linolenic Acid (C18:3) (-Linolenic acid)

Saturated
Saturated Saturated Saturated Polyunsaturated (Omega-3)

7.5 20.0
0.5 5 0.1 1.2 0.1 0.3 0.0 1.5

Source: http://www.oliveoilsource.com/page/chemical-characteristics MoFT 2013/14 5

Chemistry of Olive Oil - cont

Tryglycerides in olive oil: OOO > POO > OOL > POL > SOO
Chemical reactions involving olive oil
Interesterification Hydrogenation Hydrolysis Oxidation

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Interesterification in Olive Oil

Is a process where the fatty acids migrate and recombine with glycerol in a more random fashion under certain conditions
The distribution of fatty acids is changed on glycerol backbone, while the nature of the fatty acids remain the same. Interesterification is often used to increase the solidity of fat without partial hydrogenation. This leads to significant changes in physical properties of fat such as the melting point.
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Interesterification in Olive Oil

rearranges the fatty acids on the glycerol backbone of a triglyceride

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Interesterification in Olive Oil

The interesterification reaction may be chemical or enzymatic:
CHEMICALLY: spontaneously by heating above the melting temperature of triglyceride. It is easier and faster in the presence of metal catalysts.eg: zinc oxide, iron oxide, etc. Or alkali like NaOH. *relatively cheap and is used on an industrial scale to produce plastic saturated fat content in low or no trans fat.

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Interesterification in Olive Oil

Enzymatically: (Enzymes such as esterase or acylase act as catalyst) offers better control of products generated during the reaction.
Very specific and can be selected to cleave specific bonds esters, ie occupying a particular position on the molecule. Conducted at lower temperatures than chemical interesterification, there is less degradation. Finally, the interesterification process can produce any type of fat or oil includes heavy fats suitable for deep-frying, semisolid fats to make margarine, or liquid oils for bottling.
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Hydrogenation in Olive Oil

Hydrogenation is a process of forcing H2 into oil at high temp/pressure As a result, double bonds in oil open and becomes single bonds Catalyst used: usually nickel, but sometimes palladium, rhodium or platinum
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Hydrogenation in Olive Oil

Double bonds not only decrease in number but also migrate during hydrogenation
Oils contain cis- C=Cs and they are not uniform in structure The purpose of hydrogenation is to increase shelf life and to make oil more stable

Partial hydrogenation is usually preferred

Isomers of unsaturated fatty acids are formed Cis- bonds are converted into trans- bonds
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Factors affecting hydrogenation

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Trans Fatty Acids

Usually found in hydrogenated shortenings and margarines
Trans-fat are labeled as saturated fats
Increases LDL and lowers HDL Trans fat is bad for health as its characteristics resemble to saturated fat

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Hydrolysis in Olive Oil

Two types of reaction: chemical hydrolysis and enzymatic hydrolysis
Enzymatic occurs in olive crop whereas chemical occurs after oil is extracted from crop Enzymatic reaction depends on humidity, temperature, ferment, and various microorganisms Hydrolysis is basically a reaction which splits the esters using water
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Hydrolysis in Olive Oil

Reactions could be conducted using diluted acid or diluted alkali
Both reactions are heated under reflux
Diluted Acid
Reversible reaction Produce carboxylic acid and glycerol

Diluted alkali
Non-reversible reaction Produce salt of a carboxylate and glycerol
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Hydrolysis in Olive Oil

Hydrolysis using diluted alkali is also known as saponification because of its relationship with the soap processing. Ester linkage is broken to form glycerol and soap

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Oxidation in Olive Oil

Oxidation is one of the major causes in olive oil quality deterioration.

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Initiators of Oxidation
Heat Light (Photo-oxidation) Exposure to oxygen (triggered when the oil enters in contact with oxygen in the air, first during the milling process, and later on during storage in tanks and bottles).
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The more the heat, light and O2 exposure, the faster is the oxidation rate

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Oxidation in Olive Oil

Figure 1 shows how the oxidation of fatty acids in olive oil changes with time.
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Effects of Oxidation towards Olive Oil

Unpleasant odor and flavor:
The more the peroxides present, the more rancid the oil

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Antioxidants in Olive Oils

Vitamin E (alpha-tocopherol)
Carotenoids Phenolic compounds (simple phenols: hydroxytosol and tyrosol)
The more antioxidants and phenolics present, the lower the oxidation rate

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Antioxidants in Olive Oils

Antioxidant can supply the free radical with a replacement for its missing electron.
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Conclusion
Some products resulting from the chemical changes of olive oil:

Cosmetics
Spreads Cooking/Dressing Oils

Toiletries
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Comparison of Dietary Fats

Coconut Oil Butter Fat Palm Oil Beef Tallow Lard Cottonseed Oil Peanut Oil Soybean Oil 19% 15% 15% 13% 12% 10% 7% 0% 10% 21% 20% Saturated 30% 11% 40% 50% 60% 9% 1% 57% 71% 76% 61% 70% Monounsaturated 80% 90% 100% 27% 33% 54% 75% 1% 29% 1% 0.05% 16% 14% 51% 48% 43% 2% 1% 9% 1% 54% 0.05% 8% 48% 23% 68% 10% 0.05% 49% 47% 0.05% 19% 91% 3%1% 39% 28% 2% 0% 7%

Olive Oil
Corn Oil Sunflower Oil Safflower Oil Canola Oil

Polyunsaturated

Alpha-Linolenic Acid

Source: Vaclavik, V.A. (1998), Essentials of Food Science, An Aspen Publication, page226 MoFT 2013/14 26

References:
1. 2. 3. 4.
5. 6.

http://www.fao.org/docrep/003/x6545e/X6545E01.htm http://www.oliveoilsource.com/page/chemical-characteristics Vaclavik, V.A. (1998). Essentials of Food Science. An Aspen Publication. Page 226 Charley, H. & Weaver, C. (1998). Foods A Scientific Approach. A Merrill Prentice Hall Publication. Page 241-266 http://www.soap-making-resource.com/saponification-table.html http://www.cargillfoods.com/na/en/products/oilsshortenings/solutions/interesterification/index.jsp

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Random Interesterification

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The Characteristics of Oils in Soap

Oil or fat (acid) avocado oil coconut oil castor oil olive oil palm oil peanut oil soybean oil sweet almond oil jojoba oil kukui nut oil lard tallow SAP 133.7 191.1 128.6 135.3 142 137 135.9 137.3 69.5 135.5 138.7 140.5 Hard/Soft soft hard soft soft hard soft soft soft soft soft hard hard Cleansing fair great fair good great fair good good fair good good good
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Fluffy lather yes yes yes no no no no no no no no no

Stable lather no no yes no yes yes yes yes yes yes yes yes

Skin care amazing! fair great great fair great fair amazing! great great fair fair
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Source: http://www.soap-making-resource.com/saponification-table.html