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2 Basic Oil Chemistry
2 Basic Oil Chemistry
Man has used vegetable oils for centuries. Oil bearing nuts and animal fats were
consumed as sources of energy long before nutrition concepts were envisioned.
Oils also were used early for lighting, as medicines, as cosmetics in religious
ceremonies, and applied to weapons and utensils. The ancient oils of the Middle
East, sesame and olive, were valued because of their long stability. Sunflower
was cultivated in the Arizona–New Mexico area before the time of Christ, and
seeds from the Missouri–Mississippi river basins were among the early plants
transposed to Europe by explorers. Invention of the cotton gin in the late 1700s
led to a major cotton export trade in the United States in the early 1800s, and
to development of cottonseed oil as the first new oil of the Industrial Age in the
mid-1800s. The continuous screw press, and early methods of caustic refining,
bleaching, deodorization, winterization, and hydrogenation, including develop-
ment of the first all vegetable shortening “Crisco” (shortened name for crystal-
lized cottonseed oil) are among innovations developed. Processing of soybean,
a crop first developed in China, led to further oil industry innovations including
development of continuous solvent extractors and steam distillation technolo-
gies to reduce or remove the original raw flavor in the crude oil were developed
in the mid-1900s. As flavor and stability improved, man expanded use of oils
to: (1) cooking, (2) frying, (3) baking shortenings, (4) salad dressings, (5) food
lubricants (like release agents in baking and candy making processes), (6) flavor
carriers, and (7) dust-control agents. Each of the application requires oils with
specific physical and chemical properties.
Other oils, such as palm oil, regular canola oil, high oleic and low linolenic
canola oil, high oleic sunflower oil, high oleic safflower oil, and so on were all
commercialized much later than the animal fat and cottonseed oil.
Saturated Unsaturated
Lauric (C12) Oleic (C18:1)
Palmitic (C16) Linoleic (C18:2)
Stearic (C18) Linolenic (C18:3)
Arachidic (C20)
Behinic (C22)
10 Practical Guide to Vegetable Oil Processing
Oleic acid, which has one double bond, is called a “monounsaturated fatty
acid” while linoleic and linolenic acids are called “polyunsaturated fatty acids”
because they contain more than one double bond (2 and 3, respectively).
In this example, only single carbon-to-carbon bonds exist, and the fatty acid
is called “saturated.”
Unsaturated fatty acids contain fewer hydrogen atoms than required to fully
satisfy the valence of each carbon atom in the molecule. Thus, some carbon atoms
are connected to each other with a “double bond” as shown in the following.
The double bonds in most vegetable oils (except for drying oils used in
paints) contain two single bonds between the two double bonds in the chain.
Most of the hydrogen in double bonds of natural fatty acids is found
on the same side of the double bond, indicating a “cis position” (or “cis-
isomer”). But, some of the hydrogen atoms may move to the other side
of the bond during hydrogenation process (chemical saturation of double
bonds), to produce “trans-isomers.” These structures are further clarified in
the following.
Basic Oil Chemistry Chapter | 2 11
Both cis and trans isomers are “unsaturated,” fatty acids. However, transfor-
mation of the cis to trans configuration raises the melt-point for the oil.
A small conversion of cis to trans forms also occurs when oils are heated to
very high temperature as during hydrogenation and deodorization.
2.6.1.1 Phospholipids
These compounds are also known as phosphatides or gums. Their levels are
generally expressed in parts per million of phosphorus. The five major groups
of phospholipids found in most vegetable oils are:
1. phosphatidylcholine
2. phosphatidylethanolamine
3. phosphatidylinositol
4. phosphatidylserine
5. phosphatidic acid
Typical phospholipids contents of common vegetable oils are shown in
Table 2.1.
TABLE 2.2 Typical Free Fatty Acid (FFA) Content of Common Crude
Vegetable Oils
Oil type FFA content (%)
Most seed oils 0.5–1.5
Crude palm oil 1–4
Crude cottonseed oil 0.5–3
Extra virgin olive oil <0.8
Virgin olive oil <2
14 Practical Guide to Vegetable Oil Processing
properties and can negatively impact on oil losses in refining and process-
ing, and also on performance of the final oil. This will be discussed later in
Chapter 11. Typical levels of monoglycerides and diglycerides in various fully
processed oils are shown in Table 11.3.
2.6.6 Tocopherols
Tocopherols are naturally occurring antioxidants in vegetable oils, and one of
nature’s protections against oil oxidation. Four types of tocopherols are present:
alpha, beta, gamma, and delta. Sometimes, these forms are identified by Greek
letters α, β, γ, and δ, respectively. Alpha (α) tocopherol provides protection to
the oil against photooxidation (oxidation under visible light). Functions of beta
(β) tocopherol, found at very low concentrations in oils, are not fully known.
Gamma (γ) and delta (δ) tocopherols protect oil against autoxidation. Autoxi-
dation is the primary pathway for oil oxidation, with oil degradation occurring
even in absence of light. This type of oxidation process occurs during process-
ing, storage, distribution of oil as well as food ingredients containing oils and
during food products manufacture and their storage. The reaction is initiated
by formation of a free radical from the unsaturated oil by a metal initiator. The
reaction propagates and continues until either oxygen or unsaturated fatty acids
are exhausted in the oil.
Photooxidation can occur in unsaturated fatty acids when oil is exposed to
ultraviolet rays and a metal initiator is present in the oil. This reaction is called
photochemical reaction. This is a relatively slow reaction process like autoxida-
tion. Photooxidation occurs to the oil in presence of a sensitizer like chlorophyll
(or its oxidation products) when exposed to visible light. This reaction is very
rapid and is 1500 times faster than autoxidation.
Tocotrienols, another group of natural antioxidants, have attracted strong
attention to palm and rice bran oils, which contain 300–500 and 400 ppm of
these compounds, respectively. Tocotrienols are especially effective against
autoxidation. Autoxidation reaction mechanism is shown in Table 2.3. Rice
bran oil and corn oil also contain ferulic acid, an excellent antioxidant at high
Basic Oil Chemistry Chapter | 2 15
ND, Nondetectable.
a
Palm oil contains +CO enzyme Q-10 = 15–30 ppm.
ND, Nondetectable.
volatilize. These compounds have distinct effects on oil and product flavors and
their stability, which will be discussed in Chapter 12.
with them. The most common metals found in the crude oil are: iron, calcium,
magnesium, and sometimes very low levels of copper. Toxic “heavy metals”
may also be present in very low concentrations in crude oils. Trace metals are
removed from the crude oil by the bleaching clay, and bound by citric acid after
the deodorization process. This will be discussed later in Chapters 6 and 12.
Bleaching test
• For refined cottonseed oil Cc 8a-52 (12)
• For refined soybean oil Cc 8b-52 (11)
• For refined sunflower oil Cc 8b-52 (11)
Lovibond color
Wesson (Lovibond) method Cc 13b-45 (09)
Color (per ISO Standard) Cc 13e-92 (09)
Color (automated method) Cc 13j-97 (09)
Chlorophyll pigment
Refined and bleached oils Cc 13d-55 (09)
Crude vegetable oils Cc 13i-96 (13)
Crude vegetable oils Cc 13k-13 (13)
Trace metals
By AAS (Cr, Cu, Fe, Ni) Ca 15-75 (09)
By graphite furnace AAS (Cr, Cu, Fe, Ni, Mn) Ca 18-79 (09)
By graphite furnace direct (Cu, Fe, Ni) Ca 18b-91 (09)
By graphite furnace AAS (Pb only) Ca 18c-91 (09)
By ICP-OES (all metals) Ca 17-01 (09)
Phosphorus in oils
By AAS Ca 12b-92 (09)
By ICP-OES Ca 20-99 (09)
By IO method Ca 12a-02 (09)
Smoke point, flash point, and fire point
Cleveland open cup method Cc 9a-48 (09)
Melt point
Capillary tube method Cc 1-25 (09)
Mettler dropping point Cc 18-80 (09)
Slip melting point Cc 3-25 (09)
Slip melting point, ISO Standard Cc 3b-92 (09)
Wiley methoda Cc 2-38 (91)
a
Surplus method—could be considered obsolete.
2.8.22 Smoke Point, Flash Point, and Fire Point (Cleveland Open
Cup method)
Smoke point is directly related to the amount of FFA in the oil, and also to the
amounts of monoglycerides and diglycerides present in the oil. The flash point of
solvent-extracted crude oil must be checked at receipt to make sure it is higher
than 300°F (149°C). The smoke point for the degummed soybean oil or crude sun-
flower oil is 250°F (121°C) maximum, according to the Trading rules of NIOP.
BIBLIOGRAPHY
Food Codex Alimentarius Commission Standard 210.(1999).
Bockisch, M., 1993. Fats and Oils Handbook. AOCS Publication, USA.
Gupta, M.K., 2017. Practical Guide to Vegetable Oil Processing. AOCS Publication, Peoria, IL,
USA, 2007.
Muller-Mulot, W., 1976. J. Am. Oil Chem. Soc. 53, 732.
Ooi, C.K., Choo, Y.M., Yap, S.C., Basiron, Y., Ong, A.S.H., 1994. Recovery of carotenoids from
palm oil. J. Am. Oil Chem. Soc. 71, 423–426.
Slover, H.T., Lehmann, J., Valis, R.J., 1969. Vitamin in foods: determination of tocols and tocotri-
enols. J. Am. Oil Chem. Soc. 46, 417–420.