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Chapter 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.

2.1  COMPOSITION OF OIL


All of the world’s matter is composed from approximately 108 elements. The
smallest divisible stable particle of an element is called an “atom.” Compounds
consist of atoms of two or more elements, with the smallest divisible stable
particle called a “molecule.” Carbon (C), hydrogen (H), and oxygen (O) atoms
are the principal building blocks of fats and oils.

Practical Guide to Vegetable Oil Processing. http://dx.doi.org/10.1016/B978-1-63067-050-4.00002-7


Copyright © 2017 AOCS Press. Published by Elsevier Inc. All rights reserved. 7
8 Practical Guide to Vegetable Oil Processing

FIGURE 2.1  Formation of triglycerides.

Often, it is desirable to pictorially indicate relative positions of the ele-


ments in molecular structures. But, these must be carefully drawn by estab-
lished convention, since the world exists in three dimensions, but only two
dimensions are available for presentation on paper. In making such draw-
ings, the knowledgeable chemist recognizes that some atoms only associate
with others by extending links, while others only accept links. For example,
each oxygen atom extends two links, while, each hydrogen atom accepts only
one link. The chemistry of fats and oils is carbon chemistry, also known as
“organic chemistry.” The carbon atom is unique in that it can either extend or
accept a total of four links, with link givers, link receivers, or even with other
carbon atoms.
Oil is a mixture of 96–98% fatty acid triacylglycerols (commonly referred
to as “triglycerides”), with the balance consisting of other fat-dispersible or fat-
soluble compounds. Triglycerides consist of three fatty acids, which are sub-
stituted in the hydroxyl (alcoholic) sites of a glycerin (glycerol) backbone. The
construction of a simple triglyceride is shown in Fig. 2.1, where each fatty acid
is represented as a different “R.”
Depending on the extent to which the three former hydroxyl groups of glyc-
erol are replaced with fatty acids, the resulting compounds are known as follows.
Monoglycerides  are formed when one of the three hydroxyl groups of glycerol is replaced
by a fatty acid.
Diglycerides  are formed when two of the three hydroxyl groups of glycerol are replaced by
the same or different fatty acids.
Triglycerides  are formed when all three of the hydroxyl groups of glycerol are replaced by
fatty acids (also referred as neutral oil).
A molecule of water is formed each time a fatty acid molecule replaces a
hydroxyl group. Fig. 2.2 further shows the structures of monoglyceride, diglyc-
eride, and triglyceride molecules.
The major objective in refining and processing is to convert a shipment of
purchased crude oil into the maximum possible amount of saleable “neutral oil”
(triglycerides). Monoglycerides and diglycerides are formed when the neutral
oil reacts with water molecules under undesirable storage and handling condi-
tions. This reduces the yield of neutral oil in the refining process. It also creates
poor quality refined oil. This will be discussed further in Chapter 11.
Basic Oil Chemistry Chapter | 2 9

FIGURE 2.2  Structures of mono-, di-, and triglycerides.

2.2  DISTINCTIONS BETWEEN OILS AND FATS


A triglyceride molecule is called “oil” if it is liquid at ambient (room) tempera-
ture, and a “fat” if it is semisolid. Definitions of “room temperature” will vary
greatly with the climate of the region. For example, “room temperature” in a
tropical region can be >95°F (35°C), whereas that in a temperate region can be
68°F (20°C). A good example is coconut oil, which is liquid at room tempera-
ture in semitropical areas during the year except for the winter months when
it becomes solid and might be called a “fat,” although coconut oil is always
referred to as oil. Similarly, partially hydrogenated oil, which might be semi-
solid or solid at room temperature, is commonly referred to as oil.
Products of reactions between hydroxyl groups and organic acids are called
“esters” or sometimes “acyl- compounds.” The broad variety of products
includes waxes made by esterification of long chain alcohols and long chain
fatty acids, various food and industrial emulsifiers, noncaloric sucrose-based
frying oils, fatty acid methyl ester solvents, and biodiesel fuels.

2.3  FATTY ACIDS IN COMMON VEGETABLE OILS


Fatty acids are the building blocks of triglycerides. They generally contain 4–22
carbon atoms and are linear in structure. Sometimes, fatty acids are designated
as “short chain” (4–8 carbon atoms), “medium chain” (10–12 carbon atoms),
and “long chain” (14 or more carbon atoms). The following fatty acids are most
common in vegetable oils:

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).

2.3.1  Saturated and Unsaturated Fatty Acids


A carbon atom with all four reaction sites of the carbon atom reacted with other
elements is termed “saturated.” The structure of a fatty acid with an end car-
boxyl group (─COOH) is shown below.

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.

2.4  TYPICAL BEHAVIOR OF FATTY ACIDS


2.4.1  Unsaturated Fatty Acids
Unsaturated fatty acids are unstable and are very susceptible to oxidation even
at ambient temperatures. They tend to:
1. readily oxidize when exposed to air or oxygen,
2. form aldehydes, ketones, etc.,
3. form primarily oxidative polymers, and
4. form cyclic compounds.

2.4.2  Saturated Fatty Acids


In contrast, saturated fatty acids are relatively stable. They do not oxidize in
the presence of air or oxygen, but will decompose under high heat. They can
produce:
l thermal polymers
l toxins, such as acroleins

2.5  OBJECTIVES OF PROPER OIL PROCESSING


The objective of proper oil processing is to obtain finished oil with the follow-
ing traits:
1. long oxidative stability,
2. long thermal stability,
3. long flavor stability,
4. long storage stability, and
5. long shelf life of food products formulated with the oil.
It is critical that processors understand the basic constituents of oil, its prop-
erties, and how to maintain process conditions that deliver oil with the quality
standards listed previously.

2.6  NONTRIGLYCERIDE COMPONENTS OF OILS


As mentioned earlier, crude vegetable oils generally contain 96–98% triglycer-
ides. Although these components are present in small amounts, they can be very
influential in determining overall stability and performance of the oil. They may
be grouped as:
12 Practical Guide to Vegetable Oil Processing

1. major nontriglyceride components


2. minor nontriglyceride components

2.6.1  Major Nontriglycerides


The following components generally are present at high levels in the crude oil
and can be measured as percentages:
1. phospholipids
2. free fatty acids (FFA)
3. diglycerides
4. monoglycerides

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 2.1 Phospholipids Contents of Selected Vegetable Oils


Phospholipids Phosphorusa
Oil type content (%) content (ppm)
Crude soybean oil 1–3 317–950
Degummed soybean 0.32–0.64 100–200
Crude corn oil 0.7–0.9 222–285
Crude peanut (groundnut) oil 0.3–0.6 95–190
Crude canola oil 1.8–3.5 570–1104
Superdegummed canola oil 0.13–0.16 41–51
Crude sunflower oil 0.5–0.9 159–285
Crude safflower oil 0.4–0.6 127–190
Crude palm oil 0.06–0.95 19–30
a
The relationship between phospholipids and phosphorus contents is: phosphorous
(ppm) = [phosphatides (%) × 104]/31.7.
Basic Oil Chemistry Chapter | 2 13

2.6.2  Hydratable and Nonhydratable Phospholipids


Two types of phospholipids are present in crude oils from the standpoint of their
affinity for water:
1. Hydratable phospholipids
2. Nonhydratable phospholipids
Treatment with water at 140–158°F (60–70°C) hydrates some of the phos-
pholipids in crude oils, which settle out or can be separated by centrifugation.
For example, 600–800 ppm phosphorus in crude soybean oil can be reduced
to 200 ppm or less by simple water degumming. Phospholipids, which are
not removed by water alone are considered “nonhydratable.” The objective of
acid-pretreatment of crude oil is to convert nonhydratable phospholipids into
hydratable forms by sequestering (drawing away) absorbed bivalent cations
(like calcium and magnesium metals) which interfere with their hydratability.
Various methods for degumming crude oil are described in Chapter 3.

2.6.3  Free Fatty Acids


Fatty acids, separated from triglyceride molecules, are called “free fatty acids,
“FFA” and dissociate into two moieties—a link-accepting hydrogen ion and the
link-giving residual. Formation of FFA in the oil of stored oilseeds is a natural
occurrence, initiated by “lipase” enzymes. A small amount of FFA also formed
during seed crushing and subsequent handling and storage of the crude oil. Fatty
acids bound in triglycerides are still reactive in oxidation and hydrogenation
processes. Amounts of FFA in crude oil vary with the oil species and history of
the sample. Typical FFA values in selected crude oils are shown in Table 2.2.

2.6.4  Monoglycerides and Diglycerides


Degradation of crude oils into FFA always is accompanied by formation
of diglycerides and monoglycerides. These compounds have emulsifying

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.

2.6.5  Minor Nontriglycerides


Minor nontriglyceride components of crude oil, present in parts per million
levels, include:
1. tocopherols and tocotrienols
2. sterols and sterol esters
3. volatile and nonvolatile compounds formed from decomposition of the
triglycerides
4. color compounds
5. trace metals

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

TABLE 2.3 Monoglycerides and Diglycerides Present in Fully Processed Oils


Oil type Monoglyceride (%) Diglyceride (%)
Most seed oils 0.2–0.4 <0.5
Palm oil 0.5–3 3–7

FIGURE 2.3  Structures of tocopherols and tocotrienols.

temperatures. Rice bran oil contains another group of antioxidants known as


oryzanols, which are extremely effective as antioxidants at high temperature
applications like frying and baking. Sesame seed oil contains sesamolin, sesa-
mol, sesaminol, and episesaminol antioxidants, which are not present in other
seed oils. Further, palm oil contains CO Enzyme Q-10 a unique antioxidant
not present in the seed oils. The structures of tocopherols and tocotrienols in
Fig. 2.3 and the typical tocol contents of various oils are shown in Table 2.4.
16 Practical Guide to Vegetable Oil Processing

TABLE 2.4 Tocols Contents in Crude Oils (ppm)


Sunflower Cottonseed Soybean Corn oil Palm oila Canola
Tocopherols
Alpha 403–935 402 90–120 191 129–215 290
Beta ND–45 1.5 ND — 22–37 —
Gamma ND–34 572 740–1020 942 19–32 382
Delta ND–7 75 240–300 42 10–20 13.4
Tocotrienols
Alpha NDa ND ND 23 44–73 ND
Beta ND ND ND — 44–73 ND
Gamma ND ND ND — 260–437 ND
Delta ND ND ND — 70–117 ND
Total 440–1520 1050 1130– 1198 600–1000 685
tocols 1450

ND, Nondetectable.
a
Palm oil contains +CO enzyme Q-10 = 15–30 ppm.

Tocotrienols have three additional double bonds compared to tocopherols,


which might be the reason for their improved antioxidant effects over tocopherols.

2.6.7  Sterols and Sterol Esters


Phytosterols and phytosterol esters are often present in low concentrations sim-
ilar to tocopherols and other antioxidants mentioned previously. These com-
pounds also have antioxidant properties, although this property has not been
studied as extensively as with the tocopherols. However, sterols and their deriv-
atives have been studied more extensively in human nutrition. Like tocopherols,
different types of sterols and derivatives exist, with type and concentration vary-
ing with the oil species. Sterols and sterol ester contents of common vegetable
oils are shown in Table 2.5.

2.6.8  Volatile and Nonvolatile Compounds


Autoxidation generates a large number of oil decomposition products, including:
1. primary oxidation products, for example, peroxide value (PV).
2. Secondary oxidation products, for example, aldehydes, ketenes, etc.
3. Tertiary oxidation products, for example, alcohols, acids, oxidation poly-
mers, epoxides, cyclic fatty acids, and so on.
The majority of these compounds has low molecular weight and volatilizes
as the oil is heated. But, some fatty acid derivatives are too large and do not
Basic Oil Chemistry Chapter | 2 17

TABLE 2.5 Sterol Compounds and Their Levels in Common Crude


Vegetable Oils (ppm)
Type of
sterols Soybean Canola Sunflower Corn oil Palm
Brassicasterol ND–12.3 950 ND–9.2 ND–44.2 ND
Beta-sitosterol 918–2,460 3,600 1,348.8–2,990 4,384–14,718.6 150.6–434.7
Campesterol 284.4–992.2 1,900 177.6–593.4 1,488–5,326.1 56.1–192.5
Stigmasterol 268.2–783.1 35 168–529 344–1,701.7 25.5–97.3
Delta5 34.2–151.7 130 ND–317.4 336–1,812.2 ND–19.6
avenasterol
Delta7 25.2–213.2 76 168–1104 80–928.2 0.6–16.8
stigmastenol
Delta7 18–188.6 160 74.4–243.8 56–596.7 ND–35.7
avenasterol
Total sterols 1,800–4,100 6,900 2,400–4,600 8,000–22,100 300–700

ND, Nondetectable.

volatilize. These compounds have distinct effects on oil and product flavors and
their stability, which will be discussed in Chapter 12.

2.6.9  Color Compounds


The main color compounds in vegetable oils are carotenes and chlorophylls,
although other chromophoric compounds also are present. Among the vegeta-
ble oils, palm oil contains the highest amount of carotenes. On the other hand,
soybean and canola contain the highest amounts of chlorophylls. Most of the
carotenes are removed from the oil by heat bleaching in deodorization described
later. Most of the chlorophylls are removed from the oil during the bleaching
process using bleaching clay.
Most of the carotenes are retained in the deodorized palm oil called the “red
palm oil,” using a very special process. This oil is sold as a naturally rich-in-carotene
oil. The carotene content of this oil is 500–600 ppm, compared to 600–800 ppm in
crude palm oil (CPO). Benefits of carotenes for human eyesight have been demon-
strated in human studies in India and the Far East, and red palm oil is promoted for
this nutritional property. This oil also has higher tocopherol and tocotrienol contents
than the conventionally processed palm oil or palm olein.

2.6.10  Trace Metals


Trace metals are undesirable in processed oils because they initiate the autoxida-
tion reaction and shorten storage stabilities of oils and food products formulated
18 Practical Guide to Vegetable Oil Processing

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.

2.7  OIL ANALYSIS USED IN VEGETABLE OIL INDUSTRY


AND THEIR SIGNIFICANCE
Vegetable oil is analyzed at various stages of processing. Each analysis provides
specific information to the processor as well as to the users. The most com-
monly conducted analyses in oil processing plants are listed in the following
with brief descriptions.

Method of Analysis (Version)


Analysis AOCS Method
Iodine value (IV)
• Cyclohexane–acetic acid method Cd 1d-92 (09)
• NIR method Cd 1e-01 (09)
• Calculated from GLC Cd 1c- 85 (09)
• Cyclohexane method Cd 1b-87 (12)
FFA
• Crude and refined fats and oils Ca 5a-40 (12)
Acid value
• Of fats and oils Cd 3d-63 (09)
PV
• Isooctane method Cd 8b-90 (11)
• Chloroform methoda Cd 8-53 (03)
para Anisidine value (pAV) Cd 18-90 (97)
Soap in oil
• Titrimetric method Cc 17-95 (09)
• Conductivity method Cc 15-60 (89)
Conjugated dienes Ti 1a-64(09)
Polar material (TPM) Cd 20-91 (09)
Polymerized triglycerides Cd 22-91 (09)
Solid fat index (SFI) Cd 10-57 (95)
Solid fat content (SFC) Ca 5a-40 (12)
Fatty acid composition (FAC)
• Capillary GLC method Ce 1e-91(01)
• Packed column method Ce 1c-89 (95)
trans fatty acid (TFA)
• trans of partially hydrogenated oils by GLC-IR Cd 14b-93 (95)
• cis, cis and trans isomers by GLCa Ce 1c-89 (95)
• Isomers isolated by FTIR Cd 14-95 (09)
• By capillary GLC method Ce 1f-96 (09)
a
Surplus method—either superseded or obsolete.
Basic Oil Chemistry Chapter | 2 19

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.

Active oxygen method (AOM)a Cd 12-57 (93)


Oil stability index(OSI) Cd 12b-92 (09)
Refining loss
• Degummed, expeller soybean oil Ca 9a-52 (09)
• Degummed hydraulic and extracted soybean oil
• Extracted and reconstituted prepressed cottonseed oil
• Vegetable oils crude
Neutral oil
• Loss Ca 9F-57 (09)
• In soap stock G5 -40 (09)
Unsaponifiable matter Ca 6a-40 (11)
Saponification value Cd 3-25 (13)
Mono and diglycerides
• By capillary GLC Cd 11b-91 (09)
• By HPLC-ELSD Cd 11d-96 (09)
20 Practical Guide to Vegetable Oil Processing

Mono, di and triglycerides


• By silica gel chromatography Cd 11c-93 (09)
Alfa monoglycerides Cd 11-57 (11)
Moisture and volatiles (butter fat, margarines, oils)
• By hot plate method Ca 2b 38-(09)
• Vacuum oven method (except coconut oil) Ca 2d-25 (09)
• By distillation method Ca 2a = 45 (09)
• By Karl Fischer method Ca 2e-84 (09)
Alkalinity
• Of fats and oils Cd 3e-02 (09)
• In soda soap and products Da 7-48 (09)
Acetone insoluble matter
• In lecithin Ja 4-46 (11)
a
Surplus method—could be considered obsolete.

2.8  SIGNIFICANCE OF THE ANALYTICAL METHODS


AND RESULTS
2.8.1  Iodine Value
This method determines the degree of unsaturation in the oil. The results are
expressed as grams of iodine absorbed per 100 g of the oil sample.
Oils with higher unsaturation show higher IV values. Iodine values of most
common crude vegetable oils are listed in Table 2.6.

2.8.2  Free Fatty Acids


This method determines the amount of FFA present in the oil. Generally, results
are expressed as percent oleic acid for seed oils. It is expressed as percent pal-
mitic acid for palm oil and palm oil derivatives, and as percent lauric acid for
palm kernel or coconut oils.

TABLE 2.6 Typical Iodine Values of Common Refined Vegetable Oils


Oil type Typical iodine value
Soybean 132
Canola 120
Sunflower oil 128
Cottonseed oil 110
Palm oil 50
Basic Oil Chemistry Chapter | 2 21

2.8.3  Acid Value


The acid value for oil is the number of mg of potassium hydroxide required to
neutralize the free acid in 1 g of the oil. For easy reference:
AV = 1.99 FFA (%)

2.8.4  Peroxide Value


This method measures the primary state of oxidative of the unsaturated fatty
acids in oil. The fatty acid can be in the form of FFA or as part of a triglyceride
molecule. This method measures all substances in the oil, which oxidize potas-
sium iodide under conditions of the method as milliequivalents of peroxide per
1000 g of oil or fat. PV of freshly bleached as well as deodorized oil must be
“zero.”

2.8.5  para Anisidine Value


pAV is defined by convention as 100 times the optical density of a solution
containing 1 g of oil and 100 mL of a mixture of solvent and reagents specified
in the test method, measured in a 1-cm cuvette at 350 nm. This test measures
some of the secondary oxidation compounds of oils and fats generated from
the decomposition of the peroxides. Specifically, 2-alkenals and 2, 4-dienals
are measured by this method. Freshly deodorized oil may have a pAV content
of 2–6.

2.8.6  Soap in Oil


This titrimetric method determines alkalinity in the oil as parts per million
sodium oleate. Presence of soap in bleached oil indicates poor bleaching. Prop-
erly refined and bleached oil must have zero soap content. Soap in bleached oil
can cause numerous production and quality problems which will be discussed
later.

2.8.7  Conjugated Dienes


This spectrophotometric method determines diene linkages of unsaturated fatty
acids present in oil in terms of percent of oil. This is a measure to understand the
onset of autoxidation reaction, and will be discussed later in Chapter 12.

2.8.8  Polar Material (TPM)


This method determines the total amount of polar materials present in the oil by
column chromatography. It is used as a measure of oxidative degradation for
oil, especially in frying processes.
22 Practical Guide to Vegetable Oil Processing

2.8.9  Polymerized Triglycerides


This method determines polymerized triglycerides in fats and oils by a gel-
permeation method, and indicates the degree of thermal and oxidative abuse of
the oil.

2.8.10  Solid Fat Index


This is a dilatometric method which determines the combined volume of solid
and liquid in the sample at specific temperatures. It is an empirical measure of
solids fat content in a sample of oil at specified temperatures. The information
is used in formulating shortenings, margarines, and spreads.

2.8.11  Solid Fat Content


This Nuclear Magnetic Resonance Spectrometry (NMR) method estimates the
amount of fat solids present in the oil (fat) sample at specific temperatures. It
is also used in formulating shortenings, margarines, and spreads, and originally
was developed for the emerging modern palm oil industry.

2.8.12  Fatty Acid Composition


This capillary method identifies the fatty acids in a fat or oil by analysis of the
sample’s fatty acid methyl esters by capillary gas–liquid chromatography. The
fatty acid methyl esters are prepared according to AOCS Method Ce 2-66 (09).
This method does not identify cis or trans isomers.

2.8.13  Fatty Acid Composition


The packed column method is especially suitable for analyzing hydrogenated
fat because it is capable of providing (1) fatty acids identities and composi-
tions, and (2) TFA and cis–cis methylene-interrupted unsaturation. This method
yields slightly lower trans values as compared to the infrared spectrophotomet-
ric method (AOCS Method Cd 14-61).

2.8.14  trans Fatty Acid


TFA in hydrogenated fat is becoming increasingly critical for the vegetable oil
industry.

2.8.15  Refined and Bleached Color Test


These methods are available applicable to refined cottonseed oil soybean and
sunflower oils. These tests are particularly helpful to predict the color of the
deodorized oil that could be obtained from a given crude oil.
Basic Oil Chemistry Chapter | 2 23

2.8.16  Lovibond Color


Method Cc 13b-45 (09) compares the oil color by comparing against colored
glasses. This method can be used to measure color of all normal oils provided
there is no turbidity in the sample.
Method Cc 13e-92 (09) is preferred by the British Standard Lovibond Inter-
national trade.
Method Cc 13j-97 (09) is suitable for measuring colors of all refined,
bleached, and deodorized vegetable oils and also filtered and deodorized tal-
low. The Automated method gives results in the AOCS-Tintometer (Wesson
method) or the Lovibond color scale.
Lovibond color can be used to track degree of removal of color bodies pres-
ent in the original crude oil. Each type of oil has a characteristic Lovibond Red
color. A higher color indicates problems either with the oil or the process. These
will be discussed in detail later in Chapters 6, 8, and 12.

2.8.17  Chlorophyll Pigments


This spectrophotometric method determines the concentration of chlorophyll
in expelled, refined, and bleached oils by measuring absorption at 630, 670,
and 710 nm wavelengths. This method is not applicable to hydrogenated oils,
deodorized oils, or finished products.

2.8.18  Trace Metals (ICP)


The ICP method, or Inductively Coupled Plasma Optical Emission Spectros-
copy (ICP-OES), is used for quantitative determination of calcium, copper,
iron, magnesium, nickel, silicon, lead, sodium, and cadmium in oil, when these
impurities are present in the solubilized form in the oil. Suspended material,
such as bleaching clay or nickel catalyst cannot be detected by this method. The
detection level by this method is extremely low and precise.

2.8.19  Trace Metals (Atomic Absorption Method)


This method is suitable for crude oil and partially refined oil. It can determine
copper, chromium iron and nickel as low as 0.1 ppm in the oil.

2.8.20  Phosphorus (Graphite Furnace)


This method determines the phosphorus content in parts per million. It involves
vaporization of the oil in a suitable graphite furnace and an atomic absorption
spectrophotometer for reading.

2.8.21  Phosphorus (ICP)


This method quantitatively determines the phosphorus level in oil by using
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES).
24 Practical Guide to Vegetable Oil Processing

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.

2.8.23  Melt Point (Capillary Tube Method)


The complete melting point of fat is determined by this method.

2.8.24  Melt Point (Mettler Drop Point Method)


The temperature at which the fat sample becomes soft and flows under the specific
conditions of the test is measured by this method. This is an approximate method
for melt point because one can see higher melting solids in the melted sample
even at a temperature higher than the melt point determined by this method.

2.8.25  Active Oxygen Method (AOM)


This method measures the time in hours needed for the PV of a sample to reach
100 mEq when tested under the conditions specified. This is a measure of the
primary oxidative stability of oil. AOM provides good information oil stability
for salad dressing and applications that do not require high temperature treat-
ment for the oil. Most oil processors and end users stopped using this method
because the following method is found to be more useful to determine the oxi-
dative stability of the oil.

2.8.26  Oil Stability Index (OSI)


This method provides the tertiary oxidative state for the oil. In oil applications,
OSI is a better measure of oil stability while processing of foods formulated
with the oil and is subjected to high temperature.
The apparent basic difference between OSI and AOM is that OSI estimates
the time required to exhaust antioxidants present in the sample and begins accu-
mulating peroxides, while AOM measures the total time required for the sample
to degrade to the 100 mEq PV. The OSI method provides better information
about the secondary and tertiary oxidation of the oil. This will be discussed
further in Chapter 12.

2.8.27  Refining Loss


There are several methods for the test that apply to different oils as listed previ-
ously.
Basic Oil Chemistry Chapter | 2 25

2.8.28  Neutral Oil Loss


2.8.28.1  In Refining
The total natural oil of natural fats and oils consisting essentially of triglycer-
ides and unsaponifiable matter is determined by this method. The fatty acids
and miscellaneous nonfat substances are removed by passing through a column
of activated alumina. The loss is the difference between the amount of feed and
that recovered, expressed as percent.
This method is satisfactory for cottonseed, soybean, peanut (groundnut),
linseed, coconut, and sunflower oils.

2.8.28.2  In Soap Stock


There is always a certain amount of neutral oil that remains in the soap stock
that is discharged from the primary separator in caustic refining process. This
method allows one to determine the amount of neutral oil in the soap stock.

2.8.29  Unsaponifiable Matter


Unsaponifiable matter include those substances frequently found dissolve in
fats and oils, which cannot be saponified by the usual caustic treatment, but are
soluble in ordinary fat and oil solvents. Included in this group are high aliphatic
alcohols, sterols, pigments, and hydrocarbons.
This method is applicable to normal animal and vegetable oils and fats but
is not applicable to marine oils and the feed-grade fats.

2.8.30  Saponification Value


This method is defined as the number of milligrams of KOH required to sapon-
ify 1 g of the oil sample. This method is important in the soap making industry.
This method is applicable for vegetable oils, deodorizer distillates, and
sludges.

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.

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