Professional Documents
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This total of 80 lb per person per year represents about 38% of the
calories in the diet. With the recent push to reduce this number to
30%, the above numbers will probably decrease, but the proportions
will likely remain about the same.
Commercial (as opposed to home) use of fats and oils accounts for
most of the shortening and frying fat category, some part of the salad
oil category, fats for margarine production, and many of the miscellaneous items (confectionery coatings, oil-based whipped toppings, coffee
In This Chapter:
Functions in Food
Systems
Functions in Processing
Sensory Functions
Nutrition
CHAPTER ONE
wh iten ers, etc. ). The specifications for these fats and oils are generally
more stringent than for fats and oils used in the home. Commercial
equipment and processes are more sensitive to variations in fat characte ristics; the specified properties for the finished product are more
n arrowly defined; and compensating for ingredient variation takes
longer th an in home cooking. The people responsible for efficient op eration of such a plant must understand how fat and oil properties
affect production and product characteristics and how to write and en force speci fications for these raw ingredients, so that the outcome is
satisfactory both to the consumer and to the owners of the plant.
FUNCTIONS IN PROCESSING
Shortening has an important functional role in processing baked
foods, which is discussed in more detail in Chapter S. It provides stru cture in some products (for example, cookie dough) and lub rication in
others. In coo kie dough and cake batters, shortenin g h ol ds th e fine ly
divided air bubbles th at serve as the nuclei for leavening gases and give
a fin e grain to th e finished product. In roll-in doughs (Danish, puff pastry), plastic fat prevents adjacent dough layers from knitting together
during proofing, so the final product has a flaky, many-layered structure. Fat is the main structural element in the fillings and cream icin gs
used in and on bakery sweet goods of various sorts.
Fat for frying is important in many segments of the food in dustry:
potato chips and corn chips are deep-fried; nuts are roasted; cake
doughnuts, potatoes, and battered or breaded poultry or fish are fried .
The se and other food items depen d n ot only on the heat trans fer properties of fat, but also on the flavor imparted by the fat . Th e proper
ch oice and corr ect use of fat are necessary to ob t ain acceptable resu lts
in these products.
SENSORY FUNCTIONS
Oxidation - Chemi cal reaction
in which the double bond on a
lipid molecule reacts with
oxygen to produ ce a variety of
chemical products. The
consequences of this reaction
are loss of nutritional value and
formati on of the off-flavors
associated with rancidity.
Reversion flavor-M ild offflavor developed by a refined
oil wh en exposed to oxygen.
Reversion occurs rather easily,
and th e off-flavor, wh ile
und esirable, is not as
objectionabl e as rancidity
caused by oxidation.
Flavor. Fat con tributes flavor to foods . This is most apparent in fried
food s, because absorbed fat becomes an integral part of the finished
product. The flavor is the result of products of numerous reactions between fat and other food components such as proteins an d carbohydrates. Oxidation products of fat are also involved, giving a situation
th at is extremely com plex in terms of th e n u m ber of po ssible flavo r
com pou n ds present. Nevertheless, without these com pounds, the product would not have the characteristics we have come to associate with
fried foods . For example, when a taste panel assesses food fried in completely fresh (refin ed) oil, the typical comment is usually something
like "tasteless."
Fat or oil can contribute flavor directly, eith er in a po sitive or negative sense. Olive oil, which has a unique flavor, is prized for gourmet
salad dress ings specifically because of the flavor notes it con tributes. On
the other hand, if a fat or oil is exposed to air and allowed to oxidize
slightly, a flavor often develop s that is referred to as a "reversion flavor."
The ch aracteristics of this flavor differ in different oils ("be any,"
FUNCTIONAL PROPERTIES
"grassy," and "metallic" are some descriptive terms used) , but it is invariably considered to be negative in terms of product quality.
Texture. Several aspects of food texture (or mouthfeel) are attributable
to fat. It tenderizes the food, making it easier to bite and chew. It also
makes a food feel moister in the mouth. As an example of these two
aspects, consider the texture of steak-compared to a well-marbled
steak, the lean cut of meat is characterized as "tough" and "dry." Oil
also lubricates the food particles, helping to clear them from mouth
surfaces (teeth and palate) more readily.
These tenderizing and lubricating characteristics are primarily attributable to the liquid fraction of the fat. If the fat mel ting point is much
higher than body temperature, the fat does not melt in the mouth and
the residual solid portion gives a "waxy" mouthfeel, an undesirable
situation. This is particularly noticeable when the fat is a major component, as in fillings, icings, and confectionery coatings.
NUTRITION
As mentioned above, a major contribution of fat to the diet is as a
dense, easily stored source of calories. An example is pemmican, traditionally used by Nat ive Am ericans as rations when on an expedition
(eith er hunting or warfare). Th is was made by mixing shredded jerked
meat and dried berries in a container, then pouring melted animal fat
over the ble nd. Whil e perhaps less appetizing than the products of the
U.S. Quartermaster Corps, pemmican served the same purpose: a storage-stable, readily transportable source of food energy for consumption
during periods of high energy expenditure.
Fat also makes other positive nutritional contributions. It carries fatsoluble vitamins (A, 0, and E). Its component fatty acids are metabolized by the body into phospholipids, which are essential parts of cell
mem bran es. With out the proper balance of saturated and unsaturated
fats, the membranes are either too solid or too flu id, and cell integrity is
lost . Finally, certain po lyunsaturated fatty acids are the precursors of
lipid hormones (prostaglandins) that are needed by the body. If the diet
completely lacks these essential fatty acids, certain untoward symptoms
(h air loss, scaly skin, loss of reproductive capability) appear.
Prostaglandins-A group of
specialized lipids that play
important metabolic roles in
humans . They are formed in
the body from dietary essent ial
fatty acids.
Functional Properties
Before beginning the discussion of functional properties, certain
commonly used terms should be defined:
Fat is a natural lipid material that is more or less solid at room
temperature.
CHAPTERONE
Fatty acids. Fats are esters of fatty acid s and glycerol. Most fats occur in
the form of triglycerides, in which three fatty acids are attached to the
glycerol. Fatty acids contain the carboxyl group (COOH) and an aliphatic
carbon chain of variable length (Boxes 1-1 and 1-2). The general
formula is R-COOH, where R is the aliphatic group. With few
exceptions, fatty acids are linear, range in size from four to 24 carbons,
and contain an even number of carbons.
The chains can be saturated (having no double bonds), monounsaturated (on e double bond), or polyunsaturated (two or more double bonds).
Box 1-3 shows three fatty acids that each con t ain 18 carbon s but have
different numbers of double bonds and thus differ in saturation. In accordance with the Geneva system of nomenclature, the carbon atoms
of fatty acid chains are numbered consecutively, starting with the carbon atom of the carboxyl group as number 1 and continuing to the
carbon atom in th e terminal methoxy group. A shorthand designatio n
of fatty acids is often used, based on the number of carbon atoms in the
molecule and the degree of unsaturation (i.e., the number of double
bonds in the molecule). The most common fatty acid s in edible fats and
oils are those contain ing 16 or 18 carbon atoms. These include the saturated palmitic (CI 6:0) and stearic (CI 8:0) acids, the monounsaturated
oleic acid (CI 8:1), and the polyunsaturated acids-linoleic acid with
two double bonds (CI 8:2) and linolenic acid with t hree double bonds
(CI8:3). A list of natural fatty acid s along with their common n am es,
designations, an d main sources is given in Appendix A at the end of the
book.
An oth er naming convention is applied to unsaturated fatty acids that
ha ve a physiological function as prostaglandin precursors (see Chapter
9). Th ese are the omega (00) fatty acids. The number of carbon atoms
between the double bond and the terminal methyl group is designated
as 00 plus a number. For exam ple, the end of the linoleic acid chain is
CH3(CH z)4CH=CH-, so linoleic acid is term ed an 006 fatty acid (Box 1-4).
Similarly, olei c acid is C18:1oo9 and linolenic acid is CI8:3oo3. The 003
fatty acids have some unique nutritional properties, which are con-
CH3-CH2-CH2-CH2-CH2-COOH
Terminal
methyl group
,-------,
H H H
Carboxyl group
H
II
H-C-C-C-C-C-C-OH
Fatty acid
C6:0
FUNCTIONAL PROPERTI ES
I I
I I
I I
I I
H-C-C-C-C-C-C-C-C-C-C-C-C-C-C-C-C-C-C-OH
I I
I I I
I I
I I I
H H
I I
I I
I I I I I
I I
H H
OH
HHHHHH
HO
I I
I I
I I
I I
I I
I I I I
H H
H H
I I
I I
H 0
I I
H
L...-.....I
I I
.....
I I
HH
--', '-----'
CH=CH
Six carbons
I I
H H
6 I CHAPTER ONE
-C-C=C-C=C -
I I I I I
H H H H H
Conjugated
C=C-C-C=C-
I I I I I
H H H H H
Methylene-interrupted
H H H
I I I
C=C-C-C-C-C=C-
I I I I I I I
HHHHHHH
Isolated
two sides of the double bond are bent toward each other, and the hydrogen atoms on the double bond are on the same side (see oleic acid
in Fig. 1-1). In the trans configuration, the hydrogen atoms on the double bond are opposite each other. As a result the chain is nearly straight
(with a slight kink at the double bond), as shown for eIaidic acid in Figure 1-1. The cis isomers prevail in all the food fats and oils, although
small amounts of trans isom ers occur in fats from ruminants.
Stearic acid
m.p. 69.9C
C1B:O
Oleic acid
(cis)
m.p. lB.9C
C1B:l
Elaidic acid
(trans)
m.p. 43.0C
C1B: 1t
Linoleic acid
(cis, cis)
m.p. -9.SC
C1B:2
Fig. 1-1. Structure and melting point (mp) of several fatty acids. The types, from
top to bottom are a saturated acid (stearic, Cl8:0), a cis monounsaturated acid
(oleic, Cl8:1), a trans monounsaturated (elaidic, Cl8:1t), and a cis, cis polyunsaturated acid (linoleic, Cl8:2). Note that the melting point is higher for the saturated
fatty acid than for the unsaturated ones and that the fatty acid with a trans double
bond has a higher melting point than the fatty acid with the cis double bond .
FUNCTIONAL PROPERTIES
The melting point of fatty acids varies according to some simple rules:
//
R1 -C-OH
//
//
R2 -C-OH
HO-C-H
I 2
R1-C-O-C-H 2
HO-C-H
R2 -C-O-C-H
//
Ra-C-OH
pi
pi
Ra-C-O- C-H 2
HO-C -H2
Tripalmitin
Tristearin
PPP
555
Trielaidin
EEE
Triole in
Trilino lein
000
LLL
66
73
42
5
-13
Group B
Palmitooleopalmitin
POP
Palmitooleostearin
pas
50S
37
37
43
Gro up C
Palm itooleopalmitin
POP
Palm itoelaidop-almitin
PEP
Stearooleos tearin
Stearoelaidostearin
50S
SES
37
55
43
61
/.
R -C-O-C- H
'
HO-C-H
HO-C-H,
o I
" -H
R,-C-O-?
HO-C-H,
PI
p i
FUNCTIONAL CHARACTERISTICS
Melting point-The
temperature at which a solid
turns into a liquid. Because
they are a mixture of
com pounds, fats ap pea r to
melt over a range of
So lub ili ty. Fat (triglyceride) is mos tly alip ha tic h ydrocarbon chains and
therefore is soluble in hydrophilic solvents such as hexan e, benzene,
and acetone and inso lub le in water. Natural fats (and oils) contain
sma l1 amoun ts of more h ydrophilic ma terials, e.g., free fatty acids,
monoglycerides, phospholipids, glycolipids, and ox idation products .
These are more or less water-solub le, and are removed by washing with
water d uring refining.
Melting points. When a pu re chem ical compound is heated, it undergoes a phase transition from solid to liqui d at a sha rply defined temperature . When the liquid is cooled, the transition is reversed at the
same tem perature. The sharpness of the melti ng point is one test of the
purity of a material. Natural fats, h owever, are n ot pure compounds but
rather a mixture of trig lycerides made up of a variety of fatty acids.
Thus, fat melting is gradual, and the definition of the melting point is
dependen t upon the method being used. The various methods are dis-
FUNCTIONAL PROPERTIES
a crystals
f3'
crystals
\) IJ ~ \j
\j ~ \j \J
f3
a.
crystals
b.
Crystals, a, ~, ~'-When
triglyceride molecules in a fat
turn from a liquid to a solid as a
result of decreasing
temperature, they pack into
one of three different types of
arrangement. Crystal forms
exist only when the fat is in the
solid state. They can affect the
physical properties and
functionality of the fat.
Fig. 1-5. Photomicrographs of fat crystals in polarized light. From left to right,
a-crystals, p'-crystals, and p-crystals.
10
CHAPTER ONE
80
A fat that has the ~' crystal form is smooth and creamy. A
fat that has transformed to ~ crystals, on the other hand, has a
brittle, sandy texture. For most uses, both commercial and in
the home, the former characteristics are preferred. Manufacturers of plastic shortenings and margarines use the ~' stability
of mixed triglyceride fats to produce products with the desired
creaminess (see Chapter 4).
70
Cocoa butter
60
x
Q)
'"0
50
co
40
LL
(5
Cf)
30
Solid to liquid ratios. A natural fat is a mixture of triglycerides, some solid and some liquid at any given temperature.
10
The ratio of solid to liquid phase is an important determinant
0
20
30
40
of fat functionality. It is expressed as the solid fat index (SFI) or
10
Ternperature.v C
the solid fat content (SFC; the differences between these two
Fig. 1-6. Solid fat index profiles of two fats, terms are discussed in Chapter 2). The SFI profiles for two fats
cocoa butter and all-purpose shortening.
are shown in Figure 1-6. All-purpose shortening (e.g., Crisco)
has a relatively flat profile. It is soft enough to be worked at
10C, yet still retains some solidity at 37C (body temperaSolid fat index-A measure of
ture). By contrast, cocoa butter has a high profile with a rather steep
the amount of solid fat in a fat
descent. It is quite hard at 25C, yet is liquid at 35C. As the name imat various temperatures. It is
plies, a high SFI value for any given temperature indicates that the fat is
determined by the volume
hard
at that temperature. Roughly speaking, at an SFI greater than 35
changes that occur as a result
(for
example,
butter at refrigerator temperature), the fat is hard and not
of melting or crystallization.
readily
spread,
while at an SFI below 10 it is soft and almost liquid. The
This index relates the
relationship
between
SFI and functionality in various applications is
proportion of liquid to solid
fractions in a fat.
explored in depth in later chapters.
20
Ali-purpose shortening - -
NaOH
II
HO-C-H
HO-C-H
II
HO-C-H 2
R1-C-O-C-H 2
/9
/9
R2 -C-O-C-H
R1-C-O -C-H2
HO-C-H
I
HO-C-H 2
II
R-C-OCH 3
II
R3-C-O-C-H 2
R4-C-O-C-H 2
pi
R2-C-O-C-H
R3 -C-O- C-H2
NaK
FUNCTIONA L PROPERTI ES
11
CHEMICAL REACTIONS
Ester cleavage. The ester bonds in fat can undergo a variety of splitting
reactions (Fig. 1-7). Som e of these are important in food applications,
while others have oth er industrial sign ifican ce.
Hydrolysis. The addit ion of water yields a free fatty acid an d a free
hydroxyl group. Thi s reac tion, called saponification, is usually cat alyzed
with a base such as sodium hydroxide, and the fatty acid is neutralized
to a sodiu m soap.
Glycerolysis. Glycerol can be the hydroxyl donor, forming a monoglyceride with the fatty acid and leaving a mono- or diglyceride behind.
This reaction is the basis for making monoglyceride emulsifiers for food
use. In commercial production, a basic catalyst, usually potassium carbonate, is used.
A lcoholysis. The reaction of fat with alcohol is usually catalyzed with
an acid such as HCI or a sulfonic acid resin. For example, reaction of fat
with methanol yields the methyl esters of the fatty acids, wh ich are
used to analyze the com position of the fat by gas-phase chromatography.
Interesterification. A free fatt y acid can displace another fatty acid
from an ester, leaving a glyceride with somewhat changed properties
because its fatty acid structure has changed. This reaction is used to
change fat properties. Lard, for example, has a nonrandom fatty acid
distribution in its triglycerides. All the palmitic acid (25% of the total)
is found in the 2 position. As a result, lard crystallizes rather readil y in
the 13 form, wh ich is not desirable for bakery purposes. Heating in the
presence of sodium methoxide or metallic sodium causes the fatty acids
to shuffle their positions in th e triglycerides randomly. The resulting fat
has a low er SFI profile and is stable in the l3' crystal state, giving a more
plasti c shortening. Ano ther appli cation involves blending 20 parts fully
hydrogenated soybean oil (wh ich forms 13 crystals) with 80 parts refined
soybean oil, then interesterifying. The product has the SFI profile ap propriate for soft tub margarine, is l3' stable, and has only a trace of
trans double bonds.
Reduction. Fat ester bonds can also be split reductively, yieldin g
glycerol and long-chain alcohols. The reductant is an amalgam of
sodium and potassium metals. The resulting fatty alcohols are used to
make various dete rgents and lubricants (waxes) an d are of great
economic importance.
Oxidation. Autoxidation of fats occurs with unsaturated fatty acid
chains. The relative rates of oxi dation of oleic, linoleic, linolenic, and
arachidonic acids (wh ich have one, two, three, and four double bonds,
respectively) are I, 12, 25, and 50. The double bonds in the
polyunsaturated acids are sepa rated by methylene groups and are cis in
their configuration.
Autoxidation is a series of free radical reactions, in itiated and
propagated by free radicals reacting with methylene -CH2- groups that
are adj acent to double bonds (Fig. 1-8). (A free radical is an unpaired
electron, indicated as a h eavy do t in chemical formulas. It is a very
reactive species.) At th e begin n ing of the autoxidation process, a
Hydrolysis-A chemical
reaction in wh ich a molecule
splits into two parts. A
molecule of water also splits
into H and OH, which are
ad de d to the places where th e
original bond was broken . A
fatty acid is removed from a
g lyceride by hydrolysis of th e
ester bond.
Saponification-A chemical
react ion caused by add ition of
alkali in which the fatty acids
attached to a glycerol are
cleaved off to produ ce soap
(fatty acid salts) and a glyce rol
molecu le.
Glycero lysis- A chemical
reaction in which glycerol is
combined with one or mor e
fatty acids to form a glyceride.
Alcoh olysis-A chemical
reaction in which fatty acids
react with alcoho l to form an
ester.
Int er est erification - Cha ng ing
the positions of the fatty acids
on triglycerid es. This is a
commercial processing step to
change the physical properties
of a fat .
Reduct ion- Chan ging an acid
group on a fatty acid to an
alcoho l group. This is done
with meta l redu cing agents to
create fatty alcohols for
industrial uses.
Autoxid ati o n-A reaction in
which fats und erg o oxidative
chang es d ue to the double
bo nd s in their structure. The
reaction can initiate and
proceed without outside
influences.
Free rad ical-An unpaired
electron that is an unstable
intermediate in the
development of lipid oxidation
and rancid ity.
12
CHAPTER ONE
Peroxyl radical-An
intermediate in lipid oxidation
in which the fatty acid radical
has added two oxygen atoms
and is still a free radical. It is
characterized by the structure
COO.
Hydroperoxide-An
intermediate in lipid oxidation
in which the fatty acid has
added two oxygen atoms and a
hydrogen atom at the point of
oxidation. It is no longer a free
radical but eventually degrades
to flavor compounds associated
with rancidity.
Rancidity-An off flavor in a fat
or oil caused either by
oxidation or by the release of
flavorful fatty acids from the
triglyceride.
Stability-The resistance of a
fat source to the formation of
rancidity.
Antioxidants-Compounds
that can inhibit the
development of lipid oxidation.
-CH=CH-CH 2CH=CH-
R~RH
02
RH
-CH=CH-CH=C H-CH-
00
I
-CH=CH-CH=CH-CH-
R
,?OH
-CH=CH-CH=CH-CH4
t"----- OH
-CH=CH-CH=CH-CH-
FUNCTIONAL PROPERTIES
13
replacing -OCH3 )
tOC(CH
OH
O'
-CH=CH-CH=CH-CHI
3)3
OCH
BHA
tOC(CH
O'
3 )3
OCH 3
OH
-CH=C H-CH=CH -CHI
14
CHAPTER ONE
Phospholipids-Natural
components of fat that have
phosphorous associated with
the glycerides. Phospholipids
are surfactants that assist in
emulsification.
Lecithins-A phospholipid
found in egg yolk and
soybeans and also used as a
food ingredient. It is a
surfactant that can stabilize
emulsions.
Waxes-Lipid compounds that
are fatty acids linked to longchain fatty alcohols. They occur
naturally in unrefined oils.
Sterols-Lipid compounds
found in trace amounts that
have ring structures rather than
the straight chains associated
with fatty acids. Examples are
cholesterol in animal products
and phytosterols in plant
products.
Hydrocarbons-Lipid
compounds found in trace
amounts in fats and oils. They
are unsaturated carbon chains
such as the compound
squalene.
has declined in the United States, the amount of edible tallow and lard
has also declined. These fats all carry some amount of cholesterol with
them, and because of the connection between dietary cholesterol and
cardiovascular disease, their consumption has declined markedly.
Fish oil. Historically, marine oils have been an important fat source,
but their use has declined since midcentury. Menhaden oil, in the
partially and fully hydrogenated forms, has now been approved by the
FDA for food. Marine oils are rich in long-chain polyunsaturated fatty
acids (C20 and up). In' particular, they contain large amounts of (0-3
fatty acids (Le., acids in which the terminal double bond is three carbon
atoms removed from the end of the fatty acid chain). There is some
evidence that these fatty acids have a positive nutritional impact,
probably as precursors to various prostaglandins.
Other components
Phospholipids. Vegetable oils contain 0.1-30/0 phospholipids, which
are removed during refining. Collectively called lecithins, they comprise
several different chemical forms. Details of lecithin structure are
discussed in Chapter 3.
Waxes. Waxes are found in small amounts in most unrefined oils.
These are esters composed of a fatty acid linked to a fatty alcohol. A
typical wax, for example, may be made of stearic acid esterified to
stearoyl alcohol. While present in quite small amounts, waxes solidify
when chilled and must be removed during refining.
Sterols. Fats and oils contain a few tenths of a percent of sterol. In
animal fats this is mainly cholesterol, while in vegetable oils it is a
mixture called phytosterol.
Hydrocarbons. Most fats contain small amounts (less than 1%) of
hydrocarbons. The most common is squalene, a highly unsaturated
compound closely related to carotenes.