Analytical Methodology for Emulsifiers Used in

Fatty Foods: a Review 1

F.J. BAUR, The Procter & Gamble Co., 6071 Center Hill Road,
Cincinnati, Ohio 45224

ABSTRACT and most are quite heterogeneous mixtures. (c) The very
The current status of analytical methodology for nature of emulsifiers makes them difficult to remove from
emulsifiers used in fatty foods is reviewed. Faster and constituent proteins and carbohydrates present in finished
more precise methodology for both quality control foods. A subordinate editorial problem in dealing with this
purposes and for quantitative removal from foods is subject is the definition of the fatty food emulsifiers. No
desirable. A key problem is the quantitative removal system of classifying emulsifiers is all-inclusive. Usually
,from foods to the exclusion of interfering substances. emulsifiers are classified based upon the function or
This aspect is complicated by (a) the presence of performance in the product. This frequently means that
only a fine line may distinguish a stabilizer from an
other food ingredients such as proteins and carbo-
emulsifier, particularly since some additives may exhibit
hydrates, (b) innate heterogeneity of most of the
both properties. For the purpose of this paper, the
emulsifiers, and (c) wide variability in composition of
emulsifiers used in fatty foods in this country are those
most of the emulsifiers. The broad applicability of
listed in Table I.
chromatography is discussed, with the prediction
It will be of interest to touch, in an introductory
made that high pressure liquid chromatography will
manner, on the growth of chemical complexity of fatty
be the technique of the future. Analytical details are
food emulsifiers. Monoglycerides are the first fatty emulsi-
not included, as these are available in the cited
fier to be added to foods. They were introduced in 1933 as
publications.
a component of shortening for cake baking. They remain
the dominant emulsifier, both from the standpoints of total
I N T R O D U C T I ON use (75% of the current total tonnage being monoglyc-
Emulsifiers are the most important class of food erides) and breadth of use, reflecting not only performance
additives, insofar as amount produced and consumed is but also the fact that monoglycerides occur naturally in
concerned. 1970 production was estimated at 188 million foods. There was little additional activity on emulsifiers
pounds. In dollar volume, emulsifiers rank third behind until the late 1940's, and the major research and develop-
flavorings and stabilizers-thickeners in the various classes of ment effort and product introduction took place in the
food additives. Emulsifiers may be present in some basic 1950's. Monoglycerides are compounds of glycerol and
ingredient of a food product, or they may be added by the fatty acids. In the search for edible materials of comparable
finished product manufacturer to achieve the desired surfactant properties, it was natural to turn toward other
properties. With the trend toward already processed or polyols and other acids. Most of the resulting products are
convenience foods, emulsifiers are assuming an increasingly dealt with in this report.
important role in food processing and the quality of the
finished food products. N E E D FOR I M P R O V E D M E T H O D S
This is a review paper. Its intent is to provide insight into There are essentially two analytical methodology needs.
the current state of the analytical technology and to point First, there is a distinct need for faster and even more
out the needs for additional method development effort as precise methods. The existing methods have been adequate
they now exist. for quality control of emulsifiers as manufactured, but are
The development of analytical methods for emulsifiers not completely suitable for monitoring the output of the
used in fatty foods is difficult for three main reasons: (a) food industry's present continuous processes. Second, as
The fatty food emulsifiers have many chemical similarities will be seen, there is a need for improved methodology for
which make it difficult to separate and distinguish the the analyses of mixtures of emulsifiers, particularly in
materials when present in mixtures. These similarities are finished products. In finished goods the analyst seeks to
not surprising when one considers the basic need for fatty determine the levels of chemically simi~r heterogeneous
acid esters of polyols in order to obtain the required surface materials of variable composition, where these levels are
chemistry. (b) None of the emulsifiers is a single compound often as low as 0.1%. Methods for the separation, identifi-
cation and quantitation of food emulsifiers need further
1presented at the AOCS Meeting, October 1971, Atlantic City, improvement and refinement.
Symposium on F o o d Additives in Fat and Oil Bearing Foods. Both industry and regulatory agencies have need for

TABLE I
Emulsifiers Used in Fatty Foods
GRAS status Via petition (permitted as additives)
Sorbitan polyoxyethylene fatty acid esters (polysorbates)
Lactic acid esters o f mono- and diglycerides
Propylene glycol fatty acid esters
Lecithin Polyglycerol fatty acid esters
Mono- and diglyeerides (monoglycerides)
Sorbitan fatty acid esters
Diacetyl tartaric acid esters o f m o n o - and Lactylic esters o f fatty acids and their salts (Ca, Na)
digly cerides (TEMS) Ethoxylated monoglyeerides
Hydroxylated lecithin
Succinylated monoglycerides
Acetylated monoglycerides
Succistearin (SPGHS)

85
86 JOURNAL OF THE AMERICAN OIL CHEMISTS' SOCIETY VOL. 50

TABLE lI
CH2OR
CHOH
Methods for Analysis of Mixtures of Fatty Food Emulsifiers
CH20 ~ - CHO - CHO --CO2H
Technique Applicable emulsifiers N' I I
0 C = 0 C = 0
Sample hydrolyzed, physical and P o l y o x y e t h y l e n e types
solvent separations plus various CH 3 CH 3
qualitative tests (74)
FIG. 1. TEMS, where R = fatty acyl radicals (R~
Two paper chromatographic solvent P o l y o x y a l k y l e n e types
systems plus qualitative tests (75)
Column, thin layer, and gas liquid Lactylated monoglycerides CH2OR
chromatographies (32, 76, 77) Monoglycerides I
Polyglycerol esters CHOR
Propylene glycol esters I
Sorbitan esters CH 2
Thin layer chro mato grap hy of Citric acid esters
methanol solubles from Lactic acid esters (~ICH2CHORCH2)n
e x t r a c t e d fat, Rf and color Lecithin
response to selected sprays a Monoglycerides o
I
Poly fly cerol e stets
Polysorbates
Propylene glycol esters
~H2
CHOR
I
aUnpublished.
CH2OR

FIG. 2. Partial polyglycerol esters where R = H or fatty acyl

methods to determine emulsifiers in foods. Industry, in radical, but both present.
addition to quality control of finished product, is interested
in methodology to make sure that only those additives
approved for a particular foodstuff are present and that the rearrangement does occur in manufacture.
ingredient statement is authentic. These needs are likely to The partial polyglycerol esters are tremendously com-
increase as food formulations become even more complex. plex mixtures. Figure 2 presents the generic formula. In
manufacture, the polyglycerol is first made by heating
EMULSIFIERS BEING REVIEWED glycerol in the presence of an alkaline or acidic catalyst,
which by itself results in a very heterogeneous product. As
Table I lists the main emulsifers used in fatty foods in an example, decaglycerol, a material with an alleged average
this country. The first portion of the table covers the of ten and an actual average of five glycerol moieties, in
generally recognized as safe (GRAS) materials. Lecithin is a fact contains compounds having from 2 to ca. 30 glycerol
widely occurring natural substance commonly added to moieties. Linear species predominate, but some cyclic
fatty foods, but at a low level. Tartaric acid esters of mono- structures may occur. The polyglycerol is then esterified
and diglycerides, otherwise known as TEMS, are widely with fatty acids.
used in Europe, but to a smaller extent in this country. With the sorbitan esters, heterogenous mixtures are again
The balance of Table I lists the 11 most important encountered. A main contributing factor is that, under the
emulsifiers having food additive status, materials whose conditions of reaction, usually heating sorbitol with fatty
permitted use in foods has been established via a petition to acids alone or with an acidic or alkaline catalyst, anhydro
the FDA. The listing is in estimated priority order of sorbitols or sorbitans are produced; in fact, there is little if
present commercial use in this country. any esterified sorbitol present in the final product. The
Two additional materials are the citric acid esters of anhydro sorbitols can be monocyclic such as the 1,4 as
monc~ and diglycerides and the sugar fatty acid esters. Both pictured in Figure 3, or dycyclic such as the isosorbide
have received considerable product application attention in shown in Figure 3. Mono- and diesters are required in order
the past few years in the U.S. and abroad. to have emulsifier properties. Again the primary alcohol
group is favored in the esterification. The esters may also be
C H E M I C A L NATURE OF APPROVED EMULSIFIERS produced by transesterification using fatty acid esters.
The polysorbates or sorbitan polyoxyethylene esters are
A review of the chemical nature of the materials will
made by adding ethylene oxide to the sorbitan esters using
indicate the inherent analytical problems in this area and
an alkaline catalyst. A generic formula is shown in Figure 4.
the analytical difficulties. The general similarity between
It should be noted that in this reaction the fatty acyl
the various materials should be n o t e d - m o s t are based on
radical becomes mobile and will migrate from its initial
glycerol. Sometimes other polyols, such as propylene position on the polyol to esterify the OH group at the end
glycol, polyglycerol and sorbitol are substituted for glyc- of the polyoxyethylene chains. Both the degree of esterifi-
erol, and low molecular weight acids, such as acetic, cation and number of polyoxyethylene residues ascribed to
succinic and fumaric, are substituted for a portion of the the commercial products are estimates of the dominant
fatty acids. Also, complexity increases when either mix- species. With several sites open for condensation, variations
tures of polyols or mixtures of acids are used. This is can be considerable.
particularly true when bifunctional, both alcoholic and
acidic, reactants such as lactic, citric and tartaric acids, are
involved. Moreover the reaction conditions frequently bring A N A L Y T I CA L CONSI DERATI ONS
about random interesterification of the ester groups already The various analytical considerations that are important
present. A few examples will illustrate the preceding points. are: (a) internal quality control, (b) removal and determi-
The semistructural formula of TEMS or tartaric acid nation of a single emulsifier from a food, and (c) removal
esters of monoglycerides is shown in Figure 1. TEMS are and determination of mixtures of emulsifiers in foods.
made by the acid-catalyzed reaction of diacetyl tartaric acid The accepted methodology for quality control in the
with monoglycerides. The structure represented is a domi- manufacture of emulsifiers is summarized in Outline I. For
nant species; however the secondary alcohol can also be only two emulsifiers, lecithin and monoglycerides, have
esterified. Usually the fatty acyl radical is on the glycerol technical societies such as ours adopted control methods.
molecule and the acetyl groups are on the tartaric acid, but MacDonald has published a review on this general subject of