December, 1928 INDUSTRIAL A N I EXGINEERING CHEMISTRY -

1295

Chemistry and the Cocoa and Chocolate Industry

Frank C. Gephart
23 XAST 31ST sr. NEW Yona, N. Y

HEN Cortez returned to Spa.iu after his conquest of
Mexico he took with liim quantities of a new
foodstuff--cacao, He had found this delightful
bevera.go prepared from a mturally fermented bean, roasted
and ground in earthenware vessels, and admixed with honey
and spices. The Spaniards gradually developed a trade in
this commodity, and very soon cacao, or cocoa, made its
appearance in coffee houses in England and on the Continent,.
Its popularity and use spread with tremendous rapidity,
until today there is a world consumption of about 500,000
t,ons annually, the United Stntcs alone consritniiig shout
200,000 tons, or 40 per ceni. of the total. Iluriiig tlie last
tuienty-five years t i m e has heen an average yearly increase
i n consuniption of about GO00 toils. Siucc 1916 our annual
consimption of cocoa lrns dorililed. The importance OS cacao
The benns so fermented are then iisurilly washed and then
dried, arid sometimes clayed and polished. If these processes
nrc properly contluct.ed tlie clean fermented beans leave the
plantation free from mold and reach the manufacturer in
firsi-class condition. An excelleiit index OS tlre condition of
the beans is t,lx free fatty acid content of the cocoa butter.
1.n hems iii good condition it seldoin rillis over 1 pcr cent..
I Iiauc rleinotistrsted the prcsence of a lipase whiuli under
favorable conditions very rnpidly splits cocoa, butter. P r o p
crly fermented and dried beans contain from 5 t,o 10 per cent
of moisture and :ibout 42 per cent of cocoa butter.
Manufacturing Processes
In t,he manuiacture of the great variety of cliocolate prod-
ricts on the riinrkct toda,y roasting is the first process.
Sevoral ilnportnnt clrernienl changes take place during this
strp. Tliere is a loss of moisttire; starch is destririiaed;
vol:iiile a d s are la,rgely rctnoved; n iurtlier loss i n tho ns-
tringcney occurs; color changes are eii'ected; and, most itrr
pronounced aroma, is clevcloped :ind the lipase is

1ic cocoa hutt,cr suffers no change in coinposition, as

e m lx: detcrtcd by the detemiin;itioii of the Eat constants.
I Itis Itas liren dnmoiistr (1 by ~ I I I I I C ~ analyses
I.
~II~ of cocoa
biiitcr grqiared under itrollcd conditions froin a great
d m r l unro:rsted tmiits. The nrorna of t,lie

completely identify tlie constitueirts of t,liis dist,illate, hut

noted that it possessed an odor resembling that of coriander

Figure 1-A Battery of Cocoa Reasters

The role played by chemistry in the development of this

industry is interesting. In the early st.ages OS the industry
English, Freiich , and German investigators began studies
on the fermentation of tlie bean and established many scien-
t.ific iact.s concerning the iinmerous chemical cbaiigcs tbat
take place during this peculiar process. Witlioot going into
detail, su%ce it t o say that fernrcntation proceeds ill tile pulpy
substance in which the cacao bean is embedded, producing
alcohol and acetic acid, thereby gcner:rting heat. uirlil t.he
fermenting mass attains a tmipcrature of allout 60" C.
Within the seed the germ is Billcd, preventing later germina-
tion with a loss of fat. Various enzymes become active; Couricsy of IIwshc9 Chorolole Co , lfcrrhcy, Pa.
starches are conrerted into sugar and finally into alcohol
Fleure &A Baflerv of T r i ~ l cMills
and acetic acid; an oxidase splits a tannin complex, with a
resultant, loss of astriirgeury and change in color; R proteolytic
ferment Iiydrolg-zes a portion of the sibuminiius substances
present., with the forniation of proteose and peptone. A
change in the odorous sul~stmcespresent is brought about
by the interaction or organic acids and alcohols, mith the
formation of esters. There is a ehange in the alkaloidal
complex. Whether therc is an actual loss of alkaloid has
not yet been definitely determined.
 1296 INDUSTRIAL AND ENGINBEIUNG CNEMISTRY
desired, or i t may he conducted in stages, such as a low initial
roast, followed by heat treatment in subsequent milling
operations, resulting in a gradual development of aroma,
such as takes place in the manufacture of the so-called Lindt
chocolate. The Aavor of this particular kind of chocolate
differs from the flavor of the same chocolate prepared by a
single roast. The aroim of chocolate and the manner in
which i t may he modified are of such great importance to the
industry that furt,her and more cornpleto studies of the sub-
ject should he undertaken.
Figure 3-A Battery of Cocos Presses
The roasting and cleaning of cocoa entails a loss of from 10
to 25 per cent due to loss of moisture and other volatile
constituents and to the separation of shell. The roasted and
cracked nibs are ground in special mills to form choco1at.e
liquor, or hitter chocolate. Chocolate liquor is the hasc
from which all chocolate and cocoa preparations are made,
and contains from 50 to 55 per cent of cocoa butter. If cocoa
powder is desired, chocolate liquor is subjected to hydraulic
pressure and a portion of the cocoa butter is removed. The
resulting press cake is ground to form the cocoa powder of
commerce. The color of cocoa powder is susceptible to
temperature changes. Hence rapid chilling of the powder is
sometimes resorted to in order to “set” the color. Here again
we are working in the dark, as little is known concerning the
composition and properties of cacao red, bhe supposed color
of cocoa.
Dutch Process Cocoa
IF Dutch process, or so-called “soluble” cocoa, is desired,
alkali treatment is resorted to, before or during roasting or by
treatment of t.he liquor itself. This process originated in
Holland ahout 100 years ago. Originally alkali was added
only in sufficient quantity to neutralize the free acidity of
the beans, so that it was under scientific control, but today,
as far as I know, no such control is pmcticed in this country.
Several important changes are effected by the action of
alkali. Free acidity is neutralized; marked color changes
occur, not always in the product per se but when made up in
the cup; and an alteration in the protein and aroma takes
place, necessitating bouqueting of the finished product.
Bloomherg proved conclusively that ”Dutched” cocoas are
not more soluble than untreated cocoas, as the water extract
of such preparations, when due account is taken of the added
mineral matter, is not greater, but often less, than that in
Vol. 20. No. 12
untreated cocoa. However, they appear to be more soluble,
as they deposit less sediment and hold u p better in the cup,
owing to the presence of a small amount of soap formed by
action of the alkali on the cocoa butter. They possess a
deeper and richer color, and this no doubt is the chief reason
for their manufacture. Bloomherg’s work would have been
much more instructive had he used only sufficient alkali to
neutralize t,he free acids, as was originally done in Holland,
instead of duplicating trade conditions in this country.
Cocoa Butter
The cocoa butter which is a by-product in the manufacture
of cocoa powder is a hland neutral oil, possessing a remarkable
resistance to the development of rancidity. Lewkowitsch
has attributed this property to the fact that, being an ex-
pensive fat, cocoa butter is bandled with a great deal more
care than are the cheaper fats and oils. I do not accept this
explanation but believe that this remarkable property of
resisting rancidity is due largely to the fact that cocoa butter
is produced by a dry process and never comes in contact with
water. I know of no other oil or fat produced in this way.
Cocoa hutter will rapidly deteriorate if emulsified with water,
the free fatt,y acids increasing to as high as 30 per cent., hand
in hand with an increasing Kreis reaction, There also seems
to he some relationship between the coloring matter of cocoa
butter and its rancidity resisting properties, for even when
dry, if decolorized with carbon, it will develop rancidity quite
rapidly.
Chocolate Products
Other chocolate products, such as sweet chocolate, milk
chocolate, and chocolate bars, are made by the incorpora-
t,ion of sugar, milk, nuts, etc., in chocolate liquor. Many
t,echnical prohlems are involved in the manufacture of these
products. From amonetary standpoint the greatest problem
that confronts the industry today is that of t,he graying of
chocolate, entailing as it does losses aggregating millions of
dollars. When chocolate confections are displayed in a
warm environment or are shipped during warm weather they
soften, and, as chocolate is a mechanical mixture of dry
materials, the cocoa butter when melted gradually works its
way to the surface, resolidifying when the temperature drops.
This produces a mottled appearance, destroys the color and
gloss, and renders the confection unsalable, though not im-
pairing in any way its food value. Unfortunately, graying is
considered by the consuming public as an indicat.ion that the
candy is not. fresh, so that such candies are usually returned to
the manufacturer for exchange. Quick turnover is the best
solution of this problem. It is an extremely difficult prohlem
technically, and is rendered more difficult because of govern-
mental restrictions on the composition of chocolate.
As cocoa butter i s the most espensive ingredient of clioco-
late, a restriction of its quant,ity in chocolate products is a
desirable consideration from tho cost standpoint of the mimu-
fa,ctured article. If all other factors remain the same, cocoa
butter restriction must be cautiously done else loss of coverage
will result, and, aside from quality, coverage is of prime im-
portance to the mauufacturing confect,ioner. Ilecause of the
fact that chocolate is a niechanicnl mixture of finely divided
materials, the function of cocoa butter is that of wetting the
pariicles. Obviously, the larger the particles the less will be
the quantity of cocoa butt,er required to wet their surfaces.
In the cheaper grades of chocolate therefore we find coarser
milling and, if the manufacture of the product is properly
controlled, a lower total fat content. During the last few
years I have installed small control laboratories in chocolate
plants to enable the manufacturer to gain information on
these points.
Decemher, 1928 INDUSTRIAL AND ENGINEERING CHEMISTRY
The manufacturing processes of these products are largely
mechanical, and have been developed by machinery manu-
facturers. This explains the multiplicity of machinery in
chocolate plants. One wonders just what quality is imparted
to the product by some of these machines, and one never
fmds out, because nobody knows. There is always too much
diversity of opinion to reach a verdict and no well developed
scientific methods of measurement are available. However,
those manufacturers who use the timoestablished methods,
even though they may entail greater manufacturing cost, are
enjoying the greatest volume of business today.
The increasing consumption of cocoa is not due to the
increased consumption of cocoa powder but to the enormous
increase in the consumption of assorted chocolate candies and
chocolate bars. This has brought about a peculiar condition
within the industry-namely, an ever-increasing demand for
cocoa butter, which is used in these products to the extent
of 15 to 20 per cent as added butter, a.nd the elevation of cocoa
butter as the main product in the pressing of cocoa powder,
with cocoa powder now as the by-product. Cocoa pressers
strive for low-fat cake furnishing a greater yield of cocoa but-
ter, and, strangely enough, dietary habits arc demanding
more and more low-fat powders. This increasing demand for
cocoa butter, which is derived only from tlie cacao hean, and
which is the only fat permitted to he used under the law, has
stimulated research in an effort to provide means for the re-
covery of cocoa butter cheaper than by pressure. Several note-
worthy processes have been devised, their chief barrier to suc-
c a s being the small differential between raw material cost
and the cocoa but.ter market, coupled with the fact that cocoa
powder, tlie by-product from pressure, conimands a better
market than do the other by-products. This condition
iiaturnlly reduces the cost of production hy pressure. I,ct
me cite an example. The cocoa butter market is usually
about three times that of the raw bean market. Wit.]] hems
at 12 cents a pound, but,ter will sell at about 36 cents a pound.
Beans contain approximately 42 per cent of cocoa butter.
Then the raw material cost per pound of butter in the raw
beans as delivered is 281/2cents against the 36-cent market for
tlie finished product. Assuming a recovery of 100 per cent
aiid charging against this differential all overhead costs, the
margin is too small to be considered a safe commercial project.
These are economic considerations and should be fully con-
sidered by all those who may bo engaged in work of this
nature. Cocoa waste might be a source of raw material as
it frequently contains from 20 to 30 per cent of cocoa butter.
But a t t.he present time it cannot be obtained iiigood condition
and in sufficient quantities to make i t attractive as a raw
material. However, i t is now being used as a source of theo-
bromine, which in itself has practically no market but may
beconverted into caffeine.
Composition of Cocoa Products
We all consider chocolate as being a food of high value in
the dietary. This is true, as it is rich in fat, starch, and nitro-
gen. We know that it contains proteoses and peptones pro-
duced from the protein during the fermentation of the hean, as
well as alkaloidal nitrogen. Hence we are in error in assuming
that all of the nitrogen is in the form of protein. Some pro-
tein is present, just how much is not definitely known, and
obviously we know very little concerning its nature. Its real
nutritive value will never be known until i t is isolated and
purified and its amino acid make-up determined. D. B.
Jones, of the Bureau of Chemistry arid Soils, who several years
ago undertook a study of this problem, found that the protein
of cocoa was combined with tannin in a form which he could
not extract. This is such a very important matter that I
hope Doctor Joiies will resume his studies on this subject..
We know very little about the chemistry of the alkaloidal
1297
compounds in cocoa. Theobromine and caffeine are both
present, partly in combination and partly free. Some such
combination of the coloring matter exists, hut its real nature
has never been determined. All we know about the aroma
of cocoa is that certain trade practices produce certain results.
There is a great field here in a study of the effectof cultural,
growth upon the aroma of cocoa. Studies of the fermentation
of cocoa will probably continue to be conducted by the English,
as cocoa is a tropical plant and English holdings in the Tropics
render this problem primarily their own.
I must not close without paying tribute to the memhers of
the Food, Drug, and Insecticide Administration who have
performed such valuable service in the development.of analyti-
cal methods of analysis for chocolate products. Chocolate
is an extremely difficult substance to analyze and is becoming
increasingly more difficult from year to year. I consider tlie
Co,urfeip of H w s h r y Chomiarr Co., H e r s h w P o .
Fswre 4--A Battery of ''Cunche" or LonClfudinal Machines
The ''conche" ie L tank of steel or ~ r a n i i cbed upon which grniiiie ~r $tee
rollers run t o end fro. This i.uhbin6. ieclion iinllrrfr flavor, rmoothners. and
a fine finished rppearance to the pmducL. Used lirerly in the mimufeeture
of milk choeoliite.
methods devised by these men and women to he the host
availahle. Naturally, some of these methods have certain
imperfections that will be difficult to overcome. I refer
more particularly to the methods in use for the analysis of
milk chocolate. When they are applied to some of the prepa-
rations found on the market today erroneous conclusions
may easily be drawn. We need a simpler method for judging
the she:l content of cocoa, a colorimetric method for thc
estimation of lactose, and a more reliable method for the
determination of butter fat. When we consider that sucli
products often contain invert sugar, maltose, dextrin, and
small quantities of foreign fats, in addit,ioii to milk solids,
naturally methods for their analyses arc research problems.
The cocoa and chocolate industry is now established as
one of America's great industries, one which statist,ies prove
to he rapidly increasing in importance. I have tried to
point out some of the problems that now confront the indus-
try, the solution of which would do much to stabilize it arid
further its growth. IJntil more scientific data concerning
the chemistry of its prodnct,s are assembled by intensive
research there can be little hope of further technical progress
in its development. It is of sufficient importance as an in-
dustry to warrant the establishment of an institute to con-
duct research on tlie many problems that confront it.
Czechoslovakia Produces Glycerol from Molasses-Czccho-
slovakian raw sugar production in the year ended September,
1928, amounted to 1,253,163 tons, 01 over 200,000 tons morc
than in 1927. Czechoslovakians are producing glycerol from
molasses by fermentation.