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Th e D e Z aan ® Cocoa Manual

COCOA

Th e D e Z a a n ®
Co c oa Ma nua l CANDY &
CONFECTIONERY

BAKING &
CEREALS

BEVERAGES

DAIRY

SNACK FOODS
©2006 ADM Cocoa

All rights reserved. No part of this publication may be reproduced in any


form without written permission from ADM Cocoa BV, Netherlands.

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The De Zaan
®

Cocoa Manual
The De Zaan ® Cocoa Manual

Table o f - Cocoa butter

Cont e n ts
5. Process control 25
- Fluctuating bean characteristics
- Principles of quality assurance
- Good Manufacturing Practices
Module 1 (GMP)
History and Supply of Cocoa - Hazard Analysis Critical Control
Points (HACCP)
1. A brief history of cocoa 9 - Production coding and sampling
- Introduction - Reference samples
- Cortez
- Spread of the cocoa tree
- Main cocoa growing areas Module 3
- Early processing and trade Methods of Analysis
2. Cocoa today 12
- Major cocoa bean producing areas 1. Introduction 29
- Cultivation of cocoa 2. Sampling procedure 29
- Types of beans - Sampling—general
- Harvesting and fermentation - Sampling—bags or FIBCs
- Quality and grading 3. Cocoa liquor/cocoa powder 31
- Physical cocoa versus futures cocoa - Flavor evaluation
- Industry trends - Determination of fat content
3. World demand for cocoa 18 - Determination of pH
- Major cocoa processing countries - Determination of sieve residue
- World’s cocoa products flow - Determination of moisture content
4. Cocoa powder 36
- Visual color evaluation
Module 2 - Instrumental color evaluation
Cocoa Processing 5. Cocoa butter 39
- Refractive index
1. Introduction 21 - Melting point
2. The raw material 21 - Lovibond color
- Standards - Extinction values
- Selection - Saponification value
3. The quality factor 22 - Iodine value by Wijs method
- Definition - Unsaponifiable matter
- Customer requirements - Blue value
4. The production process 23 - Moisture and volatile matter
- Flow sheet - Peroxide value
- Bean blending - Free fatty acid content
- Cleaning, breaking, and winnow- 6. Microbiological 49
ing - Introduction
- Sterilization and alkalization - Sample preparation for total plate
- Roasting count (TPC), molds/yeasts, and
- Nib grinding Enterobacteriaceae
- Cocoa liquor - Determination of total mesophilic
- Pressing aerobe plate count
- Cocoa cake - Determination of mold and
- Cocoa powder

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yeast count - Instrumental color measurement


- Qualitative determination of Module 6
Enterobacteriaceae incl. E. coli Health and Nutritional Aspects
- Determination for presence of 1. Introduction 75
Salmonella 2. Manufacturer’s responsibility 75
3. Indicative nutritional information 75
- Fat (cocoa butter)
Module 4 - Moisture
Flavor and Flavor Development - Proteins
1. Formation of cocoa flavor 55 - Sugar and starch
- Cocoa bean variety - Dietary fiber
- Fermentation and drying - Flavonoids
- Alkalization - Organic acids
- Roasting - Methylxantines
2. Chemistry of roasting 57 - Ash
3. Sensory evaluation of cocoa flavor 60 - Minerals
- Introduction - Vitamins
- Flavor release - Energy
- Appearance, sound, mouthfeel, 4. Cocoa and allergies 82
texture, taste, smell
- Adaptation, synergism, total
impression, judgment Module 7
- Flavor memory Cocoa Liquor
- Sensory evaluation 1. Functionality and attributes of
- Difference (discrimination) tests cocoa liquor 85
- Descriptive tests - Introduction
- Sensory evaluation in the food - Standard of identity
industry - The “personality” of chocolate
- Basic cocoa flavor notes - Cocoa bean selection
- Cocoa off-flavor notes - Processing equipment
- Flavor
- Color
Module 5 - Fat content
Color and Color Development - Fineness
1. Formation of the cocoa color 67 - Free fat
- Precursors of the color component - Maintenance cost
- Alkalization and color - Rheology
development - Microbiology
- Color of cocoa butter - Lipase activity and cocoa liquor
2. Elements of color 69 2. The application of cocoa liquor 94
- The three dimensions of color - Chocolate
- The CIE color coordinates - Other applications
- Color differences 3. Packaging, storage, and
3. Measuring color 71 transportation 95
- The source of light 4. Specification of cocoa liquor 96
- The reflecting surface of the sample
- Color measuring
- Visual judgment of color

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Module 8 - Appearance
Cocoa Butter - External (“dry”) color
- Intrinsic color
1. Functionality and attributes of
cocoa butter 99 - Color matching
- Introduction - Influence of cocoa color on
- Standard of identity the final product
- Flavor - Fat content
- Flavor characteristics - pH and alkalinity
- Flavor stability - Fineness
- Color and opacity - Shell content
- Hardness - Rheology and water absorption
- Tempering—measured by means - Wettability and dispersibility
of a tempermeter 2. The application of cocoa powder 133
- Optimal tempering - Introduction
- Under tempering - Dairy products
- Over tempering - Ice cream and frozen desserts
- Solidification behavior - Bakery products
- Polymorphic crystallization - Confectionery, coatings, and
properties cocoa products
- Influence of the cocoa bean origin - Instant products and premixes
- Influence of alkalization 3. Packaging, storage, and
transportation 137
- Influence of deodorization
- Packaging
- Contraction
- Coding
- Rheology
- Transport and storage
- Gloss and shelf-life stability
- Packaging reduction
2. The application of cocoa butter 116
- Bulk and semi-bulk packaging
- Chocolate production
4. Specification of cocoa powder 140
- Confectionery fillings
- Introduction
- Other applications
- Controllable and non-controllable
3. Packaging, storage, and
transportation 117 factors
4. Specification of cocoa butter 119 - Food safety aspects
- Impurities
- Metallic iron
Module 9 - Pesticides
Cocoa Powder - Heavy metals
- Mycotoxins
1. Functionality and attributes of - Specification components
cocoa powder 121
- Flavor and color
- Introduction
- Fat content
- Standard of identity
- pH
- Flavor
- Fineness
- Range of cocoa flavors
- Moisture content
- Flavor and consistency
- Microbiological characteristics
- Guidance on tasting
- Fumigation or irradiation
- Color
- The color essential

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Bibliography 144

The ADM Cocoa Organization 150

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History and Supply of Cocoa


1
1. A brief history Cortez
of cocoa In 1519, Cortez arrived in Mexico and met
Montezuma II, a most significant patron
Introduction of cocoa. Because of the Aztecs’ belief that
Throughout history, many discoveries’ Cortez was the reincarnation of their God
future significance to man was never fully Quetzalcoatl, he was showered with gifts
appreciated at the time. The cocoa bean is and honors, including cocoa beans. The
such a discovery. Now used for a wide tributes requested by Montezuma from
range of foods and delicacies, the cocoa his subject people were in part taken in
bean enriches the lives of us all. the form of supplies of cocoa beans. The
The first time that people far from the cocoa beans were then consumed pri-
areas of its origin were confronted with marily in the form of a drink known as
the cocoa bean was thanks to Columbus. xocolatl, the Aztec name for the bitter
On his fourth voyage to America, he stimulant. Its name would later be
reportedly discovered a canoe off the applied to all products, drinkable or solid,
Yucatan Peninsula laden with fruit and that were made from the cocoa bean. It is
cocoa beans. But it was only years later at a word that perhaps has the remarkable
the beginning of the 16th century that distinction of being one of the first ever to
Cortez confirmed the remarkable value be adopted from one language and then
assigned to the cocoa beans. He found applied on a truly global scale.
that the Aztecs valued them so much that Recipes for xocolatl were rarely record-
they used them both as means of pay- ed and probably varied by location. The
ment and as the source of a beverage beans would have first been collected, left
drunk at court and religious ceremonies. to ferment naturally, sun dried, roasted in
Little is known as to how the bean earthen pots, and deshelled by hand. The
came to take on such a powerful role. One kernels were then ground on a slightly
can surmise that the realization of its concave stone called a metate using a
potential occurred in much the same way cylindrical grinder. At this point, spices
as wine. That is to say, a natural product and herbs of various kinds, including
was accidentally left in storage and sub- vanilla, might have been added to
jected to the forces of nature, and a series improve the taste. The resulting paste was
of chance events then led to the discovery then formed into cakes to cool and
of its potential. harden. For consumption, the cakes
Although its exact origins are not would be broken up, dissolved in water,
known, the Cacao tree was then exclusive and beaten to a foamy consistency.
to the Americas. The closest estimates put The attraction of this bitter drink clearly
the area of origin in and around the val- lay in the physiological effects it offered
leys of the Amazon and Orinoco Rivers. the drinker, many of which are still not
High ambient temperatures were clearly clearly explained. The fact that cocoa is
necessary for the development of the chemically very complex and that many
bean. Evidence suggests that the tree has of its components have not been fully
been cultivated for more than 3,000 years. identified confirms the complexity of this
natural bean’s biochemistry. Its stimu-

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lating effects certainly offer clear reason dependence on a single source of the
for its traditional use in medicine. (See bean. Cultivation across all of their colo-
also: Module 6: Health and Nutritional nized territories was encouraged, not
Aspects). without frustration, as the cocoa trees
were strangely susceptible
to disease. In 1525, for
example, the Spaniards
transplanted one of the
main types of cocoa beans
from Mexico to Trinidad,
where it flourished until
being completely wiped
out in an epidemic.
Over time, the cocoa tree
was planted throughout
many islands and coun-
tries of the Caribbean and
later to other continents,
all areas that offered the
ideal climatic and soil
conditions for successful
cultivation.
The popularity of the
cocoa drink at the Spanish
royal court was such that
still in the 16th century,
cocoa was declared a state
secret by decree from
King Charles V of Spain.
Cocoa was to remain a
Spanish possession.
Cortez was instructed
never to divulge its origin.
Though it was actually
known to people other
than the Spanish, no one
invested the effort to
Cocoa tree with ripe fruit
research it further. The secrets of cocoa
took almost 140 years to filter out of
Spread of the cocoa tree Spain. Eventually, through a diplomat, the
As the first main colonizing power, it was secret passed into Italy, then to Austria
the Spaniards who ruled in this region of and France, and on to northern Europe,
the Americas. The popularity of the bean where the Dutch encouraged and later
conquered the court of Spain. As imports came to dominate cocoa trade.
grew, although only under close and By the end of the 17th century, drinking
direct supervision of the Spanish royal cocoa had become so popular in Europe
court, attempts were initiated to reduce that it was serving as a source of tax

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revenue for governments, a sure sign that fraction (cocoa butter) and a partially
consumption was spreading beyond the defatted fraction (cocoa cake or powder).
small elitist groups that initiated its Another process developed by van
success. Houten was alkalization, or the “Dutch
The Food of the Gods, or Theobroma process,” a procedure of treating cocoa
cacao L., as it is known by its scientific with alkali. This was originally done in
classification, would become one of the order to improve the solubility. It was
world’s great commodities. found that at the same time, taste and
color were also changed.
Main cocoa growing areas Some years later, cocoa butter would
The spread of the cocoa bean across the come into its own: Originally used as a
world was a long and frequently inter- simple household fat, it would pave the
rupted journey. Pests and disease frus- way for the creation of chocolate.
trated many attempts to transplant the In 1847, an important discovery was
tree. Its successful cultivation required made by John Fry in England. By adding
specific climatic conditions. The tree first cocoa butter to a mixture of liquor and
spread out in regions close to its origins, sugar, chocolate was created, one of the
from Brazil and Mexico in the 15th century confectionery industry’s greatest discover-
across Central America and the Caribbean ies. This is not only an easily handled
islands in the 16th. By 1560, the Spaniards product, but it is solid at room tempera-
had introduced it to some of the Indo- ture and melts just below body tempera-
nesian islands. They brought the bean to ture. Thus, it is a product that, when
the West African island of Fernando Po, eaten, releases its flavors in an optimal
where it was later transferred to the main- manner.
land. The great growth of cocoa trade in Meanwhile, cocoa powders with differ-
the 19th century saw its expansion across ent tastes and colors became widely used
many other countries, especially in West as flavors and color ingredients in the
Africa and Southeast Asia. food industry.

Early processing and trade


The Dutch were the first to actively trade
the commodity and, until the 18th cen-
tury, dominated the world trade in cocoa.
Because of this, the Dutch also became
more involved in research into cocoa
processing. In the 16th and 17th centuries,
most processing was in the hands of the
Spanish, even though they bought most
of their beans from Amsterdam or the
Dutch port of Zeeland.
Cocoa processing developed during the
18th century in the Netherlands. In 1825,
to reduce the fattiness of the chocolate
drink, Coenraad Johannes van Houten
developed a mechanical pressing process
to fractionate the cocoa liquor, the result
of grinding the roasted beans into a fatty

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Major Cocoa Bean Producing Areas (x 1,000 MT and %)


1980/1 1990/1 2000/1 2002/3 2003/4

Africa 1,010 59 1,418 57 1,948 68 2,229 70 2,544 72

Central/South America 542 32 613 24 369 13 372 12 405 11

West Indies 47 3 51 2 54 2 56 2 57 2

Asia & Oceania 97 6 424 17 487 17 510 16 511 15

Total world production 1,696 2,506 2,858 3,167 3,517

Source: International Cocoa Organization

2. Cocoa today the tree at all seasons of the year, although


typically two crops are harvested each year.
Cultivation of cocoa The fruits grow directly from the trunk
The successful cultivation of cocoa of the tree and the thicker branches.
requires a special climate that is mostly While there may be several thousand
found within the area bounded by the flowers on a mature tree, only a small
Tropics of Cancer and Capricorn. The number matures into fruits or pods. These
majority of the world’s crop is now grown take some six months to grow from a
within 10° North and South of the equa- fertilized flower, measure 10-15 cm at the
tor. It will grow from sea level up to a center, and are 15-25 cm long. The pod
maximum of some 1,000 meters, although contains some 40 seeds or beans. After
most of the world’s crop grows at an alti- fermentation and drying, one pod pro-
tude of less than 300 meters. Tempera- duces some 40 g of beans, one bean typi-
tures must generally lie within the band cally weighing around 1 gram.
of 18°-30° C (65°-86° F). Rainfall must be Yields per hectare have risen over time
well distributed across the year, with a from around 350 kg to more than 1,500 kg
minimum of 1,000 mm. The trees must be on the most efficient farms. Today, cocoa
protected from strong winds (the root trees are cultivated in more than
system is not robust); soils must be well 40 countries around the world, across an
aerated, and pests and diseases must be estimated area of 3.6 million hectares,
carefully controlled. producing an annual crop of more than
The original cocoa tree grew to a height 3.0 million tons of dried beans ready for
of ±10 meters at maturity and preferred processing.
the shade of other larger trees. Modern
breeding methods have led to the devel-
opment of trees of a standard ±3 meters
tall to allow for easy hand harvesting.
Certain cocoa trees become productive
in three to four years, while in the past six
to seven years was common. When the
evergreen cocoa tree reaches its bearing
age, flowers and fruits begin to appear in
modest amounts. These can be found on

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Criollo is known for its flavor characteris-


tics, while the Forastero plant is known
for its ability to withstand more severe
climatic conditions. But it would be
wrong to claim that certain natural vari-
eties of cocoa are better than others. Each
has its own specific chemical and physical
characteristics that are taken into careful
consideration when beans are blended.
The ultimate quality of cocoa, whatever
its origin, is significantly affected by
weather conditions during growing, soil
status, fermentation, and drying. Storage
conditions are also important in pre-
venting deterioration of the quality.

Harvesting and fermentation


Although nearly 500 years have passed
since Cortez first witnessed the making
of hot cocoa by the Aztecs, the basic
methodology for processing cocoa beans
has remained much the same. While a
vast amount of research has been under-
taken to speed up the cocoa bean fermen-
tation process, there has been little suc-
cess. Clearly, the different stages of fer-
mentation are essential in the creation of
the complex organic components essential
to the final taste and enjoyment of cocoa.
The pods grow directly from the trunk
of the tree. Mostly they are harvested by
A cocoa pod contains some 40 seeds. hand using long-handled knives and bro-
ken open to reveal the beans and the
Types of beans
white pulp surrounding them. Beans are
Typical attributes of the bean, such as
then extracted and directly subjected to
bean size, flavor, color, and chemical com-
fermentation.
position of the fat, vary considerably in
The traditional process in West Africa,
beans of different origins. There are two
the world’s largest cocoa growing area, is
main types of cocoa bean: Criollo and
simple: Farmers place the pulp-covered
Forastero. Criollos are light colored with a
beans on the ground, cover them with
mild, nutty character. Forastero cocoas are
layers of leaves (often banana), and allow
dark brown, strongly flavored, slightly
the heap to remain for four to seven days,
bitter, and have a higher fat content. The
depending on the variety of the bean. It is
greater part of the world’s cocoa crop con-
preferable to mix the heap every two days
sists of the Forastero type, more specifi-
so that the bean mix ferments evenly. The
cally a sub-type known as Amelonado.
fermentation is critical for the future
Parts of Ecuador boast a very specific type
development of color and flavor of the
of cocoa, Cacao Nacional or Arriba. The

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cocoa, although there are still many cover in Brazil and Malaysia, other tech-
unknowns as to the exact processes occur- niques are more popular. In Brazil the
ring. Development of aroma precursors is beans are typically laid out on broad mats
essential to the eventual creation of on stilts above ground level to dry. In the
flavors. event of rain, a roof can be slid across the
A more industrial fermentation uses mats, and hot air is used to dry them. In
three to five stepwise-positioned boxes: Malaysia widespread use is made of
the highest box is filled with pulp-cov- mechanical rotary driers. After drying, the
ered beans, and after one to two days the beans are bagged and made ready for
content is mixed and transferred to the transport to buying stations and regional
lower box, a process which is repeated warehouses.
until the lowest box is reached. In four to
six days, this box fermentation can reach Quality and grading
the result of the traditional heap process. Cocoa is a natural product and suffers all
After the fermentation process is com- the risks inherent to that. The flower is
pleted, during which the white pulp is very susceptible to rain and temperature
totally degraded, the cocoa beans have to conditions during its development. The
be dried. In Africa the traditional method pod can be attacked by a variety of molds,
is to spread the beans out on mats or in insects, and rodents, and the shell may be
trays in the open air to dry in the sun. contaminated microbiologically.
Because of the high rainfall and cloud The quality of beans is assessed under

Fermentation of beans under banana leaves

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Drying of cocoa beans on mats

various headings: created during fermentation or improper


• degree of fermentation drying. Off-flavors can also be caused by
• number of defects the proximity of another strong-smelling
• number of broken beans product during storage and shipping.
• bean count (number per 100 g) The yield of a consignment of cocoa
• flavor beans is the usable proportion—the cocoa
• color nib. Bean size is important because small
• fat content beans have a proportionately lower
• fat quality amount of nib and a higher shell content,
• shell content neither conducive to a good yield. Beans
• moisture content should also be uniform in size because
• uniformity variable-sized beans are harder to break
• insect and rodent infestation and deshell. The shell percentage is
The bean cut test is used to evaluate dependent on the type of bean. Asian
defects and the degree of fermentation. beans typically have a higher shell con-
(See also Module 4: Flavor and Flavor tent than African beans. Shells should be
Development.) whole but loose. The higher the moisture
A key criterion is flavor. An expert content, the higher the chances of mold
panel grades a consignment, seeking to development. The fat content, the amount
identify off-flavors. This depends on the of foreign matter, broken beans, insect
type of bean and its handling. Moldy off- damage, and other such factors may
flavors come from molds; smoky taints negatively influence the true value of the
may come about during drying; acidic beans for the user.
off-flavors are due to excessive acid

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Cocoa beans vary in size, shape, color, and other features.


The cocoa butter should be low in free Sales are made to licensed traders and
fatty acids and show specific melting and cocoa merchants or directly to cocoa
solidification characteristics. processors. Cocoa brokers can be interme-
Good cocoa beans should be well fer- diaries who have expertise on crops and
mented, dry, and free from abnormal trade and who advise and act for both
odors and adulteration. The beans should buyers and sellers.
be reasonably uniform in size; reasonably
free from broken beans, fragments, and Physical cocoa versus cocoa futures
pieces of shell; and free of foreign matter. Physical cocoa is real cocoa, bought and
In the past, cocoa bean marketing in sold according to its actual quality, ton-
origin countries was mainly government nage, delivery time, place, and price.
controlled (purchasing from farmers, Cocoa traded on the terminal or futures
selling, and setting prices), but today free market is paper cocoa, traded according
marketing systems more often prevail. to a uniform description and lot tonnages,
When the beans are grown on very with price and delivery period as the only
small farms, the collection, grading, and variables.
financing of the crop can be rather com- In West Africa cocoa is traded through
plex. At the buying station, a farmer’s government-controlled marketing boards
crop is weighed, inspected, and paid the (Ghana) as well as by local exporters and
current market (or government set) price. cocoa processors (Ivory Coast, Cameroon,
Price discounts/premiums can be made and Nigeria), where the cocoa trade has
for poor/good quality. From the buying been privatized and deregulated. The
stations, the cocoa beans are collected and level of trade regulations and taxes levied
finally arrive at the nearest port of on cocoa usually reflects the importance
embarkation or are delivered to local of cocoa for the national economy. By and
processing plants. large, foreign ownership of cocoa farms in

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West Africa is not allowed. Industry trends


In other major producing areas, such Bulk shipment of cocoa beans has made
as Central and South America and Asia, its entrance in Europe since 1995. Instead
cocoa is freely traded and exported. of receiving the beans in traditional jute
Cocoa does not play as dominant a role bags, cocoa may now be shipped to a
in these economies. Farming in some large extent in bulk in containers or
countries like Brazil and Malaysia is done directly in vessel holds. New handling
on a much larger scale than in Africa technology, as well as innovative quality
or Indonesia. control procedures, were developed and
With more than 3.0 million tons con- implemented both at the loading and
sumed annually (2002/2003), cocoa beans discharging points, leading to a highly
are today a major commodity. The main efficient bulk transportation system.
cocoa exchanges are London and New In the countries of origin, there is a sus-
York. The physical traders of cocoa are tained trend to grind a larger part of their
located in many other cities such as cocoa bean output into semi-finished
Amsterdam, Geneva, Hamburg, London, products like cocoa liquor, butter, and
Paris, Kuala Lumpur, Philadelphia, San powder.
Salvador, and Singapore. Liberalization of the cocoa trade and
As a commodity exposed to oversupply industry in the countries of origin,
by bumper harvests, or to shortage notably those in West Africa, will con-
caused by weather or disease, the price tinue, resulting in greater transparency
of cocoa naturally varies. As with other of the cocoa trade, while various bean
commodities, the futures market allows grading systems control the quality of the
manufacturers to purchase for future beans shipped to the consuming
requirements at a known price. In that countries.
way, the prices of beans and intermediate
products are based on the market’s per-
ception of the current and future supply
and demand. Everyone can see what is
happening. Cocoa is thus traded openly.
Terminal prices, however, do not neces-
sarily reflect the values of the specific
types of beans. Each cocoa bean origin
will have its own price, selling at a
premium above the terminal price or at
a discount below it. This is because the
market recognizes that each bean origin
has a particular demand due to its spe-
cific characteristics, such as flavor, color,
and cocoa butter properties. These dis-
tinct characteristics can play a significant
role in the pricing.
Major ports of entry are Amsterdam,
Philadelphia, and Hamburg. Amsterdam
receives more than 600,000 tons of cocoa
beans annually, about 20% of the world
crop.

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Major Cocoa Processing Countries (based on bean grind)


(x 1,000 MT and %)
1980/1 1990/1 2000/1 2002/3 2003/4

Netherlands 140 9 268 12 452 15 450 15 445 14

USA 186 12 268 12 456 15 410 13 410 13

Germany 180 12 294 13 227 7 193 6 225 7

Ivory Coast 60 4 118 5 285 9 300 10 320 10

United Kingdom 80 5 145 6 151 5 133 4 130 4

France 48 3 71 3 145 5 145 5 150 5

Malaysia 7 - 78 3 125 4 135 4 200 6

Former USSR 114 7 83 4 102 3 85 3 85 3

Indonesia 13 1 32 1 87 3 115 4 120 4

Others 730 47 974 41 1,033 34 1,088 36 1,121 34

Total world grindings 1,558 2,331 3,063 3,054 3,206

Source: International Cocoa Organization

3. World demand World’s cocoa products flow


for cocoa Three products—cocoa liquor (also called
cocoa paste or cocoa mass), cocoa butter,
Major cocoa processing countries and cocoa powder—are initially made
The world demand for cocoa beans, sup- from cocoa beans. Combining cocoa
ported by relatively low cocoa prices, has liquor and cocoa butter creates chocolate.
steadily increased over recent decades as All beans, after having been cleaned,
a direct result of increased world demand deshelled, roasted, and ground, are first
for chocolate and chocolate-flavored processed into cocoa liquor. Any change
products. On the other hand, because in the supply position of one product has
cocoa is an agricultural product subject to an effect on the availability of the others.
the influences of nature, the supply fluc- For example, in the case of an increase
tuates from year to year. in chocolate consumption, a larger quan-
The bean grinding quantities do not tity of liquor and butter will be required
indicate what is actually made from to satisfy that increase in demand.
cocoa. For example, in the Netherlands, Consequently, a larger volume of cocoa
the world’s largest cocoa bean processor, powder will become available to the
almost the entire quantity of beans is market, which may not necessarily coin-
processed by the cocoa press industry cide with a simultaneous increase in the
into intermediate cocoa products rather demand for cocoa powder.
than directly into chocolate.

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Diagram of World’s Cocoa Products Flow

Cocoa powder
900

Cocoa
butter
Cocoa Cocoa PRESS INDUSTRY 700
beans nibs Cocoa liquor Chocolate

3,100 2,500 1,600 4,400


(estimate)

CHOCOLATE INDUSTRY
Cocoa liquor
900

Shell Sugar
600

Milk

It is estimated that some 65% of the up to 5% of six specific vegetable fats


world grind is pressed into about 55% of other than cocoa butter to be used in
cake (powder) and about 45% of butter. chocolate; this substitution has a quantita-
The other 35% is processed into cocoa tive and adverse effect on the supply and
liquor and almost entirely used directly demand positions of cocoa butter and
for the manufacture of chocolate. cocoa powder.
This interlocking relationship between The price of cocoa butter relative to the
liquor, butter, and powder not only has a cocoa bean also remains under pressure.
direct influence on their physical supply Whatever the extent of the individual
and demand positions, but also on their effects of these two aspects, the combina-
relative pricing against the raw material: tion causes an imbalance in the product
the cocoa bean. flow. As no cocoa butter can be made
This book basically deals with the func- without obtaining a similar quantity of
tional aspects of the three intermediate cocoa powder (and vice versa), an adjust-
products (cocoa liquor, cocoa butter, and ment will then clearly have to occur. This
cocoa powder) in their respective applica- can be quantitative (less butter produced
tions. To dwell extensively on issues of leads to less powder available), by means
commercial or legislative considerations of a price adjustment (a lower butter price
would go beyond its purpose. must lead to a higher powder price), or
Worth mentioning though, is the new through a combination thereof. Competi-
Cocoa and Chocolate Directive of the tive market forces, as usual, will ulti-
European Union (2000/36/EC), allowing mately lead to the most practical solution.

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The De Zaan ® Cocoa Manual

Cocoa Processing
2
1. Introduction 2. The raw material
Module 1: History and Supply of Cocoa Standards
gives a brief account as to where and how Certainly the condition of the starting
cocoa is grown, harvested, and shipped material, the cocoa bean, determines the
from the major cocoa growing areas. In ultimate characteristics of the end prod-
this module, we deal with cocoa pro- ucts. Close scrutiny of the raw material is
cessing into the three products that are essential, and several aspects have to be
highlighted in this book: cocoa liquor, taken into account.
cocoa butter, and cocoa powder. Cocoa is traded on terminal markets
As the prime purpose of The De Zaan® around the world, and standard contracts
Cocoa Manual is to be a practical guide to define a number of quality requirements.
the user of cocoa products, this module An average shipment of cocoa should
focuses on those elements of the produc- comply with the following:
tion process most likely to be relevant to • Fermentation - adequately fermented
users of such products. For them it is (if fermented)
important to know what stages of the • Foreign matter - nil
process are critical in view of the key • Waste - < 2%
features of the cocoa products that they • Moisture content - < 7.5%
buy as ingredients for application in • Smoky or foreign odors - absent
their products. • Bean size uniformity - reasonably
Basically the principle of processing uniform
cocoa beans into cocoa products has not • Packing weight, bag quality, and
changed in the past 150 years. Today, the marking - should be as defined
beans are still cleaned, deshelled, roasted, (if applicable)
and sometimes alkalized, then ground These standard characteristics, applied
into cocoa liquor, which is subsequently in the various grading systems in the
pressed into butter and cake. Finally, the countries of origin, are generally limited
cake is pulverized into powder. Of course, to those that can be observed by the eye
over time mechanical efficiency and the or nose (insect infestation, mold, slatiness,
quality and risk management have vastly violet beans, flat beans, off-flavors) and to
improved. Particularly the knowledge characteristics that can be defined with
and expertise with regard to controlling simple equipment (number of beans per
the intrinsic potential of the raw material 100 g, moisture content).
have expanded significantly in the past For the cocoa processing industry, other
decades. Like many other food processing characteristics have to be taken into
industries, cocoa product manufacturing account. A distinction must be made
has also become a highly automated, between those characteristics of signifi-
capital intensive, high-tech industry. cance to quantity or yield, like percentage
Before describing the basic features of of shell, moisture, and fat, and character-
cocoa processing, however, the role of the istics that are significant to the quality of
raw material in that process must first be the products finally obtained from the
discussed. beans. For cocoa butter, for example, the
free fatty acids and the triglyceride com-

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position of the fat present in the bean are many individuals of an organization, the
of great importance. For liquor and pow- disciplined management of quality stan-
der, the flavor and color potential are dards is essential.
essential.
Once released from the pod, cocoa Customer requirements
beans are subjected to a spontaneous fer- ADM Cocoa concentrates on the specific
mentation process, causing a bacterial wishes of its industrial customers. Our
load to build up. Subsequent drying of standards and internal control procedures
the beans does not lead to a microbial are upgraded and adapted constantly,
improvement, and some bacteria are acti- bearing in mind the given, unavoidable,
vated to form spores. The fermentation natural variability of an agricultural
and drying processes usually take place commodity.
in the open air on the farms. In the manufacturing world, the con-
During harvesting, post-harvesting, and cept of quality has long been understood
collection, the beans, like any agricultural and defined as the way a physical prod-
commodity, are subject to contamination uct compared to some defined ideal.
with filth and foreign matter. Close to the ideal, the quality of a product
or service was considered good; below
Selection the ideal, then quality was poor. Quality
Whenever possible, bean parcels are tended to be restricted solely to physical
selected and analyzed by ADM Cocoa attributes.
prior to shipment from the country of ori- However, today the concept of quality
gin. This is of particular importance in has expanded to mean the way a product
respect to bulk shipment of cocoa, which or service responds to the expectations of
today is more and more the standard clients, not only in terms of product safe-
method of bean transportation. ty and attributes but also in such areas as
The importance of bean selection with delivery reliability, after-sales service,
regard to the ultimately desired flavor user support, and, of course, overall
profile of cocoa liquor, as well as the fur- value. This extension of the meaning of
ther development of color and flavor quality has brought changes within food
during the alkalization step in the manu- manufacturing organizations. Not only
facture of cocoa powder, is discussed in are all departments involved; every indi-
Module 4: Flavor and Flavor Devel- vidual employee is involved as well. The
opment and in Module 5: Color and Color concept of the quality factor today is
Development. how an organization like ADM Cocoa is
able to respond in full to customer
demands.
3. The quality factor ADM Cocoa realizes that just like its
Definition own business, the businesses of its cus-
At ADM Cocoa, we have defined our pur- tomers are constantly evolving. To main-
pose as: to supply cocoa products, consis- tain its position of leadership in the sup-
tent in their attributes, based on mutually ply of cocoa ingredients, ADM Cocoa
defined functional specifications with takes customers’ current and anticipated
accompanying services to the worldwide requirements into account, whereby cus-
market at competitive prices. Because tomers are:
quality is subject to individual judgment, • creating more new products with
covers many disciplines, and involves cocoa ingredients

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• requesting more data on the proper- 4. The production


ties and applications of products
• becoming more critical, asking for
process
ever-stricter product consistency Flow sheet
• asking for more non-material added Cocoa processing at ADM Cocoa is
value, which means attention, service, described in the simplified diagram
and followup below. The various production steps and
• asking for support in rationalizing the critical control points are then discussed.
number of cocoa products required
for their growing businesses Bean blending
• becoming oriented toward keeping On the basis of the analysis of the individ-
low stocks, demanding speedy and ual bean lots, an optimal blend is pre-
flexible just in time deliveries pared. In this way, fluctuating characteris-
• trying to eliminate dependence on tics can be reduced or evened out before
product inspection of incoming the beans are further processed. An alter-
materials nate approach is to process specific lots of
In practice, this often means that identi- beans and blend the resulting cocoa
fying particular requirements, be it on liquors.
product specifications or any other aspect,
becomes a matter of close cooperation Cleaning, breaking, and winnowing
with the customer that ultimately leads to The actual production process starts with
jointly defining these requirements. the following three steps: cleaning,
breaking, and
Production Flow Sheet winnowing. Their
objective is to obtain
clean, broken,
deshelled kernels.
These kernels must
Beans Pre-
cleaning

be as uniform in size
as possible in order
Storage Pressing

to achieve constant
quality.
Blending

First, the beans are


(optional) Cake Butter

Breaking & Breaking Filtering


sieved, and foreign
matter such as
Nibs
winnowing

bamboo, twigs,
string, stones, and
Sterilization Cake Deodorization
blending (optional)

magnetic materials is
removed. The clean
Alkalizing Pulverization

beans are then


(optional)

broken to loosen the


Roasting Cooling Blending

shells from the nibs.


The breaking
process takes place
Liquor Liquor Packaging
grinding

in multiple steps to
avoid an excess of
Liquor Powder Butter fine particles. After

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the breaking step, the product is sieved important to the final flavor because the
into a number of fractions to reach opti- nib’s flavor is formed from the precursors
mal separation during winnowing. that developed during fermentation.
These fractions then go to the winn- (See Module 4: Flavor and Flavor
owing cabinets where the “lighter,” bro- Development). Roasting temperatures
ken shell is removed by a stream of air. range from 95-145° C (200-295° F)
The breaking and winnowing steps sepa- depending on the process, equipment,
rate the essential ingredient of the cocoa type of nib processed, and the end
bean, the kernel, most often described as product required.
the nib, from its shell. Strong magnets Exposure of the nib to such tempera-
remove magnetic foreign matter from the tures during roasting causes an additional
nib. The nib may then be stored, awaiting reduction in the number of microorgan-
further processing. The separated shell is isms. A low level of those organisms after
often sold to agricultural mulch or sterilization and roasting is essential for
fertilizer producers. ultimately obtaining excellent food-grade
products (cocoa powder, butter, and
Sterilization and alkalization liquor) with stringent microbiological
The microbiologically contaminated nib specifications.
is sterilized in a batch or a continuous ADM Cocoa does not carry out post-
process by wetting and heating with process sterilization by means of fumiga-
steam: the Total Plate Count (TPC) is nor- tion or irradiation at the end of the pro-
mally reduced to less than 500 per gram, duction process, as post-process steriliza-
and all pathogenic bacteria are killed. tion often serves to hide poor hygienic
After sterilization, the nib can be roasted process conditions and contamination
directly (natural process) or can be alka- with foreign matter, which is not elimin-
lized first (Dutch process). ated by post-process sterilization. Further
Alkalizing or Dutching consists of fumigation may leave toxic residues, and
treating the cocoa nibs with an alkali solu- irradiation may cause an undesired
tion such as potassium carbonate. It is change in the flavor (oxidation).
practiced primarily to modify the color
and flavor of cocoa powder or cocoa Nib grinding
liquor; for the effects of alkalization on The roasted nib is typically ground in a
the formation of flavor and color of cocoa multi-stage process. During grinding, the
products, see Module 4 and Module 5. broken kernels change from a solid to a
Alkalization can be conducted at vari- fluid mass of cocoa particles suspended in
ous points in the production process. cocoa butter. This is due to the high fat
Depending on the stage at which alkaliza- content of the bean: About half of the nib
tion takes place, different results will be is fat. Grinding breaks up the cell struc-
obtained. Nib alkalization is often ture of the cocoa nibs and releases the
preferred, as it combines optimal flavor cocoa butter.
and color development with minimal
alkali usage. Cocoa liquor
After the last stage of the grinding
Roasting process, the mass is passed through sieves
The roasting process has the objectives of and over strong magnets to remove any
reducing the water content and further remaining coarse cocoa or metal particles.
developing flavor. Roasting is particularly This finely ground fluid mass, the cocoa

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liquor, can either be stored in tanks to Cocoa butter


await pressing, or it can be shipped and The cocoa butter from the presses is fil-
used by chocolate manufacturers for tered and stored. Upon request, the butter
further processing into chocolate. can be partly or wholly deodorized.
Delivery of the various types of cocoa
Pressing butter can be either in liquid form or in
Cocoa butter constitutes about half the solid form (plastic-lined cardboard
weight of the cocoa nib. This fat is par- boxes).
tially removed from the cocoa liquor by Storage and packaging of cocoa prod-
means of hydraulic presses applying pres- ucts are discussed further in Modules 7-9
sures as high as 450 kg/cm2. Depending for Cocoa Liquor, Cocoa Butter, and
upon the pressing time and the setting of Cocoa Powder.
the press, the resulting cakes may have a
fat content of 10 to 24%.
5. Process control
Cocoa cake Fluctuating bean characteristics
After pressing, the cakes are broken into Cocoa is a natural product with consider-
kibbled cake. The pressing operation is able quality variations from year to year,
microbiologically vulnerable, as this is the from country to country, and from lot to
only part of the process when the product lot. Sometimes certain types of cocoa may
is not in a closed system and is thus not be available at all. As customers
exposed to the surroundings. Hygienic expect to receive a consistent final prod-
procedures are therefore of particular uct, fluctuation of quality characteristics
importance in the pressing department. of our end-products has to be eliminated
Kibbled cake is typically stored by fat or reduced. So the bean mix and the pro-
content and degree of alkalization and cessing conditions can be adapted based
may be blended before pulverization to on experience, technological expertise,
obtain the desired type of cocoa powder. and knowledge of the properties of the
The cocoa butter is filtered and stored raw material.
in tanks. Therefore, the critical points in pro-
cessing of cocoa beans into wholesome,
Cocoa powder safe, and consistent cocoa ingredients are:
The powder grinding lines, usually ham- • the quality of the cocoa beans; they
mer-and-disc or pin mills, pulverize cocoa should be at least well-fermented and
cake particles into the defined fineness clean.
levels. After pulverization, the powder is • the production process; the process
cooled so that the fat of the cocoa powder must be carried out according to the
crystallizes into its stable form. This pre- specified norms, with strict hygienic
vents any discoloring (fat bloom) and standards.
lump forming in the bags later, a phe- Assessing the quality of the cocoa beans
nomenon that is caused by insufficient has been described on page 21 under
crystallization of the fat at the moment of “The raw material.” Further in the
filling. Next, the free-flowing powder is process, the roasting and alkalization
passed through sieves and over magnets stages can be adapted to the specific char-
prior to packing in paper bags or in bulk acteristics of the particular cocoa bean
containers. mix. In Module 7 and Module 9, the influ-
ence of these stages of the production

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process with respect to the desired flavor Hazard Analysis and Critical Control
and color development of cocoa liquor Points (HACCP)
and cocoa powder is extensively discussed. Later, the concept of Hazard Analysis and
Variations, for example in color, flavor, Critical Control Points (HACCP) was
and pH of cocoa powder, can be reduced. developed, a comprehensive, step-by-step
Blending of different cocoa cakes or pow- quality assurance program. This goes
ders may control the characteristics of the beyond the hygienic aspects of quality
resultant cocoa powder. In this way, assurance and is a step-by-step outline for
ADM Cocoa is able to supply each type the entire production process. Assess-
of cocoa powder within the specifications, ments of hazards associated with raw
every time. materials, processing, and transport are
made.
Principles of quality assurance At ADM Cocoa, the microbiological,
Part of ADM Cocoa’s quality assurance is chemical, and physical influences of the
based on supplying the necessary infor- processing are considered in relation to
mation regarding the production process food safety and quality. After hazard
and the way in which quality control is assessment, the Critical Control Points
achieved. (CCPs) required to control the identified
One of the most important objectives of hazards are determined. For each CCP,
ADM Cocoa is to transform the naturally critical limits, procedures for monitoring,
fermented cocoa beans into wholesome and corrective actions in case of devia-
cocoa products with suitable bacteriologi- tions are established and continuously
cal specifications. To this end, bean qual- monitored.
ity is constantly being assessed and Within HACCP special attention is
controlled. given to prevention of contamination
with Salmonella after the roasting process.
Good Manufacturing Practices (GMP) The International Confectionery
Although the influence of the raw cocoa Association (ICA) offers the industry a
beans as a source of contamination is code of hygienic practice based on
greatly diminished by the procedure HACCP for the prevention of Salmonella
described above, it is essential to prevent contamination in cocoa, chocolate, and
contamination after the roasting step. For confectionery products.
this reason, processing in accordance with
the principles of Good Manufacturing Production coding and sampling
Practices (GMP) is indispensable. ADM Cocoa’s production is planned
These rules are of a preventative nature: according to deliveries defined as a
They rely not so much on the checking of quantity of product that possesses a high
the finished product but concentrate degree of homogeneity because it is made
efforts on the production process itself. at the same production unit without
They call for careful processing and use of significant changes in process conditions
specific checks throughout the production and raw material composition. Such
process. This principle was introduced by a delivery may consist of several
the Food and Drug Administration in the homogeneous batches.
USA and adopted by the Codex (Code of Each delivery is given a unique lot
Practice from 1997) and by the European identification code that is printed on the
Union (Directive 93/43/EEG). individual packing or, in the case of liq-
uid, tank car shipments, indicated on the

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accompanying documents. Traceability


for packaging (bag or carton) is obtained
with a production code.
When the food manufacturer wishes to
control incoming ingredients, e.g. cocoa
products, it is important to ensure that
representative samples are taken and
examined. It is essential that the manufac-
turer of the ingredient is able to demon-
strate the homogeneity of the delivered
quantity. With this in mind, ADM Cocoa
welcomes its customers to audit its
production facilities in order to assess
the confidence that can be placed in the
adopted control systems, procedures,
standards, and norms.
If the homogeneity of incoming ship-
ments can be assured, then a somewhat
simplified random check can be used on
the incoming lots. See also the sampling
procedure described in Module 3:
Methods of Analysis.

Reference samples
Should a customer wish to check, for
example, the color and flavor of a pow-
der, a reference sample of the type in
question is needed; delivery samples can
be checked against such reference samples.
Such samples should be packed in a well-
sealed container and kept cool and dry.
They should also be replaced twice a year.
To this end, the expiration date is shown
on the reference sample label.

Please note
The preceding information has been given
for use as a basis on which customers can
make important decisions with regard to
the extent cocoa ingredients are examined
before use. Based on the delivery history,
audits, and additional information from
ADM Cocoa staff, the customer may
make simplifications in checking deliver-
ies of ADM Cocoa products.

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Methods of Analysis
3
1. Introduction instrumental methods. The latter always
have to be calibrated and checked against
Good methods of analysis are not only the often more time-consuming official
essential for upholding the quality methods.
specifications and customer requirements The quality of the sampling is often
but also for process control purposes. more important for a reliable result than
ADM Cocoa often uses classic analytical the analysis itself; however accuracy
methodology, such as fat content by and precision of analytical methods for
extraction, moisture content by oven process control and finished goods analy-
drying, acidity (free fatty acid) by titra- sis have to be known and evaluated
tion, etc. These methods are by definition regularly. Analytical data are never
related to the specification parameters. absolute but have a “natural” uncertainty
However, many modern instrumental and or variation. The analyst has to check and
automated techniques, like spectroscopy, evaluate each analysis and each result
chromatography, and densitometry, are using his experience and knowledge. Are
used for obtaining results faster and for the results as expected, or is reassurance
additional information on the products. (reanalysis) necessary?
Always, but especially for specifications Good Laboratory Practices (GLP)
and requirements, it is necessary to are essential for validation of data. On a
define and describe the methods of regular basis, analysis of control or check
analysis clearly and in detail; this assures samples must be carried out to evaluate
consensus on the results and no analytical the performance of the methods and
bias caused by using different methods. the analysis.
In addition to our own methodology, In this Module the analytical methods
we rely on the methods of international advised by ADM Cocoa for the analysis
analytical and standard organizations of specification parameters of cocoa
like the International Organization for liquor, cocoa powder, and cocoa butter
Standardization (ISO), the International are described; a trained analyst should be
Union of Pure and Applied Chemistry able to perform the analyses and obtain
(IUPAC), and the Association of Official reliable, accurate results.
Analytical Chemists (AOAC). Analytical References are given to official methods
and microbiological experts from the (ISO, AOAC, IUPAC, ICA); many analyti-
cocoa and chocolate industries, organized cal textbooks also have chapters on the
in the International Confectionery analysis of cocoa products.
Association (ICA), developed and
approved about 50 analytical methods 2. Sampling
specifically for cocoa, cocoa products, procedure
and chocolate. These methods can be
ordered at the ICA-Secretariat, Rue Sampling—general
Defacqz 1, B-1050 Brussels, Belgium, Correct sampling procedures are essential
or at www.caobisco.com under for obtaining good and reliable analytical
ICA-publications. results. The sampling and sampling con-
ADM Cocoa uses the official analytical ditions may depend on the type of analy-
methods as well as simplified, faster, sis to be carried out, but the sample

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always has to be representative for the


product or lot. Non-sterile conditions are
sufficient for such analyses as fat or mois-
ture content, however sterile conditions
are essential when the samples have to be
analyzed microbiologically.
In processes the sampling is preferably
done automatically and in line by taking
(and combining) portions of the product
stream at regular intervals with automatic
samplers (available for liquids as well as
solids). In general the sampling procedure
can be divided into two steps:
• primary sampling of the production
lot and preparation of the “bulk” sam-
ple
• secondary sampling or preparation of
the laboratory or test sample from the
“bulk” sample
Samples should ideally be packed in
moisture- and air-tight containers/bags of
suitable size and shape, preferably be
stored in a cool and dark place, and be
labeled with the product and sample
information. This will protect the product
from any change in the relevant parame-
ters for as long as the sample is needed
for analysis or as evidence (counter sam-
ples). This includes no increase in mois-
ture (cocoa powder is very hygroscopic),
no change in color (by temperature varia-
tion or effect of light), no effect on flavor
(too high temperature and influence of air
and light), etc.
Deliveries of ADM Cocoa products can
be in liquid (tank containers) and solid
(bags or cartons) forms. Liquid deliveries
should preferably be sampled at regular
intervals during unloading of the tank.
The “bulk” sample can be sub-sampled to
give the laboratory or test sample. The
solids in liquid cocoa liquor may partly
sediment, so when the delivery is not well
stirred many samples have to be taken
and recombined (e.g. for analysis of fat
content and fineness).

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Solid deliveries can be sampled by Samples for microbiological analysis


taking primary samples from a number must be taken aseptically: The bag sur-
of pallets with cartons or bags. This process face, the knife used to cut open the bag,
is intended to assure that all units on a pal- and the sampling spoon must first be
let (with the same production code) repre- cleaned and disinfected with 70% alcohol
sent the same homogeneous product. The on cotton wool.
size of a primary sample has to be at least Secondary sampling depends on cus-
50 g to be representative for the pallet and tomer requirements:
to allow the necessary analyses. By com- • Composite samples can be prepared
paring primary samples of a delivery, the by taking and blending identical
customer can evaluate its consistency. quantities of the primary samples.
• Single primary samples may be sub-
Sampling—bags or FIBCs sampled and analyzed for specific
For cocoa powder, the following proce- parameters.
dure is advised, based on one sample
per pallet or flexible intermediate bulk
containers. 3. Cocoa liquor/
Check the dry (external) color immedi- cocoa powder
ately. Only a limited color variation both
from sample to sample as well as between
Flavor evaluation
samples and reference is allowed.
Next, other parameters can be deter- DEFINITION
mined, for instance, fat content, moisture The flavor of cocoa liquor and cocoa pow-
content, or pH. Microbiological analysis is der is evaluated by trained panel mem-
generally carried out separately. bers under standard conditions, using a
Primary sampling of a bag of cocoa standard sample as a reference.
powder from a pallet is as follows:
• Make an inverted U-shaped cut in the EQUIPMENT/MATERIALS
shrink-wrap or foil wrap. • sugar, granulated and powdered
• Make a similar but smaller cut in the • tap water, 55° C (131° F)
bag, such that the bag can easily be • beakers, glass, 400 ml
resealed with tape. • disposable cups, approx. 30 ml and
• Take a sample of 50-250 g with a clean 150 ml, with lid, (odor free)
sampling spoon (penetrating 5-10 cm • stirrers, measuring cylinders,
into the bag). thermometer (0°-100°C/32-212° F)
• Place the sample in a plastic bag or • hot plates
sterile container. Close carefully and • balance, 0.1 g accuracy
label with product type, lot number,
production code, sampling date, and GENERAL TEST CONDITIONS
name of sampler. For effective flavor evaluation, a trained
• Close the bag and then the wrap with panel of five to eight members is neces-
adhesive tape. sary, and test conditions must be
• Primary sampling of the flexible inter- standardized.
mediate bulk container is done by
opening the filling tube, taking a sam-
ple of 5-10 cm under the surface and
subsequently closing the filling tube.

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TASTE PANEL ROOM TESTING TECHNIQUE


The test conditions require a special and Each panel member evaluates a sample
separate taste panel room for concen- against the reference, separately judging
trated, undisturbed, and unobserved different aspects of odor and flavor.
testing under comfortable sitting condi- 1. Before starting an evaluation: The
tions with good lighting and temperature. mouth is rinsed with lukewarm water.
Smells, sounds, and disturbances should 2. The odor of the reference is judged
be excluded. It must be possible to spit first, then the sample, and again the
out the sample and rinse the mouth with reference.
warm tap water. Clear written instruc- 3. The nature and intensity of any differ-
tions are supplied to each panel member. ences perceived are recorded on the test
At each sample booth, general test guide- form supplied.
lines should be present. 4. The flavor of the reference is tested,
then the sample, and again the refer-
PANEL MEMBERS ence, rinsing the mouth with lukewarm
Panel members are selected and trained water each time before tasting. The
to discriminate between basic tastes and sample is then spit out, after swirling in
essential cocoa flavors and off-flavors. In the mouth for 5-10 seconds to evaluate
addition, panel member performance is and memorize the different flavor
evaluated regularly by flavor analysis aspects.
supervisors. 5. The nature and intensity of any differ-
The following basic rules apply to taste ences perceived are noted on the test
panel members: form.
• no tasting when feeling unwell
• no smoking, eating, or drinking for RESULTS
half an hour before tasting The panel members’ evaluation forms are
• no tasting on an empty stomach collected; the members are interviewed
further if necessary, and the forms are
PROCEDURE interpreted to obtain an overall impres-
Sample preparation sion of the differences against the refer-
1. Weigh 21 g of liquid cocoa liquor or ence. The overall impression is reported,
12 g of the cocoa powder to be tested if possible, in a numerical way for pur-
and 15 g of sugar into a 400 ml glass poses of historical comparison.
beaker.
2. Add 300 ml of tap water at 55° C REMARKS
(131° F) and stir to a homogeneous Reference samples should be carefully
suspension. selected, kept under cool (15° C/59° F),
3. Pour about 50 ml of the suspension into dark, and dry (relative humidity below
each of the six cups (150 ml) and close 50%) storage conditions and not be more
with a lid. than six months old.
4. Repeat these steps with the reference
sample (see remarks). REFERENCE
5. Place the samples on hot plates to keep ICA method 6/1963 (formerly 2/1963).
the contents at 50° C (122° F).

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liquid cocoa liquor to the nearest mg


(M2 in g) into the thimble, and mix
Determination of fat content
DEFINITION the liquor and sand homogeneously
The fat content of cocoa liquor and cocoa with the stirring rod.
powder according to the Soxhlet extrac- 6. Fill the thimble with a solid wad of
tion method is the percentage by mass of cotton wool and place the thimble in
fat and other components extractable with the Soxhlet extractor. Add about 50 ml
petroleum ether (p.e.). of p.e. to the tared Erlenmeyer flask,
and connect this flask to the extractor.
EQUIPMENT/MATERIALS 7. Add slowly more p.e. (about 100 ml)
• Soxhlet extractors, siphon capacity to the extractor until the solvent starts
about 100 ml, NS 29 at the bottom to siphon (see Remark 3).
and NS 45 at the top 8. Connect the condenser to the extrac-
• condensors, Dimroth with NS 45 and tor, and place the assembly on the
Call2- tube heating plate.
• Erlenmeyer flasks, 250 ml with NS 29 9. Extract the powder/liquor plus sand
• hot plate for flasks (fire-safe) in the thimble for at least eight hours
• desiccator with desiccant with 10-15 siphonings per hour (see
• vacuum drying oven set at 80° C/176° F Remark 4).
• defatted glass beads, extraction thim- 10. Disconnect the Erlenmeyer flask and
bles, round filters (Ø 15 cm) cotton distill off the p.e.
wool and boiling stones (see Remark 1) 11. Dry the flask with the residue under
• residue-free petroleum ether (p.e.), vacuum in the drying oven at 80° C
bp. 40°-60° C/104-140° F (see (176° F), for the first 15 minutes at
Remark 1) 400 mm Hg, followed by one hour at
• analytical balance, 0.1 mg accuracy less than 10 mm Hg.
• sand, acid-washed at 60° C (140° F) 12. Cool the flask in the desiccator for
• glass stirring rod, length 10 cm 30 minutes and weigh the flask.
13. Repeat the drying, cooling, and
PROCEDURE weighing until the difference between
1. Place a dry and clean Erlenmeyer two successive weighings is less than
flask with a few boiling stones for 1 mg (M3 in g).
30 minutes in the drying oven.
2. Let the flask cool in the desiccator for
RESULTS
30 minutes. 1. Calculation
3. Weigh the tare weight of the flask to The fat content of the cocoa liquor/
the nearest 0.1 mg (M1 in g). powder sample is:
4. Weigh approx. 5 g of cocoa powder to
the nearest 1 mg (M2 in g), and trans- M 3-M1
_______ X 100% (m/m)
fer the powder into an extraction M2
thimble weighted down with glass
beads in which a round filter has been Where:
folded to form a bag inside the thim- M1 = mass in g of Erlenmeyer flask (tare)
ble wall (see Remark 2), or M2 = mass in g of the cocoa liquor/
5. Bring about 10 g of sand into an powder sample
extraction thimble with a stirring rod; M3 = mass in g of the Erlenmeyer flask
weigh approx. 3 g of well-mixed with residue

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The De Zaan ® Cocoa Manual

The result should be expressed to two DEFINITION


decimal places.
The pH of cocoa liquor and cocoa powder
is the pH (negative logarithm of the
2. Repeatability
hydrogen ion concentration) of a suspen-
The difference between the results of two
sion of these products in water, prepared
independent determinations should not
and measured according to this method.
exceed 2% of the fat content (0.2% with
10% fat, 0.4% with 22% fat, and 1.1% with EQUIPMENT/MATERIALS
55% fat).
• pH meters with combined glass
REMARKS electrodes readable to 0.01 pH unit
• thermometer, 0°-100°C (32-212° F)
1. Materials and solvent have to be
with 1° C graduation
residue free; a complete blank extrac-
• buffer solutions of pH 4.00, 7.00, and
tion without cocoa liquor/powder
9.00
should be performed regularly, and the
• distilled or demineralized water,
residue should be less than 2.5 mg
carbon dioxide free on hot plate
(0.05% fat in the sample); when the
• glass beakers (150 ml) and measuring
residue is larger than 2.5 mg, the cause
cylinder (100 ml)
of this increase should be investigated.
• balance, 0.01 g accuracy
The p.e. should have an evaporation
residue of less than 1 mg per 150 ml. PROCEDURE
2. The round filter folded to the shape of
1. Calibrate one pH meter at 20° C (68° F)
a bag around a clean rod permits the
using buffers of pH 4.00 and 7.00 and
repeated use of the extraction thimble.
another pH meter at 20° C (68° F) using
It also prevents very small particles
buffers of pH 7.00 and 9.00.
from passing through the thimble into
2. Weigh 10.00 g cocoa powder to the
the flask and adding to the residue.
nearest 0.01 g into a 150 ml glass
3. During extraction the quantity of sol-
beaker.
vent in the flask should always be at
3. Slowly add, while stirring, 90 ml of
least 50 ml.
boiling hot distilled (or demineralized)
4. For the complete extraction of the fat, at
water with a measuring cylinder.
least 80 siphonings are needed, each of
4. Leave to cool to 20°-25° C (68-77° F),
them effectively emptying the extractor.
e.g. in a cold water bath, stirring
Completeness of the extraction can be
occasionally.
checked by an additional extraction
5. Measure the pH with both pH meters,
with fresh solvent in a new flask; after
and use the pH reading nearest to the
two to three hours or 20-40 siphonings
buffer range.
the residue after evaporation and
drying should be less than 1 mg. RESULTS
REFERENCE The results should be expressed to two
decimal places. The difference between
ICA method 37/1990 (formerly 115/1990).
the results of two independent determina-
tions should not exceed 0.1 pH unit.
REFERENCE
ICA method 15/1972 (formerly 9/1972).
Determination of pH

34 A rc h er Danie ls Midland Company


The De Zaan ® Cocoa Manual

detergent.
4. Add 20 ml hot water (see Remark 2),
Determination of sieve residue
DEFINITION stir the mixture with a stirring rod
1. The “wet” sieve residue (or “coarse- until all lumps have disappeared.
ness”) of cocoa liquor and cocoa pow- 5. Add 280 ml of hot water and stir
der is defined as the mass percentage of mechanically for 2 minutes without
the product that does not pass a plate producing a vortex and with the pro-
sieve with apertures of 75µ x 75µ peller near the bottom of the beaker.
according to this method. 6. Pour the hot suspension slowly
through the sieve, meanwhile moving
2. The fineness of cocoa liquor and cocoa and swirling the sieve in a circular
powder is expressed as 100% minus the manner over the sink (see Remark 3).
% sieve residue (the fraction remaining 7. Rinse the beaker, stirrer, and rod into
on the sieve). the sieve, and rinse the sieve with up
to 1.5 l of hot water until no more
EQUIPMENT/MATERIALS particles pass the sieve.
• plate sieves with apertures of 75µ x 8. Rinse the sieve and residue with
75µ ± 2µ (200 mesh), diameter 6 cm, 15-25 ml of acetone to remove water
height 7 cm, open area 25-40% (see and fat residues.
Remark 1) 9. Place the sieve on the watch glass in
• drying oven, well ventilated, set at the oven for 45 minutes (see Remark 4),
103°-105° C (217-221° F) cool the sieve and glass in the desiccator
• desiccator with desiccant for 45 minutes.
• glass beakers (400 ml), glass stirring 10. Weigh the sieve and residue and
rod, mechanical stirrer watch glass to the nearest 0.1 mg
• watch glasses, diameter about 8 cm (M3 in g).
• squeeze bottles of 500 ml (for hot
water) and 250 ml (for acetone)
RESULTS
• graduated cylinders of 25 ml and 1. Calculation
250 ml The “wet” sieve residue (or “coarseness”)
• analytical balance (accuracy 0.1 mg) of the cocoa liquor or the cocoa powder
and weighing balance (accuracy sample is:
0.01 g)
• hot water 75° C (167° F) ±5° and M3-M2
_______ x 100% (m/m)
acetone (water free) M1
• detergent (surface active agent—
concentrated) Where:
M1= mass in g of the dried sieve + watch
PROCEDURE
glass
1. Weigh a dried, clean sieve (75µ) on a M2= mass in g of the sample
dry watch glass to the nearest 0.1 mg M3= mass in g of the dried sieve + residue
(M1 in g). + watch glass
2. Weigh approx. 10 g of well-mixed The result should be expressed to two
cocoa liquor or cocoa powder to the decimal places.
nearest 0.1 g in a glass beaker (M2 in g).
3. Add with cocoa liquor 2 g of deter- The fineness percentage is:
gent or with cocoa powder 1 g of {1- (M 3-M2)} x 100% (m/m)
_______

Archer Daniels Midland Company 35


The De Zaan ® Cocoa Manual

M1
2. Repeatability
The difference between the results of two PROCEDURE
independent determinations should not 1. Dry a clean and empty weighing dish
exceed 0.04% on a 75µ sieve. or flask with stopper side by side in
the drying oven for 60 minutes at
REMARKS 103°-105° C (217-221° F)
1. Plate sieves are very delicate; they may 2. Let the dish/flask cool in the desiccator
not be touched, not even with a brush. for 30 minutes.
Dirty sieves can be cleaned with a 3. Weigh the tare weight of the dish/flask
detergent solution in an ultrasonic bath. to the nearest 1 mg (M1 in g).
Sieves should be inspected regularly for 4. Weigh to the nearest 1 mg approx. 5 g
damage with a magnifying glass. of well-mixed cocoa powder into the
2. The detergent dissolves the fat of the tared flask (M2 in g) (see Remark 2), or
cocoa liquor or the cocoa powder. 5. Add approx. 20 g of sand into the
3. When the sieve becomes clogged, tap alumina dish with lid and weigh the
the side of the sieve gently. tare weight of the dish plus sand to the
4. The watch glass collects cocoa particles nearest 1 mg (M1 in g).
passing through the sieve on drying, 6. Weigh to the nearest 1 mg, 5 g of
cooling, and weighing. well-mixed liquid cocoa liquor into the
tared dish (M2 in g); saturate the sand
REFERENCES with ethanol, and mix the sand homo-
ICA method 38/1990 (formerly 116/1990). geneously with the liquor using a
stirring rod.
7. Dry the dish/flask with stopper beside
it in the oven for four hours at 103°-
Determination of moisture

105° C (217-221° F). Then remove and


content
DEFINITION place the stopper on the dish/flask (see
The moisture content of cocoa liquor or Remark 3).
cocoa powder is the percentage of mass 8. Let cool and weigh as described above
lost drying for 4 hours at 105° C (221° F). (M3 in g).
EQUIPMENT/MATERIALS RESULTS
• drying oven, well ventilated, set at 1. Calculation
103°-105° C (217-221° F) The moisture content of the sample is:
• desiccator with desiccant
• glass weighing flask for cocoa pow- M2-M3 100% (m/m)
_______X
der, always with ground glass stop- M2-M1
per, Ø 50 mm (see Remark 1)
• alumina weighing dish with lid for Where:
cocoa liquor, Ø 70 mm M1 = mass in g of the empty stoppered
• glass stirring rod, length 10 cm dish/flask (tare)
• sand, ashed at 600° C (1112° F) M2 = mass in g of the stoppered dish/flask
• ethanol p.a. with sample
• analytical balance, accuracy 1 mg M3 = mass in g of the stoppered dish/flask
with dried sample

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The result should be expressed to one dard light, with daylight lamp of
decimal place. 6500° K (see Remark 3)
2. Repeatability • hot plates
The difference between the results of two • balance, 0.001 g accuracy
independent determinations should not
exceed 0.2%. PROCEDURE
1. Dry (extrinsic) color
REMARKS 1. Place approx. 0.5 g of the cocoa pow-
1. The flask should always be weighed der on the table surface of the cabinet.
with the stopper (on or beside it) and 2. Place one or more reference cocoa
only after conditioning in the desiccator. powder(s) in a similar way beside or
With more than four flasks, the cooling around the sample to be evaluated.
time should be 45 minutes instead of 3. Put a grease-proof paper over the
30 minutes. The correct weighing prac- samples and flatten them by gently
tices have to be adhered to. stroking the sheet with a flat hand
2. Cocoa powder is very hygroscopic; the until they touch each other.
lab sample has to be stored in an air- 4. Remove the sheet carefully.
and moisture-tight container, and the 5. Evaluate the color difference(s) with
sample transfer has to be carried out two or more persons (see Remarks 1
rapidly and carefully. and 2).
3. Drying should last exactly four hours, 2. Color (intrinsic) in milk
and the oven should not be opened dur- 1. Weigh 1.20 g of cocoa powder to be
ing this period. evaluated in a 100 ml beaker to the
nearest 0.01 g.
REFERENCE 2. Add 5 ml of pasteurized milk and
ICA method 1/1952 (formerly 3/1952). mix until a homogeneous paste is
achieved.
4. Cocoa powder 3. Add 45 ml of milk, heated to about
60° C (140° F).
4. Stir thoroughly and fill a color evalua-
Visual color evaluation
DEFINITION tion flask with the suspension.
The color of cocoa powder can be eval- 5. Repeat the above steps twice using
uated as such (the dry or extrinsic color) the reference cocoa powder, filling
or as suspension in milk or water (the two flasks with the suspension.
intrinsic color) against reference and other 6. Close the three flasks properly and
samples, using the methods below. shake them prior to the evaluation
(see Remark 4).
EQUIPMENT/MATERIALS 7. Place the suspension to be evaluated
• beakers, 100 ml and 150 ml, glass between the reference suspensions.
• spoon 8. Evaluate the color under standard
• stirring rod, length approx. 15 cm light conditions in the cabinet with
• grease-proof paper sheets, 20 x 12 cm two or more persons (see Remarks 1
• pasteurized milk and 2).
• color evaluation flasks of colorless, 3. Color (intrinsic) in water
clear glass with flat sides and screw 1. Weigh 1.20 g of the cocoa powder to
tops, 45 ml be evaluated in a 150 ml beaker to the
• color evaluation cabinet with stan- nearest 0.01 g.

Archer Daniels Midland Company 37


The De Zaan ® Cocoa Manual

2. Add 100 ml of water and bring it to a


boil on a hot plate.
3. Allow to boil for a moment, stirring
the suspension with a stirring rod.
Instrumental color evaluation

4. Fill one color evaluation flask with DEFINITION


the suspension. The instrumental color evaluation of
5. Repeat the above steps twice, using cocoa powder as such or as a slurry in
the reference cocoa powder, and fill water is expressed in L*-, C*-, and h-val-
two flasks with the suspension. ues measured with a color meter.
6. Close the three flasks properly and The L*-, a*-, and b*-values are calcu-
shake them prior to the evaluation. lated from the CIE X-, Y-, and Z-values
7. Place the suspension to be evaluated using the CIE 1976 equations. C*- and h-
between the reference suspensions. values are calculated from the a*- and b*-
8. Evaluate the color under standard values according to the following:
light conditions in the cabinet with
two or more persons (see Remarks 1 C*= (a*2+b*2)
and 2). h=arcig(b*/a*)
REMARKS
L* value – the lightness/darkness coordi-
1. The visual evaluation of the color nate; a low value indicates a
should be carried out by people who dark color, a high value indi-
have successfully passed an eye test cates a light color
(e.g. the S. Ishihara test). a* value – the red/green coordinate,
2. There should be unanimity about the with +a* indicating red and
terminology used for the evaluation of -a* indicating green
the colors: expressions such as “too b* value – the yellow/blue coordinate,
light,” “too dark,” “redder,” “greyer,” with +b* indicating yellow
etc. should have the same meaning for and -b* indicating blue
all evaluators. C* value – the chroma coordinate, indi-
3. The lamps of the color evaluation cabi- cating brightness; a higher
net should be replaced regularly to value indicates a brighter
ensure the consistency of the standard color
light conditions. h value – the hue angle; a lower value
4. To prevent the rapid sedimentation of indicates more redness, a
the suspension, the following modifica- higher value indicates more
tions can be used: yellowness
- Weigh 1.20 g of cocoa powder, 20 g of
sugar, and 0.035 g of the gelling agent
carrageenan E407 in a 100 ml beaker.
- Add 10 ml of pasteurized milk and
stir the contents to a paste with a stir-
ring rod.
- Add 40 ml of pasteurized milk heated
to approx. 60° C (140° F).
- Proceed as described in 2. Color
(intrinsic) in milk.

38 A rc h er Danie ls Midland Company


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EQUIPMENT/MATERIALS 4. Add 50 ml demineralized water at


room temperature.
• Datacolor Spectraflash SF 450 X color
5. Continue stirring for at least
spectrophotometer (or equivalent)
1 minute.
° measuring geometrics d/8 - 6. Pump the suspension through the
specular excluded
quartz flow cuvette, while stirring.
° illuminant D65 7. Read and record the L*-, C*-, and
° observer angle 10° h-values with a calibrated color
• quartz cuvette
spectrophotometer.
• tubing pump system
• magnetic stirrer REMARKS
• beakers, 400 ml, glass
The flow rate during pumping of the
• balance, 0.1 g accuracy
water/cocoa powder suspension should
• demineralized water
be so that settlement of cocoa particles is
PROCEDURE prevented. If the cocoa powder is lumpy,
the surface will be irregular when evalu-
1. Dry (extrinsic) color
ating the dry color. It is then advisable to
1. Fill a cuvette 3/4 full with the cocoa
sieve the cocoa powder through a 500µ
powder sample and tamp the powder
sieve and carefully break down the
down carefully.
lumps. Mix the powder thoroughly.
2. Then add cocoa powder until it is
heaped above the rim. REFERENCES
3. Level the powder evenly by using
1. Schulze: “Farbelehre und
the edge of a spatula with tapping
Farbemessung,” 1966 (Springer-Verlag,
movements.
Berlin).
4. Remove the surplus powder carefully
2. Clydesdale: “The measurement of
with the spatula to produce a flat
color,” Food Technology 23 (1969),
surface in line with the rim (see
16-22.
Remarks).
3. CIE, 1978: “International Commission
5. Place the cuvette carefully against the
of Illumination. Recommendations on
illuminated window of the calibrated
uniform colour spaces, colour difference
meter.
equations, psychometric colour terms.”
6. Read and record the L*-, C*-, and
(Bureau Central de la CIE, Paris).
h-values.
4. Instruction manual: Datacolor
7. Compare the values found with those
Spectraflash SF 450 X Colour
of a standard sample.
spectrophotometer.
5. DataFacts Technical bulletin nr. 004-96
2. Intrinsic color measurement
from Datacolor International.
1. Weigh 7.5 ± 0.1 g of cocoa powder in
a 400 ml beaker.
2. Add 100 ml demineralized water of
50° C (122° F) and stir with a stirring
rod until a smooth slurry is obtained
without lumps.
3. Continue stirring using a magnetic
stirrer for 10 minutes.

Archer Daniels Midland Company 39


The De Zaan ® Cocoa Manual

5. Cocoa butter Melting point


Refractive index DEFINITION
DEFINITION This method describes the determination
of the melting point of cocoa butter. The
This method describes the determination melting point is expressed as Slip Point
of the refractive index of cocoa butter. (the butter starts to melt) and/or as Clear
The refractive index is expressed as nD Point (the butter is fully liquid/molten).
(40° C/104° F).
EQUIPMENT/MATERIALS
EQUIPMENT/MATERIALS
• magnetic stirrer with hot plate
• water bath, thermostatically con- • stirring bars
trolled at 40° C (104° F) ± 0.5º and • exterior water bath
with a circulation pump • inner water bath
• refractometer, e.g. Abbe type, • plate with two holes: one for fixation
connected to the water bath of the inner water bath
• light source (sodium vapor light) • movable rubber ring for adjusting the
PROCEDURE inner water bath
• rubber plate to cover the inner bath
1. Bring the prisms of the refractometer to • thermometer, range 0°-50° C (32-122°
40º C (104° F) by connecting the refrac- F), graduation of 0.1º
tometer to a water bath. • U-tubes for melting point according
2. Place a drop of clear, filtered cocoa but- to H. Fincke
ter on the surface of the prisms and • thermometer for exterior water bath,
close the prisms. graduation of 0.5º
3. Wait a few seconds to allow the butter • water baths thermostatically con-
to obtain the temperature of the prisms. trolled at 25° C (77° F) and 32°-33° C
4. Adjust the refractometer in such a way (90-91° F)
that a clear contrast line can be read
where it crosses the scale. PROCEDURE
5. Read the refractometer at the nearest 1. Pretreatment of cocoa butter
0.0001. 1. Heat >50 g of cocoa butter to 50°-60º C
REMARKS (122-140° F), and filter through a fluted
filter, Whatman no. 3, Ø 15 cm.
The prisms should be handled with care. 2. Pour 50 g of this filtered butter into a
REFERENCES glass beaker of 100 ml and immerse
the glass beaker in a water bath,
1. IUPAC Standard Methods of the which is thermostatically controlled at
Analysis of Oils, Fats and Derivatives, 25º C (77° F).
6th Edition, Method 2.102. 3. Cool the butter while constantly
2. ISO 6320:1995 - Animal and Vegetable stirring until it assumes a pasty
Fats and Oils - Determination of consistency.
Refractive Index. 4. Prevent the inclusion of air bubbles.
5. Subsequently, immerse the glass
beaker into a water bath that is ther-
mostatically controlled at 32°-33° C
(90-91° F). Continue to stir until the

40 A rc h er Danie ls Midland Company


The De Zaan ® Cocoa Manual

butter has come to the same tempera- REFERENCES


ture. This takes about 30 minutes.
1. ISO 6321: Animal and Vegetable Fats -
6. Pour the cocoa butter into a metal
Determination of Melting Point in
tray and allow to stand for at least
Open Capillary Tubes (Slip Point).
two hours at room temperature
2. ICA Method 4/1962: Determination
(20°-22° C/68-72° F).
of the Melting Point of Cocoa Butter
(formerly 8b/1962).
Note: Seeding crystals (grated cocoa
butter) should in no case be added.
Lovibond color
2. The melting point of cocoa butter DEFINITION
1. Press a 1 cm column of pretreated
This method describes the determination
cocoa butter into the longer side of
of the color of liquid cocoa butter with the
the U-tube.
Lovibond Tintometer and Yellow, Red,
2. Use a very fine metal rod to push the
and Blue color glasses.
column of cocoa butter down to 1 cm
before the bend of the tube. EQUIPMENT/MATERIALS
3. Fix the shorter side to the thermome-
• Lovibond Tintometer, type 1A with
ter (0°-50º C/32-122° F) by means of
two identical lamps of 60W (to be
the rubber ring, and make sure that
replaced after 100 burning hours or
the bend of the tube is on the same
after three years)
level as the bulb of the thermometer.
• magnesium carbonate blocks as stan-
4. Introduce the thermometer with the
dard white (clean surface by rubbing
U-tube into the inner water bath of
the cubes together)
the melting point equipment. The
• 1-inch glass cuvette for the
water level of the inner water bath
Tintometer
has to be 1 cm below the level of the
• set of Yellow, Red, and Blue Lovibond
exterior water bath, which has a level
color glasses (clean regularly with
of about 9.5 cm high.
lens paper)
5. Slowly heat the exterior water bath
• neutrally hued filter (Grey)
while constantly stirring by means
of the magnetic stirrer. Up to 30º C PROCEDURE
(86° F), the maximum increase in tem-
1. Switch the lamps on and fill a 1-inch
perature of the inner water bath may
cuvette with clear-filtered cocoa butter
be 1º per minute. Over 30º C (86° F),
of approx. 40º C (104° F).
the increase in temperature may not
2. Place the cuvette against the opening at
exceed 0.2º per minute.
the rear side of the color compartment
6. Read the temperature when the
in the Tintometer, covering the entire
column of solid cocoa butter moves
opening.
(slips) down; this is the Slip Point.
3. Compare the color of the cocoa butter
7. Read also the temperature when the
with Lovibond color glasses: start with
column of cocoa butter is completely
40.0 Yellow and add Red (units and
molten (clear); this is the Clear Point.
tenths) and, if necessary, Blue until the
8. Give the temperature of both the Slip
combination of color glasses matches
Point and the Clear Point in ºC (or °F)
the color of the cocoa butter.
and to one decimal place.
4. If a color cannot be matched by means
of the color glasses, then use the neu-

Archer Daniels Midland Company 41


The De Zaan ® Cocoa Manual

trally hued filter (Grey). If at approx. 270 nm several peaks are


5. The color is expressed in a sum of units observed, this would mean that the cocoa
and tenths used from the Yellow, Red, butter has been treated with bleaching
and Blue color glasses. earth.

REFERENCES EQUIPMENT/MATERIALS
ISO 15305: Animal and Vegetable Fats • cyclohexane (for spectroscopy)
and Oils - Determination of Color - • diethyl ether (p.a.)
Tintometer Method. • potassium hydroxide solution (4 N)
• sodium sulfate (anhydrous)
• pipette (5 ml)
• graduated measuring cylinder
Extinction values
DEFINITION • separating funnels (100 ml)
This method describes the determination • Erlenmeyer flasks (25 ml with
of the extinction values of cocoa butter ground-glass stopper)
before and after washing with alkali. • fluted filters (Ø 7 cm, e.g. S&S
no. 597)
PRINCIPLE • water bath
The extinction values at 270 nm and • pH-indicator paper
325 nm of a 1% cocoa butter solution in • quartz-cells (1 cm)
cyclohexane, before and after washing • UV spectrophotometer
with alkali solution, are measured in a • glass beakers
1 cm cuvette; the difference in extinction
values at 270 nm and 325 nm is an indica- PROCEDURE
tion of the purity of the cocoa butter. The Measurement of the extinction values:
maximum extinction value at 270 nm for 1. Weigh 0.1 g cocoa butter to the near-
cocoa butter is 0.5, whereas after washing est 0.1 mg into a 25 ml Erlenmeyer
with alkali the extinction value should be flask (weight: G in g).
maximum 0.14; the difference is caused by 2. Add 5 ml of cyclohexane by means of
the removal of the alkaloids (caffeine and a pipette and mix.
theobromine) with the alkali washing. 3. Fill a 1 cm quartz-cell and scan the
The cocoa butter extinction values are UV spectrum between 220 nm and
indicative of the degree of contamination 290 nm by means of the UV
and aging of cocoa butter. During oxida- spectrophotometer.
tion of cocoa butter, products such as con- 4. Use cyclohexane as blank (reference).
jugated dienes and diketones are formed. 5. Register the UV curve by means of a
Measurement of the absorbance of dienes recorder.
can take place at about 232 nm, and that 6. Read the extinction values at 270 nm
of diketones can be measured at 268 nm. and 325 nm.
Absorbance of conjugated trienes can be
measured at approx. 270 nm. Pure prime Alkali washing and measurement of the
pressed cocoa butter does not contain any extinction values:
dienes, trienes, or products of decomposi- 1. Weigh about 2 g of cocoa butter into
tion. Consequently, the extinction value a 100 ml glass beaker.
must be low. Any higher extinction value 2. Add 5 ml of diethyl ether and mix.
could, for example, be an indication of 3. Pour the solution into a separating
refined cocoa butter or expeller butter. funnel of 100 ml.

42 A rc h er Danie ls Midland Company


The De Zaan ® Cocoa Manual

4. Rinse the glass beaker with 5 ml of


diethyl ether and pour into the
separating funnel.
5. Add 3 ml of potassium hydroxide
(4 N) and shake for 2 minutes.
6. Draw off the alkali layer and thor-
oughly wash out the ether layer by
means of 3 ml of distilled water.
7. Continue to wash out (five times on
average) until the water layer has
become alkali free.
8. Check by means of the indicator
paper.
9. Add 5 ml of diethyl ether and draw
off the solution into a 25 ml
Erlenmeyer flask with stopper.
10. Add about 2 g of anhydrous sodium
sulfate and allow to dry for about
one hour.
11. Filter through a fluted filter (Ø 7 cm)
into a glass beaker of 25 ml and
completely evaporate the ether on a
water bath.
12. Proceed by carrying out steps 1-6 as
described in “Measurement of the
extinction values.”
CALCULATION
Calculate the extinction values with the
following formulas:
E270 = Ext at 270 nm
______________________
20 x G
E325 = Ext at 235 nm
______________________
20 x G
Express the extinction values with two
decimal places.

REFERENCES
1. ICA method 18 and 19, 1973: UV
Extinction Values for Cocoa Butter
(formerly 8d + 8c/1973).
2. ISO 3656: Animal and Vegetable Fats
and Oils - Determination of UV
Absorbance.

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Where:
N = normality (0.5 N) hydrochloric acid
Saponification value
DEFINITION V1 = ml hydrochloric acid (0.5 N)
This method describes the determination determination
of the saponification value (S.V.) of cocoa V2 = ml hydrochloric acid (0.5 N)
butter. The S.V. is the number of mg of of the blank
potassium hydroxide required to saponify G = cocoa butter weight in g.
1 g of fat.
Express the result with one decimal place.
EQUIPMENT/MATERIALS
• 0.5 N KOH in ethanol (clear, colorless
REFERENCES
solution, stored in a brown glass bot- IUPAC Standard Methods for the
tle with a rubber or Teflon stopper) Analysis of Oils, Fats, and Derivatives,
• 0.5 N hydrochloric acid (accurately 6th Edition, Method 2.202.
standardized)
• phenolphthalein, 1% w/v solution in Iodine value by Wijs method
95% ethanol
• Erlenmeyer flask, NS 29
DEFINITION
• spiral reflux condenser NS 29 This method describes the determination
• volumetric pipette of the iodine value (I.V.) of cocoa butter
• boiling stones chips by the Wijs method. The I.V. of a fat is the
• hot plate number of grams of halogen absorbed by
100 g of fat and expressed as the weight
PROCEDURE of iodine. The I.V. is a measure of the
1. Weigh about 2 g of cocoa butter to the degree of unsaturation of fat.
nearest 1 mg into a 200 ml (NS 29)
Erlenmeyer flask.
EQUIPMENT/MATERIALS
2. Add 25.0 ml of ethanolic KOH solution • equipment has to be clean and dry
by means of a pipette. • Erlenmeyer flasks of 300-500 ml with
3. Add some boiling stones and attach the NS29 and ground stoppers
reflux condenser to the Erlenmeyer • burette, graduated in 0.1 ml
flask. • pipette, 25 ml
4. Place the flask on the hot plate and • demineralized water
gently boil for 60 minutes. • N sodium thiosulfate solution
5. Add 1 ml of phenolphthalein to the hot (standardized)
soap solution and titrate with 0.5 N • Wijs solution 0.2 N
hydrochloric acid until the color • glacial acetic acid/cyclohexane solu-
changes to colorless (V1 in ml). tion, ratio 1:1
6. At the same time, carry out a blank • potassium iodide (KI) solution in
(without cocoa butter) determination water, free from iodine or iodate
(V2 in ml). • starch solution in water
7. Calculate the saponification value with • reference sample of cocoa butter
the following formula:

56.1 x N (V2 -V1)


_______________
G

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PROCEDURE REMARKS
1. Weigh 0.32-0.38 g of the cocoa butter to Determination of the I.V. by an automatic
be analyzed to the nearest 1 mg into an titration often gives better reproducibility
Erlenmeyer flask; weigh also 0.32-0.38 g and repeatability than manual titration.
of the reference sample into an The reference sample is used to check the
Erlenmeyer flask (m in g). performance of the methodology.
2. Dose 15 ml of the glacial acetic
acid/cyclohexane solution into the REFERENCES
flasks, stopper the flasks, and dissolve 1. IUPAC Standard Methods for the
the cocoa butter. Analysis of Oils, Fats, and Derivatives,
3. Pipette 25.0 ml of 0.2 N Wijs solution 6th Edition, Method 2.205.
into the flasks, stopper, and mix 2. ISO 3961 - 1996: Animal and Vegetable
carefully. Fats and Oils - Determination of Iodine
4. Place the flasks in the dark for at least Value.
one hour but not more than 1.5 hours
(exclusion of daylight is essential).
5. Add after this time 20 ml of KI solution
Unsaponifiable matter

and 150 ml of demineralized water. DEFINITION


6. Titrate the free iodine in the contents of This method describes the determination
the flasks with the sodium thiosulfate of the % of unsaponifiable matter of cocoa
solution (Normality T) from the 50 ml butter.
burette; add 5 ml of starch solution
(indicator) at the end of the titration PRINCIPLE
and continue the titration under vigor- The unsaponifiable matter is that part of
ous shaking till the blue color just dis- the cocoa butter which, after saponifica-
appears (V2 in ml). tion, is still soluble in a non-polar solvent.
7. Carry out a blank test simultaneously The unsaponifiable matter consists of
under the same conditions and without lipids of natural origin present in press
cocoa butter (V1 in ml). butter, such as sterols, alcohols, and
hydrocarbons. The % of these substances
EXPRESSION OF RESULTS is <0.3% in pure prime press cocoa butter.
Calculate the I.V. with the formula: When the unsaponifiable matter is >0.3%,
the butter is contaminated with non-
12.69 x T x (V2-V1) volatile (at 103° C/217° F) organic matter
I.V. = ___________________
m foreign to press butter (for example min-
eral oils or shell fat).
Where:
V1 = ml of standardized sodium EQUIPMENT/MATERIALS
thiosulfate solution used for the blank • KOH p.a.
determination • petrol ether (p.e.) b.p. 40°-60° C
V2 = ml of standardized sodium (104-140° F), p.a. (free from residue)
thiosulfate solution used for the cocoa • ethanol 96%
butter samples • ethanol/water mixture 1:1 (v/v)
T = the exact Normality of the sodium • Erlenmeyer flask of 200 ml NS 29
thiosulfate solution used with reflux condenser
m = the mass, in g, of the cocoa butter • Erlenmeyer flask of 100 ml
samples • separating funnel 500 ml

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• oven 103° C/217° F (± 3°) phenolphthalein.


• heating bath—fireproof and spark-free 17. Transfer part of the p.e. into an
• desiccator with blue silica gel Erlenmeyer flask of 100 ml with
• fume cupboard boiling stones. The flask must previ-
• phenolphthalein solution, 1% (w/v) in ously be dried and tare weighed to
ethanol the nearest 0.1 mg (G2 in g).
18. Evaporate the p.e. on the heating bath
PROCEDURE in the fume cupboard.
1. Weigh approx. 5 g of cocoa butter to 19. Transfer the remainder of the p.e.
the nearest 10 mg into an Erlenmeyer quantitatively into the Erlenmeyer
flask of 200 ml (NS29) (G1 in g). flask and rinse the separating funnel
2. Add approx. 5.5 g of potassium with small amounts of p.e.
hydroxide and 50 ml of ethanol. 20. Evaporate the p.e. completely in the
3. Attach the Erlenmeyer flask to a heating bath.
reflux condenser and boil gently in a 21. Dry 100 ml flask with residue in an
heating bath for one hour. oven at 103° C (217° F) for 15 minutes,
4. Add 50 ml of distilled water through placing the flask in a horizontal
the top of the condenser. position.
5. Mix and cool down. 22. Cool in a desiccator for approx.
6. Transfer the contents of the flask into 30 minutes and weigh the flask to the
a separating funnel of 500 ml. nearest 0.1 mg.
7. Rinse the flask several times with a 23. Repeat the drying for successive
total of 50 ml of p.e. 15 minute periods until the weight
8. Transfer these p.e. rinsings into the loss between two successive weigh-
separating funnel. ings is less than 2.0 mg (G3 in g).
9. Shake the separating funnel vigorous- 24. Calculate the % of unsaponifiable
ly for 1 minute. matter with the following formula:
10. Allow to stand until there is complete
separation of the two phases. % unsaponifiable matter = 100 (G3-G2) / G1
11. Draw off the soap solution (the lower
layer) into a second separating funnel
of 500 ml. REFERENCES
12. Add small amounts of ethanol (96%) 1. IUPAC Standards Methods for the
or concentrated potassium hydroxide Analysis of Oils, Fats, and Derivatives,
solution if an emulsion has formed 6th Edition, Method 2.401.
that must be broken. 2. ISO 3596-2: Animal and Vegetable Fats
13. Extract the soap solution twice more, and Oils - Determination of Unsaponi-
each time with 50 ml of p.e. fiable Matter, part 2: rapid method
14. Draw off the soap solution into the using hexane extraction.
original Erlenmeyer flask. 3. ICA method 23/1988: Determination of
15. Collect the three p.e. layers in the first Unsaponifiable Matter in Cocoa Butter
separating funnel. (formerly 102/1988).
16. Wash out the p.e. at least three times,
each time with 50 ml of the
ethanol/water mixture (1:1), until the
ethanol/water mixture reacts neutral.
Check this by means of a drop of

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5. Mix and shake the volumetric flask in


a water bath of 40° C (104° F) continu-
Blue value
DEFINITION ously for 5 minutes.
This method describes the quantitative 6. Add 0.05 ml (one or two drops) of
determination of the blue value (B.V.) of 0.5% hydrogen peroxide solution.
cocoa butter; a B.V. of >0.05 is indicative 7. Heat, under continuous shaking, in
of a too high % of shell in the nibs from the water bath of 40° C (104° F) for
which the cocoa butter is obtained. another 3 minutes.
8. Make up the volumetric flask with
PRINCIPLE pentanol-2 to 10 ml and mix.
The B.V. of cocoa butter is the extinction 9. Also carry out a blank determination
of a blue-colored solution that is formed (steps 4-8).
after oxidation of the reaction product of 10. Measure the extinction of the pen-
behenic acid tryptamide with p-dimethyl tanol-2 solution in a cuvette of 3 cm
aminobenzaldehyde. The reaction takes compared to the blank sample (step 9)
place under acid conditions. Behenic acid at 500, 630, and 680 nm.
tryptamide is only found in the shell of 11. Calculate the B.V. with the formula:
cocoa beans.
0.4[E 630 - (E500 + E680)/2]
_____________________
EQUIPMENT/MATERIALS
3G
• carbon tetrachloride (p.a.)
• p-dimethyl aminobenzaldehyde (p.a.) Where:
• hydrochloric acid (32% p.a.) E500 = measured extinction at 500 nm
• hydrogen peroxide (30% p.a.) E630 = measured extinction at 630 nm
• pentanol-2 (p.a.) E680 = measured extinction at 680 nm
• demineralized water G = weight of the cocoa butter in g
• volumetric flasks (10 ml)
• water bath (40° C/104° F ±1°) Express the result in two decimal places.
• spectrophotometer
• cuvette (3 cm) REMARKS
• graduated pipette (1 ml) 1. If tetrahydrofuran is used instead of
pentanol-2, the extinction must be
PROCEDURE
measured at 510, 625, and 675 nm.
1. Dissolve 0.2 g of p-dimethyl Although tetrahydrofuran has a higher
aminobenzaldehyde in 20 ml of carbon M.A.C. value than pentanol-2, the latter
tetrachloride (1% solution). is preferred because of its low vapor
2. Add 1 ml of hydrogen peroxide (30%) pressure. Both liquids are poisonous.
to 60 ml of demineralized water (0.5% 2. For the B.V., the extinction is converted
solution). into that of a 2% solution (2 g in 100 ml)
3. Weigh approx. 0.2 g of liquid cocoa measured in a cuvette of 2 cm.
butter to the nearest 0.1 mg in a volu-
metric flask of 10 ml (G in g). REFERENCES
4. Add 1 ml of carbon tetrachloride, dis- ICA method 29/1988: Method for
solve the cocoa butter, and successively Determination of the “Blue Value”
add 0.5 ml of p-dimethyl aminoben- (formerly 108/1988).
zaldehyde solution and 0.05 ml (1 or 2
drops) of 32% hydrochloric acid.

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2. ISO 662 - Animal and Vegetable Fats


and Oils - Determination of Moisture
Moisture and volatile matter
DEFINITION and Volatile Matter Content.
This method describes the determination
of the moisture and volatile matter in Peroxide value
cocoa butter by heating the butter at
125° C (225° F).
DEFINITION
This method describes the determination
EQUIPMENT/MATERIALS of the peroxide value (P.V.) of cocoa but-
• boiling stones ter. The P.V. of a fat is the number of m.eq
• glass beaker with flat bottom, 100 ml of active oxygen (peroxides) per kg of fat;
• thermometer 100°-150° C (212-302° F) the P.V. relates to the oxidative stability
• hot plate (rancidity) of the fat.
• balance (accuracy 1 mg)
• watch glass
EQUIPMENT/MATERIALS
• chloroform, p.a.
PROCEDURE • glacial acetic acid, p.a.
1. Put some boiling stones into a beaker • saturated KI solution in water
and, subsequently, add 20 g of butter to (140 g/100 ml of water), free of
the nearest 1 mg. The weighed amount iodine and iodates
of butter is G1 in g, the weight of the • sodium thiosulfate 0.002 N, freshly
glass beaker plus butter is G2 in g. prepared from a 0.1 N stock solution
2. Heat the beaker on a hot plate. • starch solution 0.5%
3. During heating, continuously stir the • Erlenmeyer flask (200 ml) with NS29
fat with a thermometer, which has been and glass stopper, clean and dry
weighed together with the beaker glass • micro-burette according to Bang 5 ml
and the butter. with 0.01 ml graduations
4. Raise the temperature to 125° C (225° F)
and keep at this temperature until there
PROCEDURE
is no vapor escaping anymore. 1. Homogenize the liquid cocoa butter by
5. Check this by covering the beaker with stirring without introducing air.
a cold watch glass. The glass may not 2. Weigh 1.2-2.0 g of cocoa butter to the
steam up. nearest 1 mg into an Erlenmeyer flask
6. Allow the beaker to cool down and of 200 ml (weight G in g).
weigh again to the nearest 1 mg (G3 3. Add 10 ml of chloroform and dissolve
in g). the cocoa butter by shaking.
7. Calculate the percentage of water and 4. Add 15 ml of glacial acetic acid and,
other volatile constituents with the help subsequently, 1 ml of KI solution.
of the following formula: (G2 - G3)/G1 x 5. Shake for 1 minute and allow the
100%. Express the value obtained in Erlenmeyer flask to stand in the dark at
two decimal places. room temperature for 5 minutes.
6. Add 75 ml of distilled water and 3 ml of
REFERENCES starch solution.
1. IUPAC Standard Methods for the 7. Titrate, while shaking vigorously, the
Analysis of Oils, Fats, and Derivatives, released iodine with the sodium thio-
6th Edition. Method 2.601. sulfate solution 0.002 N. (V in ml),
Normality thiosulfite = N.

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8. At the same time, carry out a blank EQUIPMENT/MATERIALS


determination, during which no iodine
• Erlenmeyer flasks of 250 ml
may be released.
• burette of 25 ml, graduated in 0.1 ml
9. Calculate the peroxide value with the
• ethanol (p.a. 96%)
formula:
• diethylether p.a.
• KOH solution in water, approx. 0.1 N.
P.V. = (1,000 x V x N) / G.
accurately standardized
REMARKS • diethylether-ethanol (3:2) mixture,
neutralized before use with KOH
1. It is essential to reduce presence of air
solution against phenolphthalein
(oxygen) during steps 1-7 of the proce-
• phenolphthalein solution, 1% in
dure, so the flask has to be stoppered as
ethanol
much as possible or nitrogen can be
introduced into the flask regularly. PROCEDURE
Direct daylight also must be prevented.
1. Weigh 5-10 g of liquid cocoa butter to
2. The P.V. must be determined as quickly
the nearest 1 mg into a 250 ml
as possible. If this is not possible, the
Erlenmeyer flask (m in g).
sample must be stored in a cool and
2. Add 50 ml of the diethylether-ethanol
dark place.
mixture and dissolve the cocoa butter
3. The P.V. can be expressed in m.eq as
by swirling.
well as in m.mol or mg of active oxy-
3. Add a few drops of phenolphthalein
gen per kg.
solution and titrate with 0.1 N KOH
Conversion multiply the (Normality T) to the end point. (The pink
factors
____________ P.V. with
_____________ color persists for at least 10 seconds.)
m.eq/kg 1 4. Register ml KOH used (V in ml).
m.mol/kg (Lea value) 0.5
mg/kg 8
RESULTS
The ffa, expressed as oleic acid, is calcu-
REFERENCES lated with the formula:
1. IUPAC Standard Methods for the
Analysis of Oils, Fats, and Derivatives, ffa = 28.2 x T x V / m
6th Edition. Method 2.501.
1. ISO 3960: Animal and Vegetable Fats Where:
and Oils - Determination of Peroxide T = the Normality of the standardized
Value. KOH solution
V = ml of the standardized KOH solution
Free fatty acid content m = the mass (g) of the cocoa butter sample

DEFINITION The Acid Value can be calculated with the


This method describes the determination formula:
of the percentage of free fatty acid (ffa) of
cocoa butter, expressed as % oleic acid Acid Value = 56.1 x T x V / m
(then also called acidity). The ffa can be
recalculated into Acid Degree (m.eq KOH The Acidity can be calculated with the
required to neutralize 100 g of cocoa but- formula:
ter) or into Acid Value (mg KOH required
to neutralize the ffa in 1 g of cocoa butter). Acidity = 100 x T x V / m

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REFERENCES 4. Weigh 2 g of cocoa powder in a sterile


(glass) flask, add 18 ml of lactose broth
1. IUPAC Standard Methods for the
or 10 g of cocoa butter or liquor in
Analysis of Oils, Fats, and Derivatives,
90 ml of lactose broth. Close the bottle
6th Edition, Method 2.201.
and shake well.
2. ISO 660 - Animal and Vegetable Fats
5. Let the suspension stand for about
and Oils - Determination of Acid Value
30 minutes and continue with method
and Acidity.
TPC, method Molds/Yeasts, or method
Enterobacteriaceae.
6. Microbiological 6. Always carry out the same analysis
with a blank sample containing lactose
Introduction broth only.
The microbiological specifications are
based on the IOCCC methodology:
method 39/1990 (formerly 118/1990),
Determination of total
which is the reference method used for
mesophilic aerobe plate count
arbitration and calibration of other DEFINITION
methods. The TPC or total number of viable
For the microbiological control of fin- mesophilic aerobe microorganisms is
ished goods and process samples (micro- defined as the number of microorganisms
biological - HACCP), large numbers of per grams of product that develop into
samples have to be analyzed per day. colonies on a non-selective agar medium
Special methodology has been developed by incubation at 30° C (86° F) ± 1° for
and optimized for efficiency and rapid 48 hours.
availability of the results.
• Determination of total plate count MEDIA
(TPC), molds/yeasts, and • (LB): see sample preparation.
Enterobacteriaceae starts from the same • Plate Count Agar (PCA) (commer-
sample suspension in lactose broth cially available): Mix 8-13 g of PCA
(1:10 dilution). (depending upon supplier) with
• Salmonella determination starts with 500 ml of demineralized water, steril-
pre-enrichment of 4 x 375 g = 1,500 g ize for 15 minutes at 121° C (250° F),
of product per production day in ster- and cool to about 48° C (118° F).
ilized skimmed milk. These samples
could be composed of 15 x 25 g sam- PROCEDURE
ples or bigger samples from auto- 1. Take the sample suspension (1:10 dilu-
matic sampling. tion) and shake.
2. Pipette 2 ml of this suspension into
Sample preparation for total a sterile test-tube with 8 ml of LB
plate count (TPC), molds/yeasts, (1:50 dilution), and mix.
3. Pipette in each of two petri dishes 1 ml
1. Mix 13 g of lactose broth (LB, commer-
and Enterobacteriaceae
of the 1:50 dilution.
cially available) with 1,000 ml of dem- 4. Add about 15 ml of liquid PCA (about
ineralized water in a glass bottle. 48° C/118° F). Mix the suspension with
2. Sterilize the broth in an autoclave at the PCA in the dish and allow the mix-
121° C (250° F) for 30 minutes. ture to solidify (cool).
3. Allow to cool to about 45° C (113° F)
and check the pH (6.9 ± 0.1). 5. Check the sterility of the PCA by

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pouring the last remains of each bottle 7. Multiply the count by 10 and calculate
into a petri dish. the average of the two petri dishes per
6. For the blank LB samples no dilution sample.
has to be made.
7. Incubate the petri dishes bottom up at
30° C (86° F) ± 1° for 48 hours.
Qualitative determination of

8. Count the number of colonies and mul-


Enterobacteriaceae incl. E. coli

tiply this by 50. DEFINITION


9. Calculate the average of the two petri Enterobacteriaceae and/or Escherichia coli
dishes per sample. are considered to be present if micro-
organisms develop on selective media
and show positive responses according to
a specific pattern of reactions.
Determination of mold and
yeast count
DEFINITION MEDIA
The number of molds and yeasts is • LB: see sample preparation.
defined as the number of molds and • Violet Red Bile glucose agar (VRBD)
yeasts per g product that develop into (commercially available): Mix 17-21 g
colonies on selective agar media by incu- of VRBD (depending on supplier)
bation at 25° C (77° F) ± 1° for three days with 500 ml demineralized water; heat
(72 hours). to boiling and pour 6 ml into sterile
tubes and cool to room temperature.
MEDIA • Tryptone water (TW): Mix 7.5 g of TW
• (LB): see sample preparation. (commercially available) with 500 ml
• Rose-Bengal Chloramphenicol Agar of demineralized water, pour 6 ml
(RBC) (commercially available): Mix into test tube and sterilize for 15 min-
16.1 g of RBC with 500 ml of deminer- utes at 121° C (250° F).
alized water, sterilize for 15 minutes • Brilliant Green Bile Lactose Broth
at 121° C (250° F), and cool to about (BGL): Mix 20 g of BGL (commercially
48° C (118° F). available) with 500 ml of demineral-
ized water, pour into reagent tubes
PROCEDURE with Durham tubes (about 6.5 ml
1. Shake the sample suspension (1:10 dilu- liquid should fully immerse the
tion), and also analyze the blank LB. Durham tube) and sterilize for
2. Pipette 1 ml of this suspension into each 15 minutes at 121° C (250° F).
of two petri dishes. • Kovacs’ reagent.
3. Add about 15 ml of liquid RBC (about
48° C/118° F), mix the suspension with PROCEDURE
the RBC in the dish, and allow the 1. Take the remaining sample suspension
mixture to solidify (cool). (1.6 g sample in about 16 ml LB) and
4. Check the sterility of the RBC medium shake.
by pouring the last remains of each 2. Incubate this suspension and a blank
bottle in a petri dish. LB sample at 37° C (99° F) ± 1° for 20-24
5. Incubate the petri dishes bottom up at hours.
25° C (77° F) ± 1° (for 72 hours). 3. Inoculate a VRBD tube from the incu-
6. Count the numbers of mold and yeast bated suspension by stabbing with an
colonies. inoculation wire down the center to the

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bottom of the tube.


Suspect
4. Incubate the VRBD tube at 37° C (99° F)
XLD: Pink to red Non suspect
± 1° for 24 hours.
colonies with/with- White colonies
5. A sample is considered positive when
out black centers,
the whole VRBD agar has become tur-
black colonies, yel-
bid and colored purple-red to yellow,
low colonies with/
while gas formation may also cause the
without center sur-
agar to lighten.
rounded with trans-
parent medium
Positive readings have to be confirmed
MLCB: purple-
and tested for the presence (quantitative)
black colonies, No growth
of E. coli.
mauve-grey
1. Inoculate from the positive VRBD
colonies with
tube into:
cratered centers,
• a TW-tube (indol formation)
colonies with black
• a BLG-tube (lactose formation)
centers
2. Incubate both tubes at 42° C (108° F)
MSRV: Growth,
± 1° for 24 hours.
with a clear, milk- No growth
3. Add Kovacs’ reagent to the TW-tube:
white zone around
Formation of a red ring indicates the
the drop
presence of indol.
4. A gas bubble in the Durham tube indi-
cates a positive BGL.
5. E. coli was present in the VRBD tube MEDIA
when the indol (TW) as well as the 1. Pre-enrichment medium
lactose BGL-tests were positive. • Sterilized milk, pre-heated to 35-38° C
REMARKS (95-100° F).
In case of a positive reaction, the determi- 2. Selective enrichment medium
nation has to be repeated with 1 g of • Rappaport-Vassiliadis Broth (RV)
cocoa powder in 10 ml of LB. (commercially available): Mix 30-43 g
of RV broth (depending on supplier)
Determination for presence of with 1,000 ml of demineralized water,
Salmonella pour into 10 ml tubes, and sterilize
DEFINITION for 15 minutes at 121° C (250° F).
Salmonellae are considered to be present if 3. Selective media
microorganisms develop on the selective • Modified semi-solid Rappaport-
media and show positive responses to a Vassiliadis medium (MSRV).
specific number of tests (biochemical and
serological). ° Novobiocin solution (2%); dissolve
200 mg of Novobiocin into 10 ml
This method includes the motility test, demineralized water.
which allows for a negative detection
within 48 hours. (In case of a positive ° Dissolve 31.6 g of the MSRV agar
into 1,000 ml demineralized water.
motility, test isolation and confirmation
have to take place.) ° Bring to boil to sterilize (do not
autoclave).

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Archer Daniels Midland Company 53


The De Zaan ® Cocoa Manual

Flavor and Flavor Development


4
Research into the flavor of cocoa has Therefore, it was chiefly the Forastero
been a fruitful topic in the past decades. type that was exported to other parts of
Modern analytical techniques have con- the tropics in West Africa and East Asia.
tributed to a better understanding of the However, the flavor of the Forastero was
composition and the formation of the less appreciated by chocolate manufactur-
cocoa flavor components. However, even ers. In trying to combine the advantages
with all of the new and additional infor- of the Forastero and the fine flavor of the
mation recently gathered, we still do not Criollo, new hybrids were cultivated.
know exactly what constitutes cocoa These are known under the variety name
flavor. More than 480 different volatile of Trinitario. More recently, hybrids have
components divided among some 20 been cultivated by crossing Trinitario and
different chemical classes have, to date, newly collected varieties from the upper
been identified in roasted cocoa, making Amazon, which give higher yields and
it one of the most complex flavors known are more resistant and faster growing.
to mankind. Each bean variety has its own specific
potential flavor profile.
1. Formation of However, growing conditions like
cocoa flavor climate, amount and time of sunshine
The most important factors in the forma- and rainfall, soil conditions, ripening,
tion of the cocoa flavor are: time of harvesting, and the time between
• cocoa bean variety harvesting and fermentation of the beans
• fermentation and drying all contribute to the flavor formation.
• alkalization Differing conditions may lead to signifi-
• roasting cantly different flavor profiles. A good
example is the difference in flavor profile
Cocoa bean variety between cocoa produced from beans
In Module 1: History and Supply of growing in Ghana and Sabah. Although
Cocoa, we mentioned the major cocoa the variety cultivated in Sabah was origi-
bean growing countries of today. Not all nally imported from Ghana, their flavors
countries produce the same variety or are completely different.
type of cocoa. It is very important to dis-
tinguish between the various types with Fermentation and drying
regard to their differing flavor formation During fermentation, enzymatic reactions
characteristics. play a principal role in the formation of
The oldest-known type is the Criollo, the cocoa flavor precursors. Peptides and
which means “native.” This variety was amino acids are generated by proteolytic
already cultivated by the Aztecs and enzymatic breakdown of proteins. Sugar
Mayans in Central and South America. from the pulp is split into glucose and
Later, new varieties from the Amazon fructose. The peptides and amino acids
region were imported, called Forastero, and reducing sugars are the precursors
which means “foreign.” These were for the formation of the volatile flavor
appreciated particularly for their greater components formed by Maillard reactions
resistance to diseases and pests. during the later stages of the processing

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of the cocoa beans. Enzymes are also Good fermented


responsible for the conversion of the
flavonoids into tannins, leading to a
decrease in astringency of the cocoa and
changing the original purple color of the
fresh beans into the typical brown color of
cocoa.
The chemical processes involved in
fermentation are complex and not
completely understood.
Two phases can be distinguished. In the
first phase the conditions are more or less
anaerobic. The pulp sugars are converted
into alcohols by yeasts, and lactic acid
bacteria and pectins are broken down by
pectinases, which results in liquefaction
of the pulp. The liquefied pulp drains
Unfermented, violet
from the mass and allows aeration of the
mass, which starts the second aerobic
phase of fermentation. Acetic acid bacte-
ria take over and the temperature in the
mass is increased to about 50° C (122° F).
The combination of acid and heat kills the
germinal force of the bean. This is accom-
panied by the loss of cellular integrity,
which permits the mixing of substrate
and enzymes leading to the reactions that
produce the precursors of the cocoa and
chocolate flavor.
The proteins in the beans are broken
down in two stages. In the first stage,
early in the fermentation at a pH <4, the
proteins are split into hydrophobic pep-
tides by proteases. Later, during the fer- Unfermented, slaty
mentation at a pH >5, these peptides are
converted by carboxypeptidases into
hydrophilic peptides and free amino
acids. The conversion of the flavonoids by
polyphenol-oxidases into tannins takes
place during the aerobic stage of the
fermentation as oxygen is needed for the
reaction. At that stage, the saccharose
from the pulp penetrates into the bean
and is broken down into the reducing
sugars by enzymatic hydrolysis. During
sun drying, after fermentation at moisture
contents below 12%, the Maillard reaction
starts.

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All these reactions have to take place taking place during alkalization. It is
for the ultimate development of a good assumed that further reactions take place
cocoa flavor. The degree of fermentation as were earlier described during fermen-
of the cocoa bean is therefore considered tation. In an alkaline medium, the
of paramount importance. polyphenolic components are converted
The cut test is used to determine the into phenoxides, which easily oxidize into
degree of fermentation of the bean. In this quinones. The active role of the polyphe-
test, each bean out of a sample of 300 nolic components during alkalization is
beans is bisected, and the color of the inte- demonstrated by analysis of the compo-
rior of the bean is assessed by counting the nents before and after alkalization.
percentage of slate-colored and violet-col- Alkalization reduces the acidity of the
ored beans. Slaty beans are not fermented, flavor of cocoa as well as its astringency.
and violet beans are incompletely fer- Flavor aspects like typical cocoa and bou-
mented. Non-fermented beans do not lead quet are enhanced and intensified. The
to cocoa flavor development. To qualify as lowering of the astringency is caused by a
being “good fermented,” the percentage of further polymerization of the flavonoids
slaty beans should not be more than 5%. during the alkali treatment.
Cocoa beans can also be overfermented.
In this case, the beans begin to decom- Roasting
pose, and the pH rises sharply as proteins The roasting process is of great impor-
in the beans start to break down. During tance for the ultimate flavor profile of the
this process, very dark pigments are end-product. The roasting step is also
formed. They are reaction products of important because it allows the manufac-
flavonoids with amino acids. The beans turer to influence the flavor development
are then very dark colored and brittle. to a significant degree. By adapting the
Overfermented beans lead to a hammy roasting conditions, a variety of flavor
off-flavor. profiles can be obtained for cocoa liquor,
the base flavor component for chocolate
Alkalization and cocoa powder.
Alkalization is not a common step in the During the drying after fermentation,
manufacture of chocolate. However, in the Maillard reactions cause the first
the manufacture of cocoa powder, alka- meta-stable components to be formed, the
lization has a number of distinct benefits. Amadori compounds, which are conden-
It will influence both the color and the sation products of amino acids and
flavor of the end product. reducing sugars like fructose. A direct
In the alkalization process, the cocoa is correlation has been demonstrated
treated with an alkaline solution. A num- between these compounds and the forma-
ber of different alkalis are permitted and tion of the volatile cocoa flavor compo-
the process conditions can vary consider- nents.
ably. Among other criteria are the kinds of
beans, the type and quantity of alkali 2. Chemistry of
used, ratio of the active ingredients, time, roasting
and temperature. Alkalization can take Most of the various compounds found in
place in the cocoa nib (preferably) or in the flavor of cocoa are generated by the
the cocoa cake/powder. Maillard reactions. The aldehydes and
Literature reveals little of the numerous pyrazines in particular, are considered to
and complicated chemical reactions be important for the character of cocoa

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Formation of an Amadori Compound from


a Reducing Sugar and an Amino Acid
H H
(-H2O) | |
H-C = O + H 2N - R1  H-C = N - R1  H-C - N - R1
| | |
H-C-OH H-C-OH C=O
| | |
R R R

Reducing sugar + amino acid (Intermediate) Amadori compound

flavor.
The Maillard reactions play a major Compounds Found in Cocoa
part in all food preparations in which the Flavor (Flamant, 1989)
flavor is developed by a heating process
like baking, frying, or roasting. It is essen-
Component Number

Aliphatic, Alicyclic
tially a reaction between a reducing sugar
like glucose or fructose with an aldose- Hydrocarbons
group and a compound with an amino-
39

Organic acids
group. In food, this is usually an amino
51

acid, peptide, or protein. Initially the Amines


aldose group reacts with the amino-group
45

Alcohols
by removal of a molecule of H2O.
25

In cocoa, a large part of the Maillard Aldehydes 22


reactions already take place during sun Ketones
drying after fermentation, and in the first
24

Esters
stage of roasting, the Amadori com-
58

pounds are formed. The Amadori com- Lactones


pounds are reacting further in different
7

Ethers
ways depending on the reaction condi-
8

tions. For cocoa, the so-called Strecker Sulfides


Degradation is considered to be very
10

Phenols
important for the development of the
6

cocoa flavor. Heterocyclic


First, the Amadori compounds are con- Furans
verted into dicarboxylic compounds by
19

further removal of H2O molecules. These Thiazols 8


compounds reduce the α-amino acids into Thiophenes
aldehydes, and during further dehydra-
1

Pyridines
tion, the heterocyclic components like 12

pyrazines are formed. Pyrroles


From these mechanisms, it is quite
18

Oxazoles
apparent that the formation (and
15

removal) of water is the driving force in Pyrazines


these reactions. Therefore, they can only
95

Total
take place in a rather dry medium and at
463

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Maillard Reactions: Strecker Degradation


H-C=O H2N - CH - COOH
+
R2 - C = O R1

(- H2O)
NH2 NH2

H - C = N - CH - COOH H - C - N = C - COOH (- CO2) H-C H-C O=C-H


2X +
R2 - C = O R1 R2 - C - OH R1 (+ H2O) R2 - C R2 - C R1
OH O
Aldehyde

(-2x H2O)

N
N
- R2
H-C C - R2 (-H2O)
R2 -
R2 - C C-H (+O2)
N
N Pyrazine

higher temperatures. However, partic- In general, cocoa products made from


ularly in the first stages, some free water Malaysian beans have a more acidic
should be available in order to make con- flavor compared to products made from
tact between the various reactants. African-type beans. Also, in Malaysian
The roasting process is required to fur- and South American beans, the content
ther develop the desired flavor. For cocoa, of lactic acid is usually higher. During
the roasting conditions are rather mild. roasting, lactic acid is not removed, which
The product temperature at the end of the might explain the higher acidity of cocoa
roasting process should not exceed 110°- made from these beans.
120º C (230°-248° F), and the final mois- The beans from Venezuela and Ecuador
ture content should be between 1 and 2%. contain a relatively high amount of esters,
If the roasting is continued for too long, which contributes to fruity wine-like
then the more volatile components like flavor top notes, expressed as bouquet.
aldehydes, esters, and low molecular They are already present in the fermented
acids like butyric acid will be removed, cocoa beans before roasting. Because
leaving only the pyrazines and the these esters are rather volatile, they are
non-volatile acids. This results in a easily removed during roasting.
burnt flavor. Therefore, these beans should be subject-
Another important reaction during ed to a very light roast in order to keep
roasting is the change in the organic acid these bouquet
composition. The major acids in cocoa are flavors in the cocoa.
acetic, lactic, and citric acid. Acetic acid The chocolate and cocoa industries use
is volatile; the others are not. During a wide assortment of equipment, meth-
roasting, the pH increases due to the ods, and conditions for roasting cocoa.
removal of acetic acid. Differences in roasting conditions have a

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distinct effect on the flavor development. or process conditions results in a flavor


change in the end-product. Recent devel-
opment of flavor selective sensors, also
3. Sensory evaluation called “electronic noses,” could be helpful
of cocoa flavor in increasing the number of discrimin-
Introduction atory tests, but the calibration and inter-
People have a flavor memory that allows nal control of such equipment will always
both instantaneous judgment as well as require a panel of flavor experts.
comparison with experiences from the
past. The consumer’s sensory evaluation Flavor release
of foods is a process that can offer infor- One of the most important factors to be
mation often difficult to obtain from an considered when judging the properties
instrument and is critical in the assess- of a flavor is how it ultimately manifests
ment of a food product’s acceptability. or releases itself in the final product
Sensory evaluation is, in the first place, during consumption. Flavor release is the
an individual’s judgment of a taste or perceived intensity of a certain aspect of
smell of a food product. Because it is the flavor as a function of time, when the
largely a subjective process, it must be product is sensorially evaluated. It is
transformed into an objective assessment determined, for example, by the physical
to be of use to a food manufacturer in the and chemical properties of the flavor
areas of new product creation or improve- itself, by the location in the mouth and
ment and quality control. In essence, fla- the nose where the flavor is perceived as
vor evaluation is a tool with which a food well as by the texture and the tempera-
processor is able to convert the subjective ture of the product in which the flavor is
judgment of consumers into measurable incorporated.
data from which an objective analysis can In many products, fat is an important
be made. transmission medium for flavor. In such
Sensory evaluation may be defined as products, the amount of fat and its
analysis performed using the senses: melting point and melting behavior are
taste, smell, touch, sound, and sight. In important for the flavor release, as the fat
this context, the concept of “taste” should must first melt before the flavor becomes
be interpreted in a much wider sense than available. This is one of the reasons why
the direct impression on the tasting sense the cocoa flavor in different end-products
when eating. To avoid confusion between shows a different flavor profile. With
the wider and the narrower concepts of cocoa butter melting rapidly at body tem-
“taste,” the word “flavor” is often used. perature (in the mouth), the flavor release
“Flavor” encompasses the total impres- is relatively fast, allowing a variety of dif-
sion of taste (gustation), smell (olfaction), ferent flavors, each having a different
and trigeminal nerve sensations such as time-intensity curve, to be expressed in
touch, temperature, pain, and chemical unique ways. For a full flavor evaluation,
irritants (giving a heat or cooling it is important to keep the product in
response) obtained when eating a prod- one’s mouth for some time before it is
uct. Sensory evaluation is used in quality swallowed. Contact with saliva is also
control, product development, and con- essential.
sumer tests. Sensory evaluation can, for
example, provide the answer to the ques-
tion of whether a change in raw material

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Appearance, sound, mouthfeel, value) varies for the types of papillae or


texture, taste, smell position on the tongue. The four classical
The importance of products’ appearance taste sensations are salt, sweet, sour, and
is evident. Size, weight, shape, and color bitter; a fifth sensation, umami, associated
are the most important contributing char- with monosodium glutamate (MSG), is
acteristics. In the case of cocoa, this is getting acceptance, while terms like
even more obvious, as the intensity of the metallic and astringent are also named.
color will initiate a corresponding flavor The receptor cells in the taste buds regen-
expectation. Packaging also serves to erate about every 10 days, so damage is
enhance the expectations for a food item. repaired, though sickness or ill health
Sound can also play a crucial role. With may temporarily delay this.
some products, the sound generated The role of saliva is very important for
during consumption can lead to a more tasting as the nonvolatile taste stimuli
positive or negative judgment. Consider have to be dissolved before they can con-
the “crunch” of a fresh apple or the tact the taste pores of the taste buds. A
“snap” of a good chocolate bar—both are “dry” mouth or reduced saliva flow, e.g.
necessary for a positive valuation. caused by drugs or medication, results in
The mouthfeel of a product is deter- loss of taste.
mined by its texture, viscosity, and behav- The ability to taste declines slightly
ior during the (often short) period of resi- as people age, as does, to a larger extent
dence time in the mouth. This can be the ability to detect smells, especially for
described in such terms as hard, smooth, males. It has been established that elderly
crunchy, watery, powdery, greasy, waxy, people develop a preference for more bit-
or dry. The melting behavior of the fat ter and stronger, but less sweet, chocolate-
phase can be of influence also. A product flavored products. This is primarily due
can be liquid, half liquid, paste, or solid, to the fact that their threshold for bitter
all forms in which cocoa-flavored prod- compounds is higher and, therefore, they
ucts are available to the consumer. perceive the bitterness less in foods.
Chewing refines the product. In the The nose can detect the most ephemeral
meantime, the texture of the food is eval- of sensory messages. If the nose is
uated, and its temperature is adapted to pinched closed while eating, mostly
that of the mouth. It creates the desired touch; temperature; texture; and the basic
particle size and allows the release of the salt, sweet, bitter, or sour tastes can be
less volatile components of a food. As a detected. No other flavors of a food can
result, the flavor of a product can be be perceived. (Smell forms about 75% of
appreciated to its fullest extent. This is of the flavor impression.)
particular importance to the cocoa flavor High up in the nose, against the nasal
as it releases comparatively little volatile wall, lies the olfactory organ. The olfact-
flavor components by itself. ory organ is lined with a mucous mem-
Taste is appreciated by taste receptor brane, about 2-5 cm2, which has to be
cells present mainly on the tongue and penetrated by the volatile odor molecules
soft palate. The taste buds (2,000-5,000) in order for them to be perceived by the
situated in papillae on the tongue (except olfactory receptor cells, regenerating
in the middle, where the filiform papillae about every 50 days. The olfactory organ
only have a tactile function) each contain lies out of the direct stream of air that we
50-150 taste cells that respond to all taste inhale when we breathe. Only 2% of the
stimuli; only the sensitivity (threshold air we breathe reaches the receptors.

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Odoriferous molecules (stimulants) have to be excluded from panels by ade-


can reach the olfactory organ either via quate screening and training sessions.
the normal respiratory passages or in a When we evaluate a food product, each
retronasal manner. During eating, the of our five senses are used: sight, sound,
flavor of a food is primarily perceived in taste, touch, and smell. The information is
the retronasal manner. Sensitivity differs gathered and integrated into a total sen-
considerably per substance and per sory picture or impression by the brain.
person. Individuals can display differ- This judgment process is immediate and
ences in olfactory sensitivity by factors is the way in which the brain interprets
up to 1,000 for the same substance. About this impression.
150-200 odor qualities containing about The process by which a consumer
10,000 different odors can be recognized makes a judgment on a food involves
by trained persons. three separate phases. The first is the
input phase to the brain. The second is
Adaptation, synergism, the comparison of the input with what
total impression, judgment exists in the flavor memory. The third is
Adaptation, or fatigue, is the decrease in the output presented in the form of an
response with constant stimulation and is opinion. It is this opinion that is critically
observed both with smell and taste (and important for the food technologist to be
with many other senses). So, the aware of. This is where the acceptability
sensitivity to a certain stimulant declines of a new formulation will first be visible.
as a result of previous exposure to that And this opinion is very clearly a function
stimulant. At complete adaptation, the of what happens after that initial tasting.
sensitivity to the stimulant involved is Does it taste good?
completely lost. In cross adaptation, the
reduction of sensitivity is caused by expo- Flavor memory
sure to another stimulant. Adaptation is The brain has a powerful memory for fla-
time dependent (a few minutes), and it vor, retaining the most subtle features of a
can be neutralized by removing the stim- flavor with amazing accuracy. It is this
ulant (rinsing with fresh air or clean, flavor memory that represents the refer-
warm water). ence against which a new flavor is com-
Synergism is the enhanced impression pared. The memory contains details of
of taste. It is the taste impression above thousands of flavors that range from deli-
that or different from two individual com- cious to unpalatable.
ponents, so a mixture with subthreshold Experience has taught that if a product
levels of its components will produce a offers a totally new sensory picture, it
strong taste sensation. Inhibition or mix- runs a high risk of rejection. It is
ture suppression is the opposite effect, unknown. For a new flavor to be success-
where taste sensations are reduced or ful, it should be reasonably close to a
changed in a mixture of stimulants. familiar and trusted flavor impression.
It is important to realize that sensory Moreover, the expectation of the con-
sensitivity and capability differ strongly sumer should be confirmed in the actual
between individuals. The population con- tasting experience. In creating new for-
sists of about 25% “supertasters” and 25% mulations, emphasis is often placed on
“non-tasters.” For evaluation purposes, adapting known and trusted flavors
the “non-tasters” and persons with taste rather than creating completely new ones.
or smell defects (temporarily or definite) This is very much the case in the cocoa,

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chocolate, and confectionery industries. tested, usually with four to five panel
The flavor of cocoa is well known and has members. A disadvantage is that the
proven to be immensely successful. panel members have to undergo fairly
intensive and lengthy training before they
Sensory evaluation can participate. They also need regular
Sensory evaluation as we know it today retraining to keep the variations in indi-
was developed after World War II. Almost vidual judgments within narrow limits.
all food companies carry out sensory eval- The ‘70s saw the development of the
uation, notably on the product lines that Quantitative Descriptive Analysis test
carry and represent their own particular (QDA). In this method, the aspects to be
house flavor. The number of measure- tested are jointly determined by all mem-
ment methods for sensory research has bers. Eight to 10 panel members perform
increased over the past years, partly due the testing.
to the opportunities that computers offer A QDA variant is Free Choice Profiling
to process complex data. (FCP). In this method, panel members
Methods for analytical sensory evalua- individually indicate only those aspects
tion can be divided into two groups: dif- they want to test.
ference tests and descriptive tests. In dif- The principal component analysis
ference or discrimination tests, samples (PCA) is a methodology that is further
are always judged in comparison with described in Module 7: Cocoa Liquor
another sample or a standard; in descrip- under “Flavor.”
tive tests, a sample is examined on its
own to determine its sensory qualities Sensory evaluation in the food industry
and the intensities of these qualities. Sensory evaluation, as a management tool
to improve a company’s operations,
Difference (discrimination) tests requires a systematic approach. Current
Some well-known methods are the findings suggest strongly that Descriptive
Triangle Test, Paired Comparison Test, Analysis Tests provide the best informa-
Ranking Test, and Two-Out-of-Five Test. tion, which tells investigators what they
These indicate only whether or not there want to know, can be related to results
is a significant difference between sam- obtained from instruments, can be stored
ples. Difference tests are easy to carry out. for future reference, and can be collected
It is not necessary for the members of the systematically.
test panel to have intensive training, and Some of the activities to which system-
the cumulative results will indicate atic sensory evaluation can contribute
whether or not there is a significant dif- include:
ference between the samples. Therefore, it • quality control
is not surprising that difference tests are • quality assurance
often used. However, unlike descriptive • shelf-life determination
techniques, the nature of the difference is • product reformulation
not always established. • new product development - R&D
• marketing
Descriptive tests • evaluating competitive products
The first, and for a long time the only, Sensory evaluation contributions to
descriptive method was the Flavor Profile company operations can best be made
Method (FPM). The panel leader would through a team of specially trained per-
determine the aspects of the samples to be sonnel—the Sensory Evaluation Panel.

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Its evaluation work must be independent Acid (Sour)


and totally free from interference. It must One of the four basic tastes perceived on
provide an objective testing medium and the tongue, associated with acids (ASTM)
should communicate adequately with all like citric acid
company departments that are going to
use the information obtained. Astringent
ADM Cocoa uses a combination of a The chemical feeling factor perceived on
descriptive test (the QDA test) and a dif- the tongue and other oral surfaces,
ference test (the paired comparison test). described as puckering or drying, elicited
It involves the following three steps: with tannins or alum (ASTM)
• creating a glossary of terms used to
describe different sensory aspects Acrid
(cocoa flavor and flavor notes) A burnt, harsh, aromatic taste often
• training panels to judge and rate associated with burnt wood, smoke, or
those aspects roasted beans (ASTM) or a pungently bit-
• evaluating the ratings ter note often associated with astringency
The methodology for the sensory evalu- and acidity, when tasted it gives a sensa-
ation of cocoa powder can be found in tion of dryness
Module 3: Methods of Analysis under
“Flavor Evaluation.” Cocoa off-flavor notes
Burnt
Basic cocoa flavor notes Tar-like flavor
As part of the flavor evaluation, panel
members can use the following as the Earthy/Moldy
glossary of terms for cocoa products: Stale, a flavor suggestive of a badly
ventilated cellar
Cocoa
The basic cocoa note, which is derived Hammy
from a good fermented, deshelled, A flavor suggestive of smoked bacon/ham
roasted, and ground cocoa bean
Smoky
Bitter A burnt wood note
One of the four basic tastes perceived
most sensitively at the back of the tongue, Metallic
stimulated by solutions of caffeine, qui- A note suggestive of iron and copper
nine, and other alkaloids (ASTM)
Rancid
Rich or Full A flavor suggestive of oxidized butter
A full-flavor intensity contrasting with or oil
watery. It indicates the “overall” or total
flavor intensity of the product. Cardboard
A note suggestive of paper or cardboard
Bouquet
General term covering all flavor elements Baggy/Raw
over and above the cocoa character, e.g. A note suggestive of raw beans and/or
aromatic, floral, and fruity notes burlap bags

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Color and Color Development


5
After vanilla, cocoa is the most popular important for providing the raw material
food flavor in the Western hemisphere. for a consistent product. Users of cocoa
Cocoa, however, fulfills two primary products like liquor and powder, how-
functions in foods: as a colorant and as a ever, can set their own standards in pur-
flavor ingredient. In many cases, the fla- chasing specifications.
vor function dominates. In practice, this It is the combination of expertise in
double role has led to a wide range of bean selection, blending, and successful
cocoa powders adapted to applications in management of the production process
a very large range of foods. that offers the cocoa products buyer the
confidence of a product that will fulfill
1. Formation of the the requirements of both the manufac-
cocoa color turer and the final consumer.
The formation of the color of cocoa passes
through a number of stages. It starts with Precursors of the color component
the formation of precursors by biochemi- Flavonoids, a sub-group of polyphenols,
cal processes that take place in the cocoa are the primary precursors of the pigment
beans during the growth and ripening in cocoa. They occur widely in the plant
of the fruit on the tree. This process is kingdom and have a variety of functions:
largely determined by the bean varieties as pigments, as protective agents against
and the climatic conditions during disease, and as disinfectants when a plant
growth. The next stage takes place subse- is wounded. Their concentration in fresh,
quent to harvesting during fermentation unfermented cocoa beans may be approx-
and drying of the beans. This is a very imately 15%. The anthocyanidines and
important phase, as it is here that the procyanidines are flavonoids of particular
characteristic brown color of cocoa is interest as color precursors.
formed. The ultimate color of cocoa, how- The purple color in fresh, unfermented
ever, is reached after further processing of beans is due to anthocyanines.
the beans, where alkalization is the criti- These are esters of anthocyanidines and
cal step. Depending on the process condi- sugars. Procyanidines are present in cocoa
tions and the alkali used, the initial yel- as mono-, di-, and trimers of epicatechin.
lowish-brown color develops into a vari- They are also found in the form of
ety of hues from light brown to red or sugar ester derivatives. During fermenta-
even black. tion, the sugar esters are hydrolyzed by
Controlling the influence of the various enzymes. The free antho- and procyani-
stages of production on the color develop- dine molecules are then oxidized by
ment of cocoa powders is complicated enzymes to quinones. The quinones are
and difficult. reactive agents and behave as oxidizing
The color of the beans arriving from agents, oxidizing other organic molecules,
their countries of origin is beyond the which, in turn, react themselves. Quinones
immediate control of the manufacturer. react with amino acids and proteins,
The only direct control the cocoa powder forming covalently bonded complexes.
producer exercises is at the stage of bean In this way, they form various strongly
selection and blending, which is very colored pigments.
They also react with other flavonoids,

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Stereostructure of an Anthocyanin
Glycoside (Goto et al. 1978)
OH
3' OH
4'
2'

8 O+ 1' 5'
HO 7
1 OH
2 6' H
3
H 6 H
H H 5
O HO OH
4 2 3 O
H OH O 1 4 H
O O
5 OH
HO H H 6 O
HO
HO H H H
H H H OH
H

forming high-molecular weight con- quality, only a small percentage of the


densed tannins. If the molecular weight beans will show these defects. They are
of the tannin is above 3,000, it forms not so important for the color formation
complexes with proteins by hydrogen but may indicate that insufficient or sub-
bonding. As oxidation is involved, the optimum flavor will develop on roasting.
reactions take place during the second
oxidative stage of fermentation and Alkalization and color development
during sun drying of the beans. The result Reactions taking place during the alka-
is a brown pigment that is stable and lization process are complex. It is prac-
insoluble in water. ticed in many different ways by different
The conversion of flavonoids into producers, and many aspects influence
brown tannins can be demonstrated easily the color of the final product. As men-
by cutting a fresh, non-fermented cocoa tioned above, the kind of beans, type and
bean in half. The cells on the surface are quantity of alkali used, ratio of the active
destroyed, freeing the enzymes to react ingredients, time, and temperature are all
with the phenols. In a few seconds, the of influence.
color of the surface turns from deep Although alkalization in itself appears
purple to brown. to be essentially a simple process, in prac-
The concentration of anthocyanidines tice the greatest challenge is to consis-
and epicatechin are lowered during tently keep the color and flavor within a
fermentation because the anthocyanines desired range. In particular, the produc-
(the purple pigment) react, and the purple tion of dark and red cocoa powders with-
color almost vanishes. Therefore, these out the sacrifice of flavor demands great
color precursors are probably the control- skill and advanced technology.
ling factor in this enzymatic browning. At ADM Cocoa, the available techno-
In certain Theobroma cacao species, such logical expertise allows the alkalization
as the Criollo, the beans do not contain process to be easily adapted to the differ-
this purple pigment, and after fermenta- ences in the various types of cocoa beans,
tion the beans are still very lightly col- resulting in a wide range of end-products
ored. In the cut test, the color is used to with consistent colors. The color range
assess the quality of the bean. varies from light brown to reddish brown
When a consignment of beans is of good to very dark brown tints.

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Structure of Flavonoids in Cocoa


Mono- and Polymers
OH
O
HO OH

OH OH
OH
O OH
OH O
HO OH
HO

OH OH OH
OH
Epicatechin Procyanidin B

Color of cocoa butter Refining and bleaching are applied to


Flavonoid-based pigments are insoluble cocoa butters with high free fatty acid con-
in cocoa butter. The color of cocoa butter tents. These butters are usually extracted
is a result of another group of natural pig- from waste material and second-grade
ments called carotenoids. This natural col- cocoa beans. The carotenoids are then
oring occurs in such products as carrots. removed, rendering the butter colorless.
Vitamin A is one example of this group of
compounds. The amount of ß-carotene in 2. Elements of color
cocoa butter can vary and, depending on The three dimensions of color
the amount, the butter will have a more A quantitative and most accurate definition
or less yellow-orange, transparent color. of color is a recent development. The foun-
Pure prime pressed cocoa butters are not dation for the color theory was laid out by
bleached and therefore retain their typical A.H. Munsell. He was the first to describe
ivory color.

Browning During Fermentation


Polyphenol-oxydase enzyme

OH
(enzyme)
O

O2
OH O
R R
Polyphenol Quinone
S ECONDARY R EACTIONS
Oxidation : Quinone + RH2 Phenol + R
Complexation : Quinone + Amino Acid/Protein Complexes
Polymerization : Quinone + Phenol+ O2 Tannins
Tannin + Protein Complexes

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color by means of three parameters.


Lightness (L): The light or dark aspect of
a color. The lower the L value, the darker
the cocoa powder will appear.

Chroma (C): The intensity of a color by


which one distinguishes a bright or gray
color. The higher the C value, the brighter
the powder will be.

Hue (H): Color in daily speech, such as


red, yellow, or blue. For cocoa powders, a
low H value indicates a red color, and a
high H value indicates a brown color.

Munsell classified all colors and shades


on maps with color areas in an atlas
according to the coordinates above. This
meant that by comparing an object with
one of the color areas in the atlas, colors
and color differences could objectively be
described.

The CIE color coordinates


A next step in the color theory was the
quantification of colors that would enable
color calculations. This development was
based on the idea that colors are made by
mixing the additive primary colors: red
(R), green (G), and blue (B), correspon-
ding with the three types of cones in the
retina of the eye.
The disadvantage of this system was
that certain colors had to be indicated
with negative figures. This is why the
Commission Internationale d’Eclairage
(CIE) created three primaries, or tristim-
uli, indicated with the letters X, Y, and Z.
These do not exist in reality but are
derived mathematically from the original
R, G, and B primaries, with which all col-
ors can be expressed with positive fig-
ures.
The translation of X, Y, and Z values to
L*, a*, and b* values according to the CIE
system can be expressed as follows:

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L* = 116 x Y%1/3 - 16
Y% = Y/100
3. Measuring color
a* = 500 x (X%1/3 - Y%1/3) The source of light
X% = X/98.0721 The spectral color is the result of the
b* = 200 x (Y%1/3 - Z%1/3) source of light and the reflecting surface.
Z% = Z/106.8921 So for a good reproducible measurement
(1 2º Standard Observer, Standard Illuminant D65) of color, it is essential that the source of
light is standardized.
Color differences The CIE has defined four standard
Although a mathematical description of sources:
the spectral colors was now available, the Source A: Incandescent light
XYZ coordinate system still had difficul- Source B: Simulated noon sunlight
ties with the color differences calculated. Source C: Simulated overcast sky daylight
These did not correspond to visual obser- Source D65: Daylight
vation. The human eye is less sensitive to A distinction is made between the fol-
color differences in the light area than in lowing concepts:
the dark area. A calculated identical color • a source that defines the physical
difference in the dark area was therefore source of light, for instance, an elec-
experienced as greater than in the light tric bulb (source A)
area. Attempts to overcome this trans- • an illuminant that defines the theoret-
formed the XYZ coordinate system with ically defined division of spectral
the help of conversion factors. An example energy of the source of light. This is
is the Hunter color system, with coordi- an index of numbers as a function of
nates L, a, and b, which can be calculated the wavelength. Of course, “source”
from X, Y, and Z as follows: has to be as close to “illuminant” as
possible
L = 10 √Y In practice, “A” and “D65” are mainly
17.5 (1.02 X - Y) employed as the light sources. Because
a = ______________ the color measured depends on the light
√Y
source used, this should always be stated
7.0 (Y - 0.847 Z)
b = ______________ with the measurement.
√Y
The reflecting surface of the sample
A number of transformed coordinate Reflection is largely determined by the
systems are still in use. However, none of morphology of the sample. When a light
them is completely satisfactory, so no uni- beam strikes a surface, it is partly passed
versal agreement has been reached. This through, partly absorbed, and partly
is why it is always necessary to determine reflected. Light reflects at an angle of inci-
which coordinate system is being used dence of 90°, and it is diffused at an angle
when discussing color. of 45°.
The L coordinate is consistent with the When a surface is smooth, much light
Value of Lightness then introduced by will be reflected. With a rough surface,
Munsell, and from the a and b coordi- the light will mainly be diffused, i.e. light
nates, the Chroma and Hue can be calcu- is absorbed and re-emitted.
lated as follows: When using color meters, there are
two ways in which the light should be
C = √(a2 + b2) directed onto the surface of the sample to
H = arctg(b/a) minimize reflection:

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• by means of a focused light source at Instrumental color measurement


an angle of 45° to the sample surface. Color meters can be distinguished by
Reflection is then minimized. their two measurement principles:
However, the measurement can be
susceptible to the orientation of the Tristimulus colorimeter
sample relative to the light source. The diffuse reflected light that passes
Certain surface effects can result in through four filters is measured with a
differences in measurements. photometer. The filters are made in such a
• by means of an “integrating sphere,” way that they come as close to the spec-
so that the light is directed onto the tral distribution of the Standard Observer
subject from all sides from the interior as possible. The fourth filter is used to
surface of a white sphere. Then, the account for the correction in the second
color measurement is not dependent filter between 400 and 500 nm. One can
on the position of the sample relative then read the X, Y, and Z color coordi-
to the light source. However, light is nates directly. These instruments are
still reflected. In practice, this can be mostly linked to a small computer. The
eliminated by making a hole in the color differences between samples and
sphere at the place where this light is standards in one of the other coordinate
reflected most. systems can be calculated as desired.

Color measuring Color spectrophotometer


There are two basic approaches for meas- Using this principle, the whole visible
uring color. spectrum can be measured. The X, Y, and
Z color coordinates are calculated by
Visual judgment of color combining the measured spectrum and
Because of the natural human tendency to the theoretical spectra of the Standard
trust only one’s own eyes, colors are still Observer (CIE).
frequently judged only visually. To The spectrophotometer has a number
be able to do this in a reproducible man- of advantages:
ner, certain standard conditions have to • No filters are required. (These have to
be met: meet very high standards and are
• the light source, preferably one of the very hard to manufacture.)
earlier mentioned CIE standards • The color with different light sources
• the position of the sample relative to can be calculated from the measured
the light source, preferably at an spectrum. From the spectra of the
angle of 45° to each other individual components, one can cal-
• the background of the sample, uni- culate the color of a mixture.
form and preferably gray
• the distance between the eyes and the Color measurement is dealt with in
sample Module 3: Methods of Analysis.
• the size of the sample
In practice, color cabinets are mostly
used with standard light sources.

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Health and Nutritional Aspects


6
1. Introduction In this respect, ADM Cocoa is very
much aware of its responsibility to its cus-
To the Aztecs, cocoa was not only a stimu- tomers. Our products lose their identity
lant, but first and foremost a magical as soon as they are incorporated in a cus-
medicine, through which the properties of tomer’s final product. From that moment
the four elements, Fire, Water, Air, and on, they bear the name and reputation of
Earth, exercised their beneficial influence that customer.
on humans. When cocoa initially became In Module 2, Cocoa Processing, we
popular in Europe, it was also attributed indicate how this responsibility is
quite a few beneficial factors. For exam- realized.
ple, in 1717, a German physician recom-
mended cocoa as a product that: 3. Indicative nutri-
“strengthens the stomach, stimulates the tional information
spirits. It increases the venus lust, stimu-
lates the working of the brain, and eases The nutritional data on cocoa liquor
pain. It cannot be recommended enough (Table 1 on page 76), cocoa butter (Table 2
both as a food and as a medicine.” Quite on page 76), and cocoa powder (Table 3
a broad statement, and one that would on page 77) are provided. It should be
not be acceptable today without elaborate kept in mind that the values are indica-
support from scientific facts. tive. They may occasionally show signifi-
This chapter gives an overview of the cant variations due to natural fluctuations
current state of affairs with regard to the in the raw material.
health and nutritional aspects of cocoa
and cocoa products. A clear distinction
is made between facts and fiction on one
of the most popular foods known to
mankind.

2. Manufacturer’s
responsibility
The increasing awareness of the relation-
ship between the quality of the food we
eat and the effects that food may have on
our health understandably means that
increasing demands are being placed on
the food manufacturer to provide assur-
ances that the products offered to the
consumer are of high quality. This aware-
ness has resulted in many countries
creating legislation that holds manufac-
turers legally responsible for the safety of
their products.

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Table 1: Indicative Nutritional Table 2: Indicative Nutritional


Information on Cocoa Liquor Information on Cocoa Butter
Main components per 100 gram Main components per 100 gram
fat total fat
moisture moisture
55.0 g 99.9 g

crude protein
1.0 g 0.1 g
Fatty acids (%)
theobromine saturated
11.1 g

caffeine monounsaturated
1.5 g 61.5%

sugars polyunsaturated
0.1 g 35.0%

starch
0.3 g 3.5%
Fatty acid composition (%)
total dietary fiber palmitic
8.5 g

soluble dietary fiber stearic


17.5 g (C16:0) 26.0%

insoluble dietary fiber arachidic


3.5 g (C18:0) 34.5%

flavonoids palmitoleic
14.0 g (C20:0) 1.0%

organic acids oleic


3.5 g (C16:1) 0.3%

ash linoleic
1.5 g (C18:1) 34.5%

others
3.0 g (C18:2) 3.2%
Minerals
potassium
0.5%
Minerals
sodium calcium
1.0 g

calcium copper
<0.01 g 0.25 mg

magnesium iron
0.08 g 0.01 mg

phosphorus magnesium
0.3 g 0.03 mg

chloride phosphorus
0.4 g 0.45 mg

iron potassium
<0.01 g 50.0 mg

zinc
12.5 mg 20.0 mg
Vitamins
copper - A (retinol) 1.8 mg (6,000 IU)
3.5 mg

- E (tocopherol): 20.0 mg (18 IU)


2.0mg
Vitamins
- A (retinol) 1.0 mg (3,300 IU) Energy (Atwater system)
- B1 (thiamine) Kcalories
- B2 (riboflavin) Kjoules
0.1 mg 835

- B3 (niacin) Kcalories from fat


0.3 mg 3,495

- C (ascorbic acid) Kjoules from fat


0.5 mg 835

- E (tocopherol)
0.1 mg 3,495

- pantothenic acid
15.0 mg
1.0 mg
Energy (Atwater system)
Kcalories
Kjoules
520

Kcalories from fat


2,175

Kjoules from fat


460
1,925

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Table 3: Indicative Nutritional Information on Various Cocoa Powder Types


Non-alkalized Lightly alkalized Strongly alkalized
Main components per 100 gram per 100 gram per 100 gram
fat 11 g 11 g 11 g
moisture 4g 4g 4g
total N 1.25 g 4.15 g 4.10 g
N from alkaloids 0.80 g 0.80 g 0.80 g
N from crude protein 3.45 g 3.35 g 3.30 g
crude protein 21.5 g 21 g 20.5 g
theobromine 2.5 g 2.5 g 2.5 g
caffeine 0.25 g 0.25 g 0.25 g
sugars 0.5 g 0.5 g 0.5 g
starch (complex CHO) 16 g 15.5 g 15 g
total dietary fiber 34 g 33 g 32 g
soluble dietary fiber 7g 7g 6.5 g
insoluble dietary fiber 27 g 26 g 25.5 g
flavonoids 7g 6g 4g
organic acids 3g 3g 2.5 g
ash 6g 8.5 g 11 g
Minerals
potassium 2.0 g 4.0 g 5.0 g
sodium 0.01 g 0.03 g 0.04 g
calcium 0.15 g 0.15 g 0.15 g
magnesium 0.55 g 0.55 g 0.55 g
phosphorus 0.7 g 0.7 g 0.7 g
chloride 0.01 g 0.04 g 0.05 g
iron 25.0 mg 25.0 mg 25.0 mg
zinc 7.0 mg 7.0 mg 7.0 mg
copper 4.0 mg 4.0 mg 4.0 mg
Vitamins
- A (retinol) 0.2 mg (660 IU) 0.2 mg (660 IU) 0.2 mg (660 IU)
- B1 (thiamine) 0.2 mg 0.1 mg 0.05 mg
- B2 (riboflavin) 0.5 mg 0.4 mg 0.3 mg
- B3 (niacin) 1.0 mg 0.6 mg 0.5 mg
- C (ascorbic acid) 0.2 mg 0.1 mg 0.05 mg
- E (tocopherol) 0.3 mg 2.5 mg 2.0 mg
- pantothenic acid 1.5 mg 1.5 mg 1.5 mg
Energy (Atwater system)
Kcalories 205 200 200
Kjoules 860 840 840
Kcalories from fat 90 90 90
Kjoules from fat 380 380 380

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Fat (cocoa butter) Cocoa powder is hygroscopic. If a cocoa


Most commercially available cocoa pow- powder has an excessive level of mois-
ders contain between 10 and 24% fat ture, flavor may deteriorate, and the pos-
while the 10-12% fat range is the most fre- sibility of microbiological spoilage will
quently used. Cocoa butter contains spe- arise. The actual moisture content of
cific flavor ingredients, antioxidants, and, cocoa powders is lower than the moisture
as a vegetable fat, only traces of choles- content found by analysis. The method of
terol (approx. 3.0 mg/100 g). The fatty analysis used to determine the moisture
acid composition (Table 4) shows that content does not discriminate against
cocoa butter is rich in stearic, palmitic, other components that easily evaporate
and oleic acid. Recent publications sug- (such as certain organic acids) and disap-
gest that cocoa butter is less easily pear from the cocoa powder during the
digested, thus possibly influencing actual procedure. Because cocoa powder is
calorie per gram dietary calculations in hygroscopic, good packaging and storage
the future. conditions are essential to preventing the
takeup of moisture. (See also Module 9:
Table 4: Indicative Fatty Acid Packaging, Storage, and Transportation of
Composition (%) of Cocoa Butter Cocoa Powder.)
palmitic acid (C16:0) Cocoa powder is safe at a moisture con-
palmitoleic acid (C16:1) tent of up to 5%. ADM Cocoa’s produc-
26.0%

stearic acid (C18:0) tion and packaging technology ensures


0.3%

that the moisture content of their cocoa


oleic acid (C18:1)
34.5%

powders is typically below 5%, provided


linoleic acid (C18:2)
34.5%

the product is stored under proper


arachidic acid (C20:0)
3.5%

conditions.
others
1.0%

Proteins
0.2%

saturated
Proteins are essential constituents of all
monounsaturated
61.5%

living cells. Biochemically, proteins are


polyunsaturated
35%

built from amino acids as basic building


blocks. Proteins are of great nutritional
3.5%

From these factors, low digestibility, value and have numerous physiological
high levels of stearic and oleic acid, and functions.
the presence of tocopherols (vitamin E), it In the tables, the total nitrogen as well
can be concluded that consumption of as the nitrogen originating from the so-
cocoa butter may not pose a risk to called crude proteins and alkaloids are
human health. (See “Flavonoids” on page given for cocoa liquor and cocoa powder.
80 in this module and ADM Cocoa’s tech- The crude protein is calculated from the
nical information bulletin Nutritional nitrogen content. The Kjeldahl method is
Functions of Cocoa and Chocolate in Human used to establish the total nitrogen con-
Food.) tent from which the nitrogen originating
from the alkaloids is then subtracted from
Moisture the total, and the result is multiplied by
The moisture content of cocoa liquor and 6.25. (A factor based on the average nitro-
butter should not exceed the indicated gen content of vegetable proteins.) The
levels. protein from cocoa powder is low in
digestibility, probably because it forms a

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complex with certain polyhydroxyphe- Starches, as complex polysaccharides,


nols (condensed tannins). An indicative are the form in which carbohydrates are
amino acid pattern of cocoa protein is stored in plants. They are broken down
shown in Table 5. (Significant differences during digestion.
in amino acid patterns exist depending on The starch in cocoa liquor and powder
the origin of the cocoa.) The effect of the consists of approx. 36% amylose and 64%
alkalization is illustrated by the difference amylopectin.
in the indicative amino acid profile of
proteins for a natural process and an alka- Dietary fiber
lized cocoa powder. Dietary fiber in cocoa products is the col-
lective term for the structural parts of
Table 5: Indicative Amino Acid Profile plant tiss ues that are not or only
of Cocoa Powder Protein
(in g/100 g cocoa powder) partly digested. It is the modern term for
what used to be referred to as “roughage”
isoleucine
or “bulk.” In recent decades, it has been
Amino acid Non-alkalized Alkalized

established that a diet high in fiber is rec-


leucine
0.75 0.70

ommendable. Dietary fiber has been


lysine
1.22 1.13

found to reduce the risk of cancer in the


methionine digestive tract. See also ADM Cocoa’s
0.93 0.61

cystine technical information bulletin Nutritional


0.29 0.26

phenylalanine Functions of Cocoa and Chocolate in Human


0.45 0.34

Food.
tyrosine
0.94 0.85

The quantities of dietary fiber found in


threonine
0.70 0.65

a product are largely dependent on the


tryptophan
0.83 0.77
analytical method chosen to determine
valine them. In theory, dietary fiber consists of
0.26 0.24

arginine the following components:


1.17 1.10

histidine
Structural polysaccharides
1.32 1.17

- cellulose
alanine
0.32 0.28

- hemicellulose
aspartic acid
0.86 0.77

- pectic substances
glutamic acid Structural non-carbohydrate
1.96 1.84

glycine - lignin
3.28 3.08

proline Non-structural polysaccharides


0.85 0.79

- gums
serine
0.89 0.85

- mucilages
1.05 0.93

From the various analytical methods


Sugar and starch that are published for the determination
Sugars are commonly occurring carbohy- of dietary fiber, ADM Cocoa uses the
drates characterized by the presence of method developed by Prosky et al. for the
the saccharide group. They are a primary following reasons:
source of energy for the human body. • It gives an optimal picture of the
Whenever cocoa products are manufac- dietary fiber.
tured from good fermented cocoa beans • The method is relatively simple.
that are roasted in the correct manner, • It is the official method of the United
they will contain only traces of mono- States Food & Drug Administration
and disaccharides. (FDA) and the Association of Official
Analytical Chemists (AOAC).

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Flavonoids In addition to acetic acid, lactic acid,


From a nutritional standpoint, the most and citric acid, cocoa contains a small
interesting components of cocoa powder quantity of oxalic acid (approx. 0.5% on
are possibly the flavonoids. These are fat-free dry matter.)
complex aromatic compounds widely
found in nature as pigments in flowers, Methylxanthines
fruits, vegetables, and bark. Cocoa prod- Cocoa products contain theobromine,
ucts consist of a relatively high percent- caffeine, and traces of theophylline.
age of these important components. Depending on the degree of fermentation
During fermentation, roasting, and and the type of cocoa bean, the theo-
alkalization of the cocoa, mono- and bromine and caffeine contents will vary
oligomeric-catechins may be partially from 1.5-3.0% to 0.1-0.5% respectively.
polymerized into tannins. They play an The caffeine proportion of cocoa prod-
important role in color formation and ucts made from good, fermented African
partly influence flavor. In addition, with cocoa beans is in general very low: 0.1%
the increase of molecular weight, react- or less.
ivity with proteins and peptides increas- Despite its close chemical resemblance,
es. As a result, complexes that reduce the theobromine does not possess the stimu-
digestibility of the protein are created. lant effect caffeine has on the human
The determination of flavonoids is not nervous system.
simple, so that the values shown have
only an indicative character. These indica- Ash
tive values include a wide variety of The ash content of cocoa products is the
polyphenolic compounds, including sev- residue after the organic matter has been
eral flavonoids. subject to incineration. It indicates a
In literature, these compounds are measure of the presence of the inorganic
known to possess antioxidative proper- salts in the original material.
ties. This explains the long shelf life of The natural ash content of non-alka-
cocoa powder and chocolate products. lized cocoa liquor and cocoa powder is
Moreover, research carried out in connec- approx. 7.0% of the fat-free dry material.
tion with the function of food-borne The ash content in alkalized cocoa pow-
antioxidants suggests certain potential der is affected by the type and quantity of
preventive effects against a number of alkalis that are used in the alkalization
chronic conditions including cancer and process itself. The EU directive 95/2/EC
cardiovascular disease. on food additives other than colors and
sweeteners allows max. 7% potassium
Organic acids carbonate (or equivalent on fat-free dry
In the natural fermentation process of basis) to be added for alkalization. In the
cocoa beans, organic acids such as acetic U.S., the CFR 163.110 states that 3% of
and lactic acid are formed. During further potassium carbonate may be added to
processing, these are partially converted cocoa nibs for alkalization.
or volatilized, but they represent some When the ash content of cocoa powder
1.5% of cocoa liquor and 3% of cocoa is determined, it is frequently combined
powder (in non-alkalized cocoa powder with the determination of the alkalinity
as the acids in alkalized cocoa powders of the ash. This is important for certain
as salts). applications. For instance, in baking, it
does have an effect on the characteristics
of certain baked products and is a better

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and more objective parameter than pH. Energy


The latter can easily be influenced and is Interest in the caloric value of food prod-
dependent on the production process ucts is currently high because of con-
but also the age. (The pH of alkalized sumers’ sensitivity to diet.
cocoa powder may drop during storage, The amount of cocoa powder in a prod-
particularly when moisture has been uct is generally low in comparison to, for
picked up.) example, sugars and fats. The caloric
value of cocoa powder is also intrinsically
Minerals low. Cocoa powder thus contributes little
The minerals shown in the tables on to a product’s total caloric value and thus
pages 76 and 77 are those for which the has minimal effects on total energy
greatest interest exists. Naturally, there intake. The caloric values for cocoa liquor
are many other minerals present in cocoa and cocoa butter are, of course, corre-
products for which information is avail- spondingly higher.
able at ADM Cocoa’s Technical Service There are various methods available to
Departments. calculate the caloric value of cocoa pow-
Of those mentioned, potassium and der. ADM Cocoa follows the U.S. FDA
sodium are of primary importance. recommendation for the use of either the
Potassium is generally regarded as benefi- specific Atwater food factors or the
cial for humans. It fulfills a role in the general factors: 4 for protein, 4 for carbo-
synthesis of proteins and the formation of hydrate, and 9 for fat in calories per gram,
glycogen in the human body. as described by Merrill and Watt.
The natural potassium content of cocoa In the application of Atwater factors,
powder is relatively high at approx. 2%. the following calculation of caloric value
As a result of alkalization with potassium is used:
carbonate, this number may rise to 5%.
In the manufacture of dark brown pow- % fat x 0.9 (Digestibility Coefficient)
ders, sodium hydroxide is often used. x 9.3 (Heat of Combustion) + % protein
This can raise the natural sodium content x 0.42 (D.C.) x 4.35 (H.C.)
of 0.01% to more than 2%. So, in cocoa + % carbohydrate x 0.32 (D.C.)
powders in which these darker compo- x 4.16 (H.C.) = % fat x 8.37 + % protein
nents are incorporated, an increased sodi- x 1.83 + % carbohydrate x 1.33
um content may be present. = caloric value

Vitamins In this, the following should be


Vitamins are naturally occurring organic considered:
substances that are essential in very small • Digestibility Coefficient (D.C.)
quantities for the normal functioning of The digestibility coefficient is a
living cells. Cocoa products are not an measure of the proportion of a food
important source of vitamins. As shown, absorbed into the bloodstream. It is
vitamin A is negligible; the quantity of measured as the difference between
vitamin C is very low, and the B-group intake and fecal output, with an
vitamins are also low and decline further allowance made for that part of the
in alkalized cocoa powder as a result of output not derived from undigested
the alkalizing process. The presence of food residues, such as the lining of the
vitamin E (tocopherol) and to a lesser intestinal tract, digestive juices, etc.
extent, vitamin A, in cocoa butter is
an exception.

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• Heat of combustion (H.C.)


This is the energy released by the
4. Cocoa and allergies
complete combustion or oxidation of Food allergy is a phenomenon vastly mis-
a food. With allowances made for understood by the general public. For
materials not oxidized in the body, example, the American Academy of
the values are used to indicate energy Allergy, Asthma, and Immunology has
availability. found that as many as one-third of
• Carbohydrate American adults believe they are allergic
The proportion of carbohydrate is to at least one food, whereas in reality,
obtained by means of the so-called less than 2% of Americans actually have a
difference method: true food allergy. For children, this figure
100 - (crude protein + fat + ash + mois- is about 5%; however, many children
ture) seem to outgrow their hypersensitivity.
• Protein Food allergy is caused by an overreac-
In order to not overestimate the con- tion of the immune system. It identifies a
tent of carbohydrate, not crude pro- harmless substance, often a particular
tein but total nitrogenous matter protein, as an antigen. To fend off the
(obtained by multiplying total nitro- “invader,” antibodies are produced that
gen by 5.63 (Merrill and Watt)), is ultimately lead to symptoms of allergic
used as the basis for calculating diseases like asthma, eczema, and hay
carbohydrate by difference. fever. In some cases, the reactions can be
If the general factors (4, 4, and 9) are very serious and even life threatening.
used for calculating the caloric value, then Chocolate is often mentioned as being
the determination of the carbohydrate allergenic. More often than not, it must be
content is made according to the seen in the light of the above-mentioned
following difference method: gap between perception and reality.
Clinical tests have been carried out on a
100 - (crude protein + fat + dietary fiber + group of adults suspected of allergic reac-
ash + moisture) tions to chocolate. From the test results, it
was concluded that chocolate allergy is
(Because dietary fiber is not digestible.) rare in adults.
The protein content is, in this case, calcu- Nevertheless, food allergies must have
lated from total N x 6.25. the undivided attention of the food and
This last calculation leads to higher confectionery industries. In chocolate and
energy values than the Atwater approach. cocoa-flavored products, a wide range of
Considering the fact that bomb calorime- different raw materials is used in an
try measurements compare well with the almost endless variety of consumer prod-
results of the Atwater calculations, and ucts. It is of paramount importance that
taking into account recently published the food manufacturer properly labels the
information on the lower digestibility products (e.g. the presence of nuts, even
of fat-free dry cocoa components, the in trace amounts) to give the consumer
Atwater system for the energy values are the opportunity to select a food on the
shown in Tables 1-3 on pages 76 and 77. basis of the presence of possible allergens.

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Cocoa Liquor
7
1. Functionality and highlighted as they relate to quality
attributes of aspects of the end-product, while others
cocoa liquor are mentioned because they are important
to the user of liquor in the chocolate
Introduction production process itself.
Cocoa liquor is the product from which It is not uncommon to use different
cocoa butter and cocoa powder are made. words for the same product or raw mate-
It is also the base raw material for making rial. This is the case with cocoa liquor. It is
chocolate. No other ingredient in the also often called cocoa mass, sometimes
chocolate formula has such an impact cocoa paste, and in the United States, it is
on the ultimate outcome of the product as referred to as unsweetened chocolate,
cocoa liquor. Dark chocolate is basically a chocolate liquor, or simply chocolate. It
mixture of liquor, sugar, and cocoa butter, was the cocoa press industry that intro-
whereas in milk chocolate, milk powder duced the name “cocoa liquor.” As this
has also been added. industry today supplies the bulk of this
raw material to the merchant market, we
Typical Chocolate Recipes believe that the name “cocoa liquor” has
become more familiar to the cocoa and
chocolate industry as compared to other
Dark Milk

industries. In the context of this book, we


chocolate chocolate

Sugar have chosen to refer to this product as


“cocoa liquor” or simply “liquor.”
50% 45%

Cocoa liquor
Standard of identity
45% 10%

Cocoa butter 5% 25% Most countries provide a definition of


Full cream cocoa liquor in their food laws. From
milk powder Ð 20%
country to country, the definition may
vary somewhat, but in Codex Standard
In combination with the chocolate man- 141-1983, Rev. 1-2001, cocoa mass or
ufacturing process, each of these compo- liquor is described as “the product
nents has a specific influence on the final obtained from cocoa nib from cocoa
characteristics of the chocolate product. beans of merchantable quality which
However, cocoa liquor is always the dom- have been cleaned and freed from shell
inant factor in determining the chocolate as thoroughly as is technically possible
experience of the consumer. (with/without roasting and with/without
Although cocoa liquor is sometimes removal of or addition of any of its
used as a flavoring component in other constituents).”
food products, its principal use is as an The European Directive 2000/36/EC
ingredient in the manufacturing of choco- relating to cocoa and chocolate products
late. Within the scope of this chapter, we does not contain a definition of cocoa
focus particularly on the attributes of liquor. In the U.S., cocoa liquor is
cocoa liquor as a raw material for choco- described in CFR 163.111 as the solid or
late. A number of these attributes are semi-plastic food prepared by grinding

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cocoa nibs (which can be alkalized), application: the making of chocolate. It


allowing a maximum of 1.75% shell based plays such a predominant role in deter-
on alkali-free nibs. Legislators have left it mining the ultimate flavor of the choco-
up to the chocolate maker to decide in late that it is justified to extensively dwell
what stage of the production process the on the subject of how the flavor in cocoa
roasting takes place. Whole bean roasting, liquor is developed.
nib roasting, or liquor roasting can be used. The flavor of cocoa liquor is dependent
The Federation of Cocoa Commerce on three very distinct and equally impor-
(FCC) defines cocoa mass or liquor as tant factors:
obtained from cocoa nib (roasted or • the type of cocoa bean used (generic
unroasted, max. 5% shell and max. 10% background and growing conditions)
ash, both on a fat-free dry basis), mechan- • the flavor precursor development in
ically processed to a paste, which retains the bean during fermentation and
the natural fat content of the cocoa nib. drying, as well as the first steps in
In some countries, an important aspect further handling
in the marketing of chocolate is that if a • the flavor formation during subse-
certain percentage of the cocoa liquor quent processing
used is made from so-called fine or flavor Bean type and bean quality are major
beans, the final product may be called factors in determining the flavor charac-
fine grade chocolate (Edelschokolade in teristics of the final product. Subsequent
German). The International Cocoa processing can be further influenced by
Organization (ICO) listed in the the choice of equipment and by varying
International Cocoa Agreement of 1993 the processing conditions, thereby
certain cocoa bean origins as flavor beans tailoring to the specific flavor needs of
(Edelkakao in German). Cocoa beans from each individual customer. Obviously,
the following countries are designated as that specific flavor has to be reproduced
fine or flavor beans: Dominican Republic, time and again to assure that the cus-
Grenada, Jamaica, St. Lucia, St. Vincent, tomer receives what is expected: that
Samoa, Surinam, and Trinidad & Tobago. typical, recognizable, and unique house
In addition, from the following countries flavor. In short, the cocoa liquor determines
only a portion of the cocoa export may be the personality of the chocolate.
called fine or flavor beans: Colombia,
Costa Rica, Ecuador, Indonesia (Java), Cocoa bean selection
Madagascar, Sao Tomé & Principe, Papua In Module 1, the various types of beans
New Guinea, Sri Lanka, and Venezuela. with their specific characteristics were
Some chocolate manufacturers empha- discussed. Differing cocoa bean types and
size to the consumer that their products beans from different origins each have
are made of a particular cocoa bean ori- their own flavor potential. Therefore,
gin, aiming at a special market position. choosing a particular type of bean to be
However, selection of sound and well-fer- used for cocoa liquor is of paramount
mented beans of most origins, in combi- importance. This does not mean simply
nation with proper processing, can result specifying the origin of the bean, as both
in a whole range of flavors. short- and long-term influences have an
impact on the flavor potential. Among the
The personality of chocolate short-term effects are climatological
When discussing cocoa liquor, it is almost aspects and crop handling, in particular
inevitable to directly deal with its prime fermentation and subsequent drying of

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the beans. Longer-term factors are the Cocoa has established itself on every
genetic history of the bean, soil condi- cocoa-growing continent. Having
tions, the age of the trees, and crop man- resources and an actual presence in the
agement, all of which must be taken into major cocoa growing areas not only
account. During recent years we have assures that ADM Cocoa is able to pro-
seen significant changes in the availability cure the cocoa needed to produce the
of certain types of cocoa beans. Industrial desired products, but also enables partici-
processors have had to adjust to a 50% pation in rapidly changing local cocoa
drop in the supply of Brazilian cocoa. environments, as well as direct control
Malaysian bean production rose rapidly over bean quality.
in the late ‘80s, only to fall back again in
the ‘90s. The Ivory Coast has increased Processing equipment
its output to more than 40% of the total Cocoa processing has progressively devel-
world crop. Indonesia has shown a oped over the years. Many production
tremendous increase in cocoa production, systems are available, from whole bean
but the flavor potential of the beans roasting to nib roasting, special steps to
coming from the various regions is reduce the overall plate count, and thin
vastly different, as a substantial part is film techniques for even better homoge-
unfermented. nous roasting.
Crop management is another factor: In The two most commonly used roasters are:
Ecuador, producer of the unrivaled Arriba • contact roaster, in which batches of
beans, there are fewer and fewer true cocoa nibs are heated in a large
Arriba-yielding trees. They are being rotating drum
replaced by hybrids that yield a far higher • continuous air roasters, whereby
bean production per acre but lack the cocoa beans or nibs are roasted by
unique flavor of the original Arriba cocoa. direct contact with hot air
Similar examples can be found in other Some prefer liquor from whole bean
cocoa growing areas. roasting; others prefer nib-roasted liquor.
At the same time, the cocoa trade itself Both methods are very adequate and can
has experienced important changes (e.g. produce similar but also distinctly differ-
the privatization of the cocoa trade in ent types of cocoa liquor. This can be
some countries of origin), making direct even further accentuated by pretreatment
control over the selection of beans even of the nibs, during which they are wetted
more important. Obviously, only ripened, and heat treated to reduce the plate
good fermented, and adequately dried count.
cocoa beans will lead to good quality Temperature, moisture content, and air
cocoa liquor. During fermentation and throughput are very different in both
subsequent drying of the cocoa beans, the types of equipment, resulting in quite dif-
flavor precursors are developed. They ferent types of liquor. Nib contact roasters
will ultimately come to their full flavor and whole bean roasters are particularly
during roasting. The initial stages of pre- suitable for delicate top-note flavors that
treatment of the beans prior to roasting, mark the bouquet and richness of cocoa.
as discussed in Module 4, will influence On the other hand, if full-bodied choco-
the precursor formation as well. late flavors with pronounced cocoa and
Even the best starting material will fail bitter notes and lower acidity and astrin-
to deliver its potential if it has not been gency are required, an air nib roaster is
treated correctly. For that reason, ADM the better system. Nib contact roasters

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and whole bean roasters are recomm- In the manufacturing of chocolate, the
ended for processing the fine flavor beans conching process allows some of the natu-
and for low and medium roasting of West ral volatile flavoring components that do
African beans. Air roasters are excellent not have a favorable effect on the taste of
for West African cocoas that require full the chocolate to escape.
development of their typical cocoa and Each of the different types of equip-
bitter potential. See Figures 1-4 below. ment has specific features. By combining
If subsequently the cocoa liquor is sub- them in the appropriate manner, the best
jected to a thin film treatment, a process can be brought out of each of the different
whereby the astringent and acid notes are bean origins and particular bean blends.
significantly reduced, the conching time ADM Cocoa produces a range of liquors,
of the chocolate can also be reduced con- with and without subsequent thin film
siderably. See Figure 5 on page 89. treatment.

Figure 1 Figure 3
Temperature and Moisture Content Temperature and Moisture Content
During Air Roasting of Nibs During Contact Roasting of Nibs
Moisture (%) Temperature (˚C) Moisture (%) Temperature (˚C)
12 140 9 120
120 8
10 100
7
8 100 6 80
80 5
6 60
60 4
4 3 40
40
2
2 20 20
1
0 0 0 0
0 5 10 15 20 25 30 35 40 0 5 10 12.5 15 20 25 30 35 40 45 50 53
Time (minutes) Time (minutes)
Moisture Moisture
Temperature Air temperature 125°C Temperature

Figure 2 Figure 4
Temperature and Flavor Index Temperature and Flavor Index
During Air Roasting of Nibs During Contact Roasting of Nibs
Flavor Index (–) Temperature (˚C) Flavor Index (–) Temperature (˚C)
25 140 25 120
120 100
20 20
100
80
15 80 15
60
10 60
10
40 40
5 5
20 20
0 0 0 0
0 5 10 15 20 25 30 35 40 0 5 10 12.5 15 20 25 30 35 40 45 50 53
Time (minutes) Time (minutes)
Flavor Index Flavor Index
Temperature Air temperature 125°C Temperature

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Figure 5 Flavor
To be able to determine the flavor profile
of a cocoa liquor, six different descriptors
have been defined: favorable ones like
Flavor Index and Moisture Content

cocoa, bitterness, bouquet, and


During Thin Film Treatment of Liquor

richness/body, and less favorable ones


Flavor Index (–) Moisture (%)

such as astringency and acidity. Off-notes


25 2,5

are classified separately under descriptors


20 2

like burnt, hammy, smoky, moldy, earthy,


15 1,5

and woody.
10 1

The ultimately desired chocolate flavor


may vary considerably, not only from
5 0,5

manufacturer to manufacturer but also


0 0
Input After After 1st After 2nd After 3rd

regionally. Some consumers prefer a


homogenizing column column column

robust flavor, whereas others prefer a


Flavor Index

mild flavor like that of milk chocolate.


Moisture Content

Principle Component Analysis uses


biplots to determine the flavor profile.

Cocoa Liquor Processing Methods


Cocoa Beans

Whole Bean Breaking and


Roasting Winnowing

Breaking and Nib


Winnowing Roasting

Grinding Grinding

Thin Layer Liquor Liquor Thin Layer


Treatment Treatment

Treated Treated
Liquor Liquor

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An example, based on four differently The variables in the graph are indicated
processed cocoa liquors made from the as lines. The angle between two lines indi-
same blend of West African main crop cates the degree to which the variables are
cocoa beans, is given in Figure 6. inter-related, whereas the length of the
Principle Component Analysis is a line indicates the significance of the vari-
method used to easily gain insight into able. The placing of the products in the
the complex connections between many graph emphasizes the variables
variables, such as in the case of a sensoric applicable to that product. In order to be
analysis. The information contained in the meaningful, however, the two dimensions
variables is reduced by grouping the most shown in the graph must explain the
important variables on the basis of their greater part of the variation.
inter-related connection. By means of As can be deduced from the biplot,
these groups of variables (dimensions), a very different flavor profiles can be
graph can be drawn to show the essential obtained to meet the needs of the individ-
information of all the data. ual chocolate maker, from low roast, thin

Figure 6: Principle Component Analysis of Four Cocoa Liquor Types


Based on the Same Bean Blend of West African Origin

2.3
Acidity

Type 2

1.3
Full/Rich

Astringency
0.3
Type 1 Type 4
Bitterness

-0.7
Cocoa Flavor

Type 3 Bouquet
-1.7

-2.7 -1.7 - 0.7 0.3 1.3 2.3 2.9

Horizon axis: Component 1 Type 1 - Low roast + thin film treatment


Vertical axis: Component 2 Type 2 - Medium roast
Type 3 - Full roast + thin film treatment
Type 4 - Full roast

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Figure 7: Principal Component Analysis of Various Cocoas

1,9 Bitterness

1,4 *Venezuela

0,9
*Ghana
Cocoa Flavor
0,4

Full/Rich
-0,1
Acidity
Bouquet
-0,6

-1,1 Astringency *Arriba


*Sumatra

2,4 1,4 -0,4 0,6 1,6 2,6


Horizon axis: Component 1
Horizontal axis: Component 1
Vertical axis: Component 2
Vertical axis: Component 2

film-treated to fully roasted cocoas. Color


When using different cocoa bean The roasting process of good fermented
sources, the rich palette of different flavor beans renders a characteristic brown color
characteristics can be enlarged. In Figure 7, to the cocoa liquor. Differing roasting con-
the flavor profiles for four different cocoa ditions may lead to color differentiation
liquors are shown, each produced under in the liquor. A low-roasted liquor will
similar conditions and made from cocoa have a slightly lighter color compared to a
from the same source. high-roasted liquor. In chocolate, how-
Clearly, the typical flavor aspects come ever, these color differences will not be
forward: very distinctive. The color of Criollo
• Arriba, known for its unique bouquet, beans is somewhat lighter than the
with flowery, honey, and nutty top Forasteros’ color, but this difference
notes mostly disappears after roasting.
• Venezuela, with its characteristic Some bean types, the so-called light
cheesy, nutty bitterness breaking beans such as from Java and
• Sumatra, with its extreme acidity and from Madagascar, are substantially lighter
astringency in color compared to others. Both of these
• Ghana, known for its full chocolate bean types are classified as fine flavor
flavor beans, and they not only enable the

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manufacturer to produce a chocolate particle size distribution after refining, as


with typical value-added top flavor the result of which the desired viscosity
and color notes, but they may also call of the chocolate is not reached. It is there-
their chocolate fine-grade chocolate fore necessary to keep the fat content of
(Edelschokolade) in the European Union. the cocoa liquor as constant as possible.
Thus, both the applied technology and
the chocolate formula make it possible to Fineness
influence the color of the end-product. Cocoa liquor as an ingredient is ground
again during the production of chocolate,
Fat content usually on a five-roller refiner. Therefore,
Usually, cocoa butter is the most expensive the impression could mistakenly arise
ingredient in the chocolate recipe. Cocoa that the fineness of cocoa liquor is of sec-
liquor contributes a significant amount of ondary importance.
cocoa butter to the chocolate formula, so For two reasons, the fineness of the
using cocoa liquor favorably affects the cocoa liquor itself is of paramount impor-
total raw material cost of the chocolate. tance in the production of chocolate:
Depending on the bean origin and its • the availability of free fat
quality, the fat content of the nib usually • the maintenance cost of roller refiners
varies between 50 and 57%. Small beans
contain proportionately less fat and more Free fat
shell compared to large beans, and main In the nib, the cocoa butter is encapsulated
crop beans have a higher fat content than in the plant cells. During the grinding of
mid-crop beans. Seasonal effects, such as the nib into cocoa liquor, the fat is
the amount of rainfall, may cause the fat released, and the physical form of the
content to fluctuate. product, above 35° C (95° F), is changed
Cocoa liquor made from good quality into a paste. In case the plant cells remain
main crop bulk beans from West African intact, the fat will not be released and
countries such as Ghana, Ivory Coast, thus will not be available to participate in
and Nigeria have a cocoa butter content the continuous phase in the cocoa liquor
higher than 54% of the dry matter. and, later on, in the chocolate.
Criollos such as Ecuadorian and Vene- It would be optimal if all of the cocoa
zuelan beans usually have a somewhat butter in the liquor were already present
lower fat content. The resulting liquor as free fat in the kneader. The fat can,
should normally have a butter content of of course, still be released during the
50%. The same goes for Asian types such refining stage of the process, but this may
as Java beans. lead to extra slip of the upper rollers, then
It should be noted that adverse climatic to undesirable extra fine particles in the
and growing conditions have a direct chocolate. In Figure 8, the influence of the
negative influence on the butter content fineness on the viscosity of a West African
of the bean. If the fat content of the liquor cocoa liquor is demonstrated.
fluctuates too much, problems may arise There is, however, an optimum fineness
during chocolate production. and particle size distribution of the cocoa
Significant fluctuations in fat content liquor. If too many very fine particles are
will lead to differences in the consistency present, increasing the specific surface of
of the chocolate mass, requiring continu- the fat free matter exponentially, the vis-
ous adjustment of the roller refiners. This cosity of the liquor would increase as
will cause problems with respect to the well, thereby creating the opposite result.

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Figure 8: Influence of the Fineness on the Viscosity


of a West African Cocoa Liquor
Viscosity
in mPa.S
8,000

7,000

6,000

5,000

4,000

3,000

2,000

1,000

0
90.0% 97.95 99.73% 99.80% 99.95% 99.97% 99.99%

Fineness in % through 75µ

Maintenance cost lead to a difference in terms of downtime


The fat-free dry matter of cocoa liquor of the refiner of a factor 4 to 5.
consists mostly of fibrous material. Fiber Furthermore, in chocolate recipes with
material is difficult to disintegrate. The very high liquor contents, part of the
grinding of cocoa liquor demands not liquor has to be added in the conching
only a vast amount of energy, it also stage, as the total fat content would be too
causes significant wear on equipment. high to pass through the refiners without
In particular, the five-roller refiner is sub- causing problems. However, this can only
jected to this wear. Repair or maintenance be done if the cocoa liquor is sufficiently
of such refiners is costly. In cases where fine. If the cocoa liquor contains too many
the cocoa liquor being processed is too coarse particles, these particles will
coarse, further disintegration of the parti- appear in the chocolate as separate
cles will take place on the roller refining specks.
equipment, leading to excessive wear. The
difference between an adequate and an
insufficient fineness of cocoa liquor can

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Rheology Lipase activity and cocoa liquor


Obviously, both the fat content and the Enzyme activity forms an integral part of
fineness of the cocoa liquor have a direct live seeds, and the cocoa bean is no
influence on the viscosity of the product. exception to this. In particular, the fat-
Other factors, however, are also of impor- splitting lipase enzyme is undesirable in
tance, such as the moisture content, the most food products. Splitting or
time and intensity of processing, and the hydrolization of fats (triglycerides) pro-
shear forces to which the liquor is sub- duces free fatty acids and di- and mono-
jected during production. From this, one glycerides. Short chain fatty acids in partic-
can safely conclude that the lower the ular produce strong off-flavors at very low
viscosity of the cocoa liquor, the better the concentrations. For instance, when lipase is
rheological properties in the chocolate, introduced to lauric fats such as coconut
with minimal fat content. oil and sufficient water is available, saponi-
fication may occur. The resulting soapy fla-
Microbiology vor is caused by the lauric acids formed. In
Certainly, all ingredients to be used in a similar way, if lipase catalyzes the
food products should be of excellent hydrolysis of butter fat, strong rancid
microbiological quality, regardless of notes will become apparent.
whether these ingredients will be sub- This normally will not occur in cocoa
jected to an adequate reduction of micro- liquor and chocolate, but in products such
organisms during further processing into as ice cream coatings and filled chocolates
a finished product. Similarly, it is no (bonbons), conditions may be appropriate
longer sufficient for a supplier to specify for enzymatic activity. Thus, when lauric
only a maximum plate count for a partic- fats are present in chocolate product for-
ular food ingredient. mulations, lipase-free ingredients should
The water activity of cocoa liquor and be used.
chocolate is usually too low to permit
development of microorganisms. On the 2. The application
other hand, pathogenic organisms such as of cocoa liquor
Salmonellae can survive in the fat medium Chocolate
of both these products. The overall taste perception of chocolate
Furthermore, cocoa liquor, and the is, to a large extent, the result of a balance
chocolate made from that liquor, can be between the sweetness of sugar and the
used in combination with other products bitterness of the cocoa liquor. Relatively
in which microbial growth conditions are small variations may have a significant
favorable. Therefore, ADM Cocoa speci- influence on that balance. The degree of
fies that all of our cocoa liquors comply to roasting as well as the origin of the cocoa
strict microbiological values. For flavor can change the perception of the bitter-
beans that are usually subjected to mild ness of the cocoa liquor substantially. A
roasting conditions, a maximum plate chocolate product that is perceived as too
count of 25,000/g is specified, whereas for bitter can be corrected by using cocoa
standard liquors a maximum of 5,000/g is liquor with a milder flavor. Such a correc-
given. In both cases, the median value is tion, however, can often also be achieved
normally a factor 10-20 lower, and the by merely increasing the sweetness of the
presence of certain pathogens, including product. Similarly, a chocolate product
Salmonellae, is monitored. that is found to be too sweet can be har-
moniously balanced without having to

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reduce the sugar content by adding a certain loss of the typical chocolate flavor
somewhat stronger-flavored cocoa liquor. notes in the resulting cocoa powder.
Supporting flavor ingredients such as If cocoa powder is not able to give an
vanillin are often instrumental in adequate chocolate flavor in a particular
rounding off the total flavor impression. end-product, then either chocolate or
Quite a large number of spices and herbs cocoa liquor can replace it. Notably, in
have been described in literature as Europe, labeling a product “made with
enhancing the overall chocolate flavor. real chocolate” is a strong consumer mar-
The fineness of chocolate is an impor- keting tool. In that case, chocolate must
tant factor in both the color and the flavor indeed be the ingredient used. In other
of the product. parts of the world, the use of the word
The finer the chocolate, the lighter its “chocolate” seems to be of lesser impor-
color will be. The flavor experience of tance, and consequently, the alternative
such a product will also be more rounded ingredient could instead be the thin film
and more harmonious. This is particularly pre-treated cocoa liquor, which resembles
true for chocolate with a median particle the flavor of a liquor that has been sub-
size (<18µ). In coarser material (>25µ), the jected to a conching treatment.
harsher flavor components, like bitter-
ness, will come forward in a more pro- 3. Packaging, storage,
nounced manner. and transportation
As a rule, chocolate with a high liquor Cocoa liquor as a rule is used in liquid
content is very finely ground. When the form. Large users accept the product in
high amount of cocoa liquor causes the fat tank trucks in liquid form as soon as this
content of the chocolate mass to become is logistically feasible. Transportation must
too high, this mass can no longer be fed take place in clean, odor-free, dry tanks
over the roller refiners. In such a case, that are exclusively used for food-grade
part of the cocoa liquor must be directly products and that have proper insulation.
added to the conching equipment. This Loading temperature of the cocoa liquor
can only be done if the liquor has a suffi- should be between 55°-65° C (131°-149° F).
cient fineness. During transport, depending on the dis-
tance, the temperature of the liquor may
Other applications drop somewhat, but at the point of dis-
Apart from chocolate, cocoa liquor is also charge, the temperature should not be
used in other applications, though only in below 45° C (113° F).
modest amounts. In ice cream, ice cream Cocoa liquor is a dispersion of very fine
coatings, bakery products, chocolate particles in cocoa butter. When it is stored
drinks, and desserts, the use of cocoa in tanks, these particles will settle to the
liquor is sometimes preferred over that of bottom of the tank (the lower the vis-
cocoa powder. Usually, it is then a matter cosity, the quicker this will happen).
of weighing the chocolate flavor against In order to avoid settling on the bottom
the flavor of cocoa powder. part of the tank and prevent the liquor
Adding a proportionate amount of from dehomogenizing, it is necessary to
cocoa butter to cocoa powder will not stir the liquor regularly.
provide a comparable flavor to the flavor Usually, an intermittent scraping/stir-
produced from cocoa liquor. The condi- ring device is installed to keep the liquor
tions to which the liquor is subjected moving during the entire storage time and
during the press operation lead to a protect it from overheating and settling.

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Special care must also be taken to pre- In solid form, the liquor must be pro-
vent condensation in the storage tank. tected against direct sunlight and other
This may especially occur near the man- heat radiation sources during transporta-
hole or the lid of the tank. These should tion. Store in cool (15°-20° C/59°-68° F),
be properly insulated or traced. dry (RH <50%), dark conditions.
Cocoa liquor is a very stable product. Temperature fluctuations should be
Still, for prolonged optimal storage in liq- avoided. During melting of the liquor,
uid form, it is advisable to keep the tem- avoid overheating and be sure the contact
perature of the product, under stirring, temperature does not exceed 90° C (194° F).
between 40°-45° C (104°-113° F). Storage In the spirals of the melting tank, use warm
tanks can be heated by hot air in a hot water rather than steam, as this would
room where the tank is located, by a raise the contact temperature too high.
jacket, or by an internal hot water spiral. Cocoa liquor is a product with a high
Steam heating should be avoided, as this fat content—about 50% of it is cocoa but-
may raise the contact temperatures too ter. Like all high fat products, cocoa
high, causing after-roasting. liquor easily absorbs foreign odors.
Designating tanks for the exclusive stor- During storage, be sure no undesirable
age of cocoa liquor is recommended. They odors are directly exposed to the cocoa
need not be made of stainless steel. As liquor, as the product will quickly absorb
long as the tanks are used properly and these.
regularly, it is also not necessary to clean
them. If, for whatever reason, a tank has 4. Specification for
to be cleaned, the inside must be com- cocoa liquor
pletely dried and rinsed with cocoa butter The standard specification of a natural-
before it is put in use again. process (non-alkalized) cocoa liquor is
When cocoa liquor cannot be received based on West African cocoa beans and
in liquid form, it can be supplied in car- applies to an average sample of a consign-
tons in solid blocks of 25 kg or in kibbled ment leaving the production plant, deter-
form in bags of 25 kg. mined with the company’s standard

Standard Specification
Flavor
Fat content, extraction with petroleum ether
up to standard

pH
50-51% or 52-54% or 54-56%

Fineness (%), 75µ sieve, water-suspension


5.3-6.0

Moisture content (%)


99.0 min. (or micrometer fineness 10-12)

Standard plate count


1.5 max.

Molds per g
5,000 max. (or up to 25,000 max.)

Yeasts per g
50 max.

Molds and yeast per g


50 max.

Enterobacteriaceae in 1 g
100 max.

E. coli in 1 g
negative

Salmonellae
negative
negative

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methods of analysis (shown in Module 3).

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Cocoa Butter
8
1. Functionality butter in almost identical wording. In the
and attributes of USA, cocoa butter is not separately
cocoa butter defined, but it is described in CFR 163.112
as the cocoa fat removed from ground
Introduction cocoa nibs.
If it had not been for John Fry, it is debat- It seems logical that cocoa butter is
able whether chocolate as we know it made from cocoa beans, but some legisla-
today would ever have come into exis- tors have gone one step further by stipu-
tence. In 1847, he discovered one of the lating that cocoa butter can only be made
confectionery industry’s greatest inven- from cocoa beans, cocoa nibs, cocoa
tions by adding cocoa butter to a mixture liquor, cocoa cake, or cocoa dust. In other
of cocoa liquor and sugar. words: from nothing else.
Chocolate was born, and it was here to Relevant factors for cocoa butter and its
stay. Like many inventions, his discovery production are:
seems like a relatively simple matter • use of sound cocoa beans to obtain
today. cocoa butter with max. 1.75% of free
Cocoa butter was the key to John Fry’s fatty acids (FFA)
chocolate invention. Probably no other • reduction of shell content in the cocoa
edible fat available at the time would nibs (max. 1.75% on alkali-free nibs),
have produced a consumer product that, resulting in max. 0.35% unsaponifi-
right from the beginning, proved to pos- ables in press cocoa butter but in max.
sess such commercial staying power glob- 0.5% unsaponifiables in expeller and
ally. Particularly, the functional properties refined cocoa butter (larger portion of
of cocoa butter in the initial recipe made shell)
it possible to formulate the chocolate into • processing like filtering and/or cen-
a product with the specific characteristics trifuging, degumming and/or deodor-
that it still has today. izing, neutralization, and bleaching
This module deals with the functionali- Based on these factors, some legislation
ties and attributes of cocoa butter in its and several trade contracts on cocoa but-
almost sole application: the manufacture ter, e.g. of the Federation of Cocoa
of chocolate. Commerce (FCC), recognize four defined
types or quality grades of cocoa butter:
Standard of identity • Press Cocoa Butter, obtained by means
Cocoa butter is one of the most expensive of mechanical pressing of cleaned and
commodity-based vegetable fats available. ground cocoa nibs and subsequently
Therefore, it is not surprising that over only filtered/centrifuged and
the years legislators have been very par- degummed and/or deodorized
ticular in defining its standard of identity. • Expeller Cocoa Butter, obtained by the
Current legal definitions around the expeller process, often with whole
world are very similar. The Codex beans or nibs with high shell content
Standard (Codex Stan 86-81, Rev. 1-2001) and only subjected to further pro-
and the European Directive 2000/36/EC, cessing similar to Press Cocoa Butter
for instance, define the standard of cocoa

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Refractive Index nD(40˚ C/104˚ F)


Press Cocoa Butter Other Types of Cocoa Butter

Slip Melting Point 30˚-34˚ C (86-93˚ F) 30˚-34˚ C (86-93˚ F)


1.456-1.459 1.456-1.459

Clear Melting Point 31˚-35˚ C (88-95˚ F) 31˚-35˚ C (88-95˚ F)


Free fatty acids (as % m/m oleic)
Saponification value (mg KOH/g fat)
0.5-1.75% 0.5-1.75%

Iodine Value
188-198 188-198

Unsaponifiable Matter (% m/m)


33-42 33-42
max. 0.35%* max. 0.5%
*0.45% for Southeast Asian beans
• Refined Cocoa Butter, obtained by liquor has a somewhat stronger flavor
expelling or pressing, subjected to the than butter obtained from non-alkalized
same treatments as Expeller Cocoa liquor. By far, most cocoa butter today is
Butter, and neutralized and bleached made from alkalized cocoa liquor.
(refined) Particularly, the bitter and specific cocoa
flavor components are accentuated in this
Analytical criteria have been defined type of cocoa butter.
for the various types of cocoa butter: Most often, the term “natural cocoa but-
Cocoa Fat forms a separate category. ter” is used for cocoa butter that has not
This is defined as fat obtained in any way been subjected to a deodorization step, so
from part of the cocoa bean that does not it has the full cocoa butter flavor.
necessarily conform to one of the above Sometimes the term “natural cocoa but-
definitions. ter” describes the cocoa butter from non-
The chocolate industry is almost the alkalized (natural) cocoa liquor.
sole user of cocoa butter, and usually The flavor intensity of cocoa butter can
press cocoa butter is set as the standard. be managed by subjecting it to a deodor-
The other types are generally considered izing treatment. Depending on the
to be somewhat lower standard, mostly required flavor intensity, cocoa butter can
because they are often made from sub- be fully or partially deodorized. A taste
grade cocoa beans or extracted from panel can help establish to what degree of
cocoa waste material. In this module, we deodorization the cocoa butter should be
will exclusively deal with the standard of subjected in order to obtain the desired
the press cocoa butter. flavor profile. The Rostagno Aroma Index
can be used as an instrumental aid in
Flavor establishing the extent of deodorization.
The flavor of cocoa butter should be Fully deodorized butter has hardly any
investigated from two different angles: its cocoa flavor of its own, whereas non-
own typical flavor characteristics and its deodorized butter absorbs the cocoa fla-
flavor stability. Both aspects are dealt with vor components released during the
in this module. roasting process. The degree of deodor-
izing is determined by the flavor intensity
Flavor characteristics the cocoa butter user requires:
After the roasting and alkalizing steps, • In dark chocolate, which contains a
cocoa butter intrinsically incorporates all relatively high amount of cocoa liquor
of the typical cocoa flavor elements. It and a proportionately lower amount
will, therefore, have a distinct cocoa fla- of cocoa butter, the flavor contribu-
vor. Cocoa butter made from alkalized tion of cocoa butter is acceptable.

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However, depending on flavor profile Flavor stability


target and customer preferences, fully Like any fat, cocoa butter can deteriorate.
or partially deodorized cocoa butter is Fat oxidation leads to a variety of off-fla-
normally used. vors which, in combination, are usually
• In creamy milk chocolate, which con- referred to as rancidity. This can also hap-
tains much smaller quantities of cocoa pen to cocoa butter, although cocoa butter
liquor in combination with higher is one of the most stable lipids in compar-
quantities of cocoa butter and has a ison with other fats and oils.
flavor profile that usually avoids The sensitivity for oxidation can be
strong and bitter notes, fully deodor- measured in several ways. In the food
ized cocoa butter is often used. industry, the Rancimat test is often used
• In white chocolate, which contains no for establishing the oxidation stability of
cocoa liquor at all, the type of cocoa oils and fats. The longer the incubation
butter will heavily depend on flavor time the more stable the product will be.
profile and customer targets. For chil- In Table 1, a comparison is given for a
dren, who expect a smooth, creamy Rancimat test carried out at 100° C
flavor, fully deodorized butter might (212° F) on a number of natural and
be used. For adults, who expect a processed oils and fats.
cocoa flavor experience, partially or
non-deodorized butter may be
preferred.
In contrast with other refined oils and
Table 1: Rancimat Test at 100° C (212° F)
fats, cocoa butter is deodorized by means
of a light treatment with steam under vac-
uum. As this treatment is very mild, the
Cocoa Butter 213

less volatile flavor components of cocoa


Vegetable Oils
Canola Oil
butter can still be detected even if it is Olive Oil
6

fully deodorized. Also, tocopherols, the


Peanut Oil
20

natural antioxidants present in the cocoa


Soybean Oil
29

butter, are not removed.


The main reason for a mild steam treat-
11

ment lies in the need to maintain the opti-


Vegetable Fats
Coconut Oil
mal functional properties of the cocoa Hydrogenated Soybean Oil
180

butter. More stringent conditions could


Palm Oil
174

trigger interesterification of the butter.


Palm Kernel Oil
43

The unique triacylglycerols composition 45


of the butter, with the unsaturated oleic
acid on the 2- position and the saturated
Animal Fats
Butter Oil
fatty acid on the 1- and 3- positions, Lard
17

would be lost due to interesterification,


3

causing the fatty acids to be randomly


distributed. This is detrimental to the
hardness and the crystallization proper-
ties of the cocoa butter, which are sensi-
tive issues for cocoa butter users. Under
“Hardness” on page 103, we discuss this
subject in more detail.

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The reason for the high stability is is often much more sensitive to these
twofold: deviations than existing instrumental
• By nature, the composition and struc- techniques.
ture of cocoa butter give it out-
standing protection. Just over one- Color and opacity
third of all fatty acids present in the Cocoa butter has an ivory color in solid
triacylglycerols are unsaturated. By form and is yellowish in liquid form. In
far, the largest part is oleic acid. Only liquid form, its color should be clear and
about 10% of the unsaturated fatty may not contain any solid particles. In
acids is polyunsaturated linoleic acid, most cases the color of cocoa butter is not
whereas the very unstable linolenic relevant with regard to the color of the
acid is virtually absent. In addition, chocolate made from it. The brown color
almost all unsaturated fatty acids are of the fat-free dry cocoa constituents
located on the 2- position of the determines the color of the chocolate, and
triglycerides, which allows for struc- in this respect the color influence from the
tural protection. butter is negligible. There is, however,
• Cocoa is a rich source of antioxidants. one exception: white chocolate. Although
The well-known tocopherols are here the color of the milk components is
found in cocoa butter. A typical analy- dominant, the color of cocoa butter does
sis shows that cocoa butter contains have its impact as well.
about 200 mg/kg tocopherols, with Color is usually measured by means of
the larger part (170 mg/kg) consisting a Lovibond tintometer. (See Module 3:
of gamma tocopherol and the remain- Methods of Analysis.) For cocoa butter,
der being alpha and delta tocopherol normally the red color is measured, after
(15 mg/kg each). Too-stringent having standardized the yellow color on
deodorization reduces the tocopherol 40 in a 1-inch cell. The red color varies
level, resulting in reduced stability. between 1 and 2. For white chocolate, it is
In addition, cocoa is rich in flavonoids. desirable to limit the red color to a maxi-
These substances have attracted attention mum of 1.6, as otherwise the chocolate
lately because of their radical binding tends to become too dark yellow.
properties and their effectiveness in When white chocolate is exposed to UV
retarding the oxidation process. Flavo- light, the yellow color will disappear. This
noids, however, because of their polar bleaching effect occurs due to photo-oxi-
character, will remain mainly in the solid dation of the photo-sensibilizers. These
phase (cocoa powder), and their positive are present in cocoa butter (chlorophyll
influence is hardly conveyed to the cocoa derivatives) as well as in the milk con-
butter. stituents (riboflavines). As the color grad-
In order to establish oxidative deterio- ually disappears and the bleaching effect
ration, the peroxide value determination becomes noticeable, the oxidation can also
is sometimes used. (See Module 3: be sensorically detected (rancidity). It is
Methods of Analysis.) This test, however, therefore important to protect cocoa but-
often lacks accuracy, as many oxidative ter and white chocolate from direct UV
products such as n-hexanal show a much sources such as sunlight.
lower detection level than those that can Clearness of the cocoa butter is of no
be determined. An experienced taste significance for chocolate. However, it is
panel proves to be a very reliable means an indication as to whether proper pro-
to detect taste and flavor deviations and cessing conditions have been applied. It is

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important that liquid cocoa butter is com- cules, its behavior at a phase transition
pletely clear and shows no particles, resembles that of a pure chemical sub-
either in suspended form or as a sedi- stance: The fat is almost entirely solid up
ment. Turbidity of fat may be caused by to 27.5° C (81.5° F), quickly becomes soft-
contamination with moisture. In the man- er when the temperature is raised, and is
ufacturing of chocolate, this should entirely liquid above 34° C (93° F).
immediately be corrected to avoid prob- The group of symmetric triacylglycerols
lems in the production process. is often indicated with the letters SUS,
meaning saturated-unsaturated-saturated
Hardness triacylglycerol. Table 2 shows the differ-
Due to its typical chemical composition, ent types of triacylglycerols (trisaturated=
cocoa butter is a unique fat. In contrast SSS, monounsaturated=SUS/SSU, disatu-
with most other vegetable and animal rated=SUU/USU and triunsaturated=
fats, cocoa butter consists of mainly three UUU) in cocoa butters from various
triacylglycerol molecules: POS, SOS, origins, and Table 3 illustrates the differ-
and POP (P=palmitic acid, O=oleic acid, ences and variations in monounsaturated
S=stearic acid). The uniqueness of these (SUS/SSU) triacylglycerols by country
three molecules is that they strongly of origin.
resemble each other, with the unsaturated These tables show that Malaysian cocoa
oleic acid mainly located on the 2- posi- butter contains substantially lower quan-
tion and the saturated palmitic and stearic tities of unsaturated triacylglycerol mole-
acid on the 1- and 3- positions of the cules (SUU/UUU) and much higher quan-
glycerol molecule. Because cocoa butter tities of monounsaturated molecules
makes up about 80% of these three mole- (SUS). This explains why cocoa butter

Table 2
Origin Cocoa Butter and Composition of Triacylglycerols

Malaysia

Ivory Coast

Ghana

Cameroon

Brazil

0 20 40 60 80 100
sss sus ssu suu usu uuu
Contents (%)

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Table 3
Origin Cocoa Butter and Monounsaturated Triacylglycerols

Malaysia

Ivory Coast

Ghana

Average
Cameroon Low
High
Brazil

60 70 80 90 100
SUS (%)

Table 4
Origin Cocoa Butter and Iodine Value

Malaysia

Ivory Coast

Ghana
Average
Cameroon Low
High
Brazil

30 35 40 45
Iodine Value

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made from Malaysian beans is much is harder than butter from Brazil and that
harder than cocoa butter made from butter from West African beans is some-
Brazilian beans, for example. The varia- where in between these two. Penetration
tions that can be observed for Brazilian and snap tests on chocolate confirm these
beans are mainly due to the significant differences between the various origins.
fluctuations in temperature between the From the aforementioned chemical
summer and winter seasons in this region. (triacylglycerol) differences, the physical
Unsaturated fatty acids in fats can be differences in the hardness of cocoa butter
determined by means of the Iodine Value. have been explained. However, cocoa
(See Module 3, Methods of Analysis.) In butter with a low Iodine Value does not
Table 4, the variation in iodine values necessarily lead to a harder chocolate,
between the various cocoa bean origins is compared to butter with a medium Iodine
indicated. This indirect method, defining Value. There are two important reasons
the Iodine Value, proves to be an effective for this:
yardstick for the hardness of cocoa butter. • It is essential that the cocoa butter is
A more direct method for determining brought into the correct and stable
the hardness is to determine the amount crystal structure. (See page 107 under
of solid fats present in the cocoa butter. “Solidification behavior.”) An exam-
Table 5 shows the differences and varia- ple of the effects of the various tem-
tions in amounts (content) of solid fats pering methods on the hardness of
(SFC) found in cocoa butters from the chocolate is given in Table 6.
same bean origin, measured at 30° C
(86° F). From these data, it can be con-
cluded that butter from Malaysian beans

Table 5
Origin Cocoa Butter and Solid Fat Content

Malaysia

Ivory Coast

Ghana
Average
Cameroon Low
High
Brazil

20% 30% 40% 50% 60% 70%


SFC (%) at 30° C (86° F)

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Table 6
Hardness of Milk Chocolate
Effect of Cocoa Butter and Tempering

Hardness at 18° C (64° F) (MN/M2)


1.6
Tempering 26.5° C
1.4 (79.7° F)
1.2 Tempering 27.4° C
(81.3° F)
1.0
0.8
0.6
0.4
0.2
0.0
Ivory Coast Malaysia Soft Brazil

Origin of Cocoa Butter

• In chocolate recipes, fats other than early. When the temperature is low
cocoa butter, like dairy fat and possi- enough, the chocolate starts to solidify.
bly oils from added hazelnuts or Due to the crystallization heat, the tem-
almonds, are often introduced. These perature of the chocolate will change.
can have a major influence on the
ultimate hardness of the chocolate. Optimal tempering
Through eutectics, differences in vari- When chocolate is tempered properly, its
ous cocoa butters can manifest them- temperature will remain more or less con-
selves quite differently than what a stant for some time during cooling. The
mathematical calculation would lead released crystallization heat is then bal-
one to expect. anced by an equal amount of cooling
energy. Only when the liquid cocoa butter
Tempering—measured by means is transformed into solid crystals will the
of a tempermeter temperature of the chocolate drop further.
The tempering process is one of the most
important steps in the manufacturing of Under tempering
chocolate. The degree of tempering, indi- If the chocolate is insufficiently tempered
cating the quantity of stable crystals that or not tempered at all, thus making fewer
have been formed, can be measured by stable seeding crystals available, more
means of a tempermeter. With this crystallization heat will develop during
method, a certain amount of liquid choco- cooling, as more liquid fat has to be trans-
late is cooled under specific conditions, formed into the solid form. A distinct
and the temperature of the chocolate is increase in temperature can be observed at
registered with a temperature sensor. the beginning of the crystallization. It will
Initially, the temperature will drop lin- decline again after reaching a maximum.

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Table 7: Polymorphy of Crystals of Cocoa Butter


Form X-Ray Pattern Heat of Fusion Melting Point Chain Packing
KJ/mol ¡C (¡F)
I Y unknown 17.3 (63.1) double

II a 85.5 23.3 (73.9) double

III b 113.0 25.5 (77.9) double

IV b 118.0 27.5 (81.5) double

V b 137.3 33.9 (93.0) triple

VI b 148.7 36.3 (97.3) triple

This phenomenon is called under-tem- product. Small crystals are preferred.


pered chocolate, and it often leads to Solidification behavior
demoulding and fat bloom problems For the application of cocoa butter in
because insufficient stable crystals were chocolate, the solidification behavior of
present during the cooling of the end- cocoa butter is its most important func-
product. tional property. The conversion from liq-
uid into solid form is a critical step in the
Over tempering chocolate production process that not
Chocolate can also contain too many sta- only determines the quality and the shelf
ble seeding crystals. This will be percepti- life of the end-product but also requires
ble in the rheology of the chocolate. capital investments in tempering and
Because a significant part of the liquid fat cooling equipment.
has been withdrawn from the continuous A number of factors have to be taken
phase of the chocolate and is now trans- into account with regard to the solidifica-
formed to the solid form, less liquid fat is tion behavior of cocoa butter:
available for pumping the product. This • the polymorphic crystallization
type of chocolate will release little crystal- properties
lization heat during cooling, rendering a • influence of the cocoa bean origin
rather flat cooling curve. As a substantial • influence of alkalization
part of the phase transition (from liquid to • influence of deodorization
solid) has taken place before the chocolate
reaches the mould, less contraction will Polymorphic crystallization properties
occur in the mould, leading to demoulding A fat can solidify in various crystal forms
problems at the end of the process. that will then show different melting
Crystallization is a process whereby points. This is referred to as polymor-
time and temperature are important fac- phism. The density in which the fat crys-
tors. They are determinants with regard tals are packed and the ultimate crystal-
to the speed of crystallization. The higher lization form vary by crystal type. In their
the re-crystallization speed, the smaller least-stable form, the triacylglycerols can
the crystals will become, and more crys- freely rotate around their axis, resulting
tals will be formed. The number of crys- in poor packing of the crystals. Very little
tals is, in turn, important for the speed heat is required to bring them back to
with which the chocolate will solidify, their liquid form.
whereas the size of the crystals influences
the final gloss and hardness of the end-

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Figure 1
Shukoff Cooling Curve of Cocoa Butter

Temperature (° C)
35

30

25
dT/dt
20

15
5 25 45 65 85 105 125 145 165
Time (Minutes)

these crystals will liquefy again, but a part


In the case of cocoa butter, at least six will re-crystallize into the stable form.
crystal forms (I-VI) can be distinguished. By maintaining the temperature below
The most stable form is the one where the the melting point of the stable crystal
fat molecules are most densely packed form, the product (chocolate) is being
and structured in such a way that the seeded with stable crystals. These are the
least space exists between them. This basis of the crystal structure that will be
form requires the most heat to convert formed during subsequent cooling.
from the solid to the liquid form and is
indicated for cocoa butter as forms V and Influence of the cocoa bean origin
VI. Between the forms I + II and V + VI lie Cocoa butters made from different bean
the meta-stable forms III and IV. In Table origins can show different crystallization
7, the six forms, on the basis of patterns. The explanation for these differ-
the characterization of Wille and Luton, ences can be found in the different chemi-
are given. cal composition of their triacylglycerol.
All cocoa butters, regardless of origin, (See page 103 under “Hardness.”) Com-
demonstrate this polymorphic behavior. paring the solidification characteristics of
To be able to make stable end-products, cocoa butters from various origins pro-
the cocoa butter must assume the vides an indication of what these differ-
crystalline form V. This can be achieved by ences are. The Shukoff test is commonly
a process called tempering. The com- used to determine the solidification char-
pletely liquefied chocolate is cooled, usu- acteristics of cocoa butter.
ally by means of a scraped surface heat In Figure 1, the curve clearly demon-
exchanger, so that part of the fat crystal- strates when the cocoa butter begins to
lizes into unstable crystals. Subsequently, crystallize. When the line deviates from
the temperature is raised, so that most of the cooling line at a temperature of about

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Table 8
Origin Cocoa Butter and Shukoff Cooling Curve

Malaysia

Ivory Coast

Ghana
Average
Cameroon Low
High
Brazil

0.10 0.15 0.20 0.25 0.30 0.35


T/ t in ° C/Minute

Table 9
Origin Cocoa Butter and Viscosimetric Cooling Curve

Malaysia
Average
Ivory Coast Low
High
Ghana

Cameroon

Brazil

20 40 60 80 100 120
Minutes at 25° C

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Figure 2:
Thermorheographic Cooling Curve of Cocoa Butter
and Temperature During Measurement
Torsion (mN) Temperature (° C)
120 55
Temperature (° C)

100 50

45
80 Torsion (mN)
40
60
35
40
30
20 25

0 20
0 20 40 60 80 100 120
Crystallization Time (Minutes)

20° C (68° F), the α-crystals start to form. cooling curve, can give a good indication
When the line reaches its minimum, the of that transition. Cocoa butter is cooled to
a-crystals re-crystallize into the more sta- 25° C (77° F), and subsequently the
ble b1-modifications. At this stage a lot of increase in viscosity in the fat over time is
crystallization heat is generated. Due to followed at that temperature. The
the released crystallization heat, the tem- required time to reach a certain viscosity
perature increases to a maximum, is a good indication for the crystallization
whereby re-crystallization occurs into the behavior, which is shown in Table 9 on
more stable crystal modifications. The page 109.
increase in temperature between the mini- The thermorheographic (TRG) method
mum and the maximum temperature in developed by Baenitz is another way to
degrees Celsius, divided by the time in determine the crystallization behavior of
minutes between both points ( T/ t), cocoa butter during the tempering
allows such a curve to be expressed in a process. In a temperature controlled Z-
number. Table 8 on page 109 shows that kneader, cocoa butter is cooled to 24° C
these curves can differ substantially by (75.2° F). In Figure 2, a typical TRG curve
origin. is illustrated.
Brazilian butter appears to score better Two phases can be distinguished from
than Malaysian. However, it must be the curve. In the initial phase, the material
taken into account that the Shukoff curve is seeded with crystals, but as can be read
only records the formation of the a-form from the force, the cocoa butter is still liq-
and the transition to the meta-stable b1- uid. This point is indicated as t1. The
form, whereas in practice, the transition increase in temperature reveals that crys-
to the stable b-crystals is of importance. tallization heat is released. α-crystals can-
Other methods, like the viscosimetric not occur at these temperatures. Conse-

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Figure 3:
Thermorheographic Cooling Curves Comparison
Different Types of Cocoa Butter
Torsion (mN)
120
Fast crystallizing
cocoa butter
100

80 Slow crystallizing
cocoa butter
60

40

20

0
0 50 100 150
Crystallization Time (Minutes)

quently, the crystals formed are mostly of tion process has to be adapted to this.
the b1-form.
In the second phase, a marked increase Influence of alkalization
in force is seen, indicating that a transi- Alkalization of cocoa is an important step
tion from the liquid into the solid form is in influencing both flavor and color of the
occurring. This point is indicated as ttotal. solid parts of the cocoa bean: cocoa pow-
The slight increase in temperature means der. The impact of alkalization on cocoa
that re-crystallization from b1- to b-crys- butter has been demonstrated in a study
tals is occurring. In the figure, the typical in which raw, roasted, and roasted/alka-
differences in TRG behavior of a number lized cocoa have been compared. In
of cocoa butters from various origins is Table 10 on page 112, the analytical
illustrated. In this way, TRG can help results are given, comparing cocoa butters
obtain valuable additional information on from a single bean origin.
the crystallization behavior of cocoa butter. Though slight differences can be
In general, the harder the cocoa butter, noticed in the analytical data, these differ-
the more crystallization heat is released ences appear to be of minor influence. In
during the transition from the liquid to the general, it can therefore be said that the
solid form. This means that softer butter alkalization process, if properly carried
will solidify faster compared to harder but- out, has no negative impact on the prop-
ter and that milk chocolate solidifies faster erties and characteristics of the cocoa
than dark chocolate. The cooling tempera- butter.
ture profile during the chocolate produc-

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Table 10: Cocoa Butters - Effect of Alkalization and Roasting


Alkalized and
Raw Beans Roasted Beans
Roasted
% ffa 1.28 1.29 1.12
% Diglycerides 0.95 0.98 1.03
% Sat. Fatty Acids 2 pos. 1.60 1.60 1.90
Oxyd. Stab. (hrs. at 120° C/248˚ F) 40.0 41.0 41.0
Cooling Curves
Shukoff T/ t 0.21 0.20 0.18
Viscosimetric (min.) 39.0 40.0 51.0
Melting Curve
% SFC (pNMR) 30° C (86˚ F) 39.0 39.7 39.6

Influence of deodorization
The effect of deodorization on the flavor
of cocoa butter has already been dis-
cussed. It was also mentioned that a pos-
sible negative influence could be expected
due to interesterification. If the symmetric
molecule triacylglycerol is transformed
into an asymmetric molecule with the
unsaturated fatty acid on the 1- or 3- posi-
tion, the hardness and the crystallization

Table 11: Cocoa Butters -


Effect of Deodorization
Before After
% ffa 1.23 1.18
% Diglycerides 0.95 0.93
% Sat. Fatty Acids 2 pos. 1.6 1.7
Oxyd. Stab. (hrs. at 120° C/248˚ F) 39.0 41.0
Cooling Curves
Shukoff T/ t 0.18 0.19
Viscosimetric (min.) 39.0 43.0
Melting curve
% SFC (pNMR) 30°C (86˚ F) 39.0 39.8

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Figure 4: Measuring Contraction of Chocolate During Moulding

6 5

104596802

4
2 2

1
7
3

1=Chocolate in mould 4=Ventilator


2=Magnetic displacement sensor 5=Displacement registration unit
3=Moving table 6=Recorder
7=Thermostated cooling cabinet

behavior of the cocoa butter can be signif- is also of importance: The stable b-crystal
icantly influenced. form in cocoa butter has 1.5 times more
The characteristics of cocoa butter contraction property as compared to the
before and after deodorizing have been a-form. This is due to the more dense
investigated and are shown in Table 11. molecular packing of the crystals.
A minimal decrease in ffa (free fatty When properly tempered, cocoa butter
acids) can be noticed. However, the crys- has a volume contraction of about 9%. For
tallization behavior and the hardness of an average bitter chocolate recipe (33%
the cocoa butter have hardly changed. It fat), this means a volume contraction of
can therefore safely be assumed that about 3%, corresponding to a 1% linear
deodorization carried out under con- contraction. In milk chocolate, the volume
trolled conditions has no negative influ-
ence on the properties of cocoa butter, Table 12: Cocoa Butters in
other than the flavor. However, when pro-
cessing high-ffa cocoa beans, a stronger
Contraction Experiment
deodorization might be necessary, with
potential impact on color and crystalliza-
CB1 CB2
Iodine Value
tion behavior.
35.5 36.4
ffa
Contraction
1.10 1.50
Diglycerides
Contraction is an important parameter in
1.50 1.90
the manufacture of chocolate, notably Monoglycerides
when demoulding the product. Its princi-
0.20 0.20
Shukoff T/ t
ple is based on the fact that liquefied fat
0.19 0.14
has a higher volume compared to its % SFC (pNMR) 20°C (68˚ F)
solidified form. The crystal modification
75.0 71.0

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Figure 5:
Contraction of Milk Chocolate
Effect of Cocoa Butter Type and Tempering Conditions
Contraction in Mould (mm)
1.0
Temper condition 1/
0.9 fast crystallizing cocoa butter
0.8
Temper condition 2/
0.7 fast crystallizing cocoa butter
0.6
0.5 Temper condition 1/
slow crystallizing cocoa butter
0.4
Temper condition 2/
0.3 slow crystallizing cocoa butter
0.2
0.1
0
0 50 100 150
Cooling time at 15° C (minutes)

contraction is lower. Due to the eutectics types of cocoa butter (CB1 and CB2) are
caused by the milk fat in the cocoa butter, used in milk chocolate to demonstrate
a significantly smaller part of the fat mix- their different contracting properties.
ture will transform from liquid to solid Notably, the somewhat softer butter
form. However, normally the contraction with a slightly elevated ffa appears to be
will be quite adequate for demoulding. more sensitive to differences in tem-
As the proper crystal form is also an pering, and the insufficient tempering
important factor for the degree of contrac- leads to a much lower contraction com-
tion, it is of great importance that ade- pared to the product subjected to optimal
quate tempering has taken place. To tempering. Furthermore, it shows that the
demonstrate this, ADM Cocoa has devel- harder butter gives a better contraction
oped a method to measure the contrac- than the softer butter.
tion. In Figure 4 the required equipment In cases where the shrinkage may not
is schematically illustrated. be too strong, like in some enrobed prod-
A mould containing tempered chocolate ucts such as wafers and ice cream bars,
is placed in the refrigerator. Before the several options are available:
cooling starts, a measuring device with • Use softer cocoa butter, like Brazilian
two sensors is placed in the chocolate. As butter
the chocolate solidifies, the sensors, due • Produce eutectic effects by adding
to contraction of the chocolate, will have milk fat
moved accordingly. The movement of the • Slightly overtemper the chocolate
sensors as a function of time is indicated
by a recorder. Rheology
As an example, in Table 12 below and In the processing of chocolate, rheology
in the Figure 5 on page 114, two different plays an important role. Because fat is the

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continuous phase, the amount of fat avail- solids—do not contribute to the gloss.
able determines the ultimate rheology of These cause the background color against
the chocolate in liquid form. As cocoa which the gloss is visible. Gloss on white
butter is usually the most expensive chocolate is therefore hardly noticeable,
ingredient in the chocolate recipe, the whereas the gloss on dark chocolate,
quantity of cocoa butter used is mini- because of the dark background, is very
mized and adapted to a required visible. Cocoa butter crystallizes into very
rheology. small (1-2µ) crystals, resulting in a
The type of cocoa butter has no influ- smooth surface. Light is then very well
ence on the rheology. Cocoa butter, or any reflected. In addition, contact with the
other fat in liquid form, behaves similarly, smooth surface of the mould enhances the
and butter from one particular origin is gloss impression even more.
not better or worse than butter from Gloss stability depends on the degree to
another origin. which the fat crystals are stable. When fat
crystals re-crystallize under uncontrolled
Gloss and shelf-life stability conditions, which is usually a slow pro-
Cocoa butter, or the fat phase in choco- cess, larger crystals will be formed. If
late, is largely responsible for the gloss of these crystals are large enough that they
the end-product. The dispersed dry mat- can be seen with the naked eye, the phe-
ter in chocolate—sugar, dry fat-free cocoa nomenon of fat bloom occurs. A picture of
constituents, and dry fat-free milk a bloomed chocolate surface is shown on

Electron scan microscopy of smooth chocolate

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Electron scan microscopy of bloomed chocolate

page 116. When mistakes are made in moisture


Fat bloom can be caused by: management, sugar bloom can occur:
• inadequate tempering, due to slow re-crystallization of sugar crystals at the
re-crystallization of still present a- surface of the chocolate. Obviously, cocoa
and b1-crystals into large b-crystals butter has nothing to do with this.
• melting of stable b-crystals followed When a chocolate product shows fat
by slow, uncontrolled re-crystalli- bloom, it is often thought that its quality
zation has deteriorated due to mold growth, for
• fat migration due to other oils and example. The unattractive, grayish discol-
fats, e.g. from nuts or from the oration contributes to this perception. The
enrobed center migrating to the sur- occurrence of fat bloom, however, is likely
face of the chocolate due to the causes described. One well-
It is beyond the scope of this module to known contributing factor is storage
dwell extensively on this subject. It under fluctuating temperatures. Apart
should be noted that certain forms of fat from the unattractive appearance, the
bloom seem to manifest themselves easier quality of the product is not affected.
and faster in very hard fat systems as
compared to softer fat systems. 2. The application of
Finally, not all bloom is fat bloom. cocoa butter

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Chocolate production nuts gives the filling a very soft, liquid


There are two ways in which cocoa butter texture that can easily migrate through
finds its way into chocolate: as a raw the chocolate enrobing. By adding cocoa
material and as part of the cocoa liquor. butter, the texture may be regulated from
About half of the cocoa liquor consists of soft to cuttable or extrudable, and fat
cocoa butter. This means that in dark migration may be diminished. The advan-
chocolate, only a limited quantity of cocoa tage of cocoa butter is its complete com-
butter is added, whereas in milk choco- patibility with the chocolate that sur-
late, the added butter quantity forms the rounds the filling, reducing eutectics and
main part of the overall fat content. other problems to a minimum.
The amount of butter used in the choco- In the application of fillings, cocoa but-
late recipe depends on the sensory ter competes with other vegetable oils and
requirements, notably the fineness and fats that are usually lower priced. This
the desired flavor, as well as on the rheol- limits the use of cocoa butter in this appli-
ogy needed during processing of the cation to only products that are catered to
chocolate. Particularly, the ultimate appli- the higher-priced market segment.
cation of the chocolate itself dictates the
rheological requirements. The lowest Other applications
overall fat content is found in extruded Cocoa butter is defined in several phar-
and moulded chocolate. Typical fat con- macopoeia under descriptions like cocoa
tents for products like panning centers, butter (USP 1990, JAP 1991), Cacao oleum
chips, and chunks vary between 24 and (DAB 10, 1992, PhNed 8), and Theobroma
28% and for solid chocolate bars between Oil (BRIT 1998).
27 and 31%. Chocolate for shell products, For a long time, cocoa butter has been
enrobing, and panning has an intermedi- used in suppositories. Administering a
ate fat content between 30 and 40%. For medicine rectally provides an alternative to
very thin enrobing purposes and coatings oral and intravenous options. Cocoa butter
for dipping ice cream bars, fat contents of is very well suited for this purpose as it
between 40 and 50% are used, and for liquefies evenly and completely within 15
spraying applications, even higher fat minutes at a body temperature of 37.6° C
contents are required. It should be kept in (99.7° F). Also its high oxidative stability
mind that total fat contents are mentioned makes the use of cocoa butter favorable.
here; that is, the total of the added cocoa Cocoa butter is a product of nature with
butter, the cocoa butter from the cocoa its own unique properties, including
liquor, and in the case of milk and white unavoidable, natural fluctuations. Because
chocolate, also the fat from the added the pharmaceutical industry requires dif-
milk constituents. In addition, the fat ferent melting behavior, a range of crys-
from nuts like hazelnuts or almonds tallization times, and absorption of water-
should be taken into account. soluble medicines, the use of cocoa butter
in suppositories has diminished. Today,
Confectionery fillings more and more synthetic glycerides are
In the chocolate and confectionery industry, used in this application.
quite a tradition exists for high-quality The use of cocoa butter in skin creams,
fillings. soap, and shampoo should largely be
Usually, roasted nuts like almonds and seen as a marketing tool, rather than an
hazelnuts are ground and blended with actual functional property. Usually,
sugar and other ingredients, including refined cocoa butter is used for these
cocoa and milk products. The oil from the applications, and the quantities involved

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are limited. avoided. Stainless steel melting grids,


heated by water up to 90° C (194° F), are
3. Packaging, storage, recommended.
and transportation Liquid butter should be kept at temper-
Cocoa butter is mostly stored in tanks and atures of 40°-45° C (104°-113° F), prefer-
transported in special, properly insulated ably in a stainless steel or coated tank.
tank containers or tank cars in liquid The tank can best be heated by means of a
form. Usually, the butter is loaded at tem- warm water spiral or jacket. Steam
peratures from 60°-75° C (140°-167° F), heating is not to be advised because of its
depending on the destination and the high contact temperature. Heating by
transition time. During transport the tem- means of hot air in the tank storage room
perature will drop about 2°-5° C (4°-9° F) is also an option, as are piping and an
per day depending on the outside tem- adequate thermostat tracing system.
perature. At the point of discharge, the Exposure to air or oxygen should be
temperature should not have fallen below avoided as much as possible. Vertical
40° C (104° F). This limits the transport storage tanks are therefore preferred over
time to about one week. horizontal ones. Care should be taken that
Tank cars should be operated under no air is trapped in the cocoa butter due
very strict conditions. They must only be to malfunctioning pumps, for example.
used for food-grade products, and a cer- The tanks can best be filled from under-
tificate should indicate that the tanker has neath, rather than letting the butter fall
been cleaned and properly dried prior to from the top. Furthermore, air contact can
loading. be diminished by leaking an inert gas like
If bulk shipping is not possible, the nitrogen through the cocoa butter. This
cocoa butter is packed in solid form, usu- will drive out the oxygen, creating opti-
ally in cartons of 25kg (55 lbs.) that con- mal storage conditions for cocoa butter.
tain a polyethylene inner bag. The cartons Even small amounts of oxygen can initi-
are stacked on a pallet and shrink ate the oxidation process. This is why it is
wrapped. During transportation, it is important that, when blanketing, a first-
important that the product is not subjected grade inert gas free from oxygen is used.
to excessive heat. Metals and alloys like copper and
Fats are known to quickly pick up bronze, which have a catalytic effect,
volatile matters like odors from their sur- must be excluded from the processing
roundings. It is therefore very important equipment (piping, pumps, seals, etc.).
that both during transport and subse- Finally, care should be taken that fresh
quent storage cocoa butter does not come cocoa butter is not continuously being
into contact with strong-smelling prod- added to butter that has been stored for
ucts. Paint; chemicals; cleaning agents; some time. If cocoa butter is kept in stor-
spices, herbs, and other flavoring sub- age for too long, catalytic reactions can
stances should not be stored in the direct deteriorate the quality of the tank.
vicinity of cocoa butter. Therefore, it is good practice to com-
If cocoa butter is stored under dry pletely empty the tank on a regular basis.
(RH 40-70%), cool (<20° C/<68° F), and Under optimal conditions as described
dark conditions, the shelf life is at least above, liquid cocoa butter can withstand a
12 months. storage time of two months without any
When liquefying solid cocoa butter, problem.
high contact temperatures should be The figure shows the results of an accel-
erated shelf life laboratory experiment. At

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Figure 6: Effect of Moisture on Cocoa Butter During Storage


Free Fatty Acid Content and Peroxide Value After 42 Days at 80° C
Free Fatty Acid Content (%) Peroxide Value (meq 02/kg)
1.55

1.50
Free fatty acids (%)
1.45
Free fatty acids regression
1.40

1.35 Peroxide value (meq/kg)

1.30

1.25
0.00 0.05 0.10 0.15 0.20
Moisture Content (%)

these extreme high temperatures, the ffa (176° F), after which the ffa and peroxide
and the peroxide value run up so quickly value were measured. With increasing
that the maximum keeping time is moisture content, a linear, though modest,
reached after only three weeks. However, increase in ffa is noticeable. The peroxide
as mentioned, it concerns a laboratory value, on the other hand, reaches an opti-
experiment, whereby the ratio of contact mum level at 0.15% moisture.
surface and air versus the amount of fat is A possible explanation for this could be
disproportionately unfavorable. found in the hydration and sedimentation
The effects of moisture on cocoa butter of the gums present in the cocoa butter.
are shown in the pictures on pages 115 and These bind the metal ions and are then
116. In this experiment, the moisture con- removed from the fat into the sediment.
tent varies between 0.01-0.18%. The cocoa In practical terms, this means that when
butter was stored for 42 days at 80° C cocoa butter is stored for a prolonged

Specification of Typical De Zaan® Pure Prime Pressed Cocoa Butter


Acidity (%)
Iodine Value
1.75 max.

Refractive Index nD(40° C/104˚ F)


33-40

Clear Point (°C/˚F)


1.456-1.458

Blue Value
32-35/90-95

Unsaponifiables (%)
0.05 max

Absorbance (270 nm), after washing with alkali


0.35 max.

Saponification Value
0.14 max.

Peroxide Value
192-197

Color (yellow + red)


4 max.
min. 40 + 1.0/max. 40 + 2.0

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Cocoa Powder
9
1. Functionality powder are to be priorities. A dark-col-
and attributes of ored, lightly flavored chocolate pudding
cocoa powder is bound to disappoint the consumer, as
will a homemade brownie that does not
Introduction have the right texture or a chocolate milk
The two most prominent attributes of beverage in which the cocoa powder has
cocoa powder are its abilities to give color formed a difficult-to-disperse sediment on
and flavor to a wide variety of food prod- the bottom of the container.
ucts. In many instances, the consumer In the next paragraphs a number of
will directly associate brown color with these functional aspects of cocoa powder
chocolate flavor, and the darker the color, will be discussed.
the stronger the flavor expectation will be.
These two attributes of cocoa powder in Standard of identity
a food product formulation are only part Many countries have defined cocoa
of the story. Other aspects such as fineness, powder in their food laws. Depending on
fat content, pH, and alkalinity may have when these food laws were initiated and
an important functional impact on the the prevailing chemical and physical ana-
end-product in which the powder is used. lytical capabilities, as well as the process
Manufacturing parameters and other and technical advancements, these laws
ingredients in the formula may distinctly may differ on essential elements. In many
influence the overall performance of instances, a differentiation exists between
cocoa powder in the final product as well. the product definition of cocoa powder
The structure of a cake, the smoothness of and the legal specification of the product.
a pudding, the whipability of a cream, At the beginning of the 20th century, it
and the viscosity of a syrup may in part was not technically possible to mechani-
be determined by the type of cocoa cally press the cocoa liquor into cocoa
powder used. cake with a fat content below 20%. Hence,
In addition, cocoa powder may function the standard of identity for cocoa powder
as an antioxidative agent in many product in some countries indicates that the name
recipes, thereby having a positive effect “cocoa powder” is exclusively reserved
on the shelf life of these products. for a product containing a minimum of
The advantage of cocoa powder as a 20% cocoa butter. Any powder with a
flavoring and coloring agent is that many lower fat content must be declared as
types are available, differing not only in low-fat cocoa, strongly reduced-fat cocoa,
color shades and flavor profiles, but also or a similar description. And some coun-
in other aspects that make them suitable tries specify the fat content to be calcu-
for use in just about any food system, lated on dry matter, whereas others
including foods with virtually no fat require it to be calculated on the basis
content. of a maximum moisture content.
So when choosing a cocoa powder for a
specific product application, it is impor-
tant to carefully determine which func-
tionalities and attributes of the cocoa

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Relevant Regulations
Low-fat cocoa Reduced-fat
Form Cocoa Breakfast cocoa
powder cocoa powder
EU: Directive
2000/36/EC
< 20% fat 20% fat or more

USA: 21 CFR
163
<10% fat 10-<22 % fat 22% fat or more

Codex Stan. 105-


1981, Rev.1-2001
<10% fat 10-<20% fat 20% fat or more

In this module we will use the descrip- Flavor


tions “cocoa powder” as well as “high- Range of cocoa flavors
fat” and “low-fat” for practical purposes The range of De Zaan® cocoa powders
only, disregarding whether or not these available from ADM Cocoa can be
descriptions comply with the food laws of divided into two basic types: non-alka-
a particular country with respect to the fat lized or natural-process cocoa powders
content of the product. and alkalized, also called Dutch-process,
The use of cocoa powder as an ingredi- powders. These two types have their own
ent in a consumer product may also have very specific flavor profiles. In Figure 1,
an influence on how that product may or the differences in flavor, expressed in
may not be labeled. Descriptions such as acidity, cocoa, bitterness, and acridity, are
“chocolate” or “chocolate-flavored” are in indicated.
many countries reserved for products that
actually contain chocolate, whereas in • Non-alkalized cocoa powders have an
others these terms are allowed to be used acidic, somewhat astringent flavor
for products made with cocoa powder with a typical chocolate note. Many of
containing a certain minimum percentage the acids naturally present in the
of cocoa butter. cocoa bean are still present in the
This illustrates the complexity of only powder after processing. Roasting is
one aspect of the standard of identity of the principle step in the production
cocoa powder: the matter of the fat con- process that can influence the devel-
tent. Many more rules and regulations opment of the final flavor.
exist in different countries concerning the • In alkalized cocoa powders, alkaliza-
permitted production processes, the raw tion partially neutralizes the acids
materials used, the product specifications present in cocoa and reduces the
and labeling requirements, extraneous astringency. It is a precisely defined
matter, and even packaging. treatment of the cocoa solids with an
It goes beyond the scope of this module alkaline solution such as potassium
to discuss the multitude of differences in carbonate. Alkalization, in combina-
the various existing food laws. tion with the roasting process, allows
the cocoa manufacturer to directly
influence both the flavor and the color
of the final product. Depending on
the degree of alkalization, the flavor
profile can be described as ranging

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Figure 1: Flavor Profiles Cocoa Powders


with Different Alkalization Degrees
6
Acidity
5 Cocoa
Bitterness
4 Acridity

1
0
Non- Lightly Medium Strongly Strongly
alkalized alkalized alkalized alkalized “red” alkalized “black”

from mild chocolate-like to a very Guidance on tasting


pronounced, strong cocoa flavor. When testing cocoa powders for a new
Flavor is a characteristic that is very dif- product or reformulating an existing
ficult to describe. The descriptions used in product, the following should be kept in
this book can best be read when compar- mind.
ing and contrasting them with each other. Because the medium in which a cocoa
(See Module 4, Flavor and Flavor powder is tasted has a substantial effect
Development.) on the final flavor, it is wise to carry out
comparative sensory tests on the effects of
Flavor and consistency a powder on a newly formulated food
Because the consumer expects a specific product itself. For example:
product with consistent flavor characteris- • The temperature at which a final
tics, the raw materials supplier seeks to product is consumed affects its flavor.
deliver ingredients that are able to pro- Testing should always be carried out
vide this to the manufacturer. In this at the eating temperature of the prod-
respect, consistency in flavor is one of the uct. In other words, a cocoa powder
most important aspects. Here, the sensory meant for ice cream should be tested
evaluation process plays a key role. in ice cream.
Today’s consumer is probably more • Cocoa powders meant for cakes
responsive to the flavor of food than ever should be tested in cakes because
before. The food manufacturer has there- other ingredients can interact with the
fore never been more dependent on the cocoa powder. Also, texture affects
consumer’s flavor preference. As the fla- the taste perception.
vor of cocoa powder is one of the primary • When cocoa powders in chocolate
reasons for its use in confectionery and milk drinks are compared, the drinks
other food products and is judged and should have equal viscosity, as a
defined by a person’s capacity for sensing drink’s viscosity has great influence
flavors, the sensory evaluation process on the taste perception.
plays a critical role in today’s food The circumstances in which sensory
manufacturing. evaluation should be carried out can be

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compared with those for a musical instru- variations. The development of cocoa fla-
ment: Just like an instrument can only vor is dealt with in Module 4, Flavor and
function at its best when the circum- Flavor Development.
stances are also at their best, a human
being can only participate in sensory eval- Color
uation adequately when the circum- The color essential
stances are right. This means allowing for The color of food products is a factor of
complete concentration by the sensory critical importance to consumers and thus
evaluation participants without risks of to food manufacturers. Color is one of the
distraction or external influences. first messages the brain receives in
The flavor of cocoa powder is the pri- making a sensory judgment on a con-
mary reason the product is used in con- sumer product. It carries a whole range of
fectionery and foodstuffs. Cocoa is a conscious and subconscious associations
product of nature, and fluctuations in fla- that affect sensory perception and thus
vor are, therefore, unavoidable. However, appreciation. Because most consumers
ADM Cocoa has developed the tech- can detect very slight differences in color
nology and has the expertise to limit such in the red-brown sector of the visible

Color Matrix

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The sample on the left contains 11% less fat as compared


to the sample of the same powder type on the right.

spectrum, differences in the color of Non-alkalized cocoa powders usually


cocoa-flavored and chocolate products have a light brown color, whereas alka-
can be easily detected. lized powders may vary from light red-
The consistency of a product’s color is dish-brown to very dark red-brown. (See
also important to a food manufacturer, Color Matrix.)
because it reinforces the image of constant However, cocoa powder also contains a
product quality. Color variation between certain amount of cocoa butter, which,
batches may create the impression of while intrinsically almost colorless, never-
inconsistent production and quality theless affects the color of the powder.
control. When evaluating the color of cocoa pow-
The color of a product containing cocoa der it is therefore important to distinguish
has always been an indicator of taste due the two ways in which color manifests
to the relationship between color, the itself: external color and intrinsic color.
quantity of cocoa, the degree of alkaliza-
tion, and the consequent flavor modifica- External (“dry”) color
tions. Dark colors suggest a strong flavor. The color of cocoa powder as such is the
Light colors suggest a mellow or bland so-called external or dry color. This is
flavor. Cocoa powder is one of the pri- strongly influenced by an optical effect in
mary colorants used in the food industry which the fat on the solid particles affects
today. the light absorption. The higher the fat
content of the powder, the darker the
Appearance external color will appear to be.
Cocoa powder contains naturally occur- The crystallization form of the cocoa
ring colorants, most of which have been butter in the solid particles determines
influenced in the alkalizing and roasting the strength of this optical effect. When
stages of the production process. Precise cocoa powder is subjected to temperature
control of alkalizing and roasting allows fluctuations, discoloration will occur due
optimum hue and color intensity of the to a change in the crystalline form of the
powder to be obtained after grinding the cocoa butter. The crystals should be small
nib and pressing. and in the stable form. This can be

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achieved by rapid cooling and tempering. 10-12% and is based on the colors of the
Slow cooling or rapid cooling without powders in dry form. The horizontal axis
tem- depicts the actual color changes from red
pering will result in larger crystals that to brown, while the vertical axis repre-
impart a greyish hue to the cocoa powder. sents the lightness or intensity of the col-
This discoloration, however, does not ors. It is not possible to reproduce in print
affect the quality of the product nor the the true brilliance of cocoa powders.
intrinsic color in any way. Different pul- Therefore, the color range of the matrix is
verizing and tempering equipment and only indicative.
conditions (within or between locations)
may also result in more external color Influence of cocoa color on the final product
variation. The De Zaan powders cover a range of
colors from red-brown to yellow-brown,
Intrinsic color to light and dark brown to almost black.
The intrinsic color of cocoa powder is the A powder is selected by formulators and
color that the product made with the recipe experts according to the applica-
powder will ultimately have. In most fin- tion requirements and naturally, the
ished products, the external color of cocoa desired final color of the food product.
powder no longer plays a role, and only Their decision is also a function of the
the true color, the intrinsic color, is seen. other qualities they wish to impart to a
The selection of a cocoa powder for its product, such as flavor or texture.
coloring capabilities should be based on The color of the food product depends
evaluation of the color of the final prod- not only on the type of cocoa powder
uct. This is the reason why De Zaan® used, but also on certain other factors:
cocoa powders are standardized on • The other ingredients that are present
intrinsic color. As such, the external color in addition to cocoa powder also
of the powder is only of importance when influence the color. For example, milk
the final product is used as powder, like powder tends to “dilute” a brown
in the case of truffles. For such cases, the cocoa color. A product that contains
dry color may also be specified. cocoa together with milk powder has
a lighter color than the same product
Color matching without milk powder. Another phe-
The production processes at ADM Cocoa nomenon: Chocolate milk made with
are designed so that within the limits from skim milk has a darker color than
light brown and red-brown to very dark with whole milk. The color of choco-
brown, each required tint can be consis- late milk is clearly influenced by the
tently produced. As a result of this great presence of milk fat.
flexibility in the process, it is possible to • The higher the concentration of cocoa
perfectly match client color requirements. powder, the more intense the color of
The Color Matrix (see page 124) depicts the final product will be. Obviously,
only a limited number of cocoa powder products with a low concentration of
types. They are part of the wide range of cocoa powder are lighter in color.
the De Zaan cocoa powders available Utilizing powders as color boosters, a
from ADM Cocoa. light cocoa powder can be replaced
The cocoa powder Color Matrix gives by a darker powder without increas-
an idea of the color range of powders ing its concentration. In some circum-
available from ADM Cocoa. The matrix stances, a darker cocoa can be used to
only includes types with a fat content of change or intensify the flavor as well.

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• There are also technical reasons that


might favor low concentrations of
cocoa powder. Coatings based on lau-
ric fats, for instance, should contain
only a limited concentration of cocoa
butter in order to prevent fat bloom.
A very dark lauric coating could be
made with a high percentage of light
cocoa powder but with the risk of fat
bloom. An alternative would be to use
a darker cocoa powder at a lower
concentration.
• The structure of the product. A cocoa-
containing product that has been
whipped so that it contains trapped
air has a lighter color than a product
that has not been aerated. Examples
include ice cream and mousse.
The above applies to all products in
which the intrinsic color of cocoa is
important, and also in part to powder
products in which the dry color of the
cocoa powder is evident. The importance
of the fat content of cocoa powder with
regard to its dry color has already been
mentioned. However, there are other fac-
tors that are important for defining color
in dry products.
For dry products, both the colors of the
other ingredients and the concentration of
the cocoa powder determine the color of
the final product. Factors that have an
influence on such products include:
• The particle size of the other ingredi-
ents. A product in which cocoa pow-
der has been mixed with a finely
ground ingredient made of small par-
ticles will have a different coloration
from one containing a more coarsely
ground ingredient.
• The surface structure of a component
such as sugar. Crystal sugar has a dif-
ferent surface structure than finely
ground sugar. The latter, therefore,
appears whiter than the former. This
has an obvious effect on processed
sugar products.

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Indicative Composition of more chocolate-like, softer flavor.


Cocoa Powder The indicative composition that high-fat
cocoa powder contains fewer coloring
and flavoring constituents on an equal-
weight basis. On the other hand, the dry,
High fat (22-24%)
Cocoa butter
external color of high-fat powder is sub-
23% 11%
Fat-free dry cocoa stantially darker and more brilliant com-
pared to low-fat cocoa powders. (See
72 % 84 %
Moisture
page 124 under “Color.”) This can be of
5% 5%
particular interest for applications such as
• The method and extent of agglomera- truffles and dry mixes in which the dry
tion. There are various systems avail- color is of importance.
able to agglomerate cocoa-containing When low-fat and high-fat powders are
powders. Partly dissolved sugars as exchanged in a formula, a correction
well as emulsifiers can play an impor- should be made for the difference in fat-
tant role in the agglomeration pro- free dry cocoa matter between the two, if
cess. Both affect the surface of the dry the color and flavor intensity of the end
matter in particular, causing the exter- product should remain the same.
nal color to be darker. Low-fat powders are recommended for
use in compound coatings that contain
Fat content lauric fats, as a higher cocoa butter con-
Cocoa butter constitutes about half the tent has a negative influence on the gloss
weight of the cocoa nib. This fat is par- retention of these coatings.
tially removed from the cocoa liquor by Due to the lower fat content, the 10-12%
means of mechanical pressure as high as fat powders are less susceptible to
450 kg/cm2. Depending on the pressing lumping and are more free flowing. These
time and the setting of the press, the powders are therefore better suited for
resulting cocoa cake may have a fat con- products like vending mixes.
tent varying between 8 and 24%. It is In some product formulas it is desirable
technically not possible to press exactly to keep the fat content as low as possible.
to a specific percentage of cocoa butter; This goes, of course, for low calorie diet
therefore some tolerance is necessary. products, but also for products in which
However, this should be as narrow as the presence of fat should be avoided for
possible and it is generally specified with technical reasons, such as aerated prod-
a margin of ±1.0%. Most commercially ucts like a meringue or an angel food cake.
available cocoa powders contain 10-24%
fat, while the 10-12% fat range is the most pH and alkalinity
widely used. The pH of non-alkalized cocoa powder is
Although cocoa butter has hardly any dependent on the acidic components of
flavor of itself, it does contain specific fla- the cocoa beans from which the powder
vor ingredients, as cocoa powder does. It has been made. The variation in pH can
contributes to an overall rich mouthfeel in be controlled to a certain extent by
a number of products such as mousse and blending certain types of cocoa beans. In
ice cream, while in white chocolate and general the pH of non-alkalized cocoa
milk chocolate, the flavor of cocoa butter powders ranges between 5.0 and 6.0, and
can have a significant effect. Fat also it can be observed that this slight acidity
masks both the bitter element of cocoa as contributes to the typical chocolate, some-
well as the sour element, rendering a

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Figure 2:
Typical Particle Size Distribution
De Zaan® Cocoa Powders
12

10
Volume Percentage

0
0,1 1 10 100 1000
Particle size (µ)

what fruity flavor of these powders. which suggests the recommendation of


The pH of alkalized cocoa powders is low pH powders if foam development is
largely determined by the amount and an important feature of the final product
type of alkalis used during production. such as in milk shakes. Higher pH levels
The added alkalis not only influence the may also decompose some vitamins.
pH of the cocoa powder but also raise its
alkalinity and ash content. This may have Fineness
an effect on the product in which the The fineness of cocoa powder is usually
powder is used. This is particularly the determined in the liquor grinding phase of
case with bakery products (affects leaven- the production process, but cake grinding
ing) and dairy-based products (affects can also have an effect. For many applica-
milk protein stability). In our technical tions, proper tempering of the cocoa pow-
information bulletins Cocoa Powders in der is an important processing step, both
Bakery Applications; Chocolate Milk, a for the dry color and for avoiding lump
Complicated Product; and Chocolate Flavored formation. This holds true in particular for
Desserts this matter is further discussed. high-fat cocoa powders.
It can be said that the pH of cocoa pow- In most applications the fineness of
der usually has limited influence on the cocoa powder is of major importance. The
ultimate pH of the final product because finer the powder, the smaller the individ-
the amounts of cocoa powder used in the ual particles and the greater the surface
product formulas are comparatively area of the powder will be. This can affect
small. The products in which it is both flavor development and mouthfeel
processed mostly have a buffering capac- of a finished product. Also, very finely
ity. In some specific cases, however, a ground cocoa powder has a positive effect
small change in pH can adversely affect on the color intensity of the end-product,
the outcome of a product. The stability of as well as on the viscosity of products
foam, for instance, is higher at a low pH, such as syrups. Fine powders also show

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less tendency to settle out in liquid pose are unsatisfactory. In the U.S., the
products. FDA requires the shell content to be ana-
Furthermore, the finer the powder, the lyzed with AOAC method 970.23 (1990).
more quickly its effect becomes evident in
the mouth and the less the powder can be Rheology and water absorption
detected as an ingredient by itself. In Cocoa powder has an important effect on
chocolate milk or milk-based desserts, for rheology and water absorption in many of
instance, the presence of a small amount the products in which it is used. A distinc-
of coarse particles can easily be noticed. tion can be made in food systems where
They can be seen against the white back- water is the continuous phase (dough for
ground of the milk as brown specks and bakery products, desserts, toppings, and
can adversely affect the smooth mouthfeel chocolate beverages) or in products where
of the product. fat forms the continuous phase (com-
In biscuits, cookies, or cake mixes, the pound coatings, chocolate, and fillings on
fineness is a less sensitive factor, as the fat basis).
particular character of the powder is lost Whenever moisture is available, cocoa
in the overall flavor appreciation of the powder will compete with other ingredi-
final product due to its texture. However, ents to absorb it. It can take in moisture
in bakery products, fineness of powder up to 100% of its own weight. In compari-
has an effect on the water absorption in son, flour can absorb moisture up to 60%
the dough phase and thus on formulation of its own weight.
and handling characteristics. This means that in dry mixes, a balance
When considering the fineness of a in water activity will be established
cocoa powder, a distinction has to be between the various ingredients. The
made between the average fineness and water activity of cocoa powder is low:
the particle size distribution. Figure 2 With a moisture content of 5%, the water
illustrates the typical particle size distri- activity amounts to about 0.3. Flour has a
bution of selected De Zaan® cocoa pow- much higher water activity, namely 0.55,
ders. The tails of the curve do not influ- and a moisture content of 14%. In bakery
ence the average fineness of the powder. mixes, a balance will therefore be estab-
However, it is the percentage of the lished between all the ingredients.
coarse particles in the right tail, their As a consequence of the strong water
nature, and their size that may have an absorbing capacity of cocoa powder in
effect on the end-product. bakery mixes, stiffer dough and dryer
bakery products with more breakage will
Shell content occur if no moisture correction is made
Shell does not contribute to cocoa flavor when flour is partially replaced by cocoa
and cocoa color and has to be removed powder. To avoid this, the moisture con-
from the cocoa nibs as required by stan- tent in cocoa powder-containing dough
dards. With removal of most of the shell, must be adjusted. As a guideline, it can be
the microbiological status is improved. In said that 40% of the weight of the cocoa
addition, wear and tear on equipment such powder has to be added as extra moisture
as roller refiners and homogenizers by the in order to obtain an optimal result. In
hard cocoa shell particles is reduced. ADM Cocoa’s technical information bul-
Determining the shell content of cocoa letin Cocoa Powders in Bakery Applications
powder is not a simple matter. Many of this subject is extensively discussed.
the methods of analysis used for this pur- In food products containing a high

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quantity of moisture, cocoa powder also coatings manifests itself as a dispersion in


has an effect on the rheology of the ulti- the fat or oil present in the product. Here,
mate product. For example, in chocolate the fat is the continuous and the powder
milk, cocoa powder forms a network with the discontinuous phase.
the stabilizer and the milk proteins, that Cocoa powder is very finely ground,
to a large extent, avoids settling of the giving it a very large specific surface. At
cocoa particles. When this network is dis- first, the powder will show a distinct fat-
turbed by shearing forces, the product absorbing tendency, but as a result of
loses its initial viscosity and will quickly shearing forces during processing, a sub-
become thin fluid. stantial part of the fat is freed up for the
After it has come to rest again, the net- continuous phase, and then the viscosity
work will recover itself, but not entirely. drops sharply.
This phenomenon is called hysteresis. It is Another phenomenon in compounds is
a good indication of the degree to which the effect of moisture in the sugar-rich
the product is sensitive to settling of the environment. At very low concentrations
non-soluble cocoa particles. (1% and higher), an important increase in
The fat content of cocoa powder influ- the liquid chocolate or compound coating
ences the rheology as well. In water-based can be observed. Cocoa powder, with its
systems, the cocoa butter, like oil in a maximum of 5% moisture, is an impor-
water emulsion, is distributed in small fat tant source of moisture in the recipe. The
globules. The more fat available, the development of shearing forces and the
richer and more viscous the end-product evaporation of moisture take place during
will be. Therefore, high fat cocoa powder the conching. This processing step is
gives chocolate milk not only a richer fla- therefore of great importance for the rhe-
vor, but it also makes the product more ology of the end product.
viscous. These subjects are further dis- This subject is further dealt with in
cussed in ADM Cocoa’s technical informa- ADM Cocoa’s technical information bul-
tion bulletin Chocolate Milk, a Complicated letin Cocoa Powder and Compound Coatings.
Product.
In syrups and other sugar-rich products Wettability and dispersibility
such as toppings, the rheology of the end One of the problems confronting a user of
product is not stable during storage. cocoa powder is slow dispersibility in an
Aggregation and sedimentation of solid aqueous system. Manufacturers of instant
particles and sugar crystallization lead to products especially have to address this
undesirable after-thickening effects. phenomenon. In fact the problem refers
This is caused by an interaction not just to solubility (about 30% for cocoa
between cocoa particles and the sugar in powder), but rather to the whole complex
the syrup. In the toppings, it is triggered of wettability and dispersibility of cocoa
by a slow crystallization of the sugar. powder as such.
A three-dimensional network is devel- When cocoa powder is added to cold
oped that results in a higher viscosity. water or cold milk, the powder tends to
Alkalized cocoa powders have a positive float on the surface because of its poor
effect on retarding after-thickening during wettability. When one tries to disperse the
storage and are therefore recommended cocoa powder in a liquid by stirring, the
for these applications. still insufficiently wetted powder particles
Cocoa powder in almost moisture-free will partially remain in and on the surface
systems like chocolate and compound of the liquid as small lumps.

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By its nature, cocoa powder is not 2. The application of


inclined to disperse but to float on the
surface of a liquid. This is primarily due
cocoa powder
to the cocoa butter present in the powder, Introduction
which repels water and prevents the wet- As far as is known, cocoa powder is con-
ting of the powder particles. sumed in every country of the world.
Wettability and dispersibility can be While almost any cocoa powder can be
significantly improved by blending the used in any food product, considerations
cocoa powder with lecithin. As an emulsi- of taste, color, performance, legislation,
fying agent, lecithin is a mixture of phos- and cost mean that certain cocoa powders
phatides that is surface active. The are more effective than others, sometimes
lipophilic (fat-affinity) part of the mole- significantly. ADM Cocoa recognizes that
cule attaches to the cocoa butter present it is important to optimally advise the
in the cocoa powder, and the hydrophilic users of cocoa powder in their product
(water-affinity) part of the molecule formulations. It is often the combination
attracts the water in the solution. It is rec- of the type of cocoa powder, the appropri-
ommended to use lecithinated cocoa pow- ate amount in the formula, and the manu-
ders rather than adding the lecithin sepa- facturing parameters that determine the
rately during the agglomeration process desired results.
of products such as two- and three-com- In this section, consideration is given to
ponent instant cocoa beverages. (See also the most common applications of cocoa
ADM Cocoa’s brochure Sol Lecithinated powder. It does not, however, go into the
Cocoa Powders.) same detail as the numerous technical
Notwithstanding the fact that cocoa information bulletins issued by ADM
powder has poor wettability, it is very Cocoa. It is these that represent the key
hygroscopic. When exposed to a humid and comprehensive information source
environment, it will immediately attract for the cocoa powder user in a particular
moisture, which may lead to bacteriologi- area.
cal spoilage due to mold growth. Cocoa ADM Cocoa has listed cocoa powder
powder should preferably be stored applications by industrial food product
under cool (15°-20° C/59°-68° F), dark, segment. Of course, this can only be done
and dry (RH <50%) conditions, in its orig- on an arbitrary basis and is not exhaus-
inal protective packaging. (See also tive. The listing should therefore be
“Packaging, storage, and transportation” regarded as informative only.
later in this module.) The industrial product applications can
be grouped as follows:
Dairy products
- chocolate milk
- milk shakes
- custard
- mousse
- whipped toppings
- pudding
- fermented dairy products
- dairy premixes

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Legend
Cocoa

Cocoa with milk-


protein coating

Carrageenan

Micro-coagulated
particles

Interlinking of
stabilizer
Stage 1 Stage 2 Stage 3

The formulation of
Protein adheres to cocoa micro-coagulated Formation of the network
particles
Mixing, heating Pasteurization or Cooling of the product
Homogenization sterilization

A simplified model of network formation in chocolate milk

Ice cream and frozen desserts - confectionery coatings


- ice cream - ice cream coatings
- frozen yogurt - vermicelli/flakes
- novelties - spreads
- ice cream premixes - toppings
Bakery products - syrups
- cakes - extracts
- pastries - coated cereals
- brownies - breakfast cocoa powder
- doughnuts Instant products and premixes
- pies - dry 2/3 component drinking mixes
- cookies - vending mixes
- wafers - dairy premixes
- biscuits - bakery premixes
- biscuit and wafer fillings - ice cream premixes
- frozen bakery products
- breakfast cereals Dairy products
- bakery premixes Dairy products are those made pri-
Confectionery, coatings, and cocoa products marily from liquid milk. As there is a
- fudge significant risk of microbiological deterio-
- frostings and icings ration, they must be pasteurized or
- fillings sterilized. An enormous variety of cocoa-

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flavored milk-based products is available Chocolate milk, for example, is a very


to the consumer. effective way of imparting the cocoa fla-
vor, as the liquid character means almost
instant exposure of the flavor compo-
nents. The challenges of chocolate milk lie
in the stabilization of what is inherently
an unstable system. Only part of the
cocoa powder will dissolve in the milk,
whereas the majority of the particles will
settle out as sediment over a period of
time. In order to hold cocoa powder parti-
cles in suspension, a relatively high vis-
cosity is required. This can be achieved by
using a stabilizer such as K-carrageenan
that will react with milk proteins and
cocoa particles to form a three-dimen-
sional network holding these particles in
suspension. The various stabilization sys-
tems and production methods of choco-
late milk are discussed in ADM Cocoa’s
technical information bulletin Chocolate
Milk, a Complicated Product.
Puddings, mousses, and custards are
usually milk based. The addition of stabi-
lizers, sugar, emulsifiers, color, and flavor
ingredients leads to products with a spe-
cific flavor, color, viscosity, and texture.
Stabilizers and emulsifiers are of critical
importance for mouthfeel, whereas flavor
and color determine whether a dessert is
delicious and attractive to look at.
It is difficult to predict which cocoa
powder will give the optimal color and
flavor to a particular milk-based dessert.
Product formula and heat treatment are
just two of the factors that play a major
role. On the basis of defined criteria for
what the end product must comply with
powder types for a specific formulation
can be preselected. The ultimate choice,
however, will more often than not be the
result of practical and taste panel
experience.

The desired texture and air content of a


dessert are significant in determining the
type and dosing of the cocoa powder to

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be used. The lighter the texture and the most moisture has been removed in the
higher the air content, the more concen- baking process.
trated the color and the flavor of the Alkalization influences the pH, alka-
cocoa powder should be. linity, ash content, flavor, and color of the
The technical information bulletin cocoa powder. The alkalinity of the cocoa
Chocolate Flavored Desserts gives extensive powder can affect baking properties in
details on the application of De Zaan® the same way as baking soda. To select a
cocoa powders from ADM Cocoa in a cocoa powder for a baking application, it
variety of popular desserts, including a is therefore important to look not only at
number of product recipes with process- the flavor and the color but also how it
ing recommendations. will affect the baking process.
Cocoa powder readily absorbs mois-
Ice cream and frozen desserts ture. If, for example, a cake is baked and
The color and flavor of chocolate-flavored part of the flour is replaced by cocoa
ice cream come mainly from cocoa solids, powder, the baker must raise the amount
which can be introduced as a constituent of water and make a correction in the
to the ice cream, a chocolate or compound amount of baking soda, as otherwise the
coating, or in a combination thereof. Ice cake would have a volume too low and a
cream and desserts are made of similar texture too dry.
ingredients. The main component is Medium to strongly alkalized cocoa
water, which serves as a solvent and will powders are generally used in bakery
form ice crystals. Sugars affect flavor and products. As mentioned, the alkalinity of
structure. Non-fat milk solids impart the the cocoa powder may have a significant
milk flavor, and fats impart the structure effect on the color of baked products such
and creamy effect so characteristic of ice as cakes and cookies. Excessive baking
cream. Stabilizers increase the viscosity, soda (pH >8) will change the color of the
create a gel, stabilize the system, and pre- end product from yellowish-brown to
vent the ice cream from melting too easily. reddish-brown.
Emulsifiers reduce the surface tension More so than in some other product
between the fat and water phases and categories, the recipe instructions and
have the effect of arranging the fat glob- procedures for baked products containing
ules around the air bubbles to form a cocoa powders can be critically important
homogeneous structure. All of these for achieving a satisfactory product. ADM
factors affect the eating properties of the Cocoa has compiled a comprehensive
product, including the mouthfeel, and can technical information bulletin, Cocoa
be influenced by adjusting the product Powders in Bakery Applications. This publi-
formulation and the processing conditions. cation deals with the effects of cocoa pow-
ADM Cocoa’s technical information der in relation to other ingredients and
bulletin Cocoa Powders and Ice Cream the technology in a number of bakery
specifically deals with the effect that applications, including a number of prod-
cocoa powder has on the manufacturing uct formulas and recommended pro-
of ice cream and frozen desserts. cessing methods.

Confectionery, coatings, and cocoa


Bakery products products
This large product category covers many This product category comprises applica-
types of cakes, biscuits, and cookies. tions based on fat-sugar, water-sugar, and
These are essentially dry in the sense that water-fat-sugar systems.

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Fat-sugar systems are those in which Water-sugar and water-fat-sugar sys-


the main ingredients are fat, sugar, and tems include products such as syrups,
cocoa powder, such as compound coat- fudges, toppings, and frostings, where
ings and fillings. Depending on the water forms the continuous phase. This
amount and type of fat, a product will be has the effect of altering the rheology and
soft or hard at room temperature. For mouthfeel of the product to respond to
compound coatings made from different the specific demands of the application.
vegetable fats, both alkalized and non- Improved preservation is partially
alkalized cocoa powder can be used. This obtained by the addition of sugar and
is a matter of flavor and color apprecia- other preservative ingredients. This
tion and of costs: The flavor/color impact means that the quantity of sugar in these
of a lower level of alkalized cocoa powder products is often higher than in products
may be stronger than that of a higher of fat systems.
level of natural cocoa powder. In these applications, in addition to
Non-alkalized cocoa powders are non-alkalized cocoa powders, strongly
lighter in color than alkalized powders. If alkalized powders are often used. This is
milk solids are added or incorporated, the balanced by the high sugar content pres-
difference in color between alkalized and ent and its ability to mellow the some-
non-alkalized powders will become more times-pronounced flavor of the strongly
evident. The whitish milk powder func- alkalized cocoa powders.
tions as a background that will emphasize When using water in relatively high
the color and its brilliance. viscosity products, consideration must be
Cocoa powders with higher cocoa but- given to the total carbohydrate percentage
ter contents can have an adverse effect on of the cocoa components. The starches,
the gloss stability of compound coatings sugar, and dietary fiber establish a bond
made with lauric fats. with the water, as a result of which a
For ice cream coatings, alkalized cocoa thickening effect may occur over time,
powders are often used. The reason for such as in syrups.
this is that the detection of the chocolate It is important that with sugar syrups,
flavor is dulled by the low temperature of the correct proportions of the various
ice cream. The stronger flavor and darker types of sugar are chosen. An incorrect
color of the alkalized powders render choice of sugars may lead to crystalliza-
their full impact in this application. tion, which in turn produces a change in
In the technical information bulletin viscosity. In many cases, the cocoa pow-
Cocoa Powder and Compound Coatings a der is seen as the cause of this, while it is
detailed description is given as to the more often caused by problems in the
behavior of cocoa powder in different fat area of the sugars used.
systems and the composition and manu-
facturing methods of a number of Instant products and premixes
coatings. Instant cocoa products are mixes that are
added generally to cold milk or water.
Just adding a regular cocoa powder to
cold milk and stirring will not create an
attractive looking product. The reasons
for this are:
• Cocoa powder contains cocoa butter,
which behaves hydrophobically in

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cold milk. non-optimal dispersion. To improve the


• Cocoa powder is a fine powder and dispersion, the heavier sugar crystals are
contains starch, which, by nature, attached to the cocoa powder by agglom-
favors the creation of lumps of cocoa eration. The sugar crystals are moistened
in cold milk. with water/steam. The lecithinated cocoa
To prevent this, it is better to mix cocoa particles adhere to the wet sugar crystals,
powder with sugar first and then add and the agglomerated particles are then
cold milk gradually while stirring. By dried. This creates sugar cocoa agglomer-
making a high-viscosity paste, the lumps ates that are easily dispersed in cold milk.
of cocoa are easily eliminated. Lightly alkalized lecithinated cocoa
However, most consumers find it less powders are generally used in instant
convenient to make chocolate milk in this products.
way. A ready-to-use mix to be added to In vending machines, hot water is
warm or cold milk or water naturally has added to a mix of cocoa powder, sugar,
preference. For this reason, the so-called and milk powder to produce hot choco-
instant products have been developed. An late. Because the cocoa butter melts in the
instant product is generally a two- or hot water, the hydrophobic character of
three-component mix: the cocoa powder plays a less important
• Two-component mixes are mainly role. As a result, it is not recommended to
made of crystal sugar and cocoa use lecithinated cocoa powder in vending
powder. mixes. The mix, however, should be
• Three-component mixes are mainly agglomerated to ensure good mixing with
made of cocoa powder, crystal sugar, the hot water.
and milk powder. In ADM Cocoa’s technical information
Because milk consists largely of water, bulletin Cocoa Powder and Dry Mixes,
it is important to change the hydrophobic extensive information is made available
cocoa powder into a hydrophilic powder. on this particular application of cocoa
The cocoa manufacturer does this by powder.
coating the cocoa powder particles with
an emulsifier such as lecithin. The lecithin
molecule is made up of hydrophobic and 3. Packaging, storage,
hydrophilic parts. The hydrophobic part and transportation
anchors itself to the cocoa butter on the Packaging
cocoa solid particle. The hydrophilic part Cocoa powder is a complex and vulnera-
of the lecithin molecule is directed to the ble product. It is not only very hygroscopic;
outside of the cocoa particle. In this way, it also tends to quickly pick up foreign
a cocoa particle is created with an outer odors from its surroundings. Therefore,
surface that has a hydrophilic character. the product should be properly packed
When this lecithinated cocoa particle is and stored. The packaging itself must be
added to cold milk or water, it is easily able to endure transportation over long
dispersed. distances and varying handling condi-
However, if a dry mixture of sugar tions and should be able to stand up to a
crystals and lecithinated cocoa powder is prolonged storage period. The powder
added to cold water, the sugar crystals itself is a product that enjoys a long shelf
immediately fall to the bottom of the life, provided that packaging and storage
glass, followed much more slowly by conditions are adequate.
lecithinated cocoa particles. This results in

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Cocoa powder storage under optimal conditions

plastic foil and wrapping is fitted around


Depending on the geographical destina- and over the pallet to protect the bags
tion, the cocoa powder is usually packed from dirt, pests, humidity, and damage
in paper bags of either 25 kg or 50 lbs. (instability) during handling and trans-
These bags are made of multi-layer kraft portation. The pallets can be lifted from
paper and a polyethylene moisture four sides and are single, one-way (non-
barrier. The bags are stacked 30 (750 kg) returnable) transport units.
or 40 (2,000 lbs.) to a wooden pallet. A
cardboard anti-slip sheet is placed on the Coding
pallet to protect the bags at the bottom. A Each individual packaging unit of cocoa

Archer Daniels Midland Company 139


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products carries the identification of the changes. If it is subjected to a temperature


manufacturer and country of origin, the too high, it will melt. When the tempera-
product type, the product description, the ture drops again, the cocoa butter will
lot identification number, the net weight, re-crystallize, giving the cocoa powder a
and a unique production code for verifi- gray discoloration. It will also cause the
cation and identification (traceability). particles to stick together.
Pertinent information in this code Although these factors do not have an
includes the date of manufacture, the pal- influence on the intrinsic quality of the
let number, and the filling line/machine. cocoa powder, lump formation can make
Typically, each packaging unit also the powder difficult to handle in further
includes transport and storage instruc- processing.
tions, e.g. keep cool and dry. Protection of cocoa powder against
For microbiological sampling and rodents and insects is also essential. The
analysis, a different lot definition is used: greatest danger comes from damaged
a quantity of product produced and bags and unhygienic storage conditions.
handled under uniform conditions. (See The product must be stored in a clean,
Microorganisms in Foods 2, I.C.M.S.F. regularly inspected area. Rodents and
(1986), page 22.) Often, such a microbio- other pests can be controlled by traps or
logical lot consists of the product bagged electric defense mechanisms.
or filled from a single line within a lim- The following recommendations are
ited period, e.g. six-24 hours. made for adequate transportation and
storage conditions:
Transport and storage • Use only cool, dark, and dry food-
Under incorrect transport and storage grade storage areas in which the tem-
conditions, certain changes in cocoa pow- perature is between 15°-20° C
der’s physical characteristics can occur. (55°-65° F) and the RH is <50%.
For instance, if cocoa powder is com- • Stack no higher than 20 bags or two
pressed beyond a certain level, agglomer- pallets.
ation or lumping of the cocoa particles • Position the pallets with sufficient
occurs. Stacking beyond a certain height space between them and the wall to
will give rise to this pressure and must avoid local temperature variations
therefore be avoided. It is not recom- and pest infestation.
mended to stack more than 20 bags or • Keep the storage space clean and free
two pallets high. of rodents, insects, birds, and other
The air surrounding the pallets of cocoa pollutants.
powder should preferably have an RH • As much as possible, prevent sudden
<50%. This level of humidity is the upper temperature changes.
limit to hold cocoa powder in a microbio-
logically stable state. But even with an RH • Avoid exposing cocoa powder to
<50%, care must be taken that no sudden direct sunlight, hot lamps, or other
temperature changes of the surrounding direct sources of heat.
air occur. Even under favorable condi- • Ensure the absence of strong smelling
tions, this can cause condensation on the products in the vicinity, such as
inside of the packaging that may lead to coffee, tea, tobacco, spices, paints,
possible growth of mold. chemicals, and cleaning substances.
Also the cocoa butter present in the • Even though the cocoa powder has a
cocoa powder is sensitive to temperature much longer shelf life, use up stocks

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The De Zaan ® Cocoa Manual

within 12 months. 4. Specification of


Packaging reduction
ADM Cocoa’s policy with regard to
cocoa powder
product packaging is first and foremost to Introduction
properly protect the product so that the Specifications are important for the user
user receives it in an optimal condition. of cocoa powder to formulate an end-
Beyond this, the issue of packaging and product, set quality standards, and com-
its effects on the environment must be ply with food legislation. Specifications
addressed. In response to worldwide relate to consistency, quality, and safety
public concern over protection of and are only meaningful when the corre-
resources and biodegradability of packag- sponding methods of analysis are indi-
ing materials, many countries are reacting cated. These methods of analysis can be
by taking action to reduce packaging. We found in Module 3: Methods of Analysis.
are
seeking to: Controllable and
• minimize the size and quantity of non-controllable factors
packaging materials used Defining specifications is particularly
• make it reusable, if packaging is challenging for products made from raw
unavoidable materials with a natural origin. In the
• make it recyclable, if it can't be made manufacturing process of cocoa powder,
reusable there are important production steps
where quality aspects can be influenced
Bulk and semi-bulk packaging and controlled. These are:
Packaging materials and handling tech- • Alkalizing: allows control of color, fla-
nology are developing very fast. New sys- vor, and pH
tems are constantly coming onto the mar- • Roasting: allows control of flavor and
ket. However, transportation of cocoa microbiology
powder in bulk, in whatever way, is ulti- • Pressing: allows control of fat content
mately going to be the only adequate • Grinding: allows control of fineness
solution to this problem. Tank cars have
already made their entry, and the semi- However, some characteristics can be
bulk flexible intermediate containers are controlled only to a limited extent. These
rapidly gaining in popularity. For users of are the natural constituents of cocoa, for
large quantities of cocoa powder, this example: the content of starch, protein,
bulk packaging from ADM Cocoa reduces and theobromine or the cocoa butter com-
handling and logistics costs significantly position. The pH of the non-alkalized
while protecting the product’s integrity. cocoa powder is determined by the acidic
They carry between 800 and 1,000 kg components of the beans used and can
(1,750 to 2,200 lbs.), depending on the only be controlled by the selection of the
type of powder. For more information on beans.
this type of packaging, please contact one Many users of cocoa powder require
of the sales offices of ADM Cocoa listed nutritional information on the product for
on page 151. the calculation and declaration of the
nutritional value on their consumer pack-
ages. For different types of cocoa pow-
ders, this nutritional information is given
in Module 6: Health and Nutritional

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Aspects. Because cocoa beans naturally these very fine particles.


vary with origin, season, and differences Pesticides
in processing, this information is indica- Cocoa trees and their fruit are prone to
tive only and is not a part of our standard attack by microorganisms and insects. To
specifications. fight these pests, fungicides, insecticides,
and pesticides may be applied but mostly
Food safety aspects on the cocoa pod and not on the beans
ADM Cocoa is certainly aware of the themselves.
essential character of safety in food prod-
ucts. A working and certified HACCP Heavy metals
ensures that food safety hazards are con- As is true with most agricultural crops,
tinuously monitored and controlled. Many trace levels of heavy metals often found
factors can influence cocoa product food in the soil may be found in cocoa. Because
safety. A brief summary is given below. cocoa beans from origin countries com-
monly come into contact with soil, shell
Impurities removal to the levels specified under reg-
Impurities are defined as everything pres- ulatory standards is known to help limit
ent in cocoa powder that theoretically the levels of these naturally occurring
should not be there. They can be subdi- metals.
vided into two categories:
• Foreign matter relates to all items that Mycotoxins
are not intrinsic to the product and Mold growth on cocoa beans occurs on
that may have been introduced occasion. Some of these molds can pro-
during harvesting, transportation, duce mycotoxins. This may occur at the
and processing of the raw material. farms during harvesting, ripening, fer-
These non-indigenous materials, such mentation, and drying. It is thus possible
as pieces of wood, metal fragments, that mycotoxins like aflatoxins and ochra-
and sand, must be removed and care- toxine A are present on cocoa beans. It is
fully controlled. impossible to remove every impurity
• Extraneous matter can be defined as from cocoa powder during manufact-
material that is intrinsic to the uring. Regulatory authorities have recog-
processed product and includes insect nized this. However, careful selection and
fragments and cocoa shell. Its pres- handling of raw materials and good man-
ence is unavoidable but can be con- ufacturing practices help control the lev-
trolled by applying Good Manufac- els of such impurities.
turing Practices (GMP) and adequate
processing. Tolerable levels of extra- Specification components
neous matter are set in the Defect It is important to note regarding the com-
Action Levels by the Food and Drug ponents of typical De Zaan® cocoa powder
Administration in the USA. specifications that ADM Cocoa operates a
number of cocoa processing plants around
Metallic iron the globe. The raw materials supplied and
The presence of metallic iron is inherent the nature of processing may vary from
to cocoa given growing, postharvest, and one plant and/or region to another. As a
manufacturing conditions. Good manu- result, the specific attributes and values
facturing practices and the use of power- in specifications may differ simply due to
ful magnets help control the levels of the raw materials in use and the specific

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nature of the processing employed. lized (natural) cocoa powders may have
The final application for a specific cocoa wider pH ranges caused by the natural
powder is best used as a guide to deter- variation in the acidity of the cocoa beans.
mine which component values, methods
of analysis, and other product features are Fineness
most important to that application. A clear distinction must be made between
fineness determined by sieving of the dry
Flavor and color cocoa powder versus sieving the cocoa
No matter how important various fea- powder in a water suspension. The fine-
tures may be, cocoa powder is ultimately ness of powder as such is not relevant in
used in the finished product for its flavor most applications. Cocoa particles are
and color. The food industry has every partly agglomerated and do not disinte-
interest in using cocoa powders with fea- grate completely with dry sieving. How-
tures that are as optimal and consistent ever, agglomerates will immediately disin-
as possible. That is why reliable methods tegrate when the powder is brought into
are important to determining whether a suspension or when heat is applied. The
delivery conforms to a reference sample wet sieve test with warm water is, there-
in color and flavor. These methods are fore, the best determination of fineness.
outlined in Module 3: Methods of (See Module 3: Methods of Analysis.)
Analysis. Further information regarding Fineness is a characteristic for which
sensory evaluation can be found in different applications have various
Module 4: Flavor and Flavor demands. Manufacturers of chocolate
Development. Reference samples are milk will immediately notice the presence
available from ADM Cocoa. With these, of a slight amount of coarse cocoa parti-
customers can carry out their own cles in their products and may experience
checks. problems with their homogenizers.
An easy test for coarse particles is to
Fat content put cocoa powder in milk. The particles
The food legislation of many countries can be easily seen when they are placed
has divided cocoa powders into different against the light background of the milk.
categories based on their fat contents.
Within the regulations in effect, industrial Moisture content
customers select the fat content that is Some food laws allow a moisture content
optimal for their products. It is not techni- of max. 9% for cocoa powder. In practice,
cally possible to press to an exact fat per- this percentage appears to be too high.
centage; some tolerance is necessary. With rapid decreases in temperature dur-
However, this specification should be as ing storage or transport, condensation
narrow as possible. ADM Cocoa specifies inside the packaging can occur. With such
the fat content within a 2% range. a high moisture content, mold can grow
in the product. Our experiences show that
pH a moisture content of a max. of 5% is best.
The alkalization process increases the pH
value of the natural, lightly acidic cocoa. Microbiological characteristics
The degree of alkalinity is determined by It is important that limits be placed on the
the extent of alkalization and the acidity microbiological quality of cocoa powder,
of the cocoa beans. Controlled processing especially as related to specific applica-
results in definable pH ranges. Non-alka- tions. The reasons for this are:

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Archer Daniels Midland Company 149


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THE ADM COCOA


ORGANIZATION
ADM Cocoa operates 13 industrial choco-
late and cocoa ingredients factories in
eight countries on four continents. It
allows us to integrate and implement
technologies and expertise from all of
these units, and so to benefit fully from
the acknowledged operational and orga-
nizational know-how of our parent
company, Archer Daniels Midland
Company, one of the world’s leading food
processing companies.
ADM Cocoa is structured effectively
to help our customers worldwide to
make the most of chocolate and cocoa
ingredients.
If you would like to know more about
ADM Cocoa, talk to your representative
or contact us at one of the locations listed.

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ADM COCOA BV ADM COCOA PTE, LTD.


Koog aan de Zaan Singapore
the Netherlands Telephone +65 (0)6264 2611
Telephone +31 (0)75 64 64 646 Fax +65 (0)6265 6126
Fax +31 (0)75 64 64 544
admcocoa-koog@admworld.com JOANES INDUSTRIAL SA
Produtos Qu’micos e Vegetais
ADM COCOA IlhŽusÑBahia, Brazil
Milwaukee, WI Telephone +55 (0)73 234 2003
USA Fax +55 (0)73 234 2061
Telephone +1 414-358-5700
Fax +1 414-358-5838

Archer Daniels Midland Company 151

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