Beruflich Dokumente
Kultur Dokumente
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
The information contained herein is correct as of the date of this document to the best of our knowledge. Any
recommendations or suggestions are made without guarantee or representation as to results and are subject to
change without notice. We suggest you evaluate any recommendations and suggestions independently. WE
DISCLAIM ANY AND ALL WARRANTIES, WHETHER EXPRESS OR IMPLIED, AND SPECIFICALLY
DISCLAIM THE IMPLIED WARRANTIES OF MERCHANTABILITY, FITNESS FOR A PARTICULAR
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other parties. Customers are responsible for obtaining any licenses or other rights that may be necessary to
make, use, or sell products containing Archer Daniels Midland Company ingredients. De Zaan¨ is a registered
trademark of Archer Daniels Midland Company.
The De Zaan
®
Cocoa Manual
The De Zaan ® Cocoa Manual
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
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
Bibliography 144
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
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.
West Indies 47 3 51 2 54 2 56 2 57 2
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
Cocoa powder
900
Cocoa
butter
Cocoa Cocoa PRESS INDUSTRY 700
beans nibs Cocoa liquor Chocolate
CHOCOLATE INDUSTRY
Cocoa liquor
900
Shell Sugar
600
Milk
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-
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
be as uniform in size
as possible in order
Storage Pressing
to achieve constant
quality.
Blending
bamboo, twigs,
string, stones, and
Sterilization Cake Deodorization
blending (optional)
magnetic materials is
removed. The clean
Alkalizing Pulverization
in multiple steps to
avoid an excess of
Liquor Powder Butter fine particles. After
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
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
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.
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
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)
_______
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
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.
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.
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.
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:
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
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
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
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
Alcohols
by removal of a molecule of H2O.
25
Esters
stage of roasting, the Amadori com-
58
Ethers
ways depending on the reaction condi-
8
Phenols
important for the development of the
6
Pyridines
tion, the heterocyclic components like 12
Oxazoles
apparent that the formation (and
15
Total
take place in a rather dry medium and at
463
(- H2O)
NH2 NH2
(-2x H2O)
N
N
- R2
H-C C - R2 (-H2O)
R2 -
R2 - C C-H (+O2)
N
N Pyrazine
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.
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
OH OH
OH
O OH
OH O
HO OH
HO
OH OH OH
OH
Epicatechin Procyanidin B
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
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:
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.
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
flavonoids palmitoleic
14.0 g (C20:0) 1.0%
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)
0.1 mg 3,495
- pantothenic acid
15.0 mg
1.0 mg
Energy (Atwater system)
Kcalories
Kjoules
520
conditions.
others
1.0%
Proteins
0.2%
saturated
Proteins are essential constituents of all
monounsaturated
61.5%
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
Food.
tyrosine
0.94 0.85
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
- gums
serine
0.89 0.85
- mucilages
1.05 0.93
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
Cocoa liquor
Standard of identity
45% 10%
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
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
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
and woody.
10 1
Grinding Grinding
Treated Treated
Liquor Liquor
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
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
1,9 Bitterness
1,4 *Venezuela
0,9
*Ghana
Cocoa Flavor
0,4
Full/Rich
-0,1
Acidity
Bouquet
-0,6
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%
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.
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%
Molds per g
5,000 max. (or up to 25,000 max.)
Yeasts per g
50 max.
Enterobacteriaceae in 1 g
100 max.
E. coli in 1 g
negative
Salmonellae
negative
negative
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
Iodine Value
188-198 188-198
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
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 (%)
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
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
Table 6
Hardness of Milk Chocolate
Effect of Cocoa Butter and Tempering
• 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.
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)
Table 8
Origin Cocoa Butter and Shukoff Cooling Curve
Malaysia
Ivory Coast
Ghana
Average
Cameroon Low
High
Brazil
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
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-
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-
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
6 5
104596802
4
2 2
1
7
3
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
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
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
1.50
Free fatty acids (%)
1.45
Free fatty acids regression
1.40
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
Blue Value
32-35/90-95
Unsaponifiables (%)
0.05 max
Saponification Value
0.14 max.
Peroxide Value
192-197
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
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
1
0
Non- Lightly Medium Strongly Strongly
alkalized alkalized alkalized alkalized “red” alkalized “black”
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
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.
Figure 2:
Typical Particle Size Distribution
De Zaan® Cocoa Powders
12
10
Volume Percentage
0
0,1 1 10 100 1000
Particle size (µ)
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
Legend
Cocoa
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
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.
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:
ADM Cocoa, Sensory Evaluation of Cocoa Behm, Schokoladen Freuden, 1964, Ernst-
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