Physicochemical Phenomena in The Roasting of Cocoa

Food Engineering Reviews (2022) 14:509–533
https://doi.org/10.1007/s12393-021-09301-z
Physicochemical Phenomena in the Roasting of Cocoa (Theobroma

cacao L.)
Myriam Rojas1,2 · Arne Hommes2 · Hero Jan Heeres2 · Farid Chejne1
Received: 30 June 2021 / Accepted: 14 November 2021 / Published online: 13 January 2022
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021
Abstract
The quality of cocoa depends on both the origin of the cacao and the processing stages. The roasting process is critical
because it develops the aroma and flavor, changing the beans’ chemical composition significantly by chemical reactions
induced by thermal energy. Aspects have been identified as the main differences between bulk cocoa and fine cocoa, the
effect of time and temperature on the formation of the flavor and aroma, and the differences between conductive heating
in an oven, convective with airflow, and steam flow. Thermal energy initially causes drying, then non-enzymatic browning
chemical reactions (Maillard reaction, Strecker degradation, oxidation of lipids, and polyphenols), which produce volatile
and non-volatile chemical compounds related to the flavor and aroma of cocoa roasted. This review identified that the effect
of the heating rate on the physicochemical conversion of cocoa is still unknown, and the process has not been evaluated in
inert atmospheres, which could drastically influence the avoidance of oxidation reactions. The effect of particle size on the
performance of product quality is still unknown. A more in-depth explanation of energy, mass, and chemical kinetic transfer
phenomena in roasting is needed to allow a deep understanding of the effect of process parameters. In order to achieve the
above challenges, experimentation and modeling under kinetic control (small-scale) are proposed to allow the evaluation of
the effects of the process parameters and the development of new roasting technologies in favor of product quality. Therefore,
this work seeks to encourage scientists to work under a non-traditional scheme and generate new knowledge.
Keywords Cacao types · Roasting parameters · Cocoa quality · Chemical conversion · Small-scale modeling
Introduction and anti-stress effects [132]. However, the excessive con-

sumption of chocolate is generally considered unhealthy as
Cocoa Industry it can affect the nervous system, raise blood sugar levels,
and cause allergic reactions, constipation, and migraine [75].
Cocoa and derivatives are one of the most popular food types Chocolate may be consumed in its pure form (i.e., white,
in the world due to their exquisite organoleptic properties milk, or dark) or used in bakery and confectionery prod-
(i.e., flavor, aroma, texture) and high caloric and nutritional ucts, beverages, ice cream, and cosmetic applications such
value as it is rich in carbohydrates, fats, proteins, and min- as skin and hair care [141]. Cacao is the essential ingredi-
erals [118, 135]. It has even been claimed to offer health ent of chocolate and is responsible for its unique flavor and
benefits, such as antioxidant capacity, improving choles- texture [44]. Cocoa is derived from beans of the cacao tree
terol levels, lowering blood pressure, and antidepressant with the Latin name “Theobroma cacao,” meaning “food
of the gods” [84]. Cacao originates from the Amazon and
Orinoco rainforests in South America, where the tropical
* Farid Chejne climate with heavy rainfall and high temperatures creates
[email protected]
optimal growth conditions. In premodern Latin America,
1
Alliance for Biomass and Sustainability Research – cacao beans were considered so valuable that they were used
ABISURE, Universidad Nacional de Colombia, Carrera 80 as a means of payment [83]. After the Europeans’ “discov-
No 65‑223 ‑ Campus Robledo, Medellín, Colombia ery” of the Americas, chocolate became famous worldwide,
2
Department of Chemical Engineering, Engineering which initiated cacao cultivation in other tropical areas (e.g.,
and Technology Institute Groningen, Nijenborgh 4, Africa, Asia, and Oceania).
9747 AG Groningen, The Netherlands
13
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510 Food Engineering Reviews (2022) 14:509–533
General Information by Bolivia, Ecuador, Nicaragua, Colombia, Costa Rica,

Peru, and Mexico [67]. However, the world demand for fine
The total worldwide cacao production was 4,645,000 tons cocoa increases due to its superior aroma and flavor [26].
in 2018: 75.9% from Africa (main producer is Côte d’Ivoire Fine beans are associated with a high intrinsic quality due
with 43.06%), 17% from the Americas (main producer is to a more pleasant flavor and aroma and are the basis of the
Ecuador with 6.03%), and 7.1% from Asia/Oceania (with luxurious “gourmet” chocolate. Bulk cacao is mainly used
Indonesia that produces 5.8%) [65]. The processing of to produce cocoa butter as it requires the addition of sugar
cacao into chocolate (and derivatives thereof) is mainly (milk/cream and flavor enhancers) to compensate for its bit-
done in Germany, Belgium, and the Netherlands, with rev- ter taste to process it into high-volume common chocolate
enues of 5.4, 2.9, and 2.3 billion euro, respectively [27]. products [26, 66]. For bulk beans, the purple or red color of
Due to the increase of world consumption of about 91% the interior is an indicator of good quality, as this is typically
in the last 20 years, the effects due to cocoa life cycle can- associated with a high polyphenol content, which has good
not be neglected anymore. The growing demand has led to antioxidant properties, but a bitter taste (which is compen-
the intensification of cocoa cultivation by expanding to new sated for by adding lots of sugar). In fine cacao, the color
lands, including forest lands, or by the use of more excessive varies from white to light brown because of the low content
agrochemicals, which are not yet controlled [19]. However, of polyphenol therein (Fig. 1e) [133].
some Latin American farmers are applying agroforestry
systems to avoid excessive agrochemicals use and reduce
environmental impact [89]. These systems could represent Cacao Beans' Composition
the challenge of future cocoa production for its ecological
and social benefits. Freshly harvested cacao beans contain water, fats, carbo-
The global cocoa market size was valued at $44.35 Bn in hydrates, proteins, vitamins, minerals (e.g., Fe, Cu, Mg,
2019 and is projecting an increasing rate of 4.4% to reach Zn, Na, Ca, and P), active secondary metabolites (poly-
$61.34 Bn by 2027 Bianchi et al. [19], representing a posi- phenols), and methylxanthines: theobromine and caf-
tive economic impact for the industry and producers. But feine [110]. Essential compounds are the reducing sug-
it also means a need to exploit following the objectives of ars (e.g., sucrose, glucose, and fructose) and free amino
sustainable development, with a more equitable distribu- acids (e.g., leucine, alanine, phenylalanine, and tyrosine).
tion of profits, protection of the environment, and improve- These are essential because they are the main precursors
ment of the social conditions of the producing countries. in the formation of aroma compounds (i.e., during the
In cocoa production, the weakness is in the poor produc- cacao bean processing) and give chocolate its character-
ing countries whose communities do not receive the fair istic flavor. In fine cocoa, these precursors are typically
benefit. At the same time, the most promising strength for present in higher concentrations than in bulk cocoa; the
the future is the production of high-value fine cocoa and difference is about 12.5% less in the content of free amino
derived products. acids in bulk cocoa [133]. Other compounds contributing
to the characteristic cocoa taste/aroma are 3-methylbu-
tanoic acid, ethyl 2-methylbutanoate, and 2-phenyletha-
Cacao Beans’ Origin nol [46]. Polyphenol concentrations are typically higher
in bulk cocoa (86.1 ± 0.73 mg g −1) than in fine cocoa
At the age of ca. 2 years, the cacao tree produces a large (66.0 ± 0.34 mg g−1), which gives the prior a greater astrin-
pod-shaped fruit (i.e., the cacao fruit; Fig. 1a, b), which gency (an unpleasant sensation of dry, puckering mouth-
changes color during its maturation (i.e., from green to feel) [133]. However, these compounds have antioxidant
yellow, orange, and finally red or purple). Cacao beans are properties that may benefit health [52]. The most abundant
covered by mucilage (i.e., pulp) inside pods (Fig. 1c). Each polyphenols in bulk cocoa are proanthocyanins (ca. 58%),
cacao bean consists of two cotyledons (the nib) of elliptical catechins or flavan-3-ols (ca. 37%), and anthocyanins (ca.
shape (typical dimensions of 20–26 mm length, 10–14 mm 4%) [8, 23]. The methylxanthines theobromine and caf-
width, and 6–10 mm thickness [16]) and a small embryo feine increase motivation, alertness, and energy [142]. Both
plant, enclosed by the skin (the shell) (Fig. 1d). polyphenols and methylxanthines contribute to the bitter
Cacao beans are typically distinguished between the bulk taste of chocolate [10]. The theobromine to caffeine weight
and fine categories. The fine cacao beans come from the ratio is sometimes used to identify the cacao origin. This
“special” Criollo or Trinitario varieties, while the “ordi- ratio is typically 1–2 with 0.4–0.8 wt% caffeine for the Cri-
nary” bulk cacao beans come from the Forastero variety. ollo species, whereas for the Forastero species, this ratio
Ninety-five percent of the world cocoa market stems from is 5–14 with 0.1–0.25 wt% caffeine. Trinitario has values
bulk beans. The other 5% are fine beans, mainly exported between Criollo and Forastero [34, 134].
13

Food Engineering Reviews (2022) 14:509–533 511
Fig. 1 Representation of (a) cacao tree, (b) cacao fruits, (c) cacao pods, and (d, e) bulk and fine cacao beans
It should be noted that the chemical composition, and From Cacao Beans to Chocolate
thus chocolate flavor/aroma, of cocoa products, strongly
depends on the cacao beans’ genotype (variety) [54], geo- Many processing steps are required to produce chocolate
graphical origin, agroecological conditions during grow- and derivatives from cacao beans (Fig. 2), which may
ing, and the post-harvest processing techniques applied affect the final product characteristics. The mature cacao
[62]. Therefore, an analysis of the influence of different fruits are harvested manually by removing the ripe pods
processing steps in processing cacao beans into choco- from the trees. These are then opened to remove the wet
late is necessary to evaluate how each step influences the beans classified/sorted (i.e., by pulp color and texture
cocoa flavor/aroma. This work emphasizes the roasting and microbial contamination) and fermented before dry-
process. ing [86].
13

Fig. 2 Industrial processing steps from raw cacao to chocolate. (a) Precursor formation, (b) roasting, (c) flavor and aroma development, and (d)
texture improvement
13

The fermentation is done by stacking the beans on a pile or Table 1 Chocolate and cocoa industry quality standards for dried
in wooden boxes (up to 210 kg), which are protected from the cacao beans
rain and sun. This process takes 5 to 7 days at a temperature Parameter Range Reference
between 48 and 51 °C. To control the fermentation process’s
Moisture content 6.5–8.5% w.b. [70]
slight temperature increase, the beans are aerated manually
Bean count per 100 g Standard beans: ≤ 100 [71]
[126]. The cacao bean fermentation is a microbiological pro-
Medium beans: 101–110
cess where microbiomes present in the beans (e.g., Lactoba- Small beans: 111–120
cillus fermentum and Acetobacter pasteurianus) break down Very small beans: > 120
sugars of the pulp (mucilage) to alcohol, lactic acid, acetic Cut tests Insect-damaged, insect-infested, [69]
acid, and mannitol [61]. Also, other (enzymatic) reactions or insect-germinated beans
Light brown to dark brown,
take place in the pulp and beans, where peptides and free
violet, or mix of colors
amino acids are produced through proteolysis from storage Fissuring evaluation
proteins such as globulins [147]. Reducing sugars are formed Aroma (smoke and oily taints
through hydrolysis of sucrose by invertase [114, 140]. The putrid or hammy notes)
endogenous formation of the precursors (i.e., in the beans) is Maximum Cd content 0.5 mg/kg (0.8 mg/kg in special [27]
cases)
influenced by exogenous processes of the pulp, where formed
components may diffuse from the pulp into the cotyledon *w.b., wet basis
where they are retained in the drying process [33, 40].
After fermentation, the beans are dried in the sun (e.g., color and volatile compounds (i.e., responsible for the flavor/
by spreading them out on a floor or platform) until the mois- aroma) are generated. Also, roasting causes softening of the
ture content is reduced from ca. 55 wt% to 6.5–7 wt% [80]. material essential for subsequent processing [63, 76].
Sometimes, improved methods such as direct solar drying or The roasted beans are winnowed, where the cocoa nibs are
hot air drying (i.e., tunnel dryer and hybrid forced convec- separated from their shells (about 20% of the total weight)
tion and solar dryer) are adopted [4] to accelerate the process using gravity and airflow, i.e., the air carries away the light
and reduce microbial contamination in humid areas. Drying shell and the heavy nibs fall into the container [100]. Subse-
of the beans causes them to contract and decrease in den- quently, the resulting cocoa nibs are ground with stone rollers
sity, facilitating their transport and improving shelf life due (i.e., refinement) to a paste known as cocoa mass or cocoa
to the reduction microbial activity (water activity decreases liquor. The cocoa liquor is treated with alkali (i.e., alkaliza-
from 0.99 to 0.72) [28, 115]. During drying polyphenols and tion or Dutching) to improve the color and flavor and increase
some proteins degrade into free amino acids or denaturate dispersibility (see Fig. 2c). It also reduces astringency by
completely [7, 129]. Furthermore, theobromine and caffeine complex polymerization of polyphenols, therewith decreas-
contents typically decrease the drying process [35]. Addi- ing the bitterness and darkening of the cocoa [3, 51]. The
tionally, drying causes the beans to shrink and increases the conching is the next step; this is a multi-day mix that contrib-
bean porosity, mass, and heat transfer coefficient, whereas utes to the development of the final flavor and smooth texture,
the density decreases due to the drop in moisture content generally performed at temperatures above 40 °C (for dark
[80]. Some ranges of crude protein content in dried beans chocolate between 70 and 82 °C) [3, 51]. Finally, the choco-
are from 15.2 to 22%, total fat 50.4 to 55.21%, ash 2.3 to late product is molded into bars, after which it is packed and
2.9%, and carbohydrates 21.0 to 24.9%; the minerals iden- ready to market. Large producers typically use continuous
tified in mg/100 g are Fe (1.2–2.2), Cu (8.8–17.3), Mg conveyor belts, while small manufacturers do it manually.
(262.7–364), Zn (8.2–15.6), Na (2.0–3.0), Ca (143.5–170.8),
P (195.8–355), and K (2070.7–2557.9) [3, 5, 11].
In Latin America, fermentation and drying are mostly Cocoa Products’ Characteristics
done at the farms. Therefore, standardization is difficult to
achieve, causing a quality decrease in the Criollo varieties. The final cocoa products’ quality indicators can vary accord-
However, large-scale post-harvest centers are currently being ing to the consumer’s requirements. The sensorial percep-
built in Colombia to standardize the post-harvest processes tion in cocoa and chocolate is one of the most important
of fine cocoa and preserve the quality [126]. Market quality quality criteria in the industry and is related to the chemical
standards have been established for the dried cacao beans to composition. Currently, both the sensory evaluation by the
guarantee the quality of the chocolate [32] (Table 1). Pro- panel of experts and the identification of the aromatic com-
ducers supply the chocolate companies with the dried cacao pounds through a chromatographic analysis are applied. The
beans, and the processing of the chocolate begins with roast- scores resulted define the quality profile in the Cocoa and
ing. The roasting of cocoa beans (see Fig. 2b) is considered Chocolate Flavour Wheel. For cocoa roasted and chocolate,
the most critical step in chocolate processing because brown 105 sensory attributes have been selected. These attributes
13

Fig. 3 Sensorial attributes for cocoa and chocolate flavor wheel by Januszewska et al [72]
are grouped into eight flavor levels, which correspond to flavors of fine cocoa from Criollo varieties have an exclu-
the “Cocoa and Chocolate Flavour Wheel” shown in Fig. 3. sive mix of complex flavors and produce fine chocolates and
Making fine chocolates and candies attributes as Fruity, perfume applications [17]. Additionally, the cocoa industry
Floral, Sweet, and Cocoa is required, while Acidity, Bitter- has sought to highlight the quality of cocoa globally through
ness, Astringency, and off-flavors are unaccepted. That is, the competitions worldwide to identify where the best cocoa is
quality and value of chocolate are related to its unique flavor produced and improve its market.
and aroma profiles [131]. However, identifying quality is a In addition, the U.S. Food and Drug Administration
subjective issue related to the human senses and is measured (FDA) has established standards of identity and quality
by a sensory panel of experts. For example, the sound of choc- for cacao-derived products, where the ranges of ingredi-
olate when it is breaking it is an indicator of quality, where the ents (cocoa butter, sugar, dairy products) and additives
high-quality has a clean, crisp, sharp snap when broken, while (flavorings and preservatives), the process applied, and
low-quality chocolate bends rather than breaks cleanly, has a the microbiological and chemical state as well as the test-
dull sound when broken, or only crumbles [138]. ing methodologies standardized, e.g., chocolate liquor
High-quality or fine cocoa is characterized by a delicious contains not less than 50% and nor more than 60% wt. of
taste of cacao with beautiful fruit notes. The rare, complex cacao fat [43].
13

Cocoa Roasting Process reactions are responsible for forming brown compounds such
as melanoidins that change the color to roasted and aromat-
During the roasting processes, some undesired volatile ics that give it flavor and aroma.
compounds (e.g., acetic acid and alcohols) are evaporated The roaster’s technology retains the general basic design
and the moisture content is reduced to about 1% w.b. with of the past and improvements have mainly focused on heat-
a water activity decrease from about 0.5 to about 0.2 [47, ing systems such as infrared heating and infrared and con-
115]. Moisture reduction minimizes the microbial activity vection hybrids [2]. The effect of the main parameters of
and increases the glass transition temperature (Tg, improving temperature and time on variables related to quality might
the storage stability (i.e., less agglomeration of particles or be understood through modeling. This modeling must be
texture changes. Additionally, changes in the properties of linked to the kinetics of chemical reactions; therefore, it will
products such as texture; organoleptic, thermal, and rheo- make it possible to evaluate the effects of parameters not yet
logical characteristics; shelf life; brown color; and functional studied to optimize the process in terms of final quality and
and physicochemical properties occur [24, 120, 121]. energy consumption.
As such, cacao roasting phenomenology and essential
parameters have been researched extensively over the past Technologies of the Roasting Process
decades, but roasting is a complex process of a multicom-
ponent biomass; therefore, there are still unanswered ques- Since the heating profile during cocoa roasting strongly
tions and phenomena without deep explanations that are influences the product quality, specific roaster technologies
identified in this work. In the roasting process, dried cacao have been developed with high energy efficiency. The most
beans are heated from room temperature up to the roasting common equipment is heat conduction, hot air, rotary drum
temperature which is commonly from 110 to 160 °C. From roasters, or continuous roasters. The roaster technology
34 °C, the fat reaches its melting point and goes into a liq- looks to achieve uniform heating of the beans, obtain more
uid state within the beans’ structure [115]. When the beans homogeneous results, and avoid parts over-roasted or burned
are further heated to temperatures above 100 °C, moisture (Rocha et al. 2017) [112].
is removed and low molecular weight compounds such as Technologies include the three basic zones, the come
alcohols and acetic acid (formed in the fermentation pro- up (heating), constant targeted temperature, and the cool-
cess) are volatilized. Due to decreased humidity and water ing zone where the product is collected (Mohos 2017) [96].
activity (aw < 0.6), heating induces non-enzymatic brown- Since ancient times, technologies have been developed
ing reactions (NEB) [77]. NEB is mainly associated with where new systems have been adopted, increasing heat trans-
the Maillard reaction. However, other chemical reactions fer capacity and efficiency. In the beginning, a metal plate
also occur, such as Strecker degradation, lipid oxidation, and was used that contained the beans and was exposed directly
polyphenol degradation [31]. The Maillard reaction begins to the fire, while a person moved the beans with a wooden
with the condensation of a reducing sugar and an amino cane (Mayer-Potschak and Kurz 1983) [191]. Today, there
acid and after can take place through different routes such is continuous and batch equipment, with capacities ranging
as Strecker degradation, to generate aromatics such as pyra- from grams (for the home) to thousands of kilograms per
zines [48], aldehydes, esters, and ketones with a pleasant day according to the industry’s requirements (see Table 2
aroma to chocolate [10], and dark melanoidins [108]. NEB and Fig. 4). High-capacity and high-performance roasters
Table 2 Roasting equipment is Roasting equipment Capacity (kg/h) Heating principle Reference
commonly used for cocoa
Sirocco or ball 10–480 Convection from the hot air [94]
The beans are moved with a stirrer
Rotary drum All shapes and sizes Conduction from direct contact with [37]
0.1–3000 drum walls
Convection from the air flowing in
the drum
IR 0.4–46 Radiative heat Diedrich (USA)
Continuous 1–4000 Convection from hot air passes Bühler, Ger-
through each permeable layer many
Royal Duyvis
Wiener, USA
Longer Food
Machinary,
China
13

Fig. 4 Types of roasters for cocoa beans: (a) sirocco roaster designed drich (USA), (d) typical horizontal continuous bean roaster, and (e)
and patented by G.W. Barth, Ludwisburg (1900), (b) industrial drum continuous vertical roaster by Royal Duyvis Wiener (USA)
roaster up to 616 lb/h by Diedrich (USA), (c) infrared roaster by Die-
have been developed to process large volumes of bulk cocoa, roasting chemistry and the influence of process param-
while small ones are used in small companies specialized in eters on the formation or degradation of certain chemi-
fine chocolates. Given the cacao bean diversity and the trend cal compounds related to cocoa quality in the “Roasting
of the specific demand for differentiated chocolates, cocoa Chemistry” section, and in the “Mathematical Modeling to
roasting must specialize. Then, gourmet roasters have been Understand Thermochemical Processes” section, emphasis
developed that allow a wide range of programmable param- will be placed on kinetics and modeling of the process.
eters, such as time, temperature, airflow, steam injection,
and cooling time. In this way, it is possible to apply different Scope of this Review
operating conditions depending on the type of raw cacao
and the characteristics of the product desired [58]. Addition- Several reported reviews have been published on agricultural
ally, the heating systems have been improved using hybrid topics (genotypes, harvest, and post-harvest), biochemistry
systems (convection-infrared) and infrared (developed by and chemistry (fermentation conditions, the formation of fla-
Diedrich, USA) as well as the use of microwaves as a future vor and aroma precursors) [10, 46], and health applications
and promising technology [128]. (antioxidant capacity, extraction, and evaluation of molecules
The cooling system that the roasters incorporate is with pharmaceutical potential) [6, 130], and also about social
through airflow over the cocoa beans and stirring to cool areas due to the importance of this product in vulnerable
them quickly and avoid burning or over-roasting. In gen- communities in developing countries [67, 86]. In this work,
eral, the optimal operating parameters of temperature and the most relevant results of cocoa roasting and technologies
time depend on the type of roaster, raw material, and the are grouped. It is critically evaluated how the parameters
roasted cocoa’s characteristics, carried out by an operator (time and temperature) improve the quality of the product
who makes decisions based on his long experience. related to flavor and aroma. The chemical compounds that
The evolution of roasters has not been drastic, the tech- influence the aroma and their formation reaction networks
nologies keep the same principles, and no novel devel- were identified. Besides, this document identified missing
opments are known, e.g., there are no roasters that use explanations, e.g., the effect of some parameters, such as
inert heating media such as N2 or CO2 or equipment that heating rate, size particles, and reaction environment (i.e.,
minimizes the processing time by shredding the beans air or inert atmosphere). Also, his work identifies the lack
into smaller particles. Later, emphasis will be placed on of experimentation and modeling that allows knowing the
13

true nature of the process. Finally, a way towards investiga- the flavor of cocoa [20]. These pyrazines have been found in
tion under kinetic control (small-scale) able to describe the greater numbers and higher concentrations in fine cocoa beans
phenomenology present during the heating of cocoa was pro- from the Criollo variety [30, 117]. About 100 pyrazines have
posed. In this way, it would be possible to identify variations been identified in cocoa aroma, though 2,3,5,6-tetramethyl-
in liquid, solid, and gas fractions; temperature differentials; pyrazine (TMP) has been reported to constitute about 90% of
volatilization; and the kinetics of chemical reactions that will the total pyrazines in cocoa beans [45]. Furthermore, the basic
allow the development of new roasting technologies. aroma of roasted beans and chocolate is attributed to TMP and
TrMP (2,3,5-trimethylpyrazine), with TMP being considered
Roasting Chemistry the most dominant [60, 125].
In addition to pyrazines, the aroma of fine cacao is
During cocoa roasting, the aroma, flavor, and texture charac- defined by aldehydes and ketones [25]. According to Voigt
teristics of the chocolate are developed. All the chemical pro- et al. [137], three aldehydes present in chocolate have a
cesses occurring during cocoa roasting are discussed in this strong chocolate aroma (2-methylpropanal, 2-methylbuta-
section. In the “Aroma and Flavor Profile Related to Volatile nal, and 3-methylbutanal), and the more important ketones
Compounds” section, the relation between chemicals pre- favorable for cocoa flavor and quality are 2-heptanone,
sent in chocolate to its aroma and flavor profile is described, 2-pentanone, 2-nonanone, acetophenone, and acetoin [15].
with particular attention to the differentiated characteristics The total aroma of chocolate results from the contribution
of grains of the Criollo genotype and the main chemical reac- of each volatile compound present in cocoa; therefore, the
tions of roasting will be explained; in the “Maillard Reaction” variation of the concentration of these results in different
section, Maillard reaction; in the “Lipid Oxidation” section, sensory profiles. The main desired flavors of the cocoa pro-
lipid oxidation; in the “Biogenic Amines’ Formation” sec- file are presented in Table 3.
tion, biogenic amines’ formation; and in the “Formation of Considering the diverse chemical composition of
Carcinogenic Agents” section, formation of chemicals con- roasted cocoa and its relationship with quality is essential
sidered carcinogenic agents, and a table summary of the main to know the chemical reactions that govern the roasting
chemical reactions described above, and products generated process, as well as the influence of the main parameters,
and parameters of the roasting of cocoa beans. time and temperature, to look for process conditions that
favor the maximum production of desirable aromatics
Aroma and Flavor Profile Related to Volatile and reduce undesirable characteristics such as astrin-
Compounds gency, acidity, and over-roasted. The above is challeng-
ing since to achieve a complete understanding of roasting
The flavor and aroma profile of cocoa is directly related to chemistry, it would be necessary to initially study the
its chemical composition, and this determines its high or kinetics of isolated principal compounds in model sys-
low quality. Criollo cacao is of the highest quality and is tems and then compare them with the cocoa matrix. The
used in the manufacture of fine chocolates because of its above means a time-consuming job but would generate
high aroma and flavor to chocolate, with floral, fruity, and invaluable knowledge for the cocoa industry.
woody notes defined by aromatic compounds and low acid- The chemical reactions that govern the roasting process
ity and astringency perceptions [25]. So, this variety is more are Maillard reaction, Strecker degradation, lipid oxidation,
promising for future luxury applications (e.g., perfumes and and polyphenol’s degradation reactions.
fine candies) of its unique chemical composition.
The perception of the flavor and aroma of cocoa and Maillard Reaction
chocolate comprises a mixture of a large amount of vola-
tiles generated during the roasting; around 600 compounds Maillard reaction is complex, comprising several stages and
have been identified [147], where there are alcohols, esters, pathways to generate volatile compounds and high molecu-
amines, furans, phenols, acids, furans, furanones, pyrans, lar weight polymers (Fig. 5a). Maillard reaction begins by
pyrones, pyrroles, pyridines, sulfur compounds, hydro- the condensation of amino groups with a reducing sugar to
carbons, lactones, quinolines, quinoxalines, thiazoles, and produce Schiff bases and water [57, 74]. Then, a cascade
oxazoles [10, 151]. With the purpose of showing the link of chemical reactions that lead to the production of inter-
between the chemical compound and the sensory perception, mediates, aromatics, and brown polymers as melanoidins
Table 3 is made. This table shows the main volatile com- was continued [116]. The process depends on pH, tempera-
pounds present in roasted cocoa and its sensory perception. ture, type, availability, and concentration of reagents [87],
Among the groups of volatiles present in cocoa, the pyra- as presented in Table 4. Heating accelerates the rate of the
zines are highlighted, because they contribute over 40% of Maillard reaction, increasing the formation of aromatic com-
the aroma of cocoa powder and can be used as tracers for pounds (showed in the previous Table 3) of cocoa [57].
13

Table 3 Volatile compounds present in cocoa with quantities (in mg/kg) within parentheses and their sensory perception properties
Sensory perception Compounds References
Aldehydes
Sweet chocolate 3-Methylbutanal (2.69), 2‐methylbutanal (0.46), 2‐methylpropanal [21, 25, 60, 88, 107, 113]
(0.23), 5‐methyl‐2‐phenyl‐2‐hexenal (0.3), 4‐methyl‐2‐phenyl‐2‐
pentenal (0.055), 2‐phenyl‐2‐butenal (0.39), and vanillin (9.08)
Herbal, green n-Hexanal (0.135) [3, 60]
Fatty, waxy, pungent Nonanal (0.063) [88]
Bitter, grass, fruity Benzaldehyde (2.20) [60, 88]
Fruity, floral Methyl p-tolyl ketone, 2‐phenylpropanal, and 2‐phenyl [21, 88, 109, 136]
acetaldehyde (0.33)
Alcohols
Fruity, herbal 2-Heptanol (1.19) and 1‐hexanol, 2‐hexanol [21, 60, 88]
Fruity 2‐Methyl‐1‐butanol and 2-heptanone (0.48) [88, 136]
Floral 1-Phenylethylethanol, 2‐phenylethanol (3.68), benzyl alcohol [60, 113, 136]
(0.19), linalool (0.12), and 2,3-butanediol (2.68)
Vegetal Trans‐3‐Hexen‐1‐ol and 2‐pentanol (0.19) [88, 136]
Sweet chocolate 1,3-Butanediol (2.68) and 1‐propanol [113]
Esters
Fruity Ethyl octanoate (0.3%), ethyl phenylacetate (0.4%), ethyl [12, 21, 88, 133, 136]
acetate (0.31), isobutyl acetate (0.14), 2-phenylethylacetate
(1.5%), isoamyl acetate, ethyl butyrate, ethyl lactate, ethyl 2‐
methylbutanoate, ethyl valerate, ethyl hexanoate, ethyl decanoate,
ethyl laurate, and methyl salicylate
Floral Benzyl acetate, methylphenyl acetate, ethylphenyl acetate, diethyl [113, 136]
succinate, and isoamyl benzoate
Sweet chocolate Methyl cinnamate and ethyl cinnamate [21, 109]
Ketones
Floral Acetophenone (0.08) [60]
Sweet, earthy 2‐Nonanone (4.35) [12, 60]
Floral, herbal 2‐Hydroxy acetophenone [21]
Fruity, floral 2-Phenylacetaldehyde (0.33), 2‐pentanone, and 2‐heptanone [21, 88]
Furans, furanones, pyrans, pyrones, and pyrroles
Floral Linalool oxide (0.01), trans-linalool oxide, and 2‐furfuryl [12, 21, 60]
propionate
Sweet chocolate 5‐Methyl‐2‐furfural, 2‐acetylfuran, and 2‐acetylpyrrole [21, 113]
Fruity, herbal, nutty 5‐(1‐Hydrohyethyl)‐2‐furanone and furaneol [21, 81]
Nutty 3‐Hydroxy‐2‐methyl‐4‐pyrone, pyrrole‐2‐carboxaldehyde, pyrrole, [21, 81, 136]
l-pantolactone, 2‐acetyl‐5‐methylfuran, and 2‐furfural
Acids
Floral 2‐Methylpropionic acid, 3‐phenylpropionic acid, and cinnamic [21, 81]
acid
Amines, amides, nitriles, purines
Nutty, floral Benzonitrile and (2-phenylethyl)formamide [21, 136]
Pyrazines
Cocoa, coffee, green, mocha, roast 2,3,5,6-Tetramethylpyrazine (6.35) [88]
Cocoa, earth, must, potato, roast 2,3,5-Trimethylpyrazine (2.49) [88]
Nutty, chocolate, cocoa, roasted nuts 3,5-Diethyl-2-methylpyrazine (0.34) and 3,5-diethyl-2- [25]
methylpyrazine (0.019)
Peanut butter, musty nutty 2‐Ethylpyrazine (0.03) [88]
Cocoa, roasted nuts 2,6‐Dimethylpyrazine (0.17), and 2,5‐dimethylpyrazine (0.018), [60, 88]
Caramel, cocoa 2,3‐Dimethylpyrazine (0.48) [88]
Nutty, hazelnut, cereal 2,3‐Diethylpyrazine [21]
13

Table 3 (continued)
Sensory perception Compounds References
Nutty 2‐Ethyl‐6‐methylpyrazine (0.12), 2‐ethyl‐5‐methylpyrazine, 3‐ [60, 109]

ethyl‐2,5‐dimethylpyrazine, and 2‐ethyl‐3,5‐dimethylpyrazine
Candy, sweet 2,3,5‐Trimethyl‐6‐ethylpyrazine (0.43) [88]
An important pathway of Maillard is the Strecker deg- other aromatics from same precursors as pyrazines (entry 5),
radation, which leads to the initial formation of Strecker and the DKPs can be assigned to a single peptide precursor
aldehydes and, subsequently through condensation, oxi- (entry 6).
dation, and dehydration reactions, leads to pyrazines
and other aromatic heterocyclic compounds essential in
the flavor and aroma of cocoa roasted such as pyrroles, Lipid Oxidation
pyridines, imidazoles, thiazoles, oxazoles, hydrocarbons,
ketones, esters, amines, and sulfur compounds [1113, 29, Cocoa beans have a high lipid content (32–53% by
143]. weight), and their porosity increases after drying to
Table 4 shows that the formation of pyrazines is gener- 24.67% [80]. Lipids can react with oxygen and produce
ated from reducing sugars, amino acids, and peptides, the highly reactive lipid carbonyls, which react with amino
contribution of peptides being greater and catalyzed by groups to produce a cascade of chemical reactions similar
bases; also, its formation is favored at a low water activity to the Maillard pathways and generate similar volatile
and polyphenols can reduce pyrazines’ generation (entries products as Fig. 5b [144, 145]. In the reaction network of
1 to 3), alkaline pH produces more amount of α-dicarbonyls Fig. 5b, pathway a produces a new imine which is the pre-
and less HMF and methylglyoxal (entry 4), formation of cursor of the Strecker aldehyde and pathway b produces
Fig. 5 (a) Simplified mechanism for flavor generation by the Maillard reaction by [102] with modifications, (b) amino acid degradation in the
presence of lipid carbonyls’ products of lipid oxidation [145], and (c) polyphenols’ degradation by oxidation [92]
13

520
13
Table 4 Overview of chemical products and reactions during cocoa roasting
Entry Chemical product Precursors Chemical reaction Findings Additional observations References
1 ↑ Pyrazines (Pyr) Reducing sugars (RS) Maillard and Strecker degrada- Formation is catalyzed by base AAs are a nitrogen source [143]
Free amino acids (AA) tion (model systems) and do not provide carbon
Peptides skeletons
2 The contribution of peptides The generation of pyrazines was [119]
is greater than AA (model enhanced at low aw (0.33)
systems)
3 Higher polyphenol concentration Polyphenol molecules may bind [95]
reduced pyrazines formation part of the pyrazine formed
4 ↑ HMF Reducing sugars (RS) Maillard and associated path- Alkaline cocoa had higher In slightly acidic conditions, [127 ,102]
↑ N-ε-Carboxymethyllysine Free amino acids (AA) ways concentrations of α-dicarbonyls 3-DG was further dehydrated
(CML) and less of HMF and to form HMF while in alkaline
methylglyoxal conditions its fragmentation
was predominant
5 ↑ Aromatics Reducing sugars (RS) Maillard and Strecker degrada- Roasting activates reactions Reduction in the concentration [88]
Amino acids (AA) tion between reducing sugars and of free amino acids and
free amino acids or short-chain reducing sugars
peptides to generate aromatics
6 ↑ 2,5-Diketopiperazines (DKP) Peptides Maillard and associated path- DKPs can be assigned to a single DKPs are essential for a [9, 124]
ways peptide precursor balanced cocoa bitter flavor
7 ↓ Fatty acids Fats Lipid oxidation Degradation of essential fatty Decreasing nutritional value [38]
↓ Essential amino acids Amino acids (AA) acids, amino acids
8 ↑ Melanoidins Sugars Maillard, lipid oxidation, poly- Higher content of fat and Glu and Fruc react with proteins [103, 108]
Proteins phenols’ degradation polyphenols increases the and amino acids to form
Amino acids formation of melanoidins melanoidins
Lipids
9 ↑ Acrylamide Strecker degradation Reducing sugars Aasparagine react with a Asparagine provides the [42]
Amino acids reducing sugar acrylamide skeleton
*↑ Increasing or formation, ↓ Decreasing or loss, aromatics (aldehydes, ketones, pyrazines, pyrroles, furanes, pyranes, and hydrocarbons), Glu (glucose), Fruc (fructose), HMF (5-hydroxyme-

thyl-furfural)
Food Engineering Reviews (2022) 14:509–533
α-keto acids and the pathway c leads to the formation of Biogenic Amines’ Formation
biogenic amines and Strecker aldehydes. Additionally,
because of lipid carbonyl’s ability to decarboxylate and On the other hand, biogenic amines are non-volatile com-
deaminate amino acids, diverse studies have pointed to pounds, without taste and aroma, with biological activity
lipid carbonyls as alternative compounds contributing on the central nervous system that can be risky if exces-
to acrylamide formation in fat-rich food products [53]. sive concentrations are consumed [14]. The main biogenic
Also, by oxidation of lipids, nutritional compounds such amines found in cocoa and chocolate are 2-phenylethylamine,
as essential fatty acids and amino acids are degraded tyramine, tryptamine, serotonin, dopamine, and histamine
(Table 4, entry 7). During heating, the remaining water [56]. The presence of these substances in high non-dangerous
evaporates and leaves more porosity in the cocoa beans; quantities do not represent the negative effect on quality; on
then, the oxygen comes into contact with the lipids and contrast, this means cocoa can be the source of these compo-
causes oxidation reactions because always the process nents that are of high value in the pharmaceutical industry.
is done in non-insulated roasters or using hot air as a These biogenic amines are related to lipid oxidation reactions
heating medium [115]. Thus, it has been determined that during heating in oxidizing atmospheres such as air (Fig. 5b),
roasting causes a decrease in fat content especially using in the same way as some volatiles similar to the products of
high temperatures and times [82]. Roasting causes a sig- the Maillard reaction (Strecker aldehydes).
nificant increase in the primary oxidation state (peroxide
index) and secondary oxidation state of fats (Thiobarbi- Formation of Carcinogenic Agents
turic acid value) [38]. Therefore, it is essential to evaluate
inert atmospheres in the roaster chamber to identify dif- However, the excellent quality of roasted cocoa can be affected
ferences in the quality of the product. Above is a research by the presence of furans, HMF, and acrylamide [149], which
challenge that has not yet been done. That shows the need have been classified as carcinogens and are controlled by the
for further research, e.g., evaluating the effect of C O2 and WHO (World Health Organization). Both acrylamide and HMF
other compounds released and accumulated in the roaster are products of the Maillard and lipid oxidation reactions; the
chamber, which could influence chemical reactions in the amino acid asparagine is the precursor of acrylamide formation
surface and porosity of the grains. because it provides the basic molecular structure of acrylamide
(see Table 4, entry 9) [15]. In this way, both aromatic com-
pounds that provide desirable flavor and aroma to cocoa and
Polyphenols’ Degradation undesirable components can also be generated during roasting.
However, roasting is a fundamental stage in the cocoa transfor-
Polyphenols are thermolabile components; therefore, mation that deserves further attention and research for optimiza-
roasting temperature lowers the final concentration of tion purposes.
polyphenols by thermal degradation [1]. The thermal deg-
radation of polyphenols occurs by epimerization and oxi- Roasting Process Parameters and Configuration
dation/autooxidation reactions. Usually, the epimerization
reactions occur from ( −)-epicatechin to ( −)-catechin, and The main parameters of the cocoa roasting process are
from ( +)-catechin to ( +)-epicatechin [79]. Figure 5c temperature and time; then, its influence on the formation
shows the general mechanism of polyphenol degradation of chemical components that are relevant to the quality of
in cocoa given by heating in oxidizing environments. roasted cocoa is described below.
Astringency is due to the presence of high concen- Considering that the process is divided into three basic
trations of polyphenols common in bulk cocoa beans. zones as Fig. 6: (i) come up (heating), (ii) constant targeted
Various studies have been conducted to explain the deg- temperature (isothermal), and (iii) cooling. Roasting begins
radation of polyphenols during cocoa roasting looking with heating the beans from room temperature to the set
to preserve them because these have antioxidant activ- process temperature. The heating rate is slow due to conduc-
ity [68, 139, 150]. Then, in roasted cocoa, it is necessary tive heat transport within large beans (Biot > 0.1) that offer
to obtain a balance of polyphenol content that gives it significant resistance to energy flow. Therefore, in equip-
antioxidant capacity but does not affect the taste of the ment that roasts large amounts of cacao and is heated from
chocolate. In addition, the darkening due to the formation the outside without adequate bean movement and bean gas
of melanoidins is favored by a high initial content of fats contact, this heating rate ends up being much slower because
and polyphenols because they are products of oxidation it is a cluster of particles with bigger dimensions than an
reactions of lipids and polyphenols as well as Maillard individual bean. In the second step to maintain the process
(Table 4, entry 8). temperature for a set time, time is between 5 and 120 min,
13

Fig. 6 Illustrative diagram of

the stages of roasting cocoa in
a roaster
usually 10 to 60 min, and temperature is between 110 and is unknown since, due to the low conductivity, temperature
160 °C, usually 120 to 140 °C [42, 68, 79, 106]. However, differentials can be generated and consequently difference in
high temperatures, 170 and 190 °C, have also been studied, the performance of chemical reactions. Therefore, it is rec-
resulting in good catechin content using short residence ommended to do small-scale experimentation under kinetic
times [122]. Finally, the third step is the cooling of beans, control to determine the rate of compound formation, and
which is intended to be quick to avoid overcooking and loss process modeling to identify the evolution of thermal and
of aroma, depending on the technology of the roaster. mass differentials in cocoa.
Table 5 shows the effect of temperature and time of roast- In the same way, as for volatile compounds, it has been
ing on roasted cocoa’s main physicochemical changes found found that the generation of acrylamide (entry 4) tends to
in the literature. The rate of formation of pyrazines (entry 2) decrease when using high temperatures (> 150 °C); this is
is higher at high temperatures during the first 10 min of the because acrylamide is not thermally stable. Therefore, the use
process after the remaining concentration decreases [115, of high temperatures is recommended to minimize the acryla-
151]. These results suggest that short roasting times < 15 min mide concentration as a carcinogen and HMF, which affect the
favor the maximum content of pyrazines in the cocoa beans, quality of chocolate [42]. However, due to the risk of exces-
which represents a good quality of aroma given by these sive browning or thermal differentials when heated faster at
compounds. Most volatiles, including pyrazines, aldehydes, high temperatures, it is advisable to evaluate more efficient
alcohols, acids, esters, and ketones (entry 2), were gener- heating technologies such as microwaves, IR, or hybrid sys-
ated and reached maximum concentrations within the first tems, which could represent the future of roasters. On the
15 min of roasting [64]. In addition, high temperatures dur- other hand, since current research has been done under typi-
ing short times cause less generation of HMF (entry 3), cal conditions and conventional equipment, it is necessary to
i.e., shorter times achieve lower thermal damage than low leave this vision and dare to change conditions such as the use
temperature and long time [116]. Lower HMF contents are of inert atmospheres and reduction of cocoa size to improve
positive factors of quality because they have cytotoxic effects heat transfer and track the chemical variation over time.
at high concentrations. However, it should be considered Roasting causes decreasing natural products with biologi-
that the volatile compounds mentioned above, measured cal activity such as theobromine, caffeine, and polyphenols
using solid-phase microextraction (SPME–GC–MS), were (entries 5 and 6). For example, roasting for 40 min at 100
generated during roasting and remained trapped within the caused a decrease in total polyphenols of 9.7% while at 190 °C
cocoa beans. So, when finding that the highest concentra- it decreased to 39.9% [123]. It is desirable to optimize roasting
tions are during the first minutes of heating, it is evident conditions that maximize the desired compounds’ production
that there is a lack of knowledge about any low molecular while preserving a desirable sensory profile. Nevertheless,
weight compound lost by volatilization (the gas fraction) or roasting increases the content of biogenic amines (entry 7),
degradation when heating to longer residence times. Like- resulting in Trinitario beans the highest final content [104].
wise, the distribution of these compounds within cocoa bean The main biogenic amines found are 2-phenylethylamine,
13

Table 5 Effect of the main roasting parameters on physicochemical changes in roasted cocoa
Entry Influence of roasting Experimental conditions Variety Effect References
1 Formation of volatile HA vs SHS from 150 to 250 °C Forastero ↑ Rate < 15 min (150 °C) [151]
compounds (15 min) (pH = 5.6) ↑ Rate < 10 min (200 °C) [64]
2 Formation of pyrazines IR heating from 100 to 200 °C Criollo ↑ Content at 150 °C [115]
(15 min) ↓ Content at 100 and 200 °C
3 Formation of HMF HA from 125 (74 min) to Criollo ↓ Content at ↑ temperatures [116]
145 °C (40 min) (0.1–0.8 g kg−1)
4 Formation of acrylamide HA from 110 to 160 °C (15 to Forastero ↓ Content (> 150 °C) [42]
40 min) ↑ Content (< 150 °C)
5 Decreasing of methylxanthines C at 180 °C (10 min) Forastero ↓ Content of theobromine (28 to [146]
70% lost) [41]
↓ Content caffeine (around 60%
lost)
6 Polyphenols’ degradation CO from 100 to 190 °C (10 to Trinitario ↓ Content at ↑ temperatures and [123]
40 min) ↑ time [122]
9.17% lost (100 °C) to 39.9%
lost (190 °C)
7 Formation of biogenic amines HA from 110 °C to 150 °C (25 Trinitario ↑ Rate at ↑ T and (18.67 to [104]
to 85 min) with RH (0.3% to 33.46 mg/kg ff-dw)
5.0%)
8 Decreasing of moisture (Xw) HA vs SHS from 150 to 250 °C Trinitario and ↓ Rate at ↑ temperatures (~ 1%) [151]
and water activity (aw) (15 min) Criollo aw from 0.4 to 0.6 ↑ Maillard [85]
IR from 100 to 200 °C (15 min) reaction [115]
C at 110 to 170 °C (5 to 65 min)
9 Formation of melanoidins HA from 125 (74 min) to Criollo ↑ Rate at ↑ temperatures [116]
145 °C (40 min)
10 Darkening HA from 125 (74 min) to Criollo ↑ Rate at ↑ temperatures (Ea: [116]
145 °C (40 min) 132 kJ mol−1)
11 Diminution of surface area, IR from 100 to 200 °C (15 min) Criollo Melted fat and solidified after [115]
specific internal volume, and heating accumulate in the pore
the average pore size walls affecting microporosity
*HA (hot air), SHS (superheated steam), IR (infrared heating), CO (convection oven), C (conduction), RH (relative air humidity), ↑ (higher), ↓
(lower), and kg ff-dw (fat-free dry weight basis)
tyramine, tryptamine, serotonin, dopamine, and histamine [78, in depth. For example, the effect of heating rate, particle size,
105]. Biogenic amines have physiological roles in humans, and environment of reaction conditions (inert or oxidant) is
acting as local hormones and neurotransmitters in low con- still missing, opening a world of exciting science possibilities
centrations, but they can cause a range of toxicological effects that deserve to be explored. For this purpose, an efficient tool
if are consumed in excess [130]. for analyzing and understanding the cocoa roasting process are
On the other hand, roasting also produces high molecular kinetics and phenomenological modeling explained in the next
weight polymers such as melanoidins (entries 9 and 10); chapter.
they are responsible for darkening and involved in sensory
properties (i.e., taste, flavor and texture) of foods [98] and Mathematical Modeling to Understand
antioxidant activity [36]. Both the darkening and the forma- Thermochemical Processes
tion of melanoidins are greater when using high tempera-
tures and longer times. Finally, in addition to the softening In order to improve the technological processes of cocoa
of the cocoa beans, the heating causes the fat’s fusion and roasting and obtain a high-quality product in line with con-
mobility, which transports substances and obstructs empty sumer trends, it is essential to have a thorough knowledge
spaces, causing a diminution of surface area, specific inter- of the chemical, physical, and thermal phenomena in cocoa
nal volume, and the average pore size [115]. beans during roasting. In this way, the kinetic analysis of the
Consistent with the above discussion and table, there is evi- formation of volatile compounds, the degradation of natu-
dence that the analysis of the main physicochemical changes ral cocoa products, and the mathematical modeling of the
caused by roasting, mainly the generation and volatilization of process (i.e., mass and energy balances of the system) are
aromatic compounds, is valuable but has not yet been explored handy tools for a deep understanding of the roasting. With
13

these theoretical and experimental methodologies, it is pos- must consider the different scales, which can be understood,
sible to predict results accurately and reliably and optimize taking into account the concept of volume fraction (εj) for
the process. each j-phase. In this way, the cocoa roasting process can be
Modeling allows drawing, interpreting, and understand- modeled on different scales (Fig. 7d). The bulk scale (i.e.,
ing a particular process’s phenomenology by applying several beans or in a roaster), then on a smaller scale, is the
phenomenological laws of nature. With these models, it is particle models. A particle is like a small, heterogeneous
possible to identify and describe events that, through experi- cocoa bean that preserves all the phases present in the origi-
mentation, are not possible for any reason (e.g., times too nal system (a group of cells or an individual cell). Going on
short or too long to track the phenomenon). In engineering a smaller scale, there is modeling at the molecular level that
sciences, modeling is performed to predict results, design could explain specific phenomena such as forming a certain
and optimize processes, minimize the costs of experimen- compound, the mechanisms, and interactions present at the
tation and validation, and characterize and generate knowl- micro-scale.
edge of any process. For example, with modeling, it would Depending on the particle size and heating rate, both dry-
be possible to understand the physicochemical and thermal ing and devolatilization processes may occur simultaneously
changes that occur within cocoa beans during heating, and it inside the particle, and thus, one could expect wet biomass,
would be possible to predict the evolution of phenomena that dry biomass, and char at the same time. This is observed in
cannot be observed experimentally, such as heat transport case of large particles, within which large temperature gradi-
through the solid, porosity, and gas generation over time, ents are present, but for very small particles, such gradients
among others. are unlikely, and in such cases, only one of these phases can
Mathematical models can be empirically based if the be found inside the particle. For example, [55] developed
expressions between the different quantities that are mod- and validated a torrefaction model of large biomass particles
eled (temperature, concentration, moment vs input quanti- by coupling the material balance and energy to a kinetic
ties) are determined based on a statistical analysis of the model in two steps, drying and devolatilization. This model
experimental results. In this sense, they are mathematical predicted the variation of gas, water, and solid fractions over
expressions that allow predicting the magnitude at different time, as well as variations in pressure and density within the
times, and conditions are valid for the equipment where the particle.
experimentation was carried out; they cannot be considered Alean et al. [7] considered a thin layer of spherical cocoa
general models. Also, the models can have a combination of beans (bulk scale), dried by hot air at temperature “T,” abso-
respecting the balances of matter, energy, and moment that lute gas moisture, with velocity “V” and the phases gas “g”
include terms based on constitutive relations of transport and solid “g.” The material balance considered the convec-
mechanism that can be determined experimentally and there- tion, diffusion of water, and degradation of polyphenols (Y )
fore are considered semi-empirical models. Finally, the mod- (Eq. 1). The energy balance in the gas is considered the
els can be phenomenological in nature, including balance convection and phase change (Eq. 2) and the conduction in
equations and theoretical models for constitutive equations the solid (Eq. 3).
or relationships. Also, the models can be made at differ-
𝜕Y 𝜕Y 𝜕 𝜕Y
( )
ent scales macroscopic (bulk and particle) and microscopic 𝜀𝜌g = −𝜀𝜌g vg + 𝜌g Deff + 𝜌s ṁ ��
w (1)
𝜕t 𝜕x 𝜕x 𝜕x
(molecular); both are a useful emerging tool to analyze the
thermochemical process as roasting.
𝜕Tg 𝜕Tg
Some mathematical models describe the evolution over − Ua Tg − Ts − ṁ ��
( ) [ ( ) ]
𝜀𝜌g Cp,g = −𝜌g vg Cp,g w Cv Tg − Ts + 𝜆
𝜕t 𝜕x
time of variables such as density, momentum, and energy (2)
at the macroscopic level. At this macro-scale, the variation ( )
in time and physical space of these variables can be fol- 𝜕Ts 𝜕 𝜕T
Keff s + Ua Tg − Ts − ṁ ��
( )
(1 − 𝜀)𝜌s Cp,s =− w [𝜆]
lowed due to the macroscopic movement of the continuous 𝜕t 𝜕x 𝜕x
system and the transport phenomena that occur within the (3)
system due to the microscopic world. In this way, both where the bed porosity 𝜀 , i.e., the void fraction between
empirical models and Fick, Fourier, Newton, and Ohm’s beans and intra-beans. It is determined from the volume
laws can be applied. fraction 𝜌s occupied by the solid. Besides, Borda-Yepes
( et al.
In heterogeneous systems such as cocoa and other bio-
)
[22] proposed a drying model with volume variation V1 𝜕V𝜕t
.
masses (see Fig. 7c), it is necessary to consider the volume This consideration of the volume variation is a great contri-
variation and the interactions between the present phases; bution because it is helpful to apply in cocoa roasting, where
this applies to processes as drying, roasting, torrefaction
pyrolysis, combustion, and gasification. Also, the models
13

Fig. 7 Illustrative scheme of (a) types of systems single and multiphase and (b) heterogeneous system at different scales and different phases
useful for the mathematical modeling of thermochemical processes
the swelling of the beans occurs during heating due to the scale; therefore, the restrictions on the transfer of mass
strong internal pressures of gasses generated (Fig. 7c). and energy are negligible. In these cases, it is enough to
use zero-dimension models to present the conversion dur-
ing the reaction. In VRM models (Fig. 8), it is assumed
Particle Mathematical Modeling that the particle is consumed uniformly throughout the
volume at constant volume expressed as d𝛼 = k(1 − 𝛼) ,
At the particle level, the mass and energy transfer phenom- dt
where k is the kinetic coefficient of the reaction and α is
ena especially alter the behavior of the released products the conversion.
(distribution and quantity). During the heating, many gase- The decreasing nucleus models (SUCM and SUPM)
ous species are released, which, depending on the type of describe a particle dense and non-porous one, where the
biomass and operating conditions of the reactors, can favor reaction occurs at an interface, which moves to the center.
the production of tars, the loss of valuable aromatics, or SUCM is associated with the ash production, where the
heat release. ashes cover the unreacted nucleus of the particle. In this
Many authors have established that the main factors model, the size of the nucleus decreases, but the total vol-
affecting the particles’ mass transfer processes are size ume of the particle remains constant. The above models
and pressure. Niksiar and Rahimi [101] considered that can be represented by the ( same
) previous mathematical
for small particles (< 900 μm, there is a kinetic control
expression with an order of 23 .
13

Fig. 8 Type of models based on the conversion of the particle: vol- model with shrinking reacting particle (PMSP), and progressive
ume reaction model (VRM), shrinking unreacted particle model model with shrinking reacting core (PMSC) [148]
(SUPM), shrinking unreacted core model (SUCM), progressive
The progressive models (PMSP and PMSC) are exten- microstructure’s development during solid–gas reactions,
sions of the previous models, where the reaction occurs in a problem of interest in classical grain models [49, 50].
the entire volume, but intermediate conversion states appear. To study this effect, a model based on population bal-
The RPM (Ramdom Pore Model) has normally been used ances was developed by [90], to consider the distribu-
to represent progressive models. The RPM describes the tion of grain size inside the pellet and at the same time
behavior of a porous particle, whose internal surface area consider sintering through the terms of death and birth
changes depending on the conversion as (Eq. 6) in the population balance. In this way, as the chemical
reaction proceeds, the initial grain radius (r 0) increases
d𝛼 ]1∕2
(4) or decreases (r p) depending on the molar volume of the
[
= k(1 − 𝛼) ⋅ 1 − 𝜑log(1 − 𝛼)
dt
solid product and the sintering process. In contrast, the
where φ is a parameter associated with the internal structure unreacted core (rc) radius decreases (see Fig. 9). It is con-
of the porous. A high value of 𝜑 means that the initial poros- sidered that the particle is composed of a large number
ity is small and that any change in the internal surface area of grains with an initial radius distribution (see Fig. 9b);
greatly affects the degree of conversion. then, each grain changes from size due to chemical reac-
tion and sintering.
Solid–Gas Reaction Models The material balance for the gas is based on the reaction
system: (gas) + bB(solid) → cC(solid)
( +)dD(gas) only with
Gas–solid reaction systems are useful to know the the diffusive term: Jj = R2 𝜕R De R 𝜕R , where C is the
1 𝜕 2 𝜕C
dynamics of gas interactions with the solid surface. Thus, molar density of the specie j, De is the effective diffusion, R
in gas–solid reactions, the diffusivity and the kinetics is the spatial variable, and the generation term is related to
depend largely on the solid’s microstructure, which can the chemical reactions (r ) (Eq. 5).
vary due to the chemical reaction and sintering, among
others. So, grain size distribution and sintering affect the
13

Fig. 9 Graphic illustration of (a) grain size change and (b–f) evolution of the change in the size of each grain due to chemical reaction and sin-
tering [90]
𝜕C 1 𝜕
(
𝜕C
) That is, the mass transfer process is dominated by internal
𝜀 = 2 De R2 − ṙ �� (5)
𝜕t R 𝜕R 𝜕R diffusion [73, 99]. The loss of moisture resulted up to a final
value between 1.9 and 2.3% d.b. [116]. Furthermore, water
On the other hand, other authors have developed models
loss depends strictly on the temperature used with an activa-
to understand and predict the behavior of the small-scale
tion energy of 59.6 ± 0.8 kJ mol−1, which indicates that it is
pyrolysis process, so Montoya [97] developed a mathemati-
a coupled process where the phenomena of mass and energy
cal model in fast pyrolysis (1200 °C s−1) considering that
transfer are closely related.
phases solid, liquid, and gaseous coexist in the particle
Likewise, the kinetics of HMF generation by the expo-
(equations not shown). Likewise, this model considered the
nential model [116], the formation of 2,5-diketopiperazines
consumption and formation of species (reagents and prod-
(DKPs) was correlated positively with their peptide precur-
ucts) and bubble dynamics generation with a population
sor and was analyzed using a solid-state reaction of zero-
balance.
order (sigmoidal) [9].
Darkening has been evaluated with first- and zero-order
Modeling of the Cocoa Roasting Process models finding activation energy of 59 ± 8 kJ mol−1 that is
similar to that of the oxidation of polyphenols [68]; there-
Cocoa roasting modeling is complex because it is neces- fore, it was concluded that non-enzymatic browning during
sary to include some quality attributes as dependent vari- roasting is initially induced by the oxidation of polyphe-
ables [18]; these variables are subjective to the perception nols [116]. The dependence of melanoidin formation on the
of human senses so it is difficult to predict them. However, roasting temperature was also determined by the asymptotic
these variables are correlated with roasted cocoa’s chemical model, and the degradation kinetics of polyphenols during
composition, so a model able to predict the most relevant the roasting of cocoa beans was evaluated with the Weibull
chemical compounds is a current challenge for engineer- probabilistic cumulative model [68]. All the model equations
ing. On the modeling of cocoa roasting, there is little bib- are in Table 6.
liographic information; an approach towards kinetics was On the cocoa roasting process, there are several specific
primarily found where both semi-empirical and empirical points where the modeling, on a smaller scale, is necessary
models have been used all of them on bulk scale. to explain this process’s phenomenology better. Although
The main phenomenon that has been studied is the loss it is known that there are important differences directly
of water. In this way, the kinetics of moisture loss follows related to factors such as temperature and process time,
an exponential decay very similar to the drying processes; there are no studies conducted where the influence of the
such behavior was similar for all the models shown Table 6. heating rate is analyzed; therefore, its effect on the final
13

Table 6 Kinetics and phenomenological models used for the cocoa roasting process
Type Phenomena Model Equation Reference
Kinetics Moisture loss Newton MR = exp−kt [59,39, 116]

Page MR = exp −ktn
Two-term MR = exp−kt + bexpgt

b, k, g (constants), MR (moisture
ratio)
Weibull
𝛼
MR = 1 − exp−(t∕𝛽)
𝛼 , 𝛽 (shape and rate parameters)
HMF formation Exponential Ct = C0 + k0 expkt [116]
k0 (pre-exponential factor, kt (rate
of formation)
Formation of 2,5-diketopiperazines Zero order and solid-state reaction P = A0 + kt [9]
(DKPs) P (DKPs concentration), A0 (initial
concentration), k (rate constant)
Malanoidins generation Asymptotic Ct = C0 1 t t [116]
+C
Kin e −C0
kin ( initial rate melanoidin

formation), C0, Ce, and Ct
(initial, equilibrium and time t
concentrations)
Darkening First order L∗ = 1
kL t+ L1∗
0
L0∗, L∗ ( initial and time t lightness),

kL, (reaction rate)
Zero order h◦ = h◦ + kh t
h◦ 0, h◦ (hue angle value), kh
(reaction rate)
Polyphenols’ degradation Weibull probabilistic cumulative Co −Ct
=1 − exp−(t∕𝛽)
𝛼
[68]
Co −Ce
C0, Ce, Ct (initial, equilibrium and
time t concentrations), 𝛼 (shape
parameter), 𝛽 (rate parameter)
Phenomenological Effective diffusivity of water (De) Arrhenius equation De = Do exp− RT
E
[5913]
Do (diffusivity constant), E
(activation energy), R (universal
gas constant)
Diffusion of moisture from inside Fick’s second law [39, 116]
� �
∞ De n2 𝜋 2 t
−
the bean to the surface
6 ∑ 1 r2
MR = 𝜋2 n2
exp 0
n=1
MR (initial, equilibrium and
time t moisture), De (effective
diffusion), r (radius), n ( integer
number)
Thermal diffusivity (αe) Fourier law 8
∞
1 2
t 𝜋2 [9359]
exp(2n−1) 4L
∑
TR = 𝜋2 2n−1
n=1
T −T
TR = T i −Ts
TR, T0, Ts (temperature ratios,
0 s
initial, and surrounding)
chemical composition and volatilization is still unknown are used. So, another important factor that has not been
and physical properties. explained is the effect of particle size. Considering that in
The heating rate can determine the residence time of the thermochemical processes, there are coupled phenomena
the process; the efficiency of heat transfer will also depend of mass and energy transfer, so the particle size can deter-
directly on being a thermal gradient which can be gener- mine these; therefore, it is necessary to study this factor.
ated and consequently, some areas over-roasted and other Thus, particle scale modeling would be a helpful tool to
partially raw areas if very large particles as cacao beans analyze the cocoa roasting process.
13

Mathematical modeling of thermochemical processes from Consent to Participate Not applicable.

biomass for energy applications is more advanced than ther-
Consent for Publication All permissions for this document are avail-
mochemical processes for food and flavoring applications. able.
These latest applications include quality attributes and vari-
ous variables to make them viable for human consumption, Conflict of Interest The authors declare no competing interests.
making them a great challenge for the engineering sciences.
Concluding Remarks
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Physicochemical Phenomena in the Roasting of Cocoa (Theobroma

Introduction and anti-stress effects [132]. However, the excessive con-

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Nutty 2‐Ethyl‐6‐methylpyrazine (0.12), 2‐ethyl‐5‐methylpyrazine, 3‐ [60, 109]

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Fig. 6 Illustrative diagram of

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Kinetics Moisture loss Newton MR = exp−kt [59,39, 116]

Two-term MR = exp−kt + bexpgt

kin ( initial rate melanoidin

L0∗, L∗ ( initial and time t lightness),

initial, and surrounding)

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