ARTICLE REPRINT
Alchemy in the
This article
was originally WELCOME BACK as we continue our journey
published in the into the mystical world of coffee chemistry. In
May/June 2005 the last issue, we discussed the roasting process,
issue of Roast the thermal decomposition of compounds and
the formation of more than 30 organic acids, half
of which are volatile. We discussed three acids at
length, namely, chlorogenic, quinic and citric.
To review, both chlorogenic and citric
acids decrease in concentration due to thermal
decomposition and have an inverse relationship
with degree of roast, whereas quinic and caffeic
acids actually increase in concentration due to
the breakdown of chlorogenic acids.
During the roasting process, more than
800 compounds are created, 60 of which are
key coffee odorants and many of which remain
unidentified by scientists, making coffee a truly
complex beverage. What we do know is that the
contribution of organic acids to coffee flavor is of
paramount importance. Besides acidity, organic
acids play an important role in the development
of flavor precursors and aroma elucidation. In
this issue, we will probe further and investigate
some of the other minor acids in coffee and their
major impacts in the cup.
Malic Acid
Found in high concentration in apples, malic
acid commonly goes by alias of “apple acid.”
Malic acid has a greater perceived sourness than
citric acid and is commonly detected by the foliate
papillae on the side of the tongue. As such, it is
frequently used in the food industry to impart
sour/fruity characteristics commonly found in
chewing gums, ciders and low-calorie beverages.
Roasting Lab
Discovering Organic Acids
(Part 2 of 2)
by Joseph A. Rivera
After phosphoric acid, malic acid is the most
common acidulant used in food.
In a coffee plant, malic acid serves as a key
compound in several important metabolic
processes. As such, its final production within
the bean is invariably affected by environmental
conditions. As we mentioned in the last issue,
regional humidity tends to raise the level of
the fruity acids in coffee, such as coffees from
the highly humid Coban region of Guatemala.
What exactly causes this increase in “fruitiness”
remains to be determined, but my guess is that
it is an increase in the level of malic acid in the
bean. This guess may hold merit; for example, in
wine chemistry, wines that typically exhibit the
most fruitiness, such as Chardonnays, tend to
have higher levels of malic acid.
During the roasting process, malic acid’s
fate closely resembles that of citric acid. With a
melting point of 130° C (268° F), slightly below
that of sucrose, malic acid rapidly decreases in
concentration as the degree of roast increases.
While green beans contain anywhere from 0.30
to 0.70 percent of malic acid, a typical medium
roast will lose roughly 30 percent of that due to
thermal decomposition.
Acetic Acid
Acetic acid, most commonly known as the active
ingredient in vinegar, is for the most part created
during the roasting process. During roasting,
carbohydrates composed of six to 10 carbons in
length are broken into smaller fragments. These
fragments give rise to a number of different
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products, including acetic acid and others, which simply dissolve in
the coffee infusion to increase the level of soluble solids.
Depending on roasting conditions, levels of acetic acid in
roasted coffee can increase up to 25 times from its initial green bean
form. Because its production originates from the breakdown of
carbohydrates, arabica beans with almost double the concentration
of sugar than robusta will always contain more acetic acid after
roasting. But as we’ll discuss later, acetic acid is quickly lost once you
roast past a medium roast, at times exhibiting up to 90 percent loss.
Unlike some of the other acids we discussed, acetic acid is a weak
acid that dissociates only seven percent in the coffee brew. But don’t
be fooled into dismissing this acid as unimportant. For although its
contribution of protons (hydrogen) in the cup may not be significant,
it is what it does not do that is most important. It has been known
for more than 75 years that perceived acidity is not only a function
of free protons in solution, but also of the “reserved acidity” due to
undissociated acids. That is, acids that do not readily breakdown and
contribute to any great extent to pH; a property common in weak
acids such as acetic. Furthermore, research has confirmed that even
minor changes in pH due to undissociated acids can significantly
alter aroma, flavor and overall character. Trained cuppers, with their
delicate palates, have been known to detect a change in beverage pH
as small as 0.10 pH units.
Another important quality of acetic acid is that it is a volatile
molecule that our olfactory system readily detects. How can you test
that? Simply open a bottle of vinegar. As the acetic acid molecules
in vinegar begin to absorb heat due to ambient room temperature,
they begin to vibrate. These vibrations occur by the thousands with
many simultaneously colliding and eventually gaining enough
energy to escape the liquid and into the surrounding air. The room
soon fills with thousands of acetic molecules and a nasty vinegar
smell permeates the air.
Because acetic acid is so volatile, it plays an important role in
coffee aroma. Since most identified aromatic compounds are oil-
based, many remain dissolved inside oil droplets within coffee.
Interestingly, arabica has an estimated 60 percent more lipid content
than robusta, perhaps explaining why arabicas have so much more
aroma complexity.
During roasting, the level of acetic acid will peak during light
roasts, then rapidly decrease as roasting progresses due to loss by
evaporation. For roasters wishing to capitalize on this, roasting
technology has an answer. Enter pressure roasters. These
roasters minimize the loss of volatile acids and maintain higher
levels of acidity than traditional roasting by taking advantage of
simple physics. Perhaps one of the best known is the Smitherm
Continuous Pressure Roaster, into which Sivetz has put much
research. At times, pressure roasting can gain as much as 0.20
units in beverage pH. That is, it will decrease the pH in coffees
from 5.20 to 5.00 simply by using pressure versus conventional
roasting. Although 0.20 units may not seem like much, it
represents almost double the level of acidity based on the
logarithmic scale. Unfortunately, the use of pressure roasting
has mainly been suited for use with lower-quality robusta
coffee, where an increase in acidity is always desirable.
Another minor source of acetic acid is post harvest
processing. During wet processing, acetic acid is produced
as a byproduct of fermentation. Depending on regional
temperature, fermentation time can range between 12 and 36
hours. Fermentation time in excess of 48 hours typically leads
to the formation of “stinkers” as a result of excess production
of undesirable volatile acids, such as acetic, proprionic and
butyric acids. During processing, fermentation comes to
an end when the sticky mucilage is removed from the bean,
followed by thorough washing with clean water. But even
with proper washing, trace amounts of acetic acid remain in
the bean. In these trace amounts, the acid is a desirable trait,
for it contributes to a noticeable cleanliness and brightness as
compared to other dry-processed coffees.
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Phosphoric Acid

Unlike the other acids discussed so far, phosphoric

acid is not an organic acid, but rather an inorganic
acid. How do we know this? Its lack of available
carbon in its structure classifies it as such (Figure
1). Although there are many conflicting views on
the origin and role of phosphoric acid in coffee, it is
currently believed that phosphoric acid stems from
the coffee plant’s uptake of inositol hexaphosphate
or phytic acid, an organic acid.
During roasting, phytic acid decomposes to
form phosphoric acid, an acid that is 100 times
more potent than most of the organic acids
discussed so far. As such, many researchers believe
that phosphoric acid significantly contributes to
beverage acidity due to its strength and ability to
readily dissociate. In a 1999 study by the Coffee
Quality Institute, formerly the Specialty Coffee
Institute, a significant amount of phosphoric acid
was found in specific lots of Kenya AA and SL28 as FIGURE 1
compared to a Colombian Supremo. Furthermore,
experiments in which this acid was added to other As an inorganic acid, much of this acid survives the roasting
coffee origin brews significantly altered acid profiles to levels almost process, and it is believed that phosphoric acid is better extracted from
identical to Kenyan coffees. darker roasts, which is quite contrary to what we may expect. But
the puzzle still remains open, as many researchers on one side claim
that phosphoric acid, due to its potency, significantly contributes to
perceived acidity; whereas, others claim that the acid is neutralized
by an equivalent amount of potassium in the coffee brew.
The good news is that, as with all branches of science, coffee
chemistry is a continuously evolving field that every day brings new
answers to old questions. But there is still much more to explore on
our road to truly understanding the complexity of coffee. With its
myriad compounds formed and its physiological and psychological
effects on the brain, coffee is by far the most radical drink ever
introduced to mankind. Fortunately, through modern technology
and advances in chemistry, we are closer now to truly understanding
this Nectar of the Gods than we have ever been.

JOSEPH A. RIVERA holds a degree in food chemistry

and is the SCAA’s resident coffee scientist. He manages
www.coffeechemistry.com, a site dedicated to the science of coffee. He
can be reached at jrivera@coffeechemistry.com.

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