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58 March 2012 The Manufacturing Confectioner

F
ood-grade organic acids have diverse
functionality and fulfill several roles.
Acids can enhance or extend flavors,
decrease pH, preserve food and provide
pucker power. In confections, supersour,
flavor enhancement, flavor extension and
nontraditional flavors are all growing trends.
An acids job description is to extend or
enhance tartness or sour perception in addi-
tion to specic functions for gelled confec-
tions. What would orange, cherry, straw-
berry or lemon-lime be without acid as the
star player?
This paper will cover food-grade organic
acids used in confections, their chemical pro-
files, attributes, similarities, differences and
alternative forms of the acid (liquid, powder,
granular and encapsulated). A case study is
presented as an opportunity to explore the
application of acid blends for fruit flavors
since they are found naturally in some fruits.
FUNCTIONALITY OF ACIDS
Taste Modification
Acids are tart by nature. Flavor character-
istics are due primarily to the acids molec-
ular structure, solubility and the level of
buffering in the food or beverage system.
Hard candy, chews, gels and filled gels,
licorice, fruit leathers or panned hard and
soft confections all have different formula-
tions. Use of acids in formulations that are
sensitive to slight variations in pH, or the
presence of components sensitive to acids,
may require buffers to work with the acids
to provide stability. Acids offer ranges in
sourness, intensity and linger. These attrib-
utes impact and help define flavors, balance
sweetness and round out the total taste pro-
file of the flavor in confections.
In addition to taste modification, acids
perform other functional activities in con-
fections. These functional activities include
setting pectin and establishing gel strength
of gelatin gels by impacting pH of the con-
fection.
Sugar Inversion
Another beneficial function of acid is its
utilization to invert sugar. Acids used to
control sugar inversion to make invert sugar
can have dual roles depending on the candy
and pH level. Acid in hard candy contain-
ing high-fructose corn syrup and sucrose in
conventional ratios also functions to cause
low sugar inversion. Invert sugar helps to
prevent recrystallization of sugar crystals.
This helps to minimize grittiness or sandi-
ness in hard candy. Inversion, when uncon-
trolled by correct acid usage levels, can
cause candy to become sticky. Sugar inver-
sion is the hydrolysis of sugar (sucrose)
and results in the component molecules
glucose and fructose (sucrose glucose +
Acids in Confections
Food-grade organic acids in confections offer ranges in sour-
ness, intensity and linger; balance sweetness; and round out
the taste profile; and perform other functions.
Tammy Nash Jarrett
Univar
Tammy Nash Jarrett is
employed at Univar in
its Food Ingredients
division in technical
development. Prior to
Univar she has worked
at The NutraSweet
Co., Chr. Hansen Lab-
oratories and Silesia
Flavors in quality
assurance, research,
product development
and sales.
fructose). The result is cold flow; the
candy becomes hygroscopic and loses its
form/structure (Figure 1).
Impact of pH in Gelled Confections
Gelled confections manufactured with
starch, gelatin or pectin hydrocolloids are
impacted by pH. It is important to maintain
pH control and appropriate acidity levels in
gelled confections to maintain stability. Lack
of pH control may result in variations in the
gel set of pectin. The set may occur too fast
or too slow. For gelatin gels, acidity and pH
impact the strength of the gelatin set and
may degrade it. Too much acid impacts gel-
atin gel strength and decreases firmness. The
gel strength of gelatin decreases at lower
pH levels independent of acid type. A pos-
sible remedy to help gel strength in the pres-
ence of acid is to add buffering salts or
buffered acids in the formulation to help
control pH. Figure 2 illustrates the influence
of pH on gelatin gel strength. This informa-
tion is important when using acid to flavor
the gelled candy as well as acidifying or for-
tifying the candy.
Candy Fortification
Candy fortification represents another
diverse function for acid. Ascorbic acid, also
known as vitamin C, is used in gelled
gummi-type vitamin confections and regu-
lar gummi candy such as fruit snacks. Ascor-
bic acid is an essential nutrient. Ascorbic
acid is synthesized using cost-effective, nat-
ural fermentation of carbohydrates. In for-
mulating confections with ascorbic acid,
dosage levels may need to be optimized to
deliver targeted fortification levels due to
heat, light and oxygen sensitivity of the acid.
Another trend to consider with acids in
candy applications is acid sanding. This is
the application of acids to the outer layer of
the candy. Sanding the outer layer of gelled
confections has increased with the demand
for more sour taste.
Supersour Taste
Supersour taste appears to embrace the
more sour the better theme. Surface sour-
ness is meeting consumers demand for
more sourness and manufacturers uti-
lization of more acid. To accomplish
increased sourness, manufacturers are
sanding the outer surface of candy with
acid or acid-containing blends and avoid-
ing degradation of the candy. The quality of
the sanded candy depends on the steam
temperature for a sticky candy surface.
Steam for the surface should be hot and
dry for good adherence to the surface. Typ-
ically, acid is added as part of a dry-mix
blend for sanding. Blends may also include
encapsulated acids, buffering salts con-
taining acids or lower-solubility acids like
fumaric acid. A key factor to avoid product
loss is proper time, temperature and
humidity when drying the candy.
Acids in Confections
A possible remedy
to help gel strength
in the presence of
acid is to add
buffering salts or
buffered acids in
the formulation to
help control pH.
The Manufacturing Confectioner March 2012 59

Sucrose Inversion Sticky Candy


Sucrose glucose + fructose
Sugar inversion is induced by
low pH (high acid content)
high temperatures
high humidity
High inversion levels result in hygroscopicity:
Fructose is very hygroscopic
Cold ow
Figure 1
Acids Diverse Functionality
Figure 2
Gelatin Degradation
Acids offer many benefits through their
diverse functionality and characteristics.
Features and benefits of acids include nat-
uralness and different acidity profiles as
well as their impact on flavors (Figure 3).
Although scientists (i.e., sensory, product
developers and flavor chemists) consider
sourness from acids a basic taste category
with varying intensity and duration of the
sourness, the acids are not considered
equivalent. Figure 4 shows the similarities
and differences of acids.
ACIDS IN CONFECTIONS
Acids in confections offer the various attrib-
utes described earlier and have different
chemical structures and other analytical
variations as points of differentiation. Fig-
ure 5 shows the analytical attributes for
acidulants used in confections.
Acids in Confections
60 March 2012 The Manufacturing Confectioner

Acid Benet
Citric acid Natural; impacts citrus avors
refreshing; low cost in use
Lactic acid Natural; mild and lingering; good
for creamy avors with fruit notes;
enhances mint and eucalyptus
avors
Fumaric acid More sourness than other
acidulants; may help acid-coated
candy due to low solubility
Malic acid Mellow, smooth, persistent
sourness; enhances flavor profile;
can mask some flavors; works well
with high-intensity sweeteners
Figure 3
Acids Features and Benets
Similarities
Can modify avors
Adjust pH
Modify sourness
Modify sweetness
Differences
Strenth/intensity, type of avor
Cost in use
Solubility and hygroscopic tendencies
Synthesis/structure/forms/molecular weight
Figure 4
Acids Similarities and Differences
Ascorbic Acid C
6
H
8
O
6
Lactic Acid C
6
H
10
O
3
Citric Acid C
6
H
8
O
7
Fumaric Acid C
4
H
4
O
4
Tartaric Acid C
4
H
6
O
6
Figure 5
Acidulants for Confections: Attributes
HO
HO
HO
O
O
OH
H
HO
HO
O
O
OH
OH
O
Molar weight: 192g mol
-1
Melting point (MP): 153C
Solubility: 57.6% (wt/wt)
Synthesis: fermentation
Physical appearance: solid (granular,
ne granular, powder)
Anhydrous
Monohydrate
Taste: strong tart; gives an immediate
sharp reaction
Acidity (pK
a
): 3.13, 4.76, 5.4
Molar weight: 176.12g mol
-1
Appearance: white or light yellow solid
(granular or ne granular)
Melting point (MP): 190-192C; 463-
465K; 374-378F (decomp.)
Solubility in water: 33g/100ml
Synthesis: fermentation
Acidity (pK
a
): 4.10 (rst), 11.6 (second)
O
O
OH
OH
H
3
C
O
OH
OH
HO
O OH
OH
O
P
O
OH
OH
OH
O
O
HO
OH
OH
OH
Molar weight: 116.07g mol
-1
Melting point (MP): 286C
Solubility: 0.61% (wt/wt)
Synthesis: synthetic
Form: white, crystalline
Taste: tart
Acidity (pK
a
): 3.03, 4.47
Molar weight: 90.08 g mol
-1
Melting point (MP): 53C
Solubility: soluble
Synthesis: fermentation (mix w/L- form)
Taste: mild
Form: liquid (88%); also available as
powder
Acidity (pK
a
): 3.86
Molar weight: 134.09
Melting point (MP): 130C
Solubility: 25C ~58% (wt/wt)
Synthesis: synthetic
Taste: smooth, tart
Form: granular
Acidity (pK
a
): 3.40, 5.05
(not typically in confections)
Molar weight: 98.00
Melting point (MP): 41C
Solubility: miscible
Source: minerals
Taste: sharp and bland
Form: liquid (75%+)
Inorganic
Acidity (pK
a
): 2.15, 7.20, 12.35
Phosphoric Acid H
3
PO
4
D,L Malic Acid C
4
H
6
O
5
Molar weight: 150.1 g mol
-1
Melting point (MP): 206C/403F
Solubility: 58% (wt/wt)
Synthesis: natural (L+)
Taste: strong/tart
Form: solid, ne granular
Acidity (pK
a
): 3.02, 4.34
Chemical structures and analytical char-
acteristics of acids (e.g., form, solubility,
molecular weight) impact the choice of
acid used for various profiles in confec-
tions. The strength of the acid impacts the
intensity of sourness observed in confec-
tions. Acid strength is measured by disso-
ciation the measurement of release of the
hydrogen ion. Hydrogen ion dissociation
is represented by dissociation constants
(K
a
) and reported as K
a
values. The val-
ues are established experimentally and
found in technical literature.
For example, high K
a
values represent
strong acids. Some acids have more than one
hydrogen ion to contribute and may have
more than one K
a
value. Figure 6 is a chart of
common acids showing the number of hydro-
gen ions available for dissociation.
Acid choice for confections may be influ-
enced by storage conditions available to
manufacturers. Some acids are hygroscopic
and will harden at inappropriate tempera-
tures and humidity levels during storage.
Ingredients that compact, become hard or
lack flow properties have a negative impact
on manufacturing. It is difficult to resolve
issues if equipment or conditions are not
available to grind or solubilize the ingredi-
ent for processing. In some cases, liquid acid
solutions are available for manufacturing.
One typical solution for confections is 50
percent citric acid. Lactic acid is also avail-
able as a solution (Figure 7).
Acid Profiles
As available acidulants at manufacturing
sites and formulations evolve with new
trending candy types, consideration must
be given to the acids sourness for the
desired sweetness and flavor profiles. Acid
sourness can vary with each respective acid.
Acids also have different sourness/tartness
intensities, taste perception and linger. Some
organic acids like those used in confections
offer quick sour sensation and dissipate
quickly. Examples would be citric acid and
tartaric acid. Acids like fumaric, malic and
lactic may linger longer depending on other
formulation parameters. These attributes
could be helpful with sweeteners and fla-
vors to balance the overall taste profile.
Sweeteners and flavors should work
together. Acid selection may help with bal-
ancing the profile. For example, if a sweet-
ener lingers longer in taste, organoleptically
it may be better for the flavor to extend
with the sweetener. In this situation it may
be more advantageous to use an acid with
a longer linger to balance the profile. As a
case in point, consider nonsucrose confec-
tions with bulking agents and high-inten-
sity sweeteners or consider candy formula-
tions with alternative sweeteners having
different sweetness onset and linger. It may
be favorable to use the traditional acid for
the flavor with an additional acid to com-
plement the overall taste of the confection.
In the example with the sweetener having
a longer linger, one may consider using
Acids in Confections
Acid choice for
confections may
be influenced by
storage conditions.
Some acids are
hygroscopic and
will harden at
inappropriate
temperatures and
humidity levels
during storage.
The Manufacturing Confectioner March 2012 61

Acid Storage/handling
Citric Hygroscopic solid
Available as 50% solution
Fumaric Nonhygroscopic solid
Malic Hygroscopic solid
Lactic Liquid, powder, buffered*
(*form used in candy)
Tartaric Hygroscopic
Phosphoric
Inorganic Corrosive
Figure 7
Acids Storage/Handling
Protons Acid
1 Lactic
Acetic
2 Fumaric
Malic
Tartaric
3 Citric
Phosphoric
Figure 6
Hydrogen Ions in Common Acids
Acids in Confections
Use of acids in
candy should be
optimized to deliver
flavor or broaden
the flavor profile in
the presence of
sweetness and
complementing
target flavor.
62 March 2012 The Manufacturing Confectioner

malic acid. It lingers longer and may carry


through with the sweetener and flavor.
At this point, we have covered different
aspects of acids from their profiles to per-
formance. From an application point of
view, acids can help provide different per-
ceptions in confections. Attributes such as
molecular weight, solubility and strength all
have a role in an acids profile in the appli-
cation. The same role is demonstrated in
various fruits and fruit flavors.
ACIDS AND FRUIT FLAVORS
Consider the natural acids available in fruit.
Some fruits naturally have more than one
acid present in the fruits profile.
In formulating confections with fruit fla-
vors, evaluations should include the natu-
rally occurring acids of the fruits repre-
senting those respective flavors. Blends of
acids may characterize fruit flavors closer
to the natural fruit. Some common fruit
flavors with main and secondary acids are
shown in Figure 8.
Development of candy with fruit flavors
such as orange, cherry, and apple may be
more characteristic of the true fruit flavor
if formulated with acids found in the nat-
ural fruits. Fruit flavors described as raw
fruit, juicy, cooked or ripe also
impact the choice of acid or acid blend to
characterize the flavor as well as the inten-
sity, linger and onset of sourness. As the
flavor profile is defined, acid can help build
the profile. The tart taste in the candy can
represent growth stages of the fruit such
as green, sharp or ripe for fruits like apple
and strawberry. The different stages of
growth may have different concentrations
of the main and secondary acids and
increase as the fruit ripens. The flavor pro-
files may also represent stages in process-
ing which would allow for changes in acid
or acid levels. Use of acids in candy should
be optimized to deliver flavor or broaden
the flavor profile in the presence of sweet-
ness and complementing target flavor.
Candy with unbalanced sweetness in the
presence of acids could result in it being
flat or overly sweet. It becomes more
important to select the proper acid based
on the intensity and duration of the acid
for the overall flavor.
Taste Profile Comparisons
Anhydrous citric acid serves as the stan-
dard for relative intensity and duration and
is set with an intensity of 100 (Figure 9).
Lactic acid has a higher intensity and longer
taste duration than citric acid. In compari-
son, fumaric acid has much less intensity,
but has longer taste duration. These char-
acteristics are influenced by the acids low
solubility and chemical structure.
Flavor Intensity
Orange flavor has higher flavor intensity in
the presence of citric acid followed by lac-
tic acid (Figure 10). Observe cherrys
higher favor intensity with malic acid and
lactic acid compared to citric acid. Straw-
Fruit
Main Secondary
Acid Acid(s)
Apple Malic Tartaric, fumaric
Cherry Malic Tartaric
Orange Citric Malic
Peach Malic Citric
Mango Citric Malic, tartaric
Strawberry Citric Malic, tartaric
Grape Malic Tartaric
Figure 8
Acids Naturally Present in Fruits
Acid Intensity Taste Duration
Lactic Acid
(80% solution) 13010
Citric Acid
Monohydrate 109
Anhydrous 100
Malic Acid 905
Tartaric Acid 855
Fumaric Acid 755
Figure 9
Taste Comparisons
Acids in Confections
The experiment
allowed a
demonstration of
the traditional use
of citric acid in
citrus fruit flavors
and the potential
improvement of the
total taste profile
with the addition of
malic acid to the
candy.
The Manufacturing Confectioner March 2012 63
berry flavor with lactic acid also shows an
increased flavor intensity in the data com-
pared to citric acid. The data presented
supports evaluating different acids in fla-
vor profiles which may result in increases
in flavor perception and flavor intensity.
ACIDULANT CASE STUDY
Orange Hard Candy
Acidulants in applications can be discussed
in terms of case studies. In one case study,
orange hard candy was commercially man-
ufactured to demonstrate the impact of acids
and acid blends on flavor, sweetness and
tartness perception. The experiment allowed
a demonstration of the traditional use of cit-
ric acid in citrus fruit flavors and exploration
of the potential improvement of the total
taste profile with the addition of malic acid
to the candy. The orange hard candy sam-
ples were wrapped in different color papers
to aid in evaluations. For the tasting analy-
sis, people were given six orange candy sam-
ples with different treatment. Each candy
piece was evaluated in the mouth for a
period of time and descriptors were used to
describe the orange flavor character, sweet-
ness and tartness.
The tasting exercise with orange-
flavored hard candy provided an oppor-
tunity to evaluate candy in the presence
of the traditional acidulant for orange fla-
vor (citric acid) and citric acid blends. The
participants comments were varied with
the differences found with each acid treat-
ment. However, the general consensus for
the most flavorful and balanced treatment
of the orange-flavored candy was the blend
of citric and malic acid. It is important to
note the following observations regarding
characteristics for malic acid:
Malic acid provides a smoother flavor
and flavor release
Malic acid acts as a flavor blender
Malic acid provides more buffering
capacity at low pH
These three attributes may account for the
observations with the samples described
in the case study.
Throughout the discussions in this paper,
we have reviewed various acids used in
confections. We have reviewed the physi-
cal, chemical and sensorial attributes for
typical acids found in fruits as well as prac-
tical applications derived from evaluating
acids with a new perspective. Blends of
acids may bring more defined flavor pro-
files in addition to possible cost- savings as
a result of decreased usage levels.
CONCLUSION
In summary, we have learned that acids
have diverse features and functionality.
Acids vary in molecular weight, pK
a
val-
ues, forms (fine granular, granular, pow-
der, and liquid), solubility and manufac-
ture. Acids provide various functions in
confections: adjusting pH, impacting
sucrose inversion, facilitating gelling prop-
erties, determining firmness of gelatin gels
and modifying taste. Acids provide taste
characteristics associated with tartness/sour
intensity, solubility and flavor. Acid selec-
tion in confections may facilitate balance
between flavor, sweetness and tartness. In
reviewing the characteristic acids in fruits
and fruit flavors, combinations of acids may
provide opportunities for flavors to char-
acterize or enhance the true fruit taste per-
ception in confections. n
Presented at the AACT National Technical Seminar
Figure 10
Flavor Intensity Proles