POTENTIOMETRIC ANALYSIS OF CITRIC ACID IN SPORTS DRINK GATORADE®

Daniela Delgadillo Restrepo 1, Camilo Andrés Martínez Ariza 1

1
Departamento de Ingeniería Química y Ambiental. Facultad de Ingeniería. Universidad
Nacional de Colombia, Bogotá, D.C., Colombia
Emails: ddelgadillor@unal.edu.co, camartinezar@unal.edu.co

ABSTRACT

Citric acid is one of the most used additives to enhance food´s flavor, appearance and most
importantly to preserve it. In the following article, the results of the potentiometric titration of
sports drink Gatorade® are presented. The main objective of this analysis was to determine the
molar concentration of citric acid in the beverage and its acidity constant (pKa). In order to
achieve this, a 0,092 M sodium hydroxide solution was used as a titrant and the pH of the
reaction was measured every 0,2 mL of added titrant. After completing the process, the
equivalence point of the neutralization reaction was found and with this value and the
stoichiometry of the reaction, the molar concentration of citric acid and its acidity constant were
calculated, obtaining results of 0,011 M and 5,38 respectively, concluding that there's a
minuscule amount of citric acid in Gatorade® and that the obtained pKa is most likely the one of
dihydrogen citrate due to the reactions that take place between citric acid and other beverage
components. To analyze the exactitude of the percent error of the pKa was of 13,03% in the pKa,
probably because it wasn´t pure citric acid the one being analyzed and as the pH sensor was not
sensitive enough to measure the exact values.

Keywords: Polyprotic acid, Potentiometry, Citric acid, pH, pKa.

1. INTRODUCTION

Most food and drinks have additives which help them last longer, regulate their pH, modify taste,
color and prevent the transformation of the product. The amount of additives that can be
contained in food and beverages is constrained by the Health Ministry of each country and the
United Nations´ Food and Agriculture Organization (FAO).

Citric acid (2-hydroxy-1,2,3-propanetricarboxylic acid, C6H8O7) is one of the most used additives
in the food industry. It is a white, odourless crystalline solid, that can be found in certain fruits
such as limes and oranges, or it can be produced by the fermentation of carbohydrate solutions
carried by the fungus Aspergillus niger. According to de FAO and to the Colombian Health
Ministry the amount of citric acid added to food will never be used in an excessive or unhealthy
amount that exceeds the limit, in order to achieve its purpose [1-2].

One of the most used techniques for the quantitative analysis of a solution is potentiometric
titration. In this procedure, a solution of known concentration is added to one of unknown
concentration; pH is measured throughout the process using a potentiometer, a titration curve is
built and based on it and on the stoichiometry of the ongoing reaction between titrant and titrand,
the concentration of the titrand can be found.

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 Gatorade® is a soft drink which contains citric acid, it works as a conservant and flavor enhancer
for the beverage. The concentration of this acid in the drink can be determined by a
potentiometric titration. Given that citric acid is a weak polyprotic acid (which means it has three
ionizable carboxylic groups and that it is able to react with various metal ions [3]) it is suitable to
titrate it with a strong base such as sodium hydroxide. Citric acid reacts with sodium hydroxide
according to equation 1 where 3 mol of sodium hydroxide react with one mol of citric acid to
produce 3 mol of water and one mol of sodium citrate.

3NaOH(ac) + C6H8O7(ac) ⇌ 3H2O(l)+ Na3C6H5O7(ac) (1)

The main gist of this experiment, is to find the concentration and pKa values of citric acid in
Gatorade® through a potentiometric titration, analyze the behavior of this acid in the drink and
how it interacts with the other components of it.

2. METHODOLOGY

2.1. Gatorade® titration

To begin, 10 mL of Gatorade® (tropical flavor, batch: L1C0002894032, expiration date: 8/9/19)

were measured and then diluted in approximately 20 mL of water, this dilution was placed in a
beaker with the magnetic stirrer and the beaker was put over the stirring-heat plate. Furthermore,
a burette was filled with standardized 0,092M sodium hydroxide. Stirring was set to a medium
speed, then the sodium hydroxide solution was added to the Gatorade® dilution drop by drop and
with the help of the LabQuest 2 calculator and a Vernier pH sensor with an accuracy of +/- 0,2
units, the pH of the ongoing reaction was measured every 0,2 mL of added NaOH. The addition
of sodium hydroxide was stopped when the pH remained constant.

3. RESULT ANALYSIS

After the procedure mentioned above was completed, with the collected data, the titration curve
and its first derivative were plotted as shown in Figure 1. Graph A shows the change in pH as a
function of the added volume of titrant. Graph B illustrates the first derivative of the function
plotted in graph A.

Figure 1. (A)Titration curve of Gatorade® (10 mL) with 0,092 M NaOH. (B) Titration curve´s
first derivative.

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As it can be observed, in Graph B, there´s a maximum point, which indicates the volume of
added titrant in which the equivalence point of the reaction shown in equation 1 was
reached. With this volume, concentration of NaOH and stoichiometry shown in equation
1, the molar concentration and pKa of citric acid were calculated. The used data and
results are shown in Figure 2.

Added NaOH Volume in Equivalence Point (mL) 3,49 +/- 0,01

NaOH Molar Concentration 0,092
Gatorade ® Volume (mL) 10,00 +/- 0,01
Sodium Hydroxide mol 0,000321
Citric Acid mol 0,00011
Citric Acid Molar concentration 0,011
pKa 5,38
®
Figure 2. Gatorade potentiometric titration data and results

The molar concentration of citric acid in Gatorade® is a very small value, there are only 0,011
mol or 2,1 grams of citric acid in a liter of this drink. The amount of citric acid added to food is
usually lower than 3,00 grams, this small amount is enough to regulate pH and enhance the drink
´s flavor [1]. Gatorade® does not report the exact amount of citric acid on it, most likely because
it is an insignificant amount next to the ones of its other components.

According to the Merck Index by Windholz , citric acid, as a triprotic acid, has three pKa values,
3,13, 4,76 and 6,40 [3-4]. The obtained pKa, 5,38, is closer to the second pKa value of this acid.
To evaluate the exactitude of the obtained value, the percent error was calculated, resulting in an
error of 13,03%.

As the found pKa most likely corresponds to the second value where dihydrogen citrate(C6H7O7-)
is losing a proton to become hydrogen citrate(C6H6O72-), it is important to explain where citric
acid lost its first hydrogen. Gatorade® has other components as metal ions (Na+, K+ and Cl-),
sodium citrate (Na3C6H5O7) and monopotassium phosphate (KH2PO4), citric acid can react with
sodium and potassium ions but these come from the other two mentioned components. Sodium
citrate is added to the drink to regulate pH, creating a buffer as a salt of citric acid, so these two
co-exist on equilibrium in the drink. The only explanation, is that citric acid reacts with
monopotassium phosphate to create potassium citrate and phosphoric acid as shown in equation
2:

C6H8O7 (ac)+3KH2PO4(ac) ⇌ K3C6H5O7 (ac)+3H3PO4 (ac) (2)

Gatorade® has a pH of 3,39, by observing the pKa values for phosphoric acid, it can be seen that
at pH 2,2 it dissociates into a hydrogen ion and dihydrogen phosphate (H2PO4) [4], meaning that,
the reaction shown in equation 2 occurs on equilibrium, so citric acid donates a proton to
monopotassium phosphate, then phosphoric acid is ionized in the drink, leaving dihydrogen
phosphate as a product. When the titration with NaOH is made, the acid with the smallest pKa
reacts, in this case, the second pKa for citric acid is 4,76 and 7,2 for phosphoric acid [3-4] which

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explains why citric acid is the one which reacts with sodium hydroxide as in equation 1, and why
the obtained pKa is closest to the second value reported in literature.

There can also be a simpler explanation to the high pKa value that was determined in the
titration, which is that Gatorade® has many other components as the metal ions such as Na+, Cl-
and K+, phosphates and ascorbic acid (C6H8O6) from Vitamin C, even if these aren´t contained in
a significant amount, there´s a possibility that they react between them and form acidic
compounds other than citric acid that could react with NaOH in the titration and alter the whole
procedure.

4. CONCLUSIONS

After the analysis, there are various conclusions that can be made. First of all, from the obtained
citric acid´s concentration in Gatorade® (0,011M), it can be determined that there are only 2,1
grams of citric acid in a liter of it; this amount probably isn´t reported on the drink´s label
because it is insignificant next to the ones of the other components, and just a small amount of it
is required to enhance its flavor. Now, the pKa value that was determined through the titration
was 5,38. This value is closer to the pKa of the second ionizable proton of citric acid (4,76 [4]).
This value´s error was of 13,03%, probably because the drink as a whole, has other substances 
that can react with citric acid such as monopotassium phosphate, changing the way in which this 
acid is present in the drink. Finally, it´s very important to mention that calculating the pKa of a 
substance which isn´t pure, as citric acid in Gatorade®, won´t give an exact result, due to the 
ongoing reactions between the drink´s components and other acids such as ascorbic acid and 
phosphoric acid that can intervene on the titration process and alter the results.

5. BIBLIOGRAPHY

1. Food and Agriculture Organization of the United Nations. (2014). Citric Acid. Rome,
2014. (Monograph No.16). Retrieved from
http://www.fao.org/fileadmin/user_upload/jecfa_additives/docs/monograph16/additive­
135­m16.pdf 

2. Colombian Health Ministry. (1991). Antioxidantes en Alimentos. Bogota, 1990. 
( Resolution No.4124). Retrieved from  https://www.invima.gov.co/resoluciones­en­
alimentos/resolucion_4124_1991.pdf/download.html

3. Apelblat,A. (2014). Citric Acid. Springer Cham Heidelberg New York Dordrecht
London , p. 143-236.

4. Windholz, M.(1983). The Merck Index. Germany, p. 330-341

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