In the Laboratory

Quantitative Determination of Citric and Ascorbic Acid W

in Powdered Drink Mixes
A High School or General Chemistry Experiment
Samuella B. Sigmann* and Dale E. Wheeler
A. R. Smith Department of Chemistry, Appalachian State University, Boone, NC 28608; *sigmannsb@appstate.edu

Numerous student experiments have been developed to Experimental Over view

determine the quantity of citric acid by sodium hydroxide
titration in a sample of food or drink (1–7). Most food Common, commercially available powdered drink mixes
samples that contain citric acid also contain ascorbic acid. (e.g., Kool-Aid), contain citric and ascorbic acid in an ap-
Since both citric and ascorbic acid react with sodium hydrox- proximately 100:1 (w兾w) ratio. Titration with standardized
ide during titration, the total acid content (both citric and NaOH gives the amount of NaOH neutralized by the total
ascorbic acid) of the sample is actually being determined as acid in the sample. The amount of NaOH neutralized by
seen in eqs 1 and 2: ascorbic acid is equal to the amount of ascorbic acid deter-
mined by titration of the sample with KIO3. The amount of
C3H5O(COOH)3 + 3NaOH NaOH neutralized by citric acid is determined by subtrac-
citric acid (1) tion as shown in eq 7:
C3H5O(COO)3Na3 + 3H2O
amount NaOH amount NaOH amount NaOH
neutralized − neutralized = neutralized (7)
C6H8O6 + NaOH C6H7O6Na + H2O (total acid) (ascorbic acid) (citric acid)
ascorbic (2)
acid The amount of citric acid is determined according to eq 1.
This article describes the development of the experiment and
In these experiments, the amount of ascorbic acid is gener- presents data obtained by the authors. Student-generated data
ally assumed to be insignificant with respect to the amount are also included and compared to that generated by the au-
of citric acid present and the total acid amount is equated to thors.
the citric acid alone. Students gain practical experience in titration techniques.
There are also numerous student experiments that de- Concepts of acid–base chemistry as well as oxidation–reduc-
termine the amount of ascorbic acid in a sample by various tion reactions can be demonstrated. Calculations to deter-
redox titrations (8–10). One example is oxidation of ascor- mine the mass of each of the two acids present and percent
bic acid by potassium iodate, KIO3 (11). Ascorbic acid is by mass of each acid in the sample may be performed and
readily oxidized by KIO3 in a 3:1 ratio according to eqs 3–6: enables students to relate learned information to “real-world”
commercially-available products. For ascorbic acid, the per-
IO3− + 5I − + 6H + 3I2 + 3H2O (3) cent RDA (Recommended Dietary Allowances) may be cal-
culated and compared to the value listed on the package label
(5).
C 6H 8O 6 + I 2 C6H6O6 + 2H+ + 2I −
ascorbic (4) Experimental Development by the Authors
acid
A standardized 0.09740 M solution of NaOH was pre-
I2 + I − I3−
(5) pared. The reaction ratios of citric acid (1:3) and ascorbic
acid (1:1) to NaOH were verified by titration using thymol
blue as the indicator according to eqs 1 and 2. The citric
I3− + starch starch–I3− complex acid was Certified ACS grade (Fisher Scientific). Pure L-ascor-
(6)
(blue) bic acid was purchased at a local health food store. The ratio
of ascorbic acid to KIO3 (3:1) was verified by titration ac-
Even for low concentrations of ascorbic acid, this method is cording to eqs 3–6.
extremely accurate. Ascorbic acid has been reported for use Thymol blue was selected as the best indicator for the
as a primary standard for I2 (12). Citric acid is not oxidized student procedure. In the titration with KIO3, the endpoint
by KIO3. was marked by the appearance of the blue starch–I3− com-
This article describes a procedure by which the above plex. These indicators worked well in all but the darkest pow-
reactions are used to quantitatively determine: first, the dered drink mixes. Blue and purple mixes were avoided for
amount of total acid; second, the amount of ascorbic acid; this procedure.
and lastly, the amount of citric acid in a given sample of pow- The precision and accuracy of the method was tested.
dered drink mix. One liter of a solution with known amounts of citric acid

www.JCE.DivCHED.org • Vol. 81 No. 10 October 2004 • Journal of Chemical Education 1479

 In the Laboratory

and ascorbic acid in a 100:1 (w兾w) ratio was prepared and
analyzed. The results of six trials are shown in Table 1.
Experimental Procedure
Students work in pairs and each pair is given a package
of commercial powdered drink mix to be weighed and quan-
titatively dissolved with water in a 250-mL volumetric flask.
One student analyzes the solution for total acid by titration
with a standardized ∼0.1 M NaOH prepared by the instruc-
tor; students must note the actual concentration. The sec-
ond student analyzes the solution for ascorbic acid content
by titration with 0.00100 M KIO3, also prepared by the in-
structor. This procedure requires two hours of laboratory
time. Complete student procedures and data sheets for this
experiment, as well as procedure variations are available in
the Supplemental Material.W
Equipment
In addition to standard laboratory glassware, this pro-
cedure requires two burets and an analytical balance. The pro-
cedure also requires the use of a 250-mL volumetric flask and
volumetric pipets (10-mL and 50-mL). Graduated glassware
may be substituted for these. Required chemicals are potas-
sium iodate (KIO3), potassium iodide (KI), hydrochloric acid
(HCl), sodium hydroxide (NaOH), soluble starch, and thy-
mol blue indicator. A detailed equipment and reagent list is
available in the Supplemental Material.W
Hazards
HCl is corrosive and NaOH is caustic. Handle both with
care. KIO3 is an oxidizing agent. Solid KI is a possible skin
and lung irritant. Solutions of KIO3, thymol blue and soluble
starch pose minimal risk to students. Always wear eye pro-
tection in the lab.
Table 1. Typical Results for Precision and Accuracy
of the Experimental Method
Data Citric Acid Ascorbic Acid
Number of Trials 6 6
Mass added/g 20.3018 0.2114
a
Precision 20.80 ± 0.11 0.2067 ± 0.0006
Accuracy (% Error) 2.5 ᎑2.3
a
Mass values for the acids are reported as the experimental mean with
a 95% confidence interval.
powdered drink mixes are consistent with the package label-
ing. Mass values for the acids are reported as the experimen-
tal mean with a 95% confidence interval.
Actual sample information for Kool-Aid brand powdered
drink mixes is proprietary and percent error for the experi-
mental masses cannot be reported. The experimental values
of “percent by mass” for citric acid range from 76.6% to
97.0% and citric acid is listed as the primary ingredient on
all packages tested. Experimental values for ascorbic acid
range from 0.751% to 1.23% and ascorbic acid is listed as a
much less significant ingredient on each package tested. The
percent RDA listed on the packages is 10% (of 70 mg) per
serving, which agrees with the results listed in Table 2.
Thirteen students in the quantitative analysis course at
our university performed this experiment and their average
results for two flavors of Kool-aid are shown in Table 3. The
students’ results are similar to our findings in Table 2. Some
variation between the authors’ results and the students’ re-
sults could be due to lot variation. While the results reported
are for Kool-Aid, other brands of powdered drink mixes were
tested and worked equally well.
Summar y

Results and Discussion Consumer product-based experiments are always popu-

lar with students. This experiment provides a safe, reliable,
The authors’ results for Kool-Aid brand powdered drink and low-cost quantitative method to analyze one such prod-
mixes are shown in Table 2. The results of the analysis of uct for acid content.

Table 2. Authors‘ Results For Some Common Powdered Drink Mixes

Package Wgt/ Mass of Av % Mass of Av %
Kool-Aid Flavor % RDA
g Citric Acid/g by Mass Ascorbic Acid/g by Mass
Cherry 4.3819 3.88 ± 0.11 88.7 0.0550 ± 0.0015 1.230 9.8
Strawberry 4.2783 3.30 ± 0.03 77.6 0.0356 ± 0.0004 0.883 6.3
Lemonade Tea 5.2716 4.66 ± 0.01 88.6 0.0408 ± 0.0002 0.774 7.3
Orange 4.6641 3.56 ± 0.01 76.6 0.0562 ± 0.0006 1.200 10.
Lemonade 7.1075 6.31 ± 0.04 88.9 0.0564 ± 0.0021 0.781 10.
Lemon–Lime 3.9280 3.80 ± 0.02 97.0 0.0367 ± 0.0002 0.934 6.6
Pink Lemonade 6.7718 6.13 ± 0.05 90.7 0.0509 ± 0.0002 0.751 9.1
NOTE: All data for three trials except Lemon–Lime (citric acid) and Cherry (ascorbic acid), which were four trials.

1480 Journal of Chemical Education • Vol. 81 No. 10 October 2004 • www.JCE.DivCHED.org

 In the Laboratory

Table 3. Students’ Results tory; Pauling, L. Ed.; W. H. Freeman: San Fransisco, CA, 1966;
Kool-Aid Citric Acid/ Ascorbic Acid/ RDA
pp 167–168.
Flavor (% by Mass) (% by Mass) (%) 3. Stone, M. B.; Soliah, L.; Craig, J. Qual. Plant. Plant Foods
Hum. Nutr. 1982, 31, 327–332.
Orange 76.3 1.25 10.
4. Digital Library: Chemistry Laboratory Series, Acids, Bases and
Lemon–Lime 97.8 1.34 10. Buffers.Titration Analysis of Weak Acid Solutions: Potassium Acid
Phthalate, Acetic Acid in Vinegar, and Citric Acid in Fruits and
Acid/Base Titration of Ascorbic Acid, http://
archive.thomson.com/pam/TC_new_user.htm
Acknowledgments 5. Roberts, J. L., Jr.; Hollenberg, J. L.; Postma, J. M. General
Chemistry in the Laboratory; W. H. Freeman: New York, 1987;
The initial work for this article began as a project for pp 427–432.
the North Carolina program, Summer Ventures in Science 6. Thompson, S. Chemtrek—Small Scale Experiments for General
and Mathematics. We would also like to thank the A. R. Chemistry; Allyn and Bacon: Needham Heights, MA, 1990;
Smith Department of Chemistry at Appalachian State Uni- Chapter 11.
versity. 7. Supplement Watch. http://www.supplementwatch.com/supatoz/
supplement.asp?supplementId=61 (accessed May 2004).
W
Supplemental Material 8. Sirota, G. R.; MacInnis, W. K.; Rasmussen, P. W. J. Chem.
Educ. 1979, 56, 421.
A student laboratory handout, including procedures,
9. Chemical Education Resources; http://www.cerlabs.com/ (ac-
sample calculations, and data sheets, and notes for the in-
cessed May 2004); Reed, R. G.: Kotz, J. C. ANAL 442—Ana-
structor, including solution preparation and laboratory setup,
lyzing Food Products for Vitamin C.
are available in this issue of JCE Online.
10. Chemical Education Resources; http://www.cerlabs.com/ (ac-
cessed May 2004); Silverstein, T. P.; Johnson, E. R. ANAL
Literature Cited
501—Determining the Effects of Cooking on the Vitamin C
1. Canella, A. W. Modular Laboratory Program in Chemistry; Content of Green Pepper.
Spencer, J. N., Neidig, H. A., Eds.; Willard Grant Press: Bos- 11. Bailey, D. N. J. Chem. Educ. 1974, 51, 488.
ton, MA, 1983. 12. Silva, C. R.; Simoni, J. A.; Collins, C. H.; Volpe, P. L. O. J.
2. Frantz, H. W.; Malm, L. E. Chemical Principles in the Labora- Chem. Educ. 1999, 76, 1421–1422.

www.JCE.DivCHED.org • Vol. 81 No. 10 October 2004 • Journal of Chemical Education 1481