In the Laboratory

Quantitative Determination of Citric and Ascorbic Acid 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 determine the quantity of citric acid by sodium hydroxide titration in a sample of food or drink (17). Most food samples that contain citric acid also contain ascorbic acid. Since both citric and ascorbic acid react with sodium hydroxide during titration, the total acid content (both citric and ascorbic acid) of the sample is actually being determined as seen in eqs 1 and 2:
C3H5O(COOH)3 + 3NaOH citric acid (1) C3H5O(COO)3Na3 + 3H2O

Experimental Over view Common, commercially available powdered drink mixes (e.g., Kool-Aid), contain citric and ascorbic acid in an approximately 100:1 (ww) ratio. Titration with standardized NaOH gives the amount of NaOH neutralized by the total acid in the sample. The amount of NaOH neutralized by ascorbic acid is equal to the amount of ascorbic acid determined by titration of the sample with KIO3. The amount of NaOH neutralized by citric acid is determined by subtraction as shown in eq 7:

C6H8O6 + NaOH ascorbic acid

C6H7O6Na + H2O

amount NaOH amount NaOH amount NaOH neutralized neutralized = neutralized (7) (total acid) (ascorbic acid) (citric acid)
The amount of citric acid is determined according to eq 1. This article describes the development of the experiment and presents data obtained by the authors. Student-generated data are also included and compared to that generated by the authors. Students gain practical experience in titration techniques. Concepts of acidbase chemistry as well as oxidationreduction reactions can be demonstrated. Calculations to determine the mass of each of the two acids present and percent by mass of each acid in the sample may be performed and enables students to relate learned information to real-world commercially-available products. For ascorbic acid, the percent RDA (Recommended Dietary Allowances) may be calculated and compared to the value listed on the package label (5). Experimental Development by the Authors A standardized 0.09740 M solution of NaOH was prepared. 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 acid was Certified ACS grade (Fisher Scientific). Pure L-ascorbic acid was purchased at a local health food store. The ratio of ascorbic acid to KIO3 (3:1) was verified by titration according to eqs 36. Thymol blue was selected as the best indicator for the student procedure. In the titration with KIO3, the endpoint was marked by the appearance of the blue starchI3 complex. These indicators worked well in all but the darkest powdered drink mixes. Blue and purple mixes were avoided for this procedure. The precision and accuracy of the method was tested. One liter of a solution with known amounts of citric acid
Journal of Chemical Education 1479

(2)

In these experiments, the amount of ascorbic acid is generally assumed to be insignificant with respect to the amount of citric acid present and the total acid amount is equated to the citric acid alone. There are also numerous student experiments that determine the amount of ascorbic acid in a sample by various redox titrations (810). One example is oxidation of ascorbic acid by potassium iodate, KIO3 (11). Ascorbic acid is readily oxidized by KIO3 in a 3:1 ratio according to eqs 36: IO3 + 5I + 6H + C 6H 8O 6 + I 2 ascorbic acid 3I2 + 3H2O (3)

C6H6O6 + 2H+ + 2I (4)

I2 + I

I3

(5)

I3 + starch

starchI3 complex (blue)

(6)

Even for low concentrations of ascorbic acid, this method is extremely accurate. Ascorbic acid has been reported for use as a primary standard for I2 (12). Citric acid is not oxidized by KIO3. This article describes a procedure by which the above reactions are used to quantitatively determine: first, the amount of total acid; second, the amount of ascorbic acid; and lastly, the amount of citric acid in a given sample of powdered drink mix.
www.JCE.DivCHED.org

Vol. 81 No. 10 October 2004

In the Laboratory

and ascorbic acid in a 100:1 (ww) 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 quantitatively 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 instructor; students must note the actual concentration. The second student analyzes the solution for ascorbic acid content by titration with 0.00100 M KIO3, also prepared by the instructor. 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 procedure requires two burets and an analytical balance. The procedure 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 potassium iodate (KIO3), potassium iodide (KI), hydrochloric acid (HCl), sodium hydroxide (NaOH), soluble starch, and thymol 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 protection in the lab. Results and Discussion The authors results for Kool-Aid brand powdered drink mixes are shown in Table 2. The results of the analysis of

Table 1. Typical Results for Precision and Accuracy of the Experimental Method Data Number of Trials Mass added/g Precision
a

Citric Acid 6 20.3018 20.80 0.11 2.5

Ascorbic Acid 6 0.2114 0.2067 0.0006 2.3

Accuracy (% Error)

Mass values for the acids are reported as the experimental mean with a 95% confidence interval.

powdered drink mixes are consistent with the package labeling. Mass values for the acids are reported as the experimental mean with a 95% confidence interval. Actual sample information for Kool-Aid brand powdered drink mixes is proprietary and percent error for the experimental 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 results 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 Consumer product-based experiments are always popular with students. This experiment provides a safe, reliable, and low-cost quantitative method to analyze one such product for acid content.

Table 2. Authors Results For Some Common Powdered Drink Mixes Kool-Aid Flavor Cherry Strawberry Lemonade Tea Orange Lemonade LemonLime Pink Lemonade Package Wgt/ g 4.3819 4.2783 5.2716 4.6641 7.1075 3.9280 6.7718 Mass of Citric Acid/g 3.88 0.11 3.30 0.03 4.66 0.01 3.56 0.01 6.31 0.04 3.80 0.02 6.13 0.05 Av % by Mass 88.7 77.6 88.6 76.6 88.9 97.0 90.7 Mass of Ascorbic Acid/g 0.0550 0.0015 0.0356 0.0004 0.0408 0.0002 0.0562 0.0006 0.0564 0.0021 0.0367 0.0002 0.0509 0.0002 Av % by Mass 1.230 0.883 0.774 1.200 0.781 0.934 0.751 % RDA 9.8 6.3 7.3 10. 10. 6.6 9.1

NOTE: All data for three trials except LemonLime (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 Kool-Aid Flavor Orange LemonLime Citric Acid/ (% by Mass) 76.3 97.8 Ascorbic Acid/ (% by Mass) 1.25 1.34 RDA (%) 10. 10.

3. 4.

Acknowledgments The initial work for this article began as a project for the North Carolina program, Summer Ventures in Science and Mathematics. We would also like to thank the A. R. Smith Department of Chemistry at Appalachian State University.
W

5.

6.

7. 8. 9.

Supplemental Material

A student laboratory handout, including procedures, sample calculations, and data sheets, and notes for the instructor, including solution preparation and laboratory setup, are available in this issue of JCE Online. Literature Cited
1. Canella, A. W. Modular Laboratory Program in Chemistry; Spencer, J. N., Neidig, H. A., Eds.; Willard Grant Press: Boston, MA, 1983. 2. Frantz, H. W.; Malm, L. E. Chemical Principles in the Labora-

10.

11. 12.

tory; Pauling, L. Ed.; W. H. Freeman: San Fransisco, CA, 1966; pp 167168. Stone, M. B.; Soliah, L.; Craig, J. Qual. Plant. Plant Foods Hum. Nutr. 1982, 31, 327332. Digital Library: Chemistry Laboratory Series, Acids, Bases and 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 Roberts, J. L., Jr.; Hollenberg, J. L.; Postma, J. M. General Chemistry in the Laboratory; W. H. Freeman: New York, 1987; pp 427432. Thompson, S. ChemtrekSmall Scale Experiments for General Chemistry; Allyn and Bacon: Needham Heights, MA, 1990; Chapter 11. Supplement Watch. http://www.supplementwatch.com/supatoz/ supplement.asp?supplementId=61 (accessed May 2004). Sirota, G. R.; MacInnis, W. K.; Rasmussen, P. W. J. Chem. Educ. 1979, 56, 421. Chemical Education Resources; http://www.cerlabs.com/ (accessed May 2004); Reed, R. G.: Kotz, J. C. ANAL 442Analyzing Food Products for Vitamin C. Chemical Education Resources; http://www.cerlabs.com/ (accessed May 2004); Silverstein, T. P.; Johnson, E. R. ANAL 501Determining the Effects of Cooking on the Vitamin C Content of Green Pepper. Bailey, D. N. J. Chem. Educ. 1974, 51, 488. Silva, C. R.; Simoni, J. A.; Collins, C. H.; Volpe, P. L. O. J. Chem. Educ. 1999, 76, 14211422.

www.JCE.DivCHED.org

Vol. 81 No. 10 October 2004

Journal of Chemical Education

1481