John Black Analytical Chemistry Titration of Unknown Weak Acid with a Strong Base Introduction: Titration is a fundamental analytical

technique used in the chemistry lab to determine an unknown concentration of a particular analyte. An acid-base titration is a specific method that employs titrating a weak base with a strong acid or a weak acid with a strong base. Normally such a titration is monitored with an indicator that changes color around the equivalence point or a pH meter. In this experiment a secondary standard solution of NaOH was prepared and used to titrate an unknown acid. The titration was monitored with a pH meter and the subsequent data was used to form a titration curve. Interpreting the curve utilizing the underlying theory behind the Henderson-Hasselbach equation and stoichiometric reactions, the unknown acid (unknown F) was determined to be malonic acid.

Figure 1: Structure of Malonic Acid1 Experimental Preparation of NaOH Secondary Standard To begin, an approximate 0.1 M sodium hydroxide solution was prepared by dissolving 2.103 g of NaOH in approximately 500 mL of DI water in a plastic bottle. Immediately following, 5 samples of 0.5 g potassium hydrogen phthalate, KHP, were accurately weighed in 125 mL Erlenmeyer flasks. Sample Pilot KHP (g) 0.4687 Moles PHP 0.002295

1 0.5105 0.0024996 2 0.5265 0.002578 3 0.5060 0.0024776 4 0.5035 0.0024654 Table 1: Table 1 shows the actual masses of KHP used and the corresponding moles as calculated from the provided molecular weight of 204.221 g/mol. They were dissolved in about 25 mL of water, and 3 drops of phenolphthalein were added. The first sample was run as a pilot titration and the other four were titrated carefully to the lightest visible pink. The results were used to calculate the actual molarity of sodium hydroxide. Titration of Unknown Acid The acid was prepared by dissolving 0.5007 g of the unknown F acid in a 250 mL Erlenmeyer flask with 100 mL of DI water. This solution was then quantitatively transferred to a 250 mL volumetric flask and diluted to the mark. 25 mL of this solution was then pipetted into a beaker with 50 mL Di

water. This solution was then quickly titrated with the secondary standard NaOH in increments of 1-1.5 mL and the pH was recorded with a pH meter. A rough graph was constructed to estimate the endpoint of the titration curve:

Rough Titration Curve for Unknown Acid

12 10 8 pH 6 4 2 0 0 2 4 6 8 10 12 Volume of NaOH (mL) Series1

Graph 1: The above graph was the rough titration curve plotted from data in Appendix A to estimate the endpoint. From the data the endpoint was estimated to be between 9-10 mL for that particular volume of solution.A more accurate titration curve was then calculated by pipetting 100 mL of the unknown acid solution into a beaker and titrating with NaOH secondary standard. The approximated endpoint of this titration was calculated to be between 36-40 mL from the pilot titration. The base was added in 1.5 mL increments until within 8 mL of the approximated endpoint (28 mL). Four 1 mL increments were added and then 0.5 mL increments until the pH leveled off. The titration was finished off with the addition of 1.5 mL increments until a total volume of 49 mL was reached. Results and Discussion: Standardization of NaOH Solution NaOH (mL) Concentration [M] 22.58 0.1016 1 24.52 0.1019 2 25.42 0.1014 3 24.31 0.1019 4 24.25 0.1017 Average 0.1017 Stdev 0.21% Table 2: Calculation of molarity of NaOH from the titration of KHP. Sample Pilot Mols PHP 0.002295 0.0024996 0.002578 0.0024776 0.0024654

Titration of Unknown Acid

Titration Curve of Unknown Acid 14 12 10 pH 8 6 4 2 0 0 10 20 30 40 50 60 Volume of NaOH (mL) Series1

Graph 2: Titration curve of unknown acid with NaOH secondary standard. Compiled from data in Appendix A
First Derivative 6 5 4 pH/mL 3 2 1 0 0 10 20 30 40 50 Volume NaOH (mL) Series1

Graph 3: First Derivative of the titration curve in Graph 3. Raw data in Appendix A.

Second Derivative 10 8 6 4 (pH/mL) 2 0 -2 -4 -6 -8 -10 Volume NaOH (mL) 0 10 20 30 40 50 Series1

Graph 4: The second derivative of the titration curve. Raw Data in Appendix A. Second Derivative (Zoomed)
0.08 0.06 0.04
(pH/mL)

0.02 0 -0.02 -0.04 -0.06 Volume NaOH 0 10 20 30 40 Series1

Graph 5: The second derivative zoomed in before the second equivalence point. From the second derivative graph, the endpoint was estimated to be 37.75 mL of NaOH. The stoichiometric calculation was used below for this diprotic acid: (0.03775 L)*(0.1017 M NaOH) = 0.003840 mols NaOH. NaOH:Acid= 2:1

0.001920 mols of acid in 100 mL. * 2.5 = 0.004800 mols of total acid in 250 mL 0.5007g of unknown/0.004800 mols = 104.3 g/mol The molar mass of the unknown is comparable to the literature molar mass value of malonic acid: 104.1 g/mol. The pKas of this acid were estimated from the second derivative graph (Graph 5) where the graph crosses the x-axis and from the titration curve. The pKas were estimated to be 2.6-2.9 and 5.5-5.7, which corresponds to the literature pKa values of malonic acid of 2.83 and 5.61. From the titration plot obtained through a pH meter and stoichiometric calculations, the unknown acid F was determined to be malonic acid. The preparation of NaOH as a secondary standard was key for the stoichiometric calculations which led to accurate prediction of the molar mass. NaOH is not obtainable as a primary standard due to its tendency to dissolve atmospheric CO2, which changes its concentration. The error in PKa values could have been due to user measurement error, pH meter insensitivity, and/or the solvation of atmospheric CO2 during the titration. References: 1. Weiner, Nathan. Malonic Acid. Org. Synth.; Coll. Vol. 2: 376 Appendix A: Original Volume (mL) 0 1 2.5 4 5.5 7 8.5 10 11.5 13 pH 1.125 2.41 2.5 2.43 4 2.4 5.5 2.51 7 2.58 8.5 2.65 10 2.76 11.5 2.87 13 2.98 14.5 3.12 0.022222 14.5 0.022222 0.008889 13 0.008889 0.013333 11.5 0.013333 -1.9E-16 10 -1.9E-16 1.94E-16 8.5 1.94E-16 0.017778 7 0.017778 -2E-16 5.5 -2E-16 -0.01778 4 -0.01778 0.062222 2.5 0.062222 -0.02667 1.125 -0.02667 First Derivative Volume (mL) Second Derivative Volume (mL)

16 14.5 16 17.5 19 20.5 22 23.5 25 26.5 28 29 30 31 32 32.5 33 33.5 34 34.5 35 35.5 36 36.5 37 3.28 17.5 3.49 19 3.78 20.5 4.2 22 4.58 23.5 4.87 25 5.06 26.5 5.23 27.875 5.38 29 5.52 30 5.62 31 5.72 31.875 5.82 32.5 5.93 33 5.98 33.5 6.04 34 6.11 34.5 6.18 35 6.26 35.5 6.35 36 6.46 36.5 6.59 37 6.74 37.5 7.04

0.035556 0.057778 -0.01778 -0.04 -0.04444 -0.00889 -0.00889 -0.00444 0.006667 -8.9E-16 8.88E-16 0.01 -0.02 0.04 0.04 -3.6E-15 0.04 0.04 0.08 0.08 0.08 0.6 0.76 8.36

16 17.5 19 20.5 22 23.5 25 26.5 27.875 29 30 31 31.875 32.5 33 33.5 34 34.5 35 35.5 36 36.5 37 37.5

0.035556 0.057778 -0.01778 -0.04 -0.04444 -0.00889 -0.00889 -0.00444 0.006667 -8.9E-16 8.88E-16 0.01 -0.02 0.04 0.04 -3.6E-15 0.04 0.04 0.08 0.08 0.08 0.6 0.76 8.36

38 37.5 38 38.5 39 39.5 40 40.5 41 41.5 42 42.5 43 44.5 46 47.5 49 7.53 38.5 10.11 39 10.58 39.5 10.84 40 10.98 40.5 11.09 41 11.18 41.5 11.25 42 11.31 42.5 11.36 42.25 11.4 42.75 11.44 11.48 11.49 11.51 11.51 0.08

-8.44 -0.84 -0.48 -0.12 -0.08 -0.08 -0.04 -0.04 -0.04 -7.1E-15

38 38.5 39 39.5 40 40.5 41 41.5 42 42.5

-8.44 -0.84 -0.48 -0.12 -0.08 -0.08 -0.04 -0.04 -0.04 -7.1E-15

0.08