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Problem Set 3: Acid-Base Equilibria and Titration Curves 1.

Sketch the titration curves for each of the following systems. Calculate and indicate on each sketch, the equivalence point volume, the initial pH of the solution, and at least one other pH on the titration curve. Also be sure to indicate the approximate pH of the equivalence point if this is not the second point that you choose. (a) 10.00 mL of 0.0500 M HNO3 (beaker) titrated with 0.100 M NaOH (buret) (b) 10.00 mL of 0.0500 M benzoic acid (Ka = 6.46 x 10-5) (beaker) titrated with 0.100 M NaOH (buret). (c) 10.00 mL of 0.0500 M TRIS (Kb =1.20 x 10-6) (beaker) titrated with 0.100 M HCl 2. In order to carry out a study of enzyme behavior, a biochemist needed a buffer with a pH of 5. The following reagents were available. Benzoic acid Sodium benzoate C6H5COOH CH3CH2COONa MW 122.1g MW 144.1g pKa = 4.18

(a) Calculate the ratio of molar concentrations of benzoate/benzoic acid in a pH 5.00 buffer made with these compounds. (b) Calculate the weight of sodium benzoate that you would need to add to 100 mL of 1.0 M benzoic acid to obtain a pH 5.00 buffer. (c) Calculate the moles of benzoic acid and benzoate that will result if you add 10.0 mL of 1.0 M HCl solution to the 100 mL of buffer you prepared in part (b) 3. Explain why the pH of a 0.10 M solution of sodium acetate differs from the pH of a 0.10 M solution of sodium nitrate. Identify the pH of at least one of the solutions and indicate whether the other solution will have a higher or lower pH. Ka acetic acid 1.8 X 10-5 4. Calculate the pH of a solution made by dissolving 0.0100 mol of NH3 in 1.000L of solution. The Kb for ammonia is 1.8 x 10-5. 5. You have available 1.00 moles of each of the following weak acids (HA) and unlimited amounts of their corresponding conjugate base salts (A-). Ka Weak Acid Hydrosulfuric acid 9.1 x 10-8 Acetic acid 1.76 x 10-5 Nitrous acid 4.6 x 10-4 Which acid/conjugate base pair would you choose to design a buffer system with a pH of 4.60? How many moles of acid and conjugate base would you dissolve into 2.00L of water so that your buffer would have the largest buffering capacity?

6. Vitamin C is ascorbic acid (HC6H7O6) for which Ka is 8.0 x 10-5 Calculate the pH of a solution made by dissolving a 500-mg tablet of pure vitamin C in water and diluting the solution to 100 mL. 7. Tris is short for tris(hydroxymethyl)aminomethane. This weak base is widely used in biochemical research for the preparation of buffers. It offers low toxicity and a pKb (5.92) that is convenient for the control of pH in clinical applications. A buffer solution is prepared by mixing 0.050 mol of tris with 0.025 mol of HCl in a volume of 2.00L. Compute the pH of the solution. 8. Sodium benzoate, the sodium salt of benzoic acid, is used as a food preservative. A sample containing solid sodium benzoate mixed with sodium chloride is dissolved in 50.0 mL of 0.500 M HCl, giving an acidic solution (benzoic acid mixed with HCl). This mixture is then titrated with 0.393 M NaOH. After the addition of 46.50 mL of the NaOH solution, the pH is found to be 8.2. At this point, the addition of one more drop (0.02 mL) of NaOH raises the pH to 9.3. Calculate the mass of sodium benzoate (NaC6H5COO) in the original sample. (Hint: At the equivalence point, the total number of moles of acid [here HCl] equals the total number of moles of base [here NaOH and NaC6H5COO]). 9. A 75.00-mL portion of a solution that is 0.0460M in HClO4 is treated with 150-mL of 0.0230 M KOH(aq). Is the pH of the resulting mixture greater than, less than, or equal to 7.0. 10. Suppose a 0.100 M solution of each of the following substances is prepared. Rank the pH of the resulting solutions from lowest to highest: KF, NH4I, HBr, NaCl, LiOH.