CHEMISTRY. Section II (Total time 95 minutes) Part A Time 55 minutes YOU MAY USE YOUR CALCULATOR FOR PART A.

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1 2007 AP CHEMISTRY FREE-RESPONSE QUESTIONS CHEMISTRY Section II (Total time 95 minutes) Part A Time 55 minutes YOU MAY USE YOUR CALCULATOR FOR PART A. CLEARLY SHOW THE METHOD USED AND THE STEPS INVOLVED IN ARRIVING AT YOUR ANSWERS. It is to your advantage to do this, since you may obtain partial credit if you do and you will receive little or no credit if you do not. Attention should be paid to significant figures. Be sure to write all your answers to the questions on the lined pages following each question in the booklet with the pink cover. Do NOT write your answers on the green insert. Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent. HF(aq) + H 2 O(l ) H 3 O + (aq) + F (aq) K a = Hydrofluoric acid, HF(aq), dissociates in water as represented by the equation above. (a) Write the equilibrium-constant expression for the dissociation of HF(aq) in water. (b) Calculate the molar concentration of H 3 O + in a 0.40 M HF(aq) solution. HF(aq) reacts with NaOH(aq) according to the reaction represented below. HF(aq) + OH (aq) H 2 O(l) + F (aq) A volume of 15 ml of 0.40 M NaOH(aq) is added to 25 ml of 0.40 M HF(aq) solution. Assume that volumes are additive. (c) Calculate the number of moles of HF(aq) remaining in the solution. (d) Calculate the molar concentration of F (aq) in the solution. (e) Calculate the ph of the solution. -6- GO ON TO THE NEXT PAGE.

2 AP CHEMISTRY 2007 SCORING GUIDELINES Question 1 HF(aq) + H 2 O(l ) Æ H 3 O + (aq) + F (aq) K a = Hydrofluoric acid, HF(aq), dissociates in water as represented by the equation above. (a) Write the equilibrium-constant expression for the dissociation of HF(aq) in water. + [H3O ][F ] K a = One point is earned for the correct expression. [HF] (b) Calculate the molar concentration of H 3 O + in a 0.40 M HF(aq) solution. [H3O ][F ] K a = = [HF] + ( x)( x) = x Assume x << 0.40, then x 2 = (0.40)( ) x = [ H 3 O + ] = M One point is earned for the correct setup (or the setup consistent with part (a)). One point is earned for the correct concentration. HF(aq) reacts with NaOH(aq) according to the reaction represented below. HF(aq) + OH (aq) H 2 O(l) + F (aq) A volume of 15 ml of 0.40 M NaOH(aq) is added to 25 ml of 0.40 M HF(aq) solution. Assume that volumes are additive. (c) Calculate the number of moles of HF(aq) remaining in the solution. mol HF(aq) = initial mol HF(aq) mol NaOH(aq) added = (0.025 L)(0.40 mol L 1 ) (0.015 L)(0.40 mol L 1 ) = mol mol = mol One point is earned for determining the initial number of moles of HF and OH. One point is earned for setting up and doing correct subtraction. (d) Calculate the molar concentration of F (aq) in the solution. mol F (aq) formed = mol NaOH(aq) added = mol F (aq) mol F ( aq) ( ) L of solution = 0.15 M F (aq) One point is earned for determining the number of moles of F (aq). One point is earned for dividing the number of moles of F (aq) by the correct total volume.

3 AP CHEMISTRY 2007 SCORING GUIDELINES Question 1 (continued) (e) Calculate the ph of the solution. [HF] = mol HF L = 0.10 M HF [H3O ][F ] K a = [HF] M ( ) 0.15 M [HF] [F ] K a = ph = log ( ) = 3.32 = + 3 [H O ] One point is earned for indicating that the resulting solution is a buffer (e.g., by showing a ratio of [F ] to [HF] or moles of F to HF ). OR ph = pk a + log [F ] [HF] One point is earned for the correct calculation of ph. = log ( ) + log 0.15 M 0.10 M = = 3.32

4 2007 The College Board. All rights reserved.

5 2007 The College Board. All rights reserved.

6 AP CHEMISTRY 2007 SCORING COMMENTARY Question 1 Overview This question assessed students understanding of aqueous equilibrium of a weak acid, stoichiometry of aqueous reactions, and buffer calculations. For parts (a) and (b) students were given a chemical equation describing the equilibrium of a weak acid in aqueous solution; they were expected to write a correct expression for the equilibrium constant and to use the equilibrium-constant expression and its value to determine [H 3 O + ] in a solution of known concentration. The remainder of the problem challenged students to first perform stoichiometric calculations to determine the number of moles or the concentration of species present when solutions of a weak acid and a strong base are combined. The final part of the question asked them to demonstrate mastery of the concept of buffered solutions by determining the ph of the resulting solution. Sample: 1A Score: 9 This response earned all 9 points: 1 for part (a), 2 for part (b), 2 part (c), 2 for part (d), and 2 for part (e). Sample: 1B Score: 6 The point was not earned in part (a) because the concentration of water is erroneously included in the equilibriumconstant expression. However, the concentrations are correctly substituted into the equilibrium equation and [H 3 O + ] is calculated correctly, so 2 points were earned in part (b). Both points were earned in part (c), and both points were earned in part (d). The student does not recognize that the resulting solution is a buffer, treating the solution as a strong acid, and therefore did not earn any points for part (e). Sample: 1C Score: 4 All available points were earned in parts (a) and (b). In part (c) the first point was earned for determining the number of moles of HF and NaOH initially present, but the second point was not earned because the correct reaction stoichiometry is not applied. No points were earned in part (d) because the student does not determine the correct number of moles of F present and does not obtain the correct volume of solution. No points were earned in part (e) because the student does not indicate that the resulting solution is a buffer, erroneously setting [OH ] = 0.40 M.

7 Student Performance Q&A: 2007 AP Chemistry Free-Response Questions The following comments on the 2007 free-response questions for AP Chemistry were written by the Chief Reader, Eleanor Siebert of Mount St. Mary s College in Los Angeles, California. They give an overview of each free-response question and of how students performed on the question, including typical student errors. General comments regarding the skills and content that students frequently have the most problems with are included. Some suggestions for improving student performance in these areas are also provided. Teachers are encouraged to attend a College Board workshop to learn strategies for improving student performance in specific areas. Question 1 What was the intent of this question? This question assessed students understanding of aqueous equilibrium of a weak acid, stoichiometry of aqueous reactions, and buffer calculations. For parts (a) and (b) students were given a chemical equation describing the equilibrium of a weak acid in aqueous solution; they were expected to write a correct expression for the equilibrium constant and to use the equilibrium-constant expression and its value to determine [H 3 O + ] in a solution of known concentration. The remainder of the problem challenged students first to perform stoichiometric calculations to determine the number of moles or the concentration of species present when solutions of a weak acid and a strong base are combined. The final part of the question asked them to demonstrate mastery of the concept of buffered solutions by determining the ph of the resulting solution. How well did students perform on this question? Students did a good job answering this question, earning a mean score of 4.48 out of a possible 9 points. The distribution of scores was quite uneven, possibly due to interdependence among parts of the question, but the large percentage of scores of 8 and 9 indicated that many of the students had mastered the concepts. Even with the peaks and valleys of the score distribution, there was little clustering of scores and the entire range was utilized. Students were generally successful on parts (a) and (b), and responses that earned 1 to 3 points usually garnered them here. Parts (c), (d), and (e) offered more challenges. Students who were able to shift gears and recognize that parts (c) and (d) were fundamental stoichiometry problems were quite successful; however, many students continued to apply equilibrium concepts and equations to these parts and

8 consequently did not earn most of the available points. Similarly, students who recognized the solution as a buffer were generally able to earn at least 1 point, and often 2 points, on part (e); however, this was a minority of the exam-takers. What were common student errors or omissions? Part (a): This part was most frequently correct, and students who earned 1 point usually wrote a correct equilibrium-constant expression. Common errors included omitting charges in the equilibrium-constant expression and including the solvent in the equilibrium-constant expression. Part (b): This part was also answered correctly quite frequently. Common errors included failing to recognize that [H 3 O + ] eq = [F ] eq in this solution, incorrectly assuming that [F ] = [HF], or substituting an incorrect value for the initial [F ]. Many students did not make the justified approximation that Δ[HF] << initial [HF], and a number of them tried unsuccessfully to solve a quadratic equation (frequently using the quadratic formula!). Many students failed to round the final answer appropriately. Parts (c) and (d): Four points were available for parts (c) and (d), and these parts were tied together. Many students combined their work on these parts of the question. Common errors included incorrectly attempting to apply principles of equilibrium and equilibrium calculations, and failing to understand the distinctions among the amount of substance initially present, the amount that reacts, and the amount that remains. Many students did not answer the questions that had been asked; they often gave a concentration rather than the number of moles of HF in part (c), or the number of moles of F rather than the concentration in part (d). Many students did not make the distinction between L and ml, and some made simple arithmetic errors (e.g., 25 ml + 15 ml = 35 ml). Part (e): This was the most challenging part for students to answer correctly. A common error was failing to recognize that both a weak acid and its conjugate base are present in the solution. Students also had trouble determining the ph of a weak acid or a weak base. Many students treated the solution as either a strong acid or a strong base and attempted to calculate the ph as the log 10 of the concentration of some species present. Many students substituted incorrect concentrations into the equilibrium-constant expression or the Henderson-Hasselbalch equation. Based on your experience of student responses at the AP Reading, what message would you like to send to teachers that might help them to improve the performance of their students on the exam? Continue to stress fundamental stoichiometry and the distinctions among initial amounts (or concentrations), reacting amounts, and final or equilibrium amounts. Be sure to address the distinctions among number of moles, volume, and concentration, and the relationships among them; students need to understand which one is asked for in the question. Work to ensure that students can recognize the qualitative aspects of a problem before attempting to apply equations. Deemphasize overly complex numerical calculations. Students are often unable to solve quadratic equations correctly in a test setting, and justifiable approximations will generally obviate the need to solve quadratic equations on the examination. 2