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AP® Chemistry
                                       2009 Scoring Guidelines
                                               Form B




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AP® CHEMISTRY
                           2009 SCORING GUIDELINES (Form B)

                                           Question 1 (10 points)

A pure 14.85 g sample of the weak base ethylamine, C2H5NH2 , is dissolved in enough distilled water to make
500. mL of solution.

(a) Calculate the molar concentration of the C2H5NH2 in the solution.

                                            1 mol C2 H 5 NH 2
       nC2H5NH2 = 14.85 g C2H5NH2 ¥                                            One point is earned for the
                                           45.09 g C2 H 5 NH 2
                                                                               correct number of moles.
                 = 0.3293 mol C2H5NH2
                    0.3293 mol C2 H 5 NH 2                                     One point is earned for the
       MC2H5NH2 =                          = 0.659 M                             correct concentration.
                           0.500 L


The aqueous ethylamine reacts with water according to the equation below.
                                                  →
                             C2H5NH2(aq) + H2O(l) ← C2H5NH3+(aq) + OH−(aq)

(b) Write the equilibrium-constant expression for the reaction between C2H5NH2(aq) and water.

                       [C2 H 5 NH3+ ][OH - ]
                Kb =                                          One point is earned for the correct expression.
                           [C2 H 5 NH 2 ]



(c) Of C2H5NH2(aq) and C2H5NH3+(aq), which is present in the solution at the higher concentration at
    equilibrium? Justify your answer.

      C2H5NH2 is present in the solution at the higher concentration at
      equilibrium. Ethylamine is a weak base, and thus it has a small               One point is earned for the
      Kb value. Therefore only partial dissociation of C2H5NH2 occurs in         correct answer with justification.
      water, and [C2H5NH3+] is thus less than [C2H5NH2].




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AP® CHEMISTRY
                                  2009 SCORING GUIDELINES (Form B)

                                                 Question 1 (continued)

(d) A different solution is made by mixing 500. mL of 0.500 M C2H5NH2 with 500. mL of 0.200 M HCl.
    Assume that volumes are additive. The pH of the resulting solution is found to be 10.93.

   (i)     Calculate the concentration of OH−(aq) in the solution.

         pH = −log[H+]
         [H+] = 10−10.93 = 1.17 × 10−11
                     Kw           1.00 ¥ 10 -14
         [OH−] =              =                 = 8.5 × 10−4 M
                    [H + ]        1.17 ¥ 10 -11
                                                                                     One point is earned for
         OR                                                                         the correct concentration.

         pOH = 14 − pH = 14 − 10.93 = 3.07
         pOH = −log[OH −]
         [OH−] = 10−3.07 = 8.5 × 10−4 M


   (ii) Write the net-ionic equation that represents the reaction that occurs when the C2H5NH2 solution is
        mixed with the HCl solution.

           C2H5NH2 + H3O+ → C2H5NH3+ + H2O                             One point is earned for the correct equation.



   (iii) Calculate the molar concentration of the C2H5NH3+(aq) that is formed in the reaction.

                                                  0.500 mol
         moles of C2H5NH2 = 0.500 L ×                       = 0.250 mol                   One point is earned for the
                                                    1.00 L
                                                                                          correct number of moles of
         moles of H3O+ = 0.500 L ×
                                            0.200 mol
                                                      = 0.100 mol                            C2H5NH2 and H3O+.
                                              1.00 L

                                  [C2H5NH2]       [H3O+]          [C2H5NH3+]
              initial value         0.250          0.100              ~0
                    change         −0.100         −0.100            +0.100
               final value          0.150           ~0                0.100
                                                                                              One point is earned
                    + 0.100 mol C2 H 5 NH3 +                                             for the correct concentration.
         [C2H5NH3 ] =                        = 0.100 M
                             1.00 L




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AP® CHEMISTRY
                      2009 SCORING GUIDELINES (Form B)

                                     Question 1 (continued)

(iv) Calculate the value of Kb for C2H5NH2 .

                                                                                One point is earned for the
               0.150 mol C2 H 5 NH 2                                             correct calculation of the
   [C2H5NH2] =                       = 0.150 M
                     1.00 L                                                     molarity of C2H5NH2 after
                                                                                      neutralization.

        [C2 H 5 NH3+ ][OH - ]   (0.100)(8.5 ¥ 10 -4 )
   Kb =                       =                       = 5.67 × 10−4                   One point is earned
            [C2 H 5 NH 2 ]            0.150
                                                                                     for the correct value.




                                 © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                               2009 SCORING GUIDELINES (Form B)

                                             Question 2 (8 points)
                                                         +
                                       S2O32–(aq) ææÆ SO32– (aq) + S(s)
                                                   H
                                                     æ

A student performed an experiment to investigate the decomposition of sodium thiosulfate, Na2S2O3 , in acidic
solution, as represented by the equation above. In each trial the student mixed a different concentration of sodium
thiosulfate with hydrochloric acid at constant temperature and determined the rate of disappearance of
S2O32−(aq). Data from five trials are given below in the table on the left and are plotted in the graph on the right.




(a) Identify the independent variable in the experiment.

            The initial concentration of S2O32−(aq)                One point is earned for the correct answer.


(b) Determine the order of the reaction with respect to S2O32−. Justify your answer by using the information
    above.

       Using trials 1 and 2:

       rate 2   k2 [S2 O32 - ]m2                                                     One point is earned
              =
       rate1    k1[S2 O32 - ]m1                                                     for the correct order.

       0.030 M s -1       [0.075]m
                      =
       0.020 M s -1       [0.050]m

       1.5 = (1.5)m, so m = 1 and the reaction is first order                      One point is earned for
       with respect to S2O32−.                                                     a correct justification.

       Note: Other correct justifications are acceptable.



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AP® CHEMISTRY
                                2009 SCORING GUIDELINES (Form B)

                                                   Question 2 (continued)

(c) Determine the value of the rate constant, k , for the reaction. Include units in your answer. Show how you
    arrived at your answer.

                                               rate
       rate = k [S2O32−] ⇒            k =
                                            [S2 O32 - ]
                                                                                           One point is earned
                                                 0.020 M s -1
       Using the data from trial 1, k =                       = 0.40 s−1                  for the correct value.
                                                   0.050 M
       OR
                                                                                           One point is earned
       the rate constant is equal to the slope of the line                                 for the correct units.
               (0.052 - 0.020) M s -1   0.032 M s -1
       k =                            =              = 0.40 s−1
                  (0.13 - 0.05) M         0.08 M



(d) In another trial the student mixed 0.10 M Na2S2O3 with hydrochloric acid. Calculate the amount of time it
    would take for the concentration of S2O32− to drop to 0.020 M .

                                                 [A]t
       ln[A] t − ln[A]0 = − kt         ⇒    ln        = − kt
                                                 [A]0
                                                                                          One point is earned
                   2-                                                                    for the correct setup.
            [S2 O3 ]t
       ln                  = − kt
            [S2 O32 - ]0
                                                                                       One point is earned for
            0.020                                           -1.61
       ln         = (−0.40 s−1)( t )        ⇒    t =                 = 4.0 s        the correct answer with units.
            0.10                                          -0.40 s -1




(e) On the graph above, sketch the line that shows the results that would be expected if the student repeated the
    five trials at a temperature lower than that during the first set of trials.

      The line drawn should start on the y-axis at a lower
      point than the line already plotted and should have a                One point is earned for an acceptable line.
      less steep slope.




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AP® CHEMISTRY
                             2009 SCORING GUIDELINES (Form B)

                                             Question 3 (10 points)

                                           2 H2O2(aq) → 2 H2O(l) + O2(g)

The mass of an aqueous solution of H2O2 is 6.951 g. The H2O2 in the solution decomposes completely according
to the reaction represented above. The O2(g) produced is collected in an inverted graduated tube over water at
23.4°C and has a volume of 182.4 mL when the water levels inside and outside of the tube are the same. The
atmospheric pressure in the lab is 762.6 torr, and the equilibrium vapor pressure of water at 23.4°C is
21.6 torr.

(a) Calculate the partial pressure, in torr, of O2(g) in the gas-collection tube.

       Patm = PO2 + PH2O ⇒            PO2 = Patm − PH2O
                                                                    One point is earned for the correct answer.
        PO2 = 762.6 torr − 21.6 torr = 741.0 torr


(b) Calculate the number of moles of O2(g) produced in the reaction.

                                 PV
       PV = nRT       ⇒    n =
                                 RT
                             1 atm                                                            One point is earned for
       P = 741.0 torr ×              = 0.9750 atm
                            760 torr                                                         the correct substitutions.
       T = 273.15 + 23.4°C = 296.6 K
                              1L                                                                One point is earned
       V = 182.4 mL ×               = 0.1824 L
                           1,000 mL                                                           for the correct answer.
                PV         (0.9750 atm)(0.1824 L)
        nO2 =      =                                      = 7.304 × 10–3 mol
                RT   (0.0821 L atm mol -1 K -1 )(296.6 K)


(c) Calculate the mass, in grams, of H2O2 that decomposed.

                                                                                              One point is earned for
                                                                                             the conversion of mol O2
                                 2 mol H 2 O2   34.0 g H 2 O2                                      to mol H2O2.
     (7.304 × 10–3 mol O2) ×                  ×               = 0.497 g H2O2
                                  1 mol O2      1 mol H 2 O2
                                                                                                One point is earned
                                                                                               for the correct mass.


(d) Calculate the percent of H2O2 , by mass, in the original 6.951 g aqueous sample.

             0.497 g H 2 O2
                            × 100 = 7.15%                         One point is earned for the correct answer.
             6.951 g sample



                                         © 2009 The College Board. All rights reserved.
                                 Visit the College Board on the Web: www.collegeboard.com.
AP® CHEMISTRY
                            2009 SCORING GUIDELINES (Form B)

                                            Question 3 (continued)

(e) Write the oxidation number of the oxygen atoms in H2O2 and the oxidation number of the oxygen atoms in
    O2 in the appropriate cells in the table below.

                                                         Oxidation Number
                                         Substance
                                                         of Oxygen Atoms
                                            H2O2
                                             O2




      In H2O2 , the oxidation number of O is −1.                          Two points are earned for
                                                                        the correct oxidation numbers
      In  O2 , the oxidation number of  O  is   0.                              (1 point each).


   (f) Write the balanced oxidation half-reaction for the reaction.

                                                        One point is earned for the correct reactant and products.
        H2O2(aq) → O2(g) + 2 H+(aq) + 2 e−
                                                                 One point is earned for correct balancing.




                                       © 2009 The College Board. All rights reserved.
                               Visit the College Board on the Web: www.collegeboard.com.
AP® CHEMISTRY
                              2009 SCORING GUIDELINES (Form B)

                                            Question 4 (15 points)

(a) A barium nitrate solution and a potassium fluoride solution are combined and a precipitate forms.

     (i) Balanced equation:
                                                                 Two points are earned for the correct reactants
                                                                                (1 point each).
                   Ba2+ + 2 F − → BaF2
                                                                   One point is earned for the correct product.

                                                                   One point is earned for correctly balancing
                                                                       the equation for atoms and charge.



      (ii) If equimolar amounts of barium nitrate and potassium fluoride are combined, which reactant, if any, is
           the limiting reactant? Explain.

        According to the balanced chemical equation, twice as
        much potassium fluoride is required to completely react
        with the barium nitrate. Because there are equimolar
                                                                              One point is earned for a correct
        amounts of barium nitrate and potassium fluoride, there is
                                                                             answer that is consistent with part (i).
        not enough potassium fluoride to react with all of the
        barium nitrate, so potassium fluoride is the limiting
        reactant.



(b) A piece of cadmium metal is oxidized by adding it to a solution of copper(II) chloride.

      (i) Balanced equation:
                                                                 One point is earned for both correct reactants.
                   Cd + Cu2+ → Cd2+ + Cu
                                                                 One point is earned for both correct products.

                                                                   One point is earned for correctly balancing
                                                                      the equation for atoms and charge.



      (ii) List two visible changes that would occur in the reaction container as the reaction is proceeding.

        In the solution, the blue color of the copper(II)
        cation would decrease, and eventually the
        solution would become colorless.                         Two points are earned for correctly describing
        Reddish-brown (or black) copper metal would                        the changes (1 point each).
        plate out onto the piece of silvery cadmium
        metal.



                                       © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                              2009 SCORING GUIDELINES (Form B)

                                           Question 4 (continued)
(c) A hydrolysis reaction occurs when solid sodium sulfide is added to distilled water.

     (i) Balanced equation:                                      One point is earned for both correct reactants.

           Na2S + H2O → 2 Na+ + HS− + OH−                      One point is earned for any two correct products;
                                                               2 points are earned for all three correct products.
                              OR
         Na2S + 2 H2O → 2 Na+ + H2S + 2 OH−                        One point is earned for correctly balancing
                                                                      the equation for atoms and charge.


      (ii) Indicate whether the pH of the resulting solution is less than 7, equal to 7, or greater than 7. Explain.


        The pH of the resulting solution is greater than 7.              One point is earned for a correct
        The hydrolysis reaction of S2− produces the base                answer that is consistent with part (i).
        OH −, thus raising the pH above 7.




                                       © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                            2009 SCORING GUIDELINES (Form B)

                                             Question 5 (9 points)

Answer the following questions about nitrogen, hydrogen, and ammonia.

(a) In the boxes below, draw the complete Lewis electron-dot diagrams for N2 and NH3.




                The correct structures are                        Two points are earned for the correct
               shown in the boxes above.                        Lewis electron-dot diagrams (1 point each).


(b) Calculate the standard free-energy change, ΔG °, that occurs when 12.0 g of H2(g) reacts with excess
    N2(g) at 298 K according to the reaction represented below.
                                        →
                        N2(g) + 3 H2(g) ← 2 NH3(g)                    ΔG298 = −34 kJ mol−1

                                                                                            One point is earned for
                      1 mol H 2   1 mol reaction      -34 kJ                               the correct stoichiometry.
        12.0 g H2 ×             ×                ×                = – 68 kJ
                      2.0 g H 2     3 mol H 2      1 mol reaction
                                                                                            One point is earned for
                                                                                             the correct answer.


(c) Given that ΔH 298 for the reaction is −92.2 kJ mol−1, which is larger, the total bond dissociation energy
    of the reactants or the total bond dissociation energy of the products? Explain.


      ΔH 298 = Σ (bond energy of the reactants) − Σ (bond energy of the products)

      Based on the equation above, for ΔH 298 to be negative, the total bond
                                                                                              One point is earned
      energy of the products must be larger than the total bond energy of                    for the correct answer
      the reactants.                                                                        with the correct equation
      OR                                                                                        and explanation.
      More energy is released as product bonds are formed than is absorbed as
      reactant bonds are broken.


                                       © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                            2009 SCORING GUIDELINES (Form B)

                                           Question 5 (continued)
(d) The value of the standard entropy change, ΔS298 , for the reaction is −199 J mol−1K−1. Explain why the value
    of ΔS298 is negative.

      All of the reactants and products in the reaction are in the gas phase, so
      the sign of the entropy change will depend on the number of moles of
      particles in the reactants and products. There are more moles of reactants
                                                                                           One point is earned for
      (four) compared with moles of products (two), so there is a greater
                                                                                           the correct explanation.
      number of microstates in the reactants than in the products. Therefore the
      entropy decreases as the reaction proceeds (fewer possible microstates),
      and the sign of the entropy change is negative.



(e) Assume that ΔH ° and ΔS ° for the reaction are independent of temperature.
    (i) Explain why there is a temperature above 298 K at which the algebraic sign of the value of ΔG ° changes.

      ΔG° = ΔH° − TΔS°
      As the temperature increases |TΔS°| will at some point
      exceed |∆H°|. Because both ΔH° and ΔS° are                   One point is earned for the correct explanation.
      negative, the sign of ΔG° will then change from
      negative to positive.


    (ii) Theoretically, the best yields of ammonia should be achieved at low temperatures and high pressures.
         Explain.

      Low temperatures: The reaction is exothermic. By Le Chatelier’s
      principle, decreasing the temperature drives the reaction to the
      right to produce more heat energy, and thus more ammonia is               One point is earned for explaining
      produced.                                                                increased yield at low temperatures.
      High pressures: For this reaction, higher pressure is achieved by
      decreasing the volume of the container. As pressure increases, the
      reaction equilibrium shifts in the direction that reduces the total
      number of particles (by Le Chatelier’s principle). In this case, the      One point is earned for explaining
      product has fewer moles of particles than the reactants; thus             increased yield at high pressures.
      product would be favored. Higher pressure therefore results in an
      increase in the amount of ammonia.




                                       © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                             2009 SCORING GUIDELINES (Form B)

                                             Question 6 (9 points)

Answer the following questions about electrochemical cells.




It is observed that when silver metal is placed in aqueous thallium(I) fluoride, TlF, no reaction occurs. When the
switch is closed in the cell represented above, the voltage reading is +1.14 V.

(a) Write the reduction half-reaction that occurs in the cell.

                      Ag+ + e− → Ag                               One point is earned for the correct equation.



(b) Write the equation for the overall reaction that occurs in the cell.

                  Tl + Ag+ → Tl+ + Ag                             One point is earned for the correct equation.



(c) Identify the anode in the cell. Justify your answer.

       The anode is where oxidation occurs. In the overall reaction Tl is             One point is earned for the
       oxidized to Tl+, so the anode is the Tl electrode in the left cell.         correct answer with justification.



(d) On the diagram above, use an arrow to clearly indicate the direction of electron flow as the cell operates.

       The arrow should show electron flow in the direction from the Tl                     One point is earned
       electrode through the wire to the Ag electrode.                                      for a correct arrow.




                                        © 2009 The College Board. All rights reserved.
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AP® CHEMISTRY
                            2009 SCORING GUIDELINES (Form B)

                                           Question 6 (continued)

(e) Calculate the value of the standard reduction potential for the Tl+/Tl half-reaction.


              Ecell = Ered − Eox
                                                                One point is earned for the correct setup.
              +1.14 V = +0.80V − Eox
                                                               One point is earned for the correct answer.
              Eox = −0.34 V


The standard reduction potential, E° , of the reaction Pt2+ + 2 e− → Pt is 1.20 V.

(f) Assume that electrodes of pure Pt, Ag, and Ni are available as well as 1.00 M solutions of their salts. Three
    different electrochemical cells can be constructed using these materials. Identify the two metals that when
    used to make an electrochemical cell would produce the cell with the largest voltage. Explain how you arrived
    at your answer.


                                         E°(V)
              Ni2+ + 2 e− → Ni          −0.25
              Ag+ + e−       → Ag        0.80
              Pt2+ + 2 e− →      Pt      1.20

                     Ecell = Ered − Eox                                    One point is earned for the
                                                                        correct answer with justification.
        The two metals that yield the largest Ecell
        are those with the biggest difference in E°,
        namely, Pt and Ni (see Ecell calculation
        below).
             Ecell = +1.20 − (−0.25) = +1.45 V



(g) Predict whether Pt metal will react when it is placed in 1.00 M AgNO3(aq). Justify your answer.


       When Pt metal is added to 1.00 M AgNO3 , the only redox
       reaction that could occur would be for Pt to become oxidized                   One point is earned
       as Ag+ is reduced.                                                          for comparing E° values.
       Ecell = Ered − Eox = +0.80 V − (+1.20 V) = −0.40 V                           One point is earned for
       Because Ecell for that reaction is negative, no reaction will               the correct interpretation.
       occur.




                                       © 2009 The College Board. All rights reserved.
                               Visit the College Board on the Web: www.collegeboard.com.

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Chemistry AP Scoring Guidelines from B 2009

  • 1. AP® Chemistry 2009 Scoring Guidelines Form B The College Board The College Board is a not-for-profit membership association whose mission is to connect students to college success and opportunity. Founded in 1900, the association is composed of more than 5,600 schools, colleges, universities and other educational organizations. Each year, the College Board serves seven million students and their parents, 23,000 high schools and 3,800 colleges through major programs and services in college readiness, college admissions, guidance, assessment, financial aid, enrollment, and teaching and learning. Among its best-known programs are the SAT®, the PSAT/NMSQT® and the Advanced Placement Program® (AP®). The College Board is committed to the principles of excellence and equity, and that commitment is embodied in all of its programs, services, activities and concerns. © 2009 The College Board. College Board, Advanced Placement Program, AP, AP Central, SAT, and the acorn logo are registered trademarks of the College Board. PSAT/NMSQT is a registered trademark of the College Board and National Merit Scholarship Corporation. Permission to use copyrighted College Board materials may be requested online at: www.collegeboard.com/inquiry/cbpermit.html. Visit the College Board on the Web: www.collegeboard.com. AP Central® is the official online home for AP teachers: apcentral.collegeboard.com.
  • 2. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 1 (10 points) A pure 14.85 g sample of the weak base ethylamine, C2H5NH2 , is dissolved in enough distilled water to make 500. mL of solution. (a) Calculate the molar concentration of the C2H5NH2 in the solution. 1 mol C2 H 5 NH 2 nC2H5NH2 = 14.85 g C2H5NH2 ¥ One point is earned for the 45.09 g C2 H 5 NH 2 correct number of moles. = 0.3293 mol C2H5NH2 0.3293 mol C2 H 5 NH 2 One point is earned for the MC2H5NH2 = = 0.659 M correct concentration. 0.500 L The aqueous ethylamine reacts with water according to the equation below. → C2H5NH2(aq) + H2O(l) ← C2H5NH3+(aq) + OH−(aq) (b) Write the equilibrium-constant expression for the reaction between C2H5NH2(aq) and water. [C2 H 5 NH3+ ][OH - ] Kb = One point is earned for the correct expression. [C2 H 5 NH 2 ] (c) Of C2H5NH2(aq) and C2H5NH3+(aq), which is present in the solution at the higher concentration at equilibrium? Justify your answer. C2H5NH2 is present in the solution at the higher concentration at equilibrium. Ethylamine is a weak base, and thus it has a small One point is earned for the Kb value. Therefore only partial dissociation of C2H5NH2 occurs in correct answer with justification. water, and [C2H5NH3+] is thus less than [C2H5NH2]. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 3. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 1 (continued) (d) A different solution is made by mixing 500. mL of 0.500 M C2H5NH2 with 500. mL of 0.200 M HCl. Assume that volumes are additive. The pH of the resulting solution is found to be 10.93. (i) Calculate the concentration of OH−(aq) in the solution. pH = −log[H+] [H+] = 10−10.93 = 1.17 × 10−11 Kw 1.00 ¥ 10 -14 [OH−] = = = 8.5 × 10−4 M [H + ] 1.17 ¥ 10 -11 One point is earned for OR the correct concentration. pOH = 14 − pH = 14 − 10.93 = 3.07 pOH = −log[OH −] [OH−] = 10−3.07 = 8.5 × 10−4 M (ii) Write the net-ionic equation that represents the reaction that occurs when the C2H5NH2 solution is mixed with the HCl solution. C2H5NH2 + H3O+ → C2H5NH3+ + H2O One point is earned for the correct equation. (iii) Calculate the molar concentration of the C2H5NH3+(aq) that is formed in the reaction. 0.500 mol moles of C2H5NH2 = 0.500 L × = 0.250 mol One point is earned for the 1.00 L correct number of moles of moles of H3O+ = 0.500 L × 0.200 mol = 0.100 mol C2H5NH2 and H3O+. 1.00 L [C2H5NH2] [H3O+] [C2H5NH3+] initial value 0.250 0.100 ~0 change −0.100 −0.100 +0.100 final value 0.150 ~0 0.100 One point is earned + 0.100 mol C2 H 5 NH3 + for the correct concentration. [C2H5NH3 ] = = 0.100 M 1.00 L © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 4. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 1 (continued) (iv) Calculate the value of Kb for C2H5NH2 . One point is earned for the 0.150 mol C2 H 5 NH 2 correct calculation of the [C2H5NH2] = = 0.150 M 1.00 L molarity of C2H5NH2 after neutralization. [C2 H 5 NH3+ ][OH - ] (0.100)(8.5 ¥ 10 -4 ) Kb = = = 5.67 × 10−4 One point is earned [C2 H 5 NH 2 ] 0.150 for the correct value. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 5. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 2 (8 points) + S2O32–(aq) ææÆ SO32– (aq) + S(s) H æ A student performed an experiment to investigate the decomposition of sodium thiosulfate, Na2S2O3 , in acidic solution, as represented by the equation above. In each trial the student mixed a different concentration of sodium thiosulfate with hydrochloric acid at constant temperature and determined the rate of disappearance of S2O32−(aq). Data from five trials are given below in the table on the left and are plotted in the graph on the right. (a) Identify the independent variable in the experiment. The initial concentration of S2O32−(aq) One point is earned for the correct answer. (b) Determine the order of the reaction with respect to S2O32−. Justify your answer by using the information above. Using trials 1 and 2: rate 2 k2 [S2 O32 - ]m2 One point is earned = rate1 k1[S2 O32 - ]m1 for the correct order. 0.030 M s -1 [0.075]m = 0.020 M s -1 [0.050]m 1.5 = (1.5)m, so m = 1 and the reaction is first order One point is earned for with respect to S2O32−. a correct justification. Note: Other correct justifications are acceptable. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 6. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 2 (continued) (c) Determine the value of the rate constant, k , for the reaction. Include units in your answer. Show how you arrived at your answer. rate rate = k [S2O32−] ⇒ k = [S2 O32 - ] One point is earned 0.020 M s -1 Using the data from trial 1, k = = 0.40 s−1 for the correct value. 0.050 M OR One point is earned the rate constant is equal to the slope of the line for the correct units. (0.052 - 0.020) M s -1 0.032 M s -1 k = = = 0.40 s−1 (0.13 - 0.05) M 0.08 M (d) In another trial the student mixed 0.10 M Na2S2O3 with hydrochloric acid. Calculate the amount of time it would take for the concentration of S2O32− to drop to 0.020 M . [A]t ln[A] t − ln[A]0 = − kt ⇒ ln = − kt [A]0 One point is earned 2- for the correct setup. [S2 O3 ]t ln = − kt [S2 O32 - ]0 One point is earned for 0.020 -1.61 ln = (−0.40 s−1)( t ) ⇒ t = = 4.0 s the correct answer with units. 0.10 -0.40 s -1 (e) On the graph above, sketch the line that shows the results that would be expected if the student repeated the five trials at a temperature lower than that during the first set of trials. The line drawn should start on the y-axis at a lower point than the line already plotted and should have a One point is earned for an acceptable line. less steep slope. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 7. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 3 (10 points) 2 H2O2(aq) → 2 H2O(l) + O2(g) The mass of an aqueous solution of H2O2 is 6.951 g. The H2O2 in the solution decomposes completely according to the reaction represented above. The O2(g) produced is collected in an inverted graduated tube over water at 23.4°C and has a volume of 182.4 mL when the water levels inside and outside of the tube are the same. The atmospheric pressure in the lab is 762.6 torr, and the equilibrium vapor pressure of water at 23.4°C is 21.6 torr. (a) Calculate the partial pressure, in torr, of O2(g) in the gas-collection tube. Patm = PO2 + PH2O ⇒ PO2 = Patm − PH2O One point is earned for the correct answer. PO2 = 762.6 torr − 21.6 torr = 741.0 torr (b) Calculate the number of moles of O2(g) produced in the reaction. PV PV = nRT ⇒ n = RT 1 atm One point is earned for P = 741.0 torr × = 0.9750 atm 760 torr the correct substitutions. T = 273.15 + 23.4°C = 296.6 K 1L One point is earned V = 182.4 mL × = 0.1824 L 1,000 mL for the correct answer. PV (0.9750 atm)(0.1824 L) nO2 = = = 7.304 × 10–3 mol RT (0.0821 L atm mol -1 K -1 )(296.6 K) (c) Calculate the mass, in grams, of H2O2 that decomposed. One point is earned for the conversion of mol O2 2 mol H 2 O2 34.0 g H 2 O2 to mol H2O2. (7.304 × 10–3 mol O2) × × = 0.497 g H2O2 1 mol O2 1 mol H 2 O2 One point is earned for the correct mass. (d) Calculate the percent of H2O2 , by mass, in the original 6.951 g aqueous sample. 0.497 g H 2 O2 × 100 = 7.15% One point is earned for the correct answer. 6.951 g sample © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 8. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 3 (continued) (e) Write the oxidation number of the oxygen atoms in H2O2 and the oxidation number of the oxygen atoms in O2 in the appropriate cells in the table below. Oxidation Number Substance of Oxygen Atoms H2O2 O2 In H2O2 , the oxidation number of O is −1. Two points are earned for the correct oxidation numbers In  O2 , the oxidation number of  O  is   0. (1 point each). (f) Write the balanced oxidation half-reaction for the reaction. One point is earned for the correct reactant and products. H2O2(aq) → O2(g) + 2 H+(aq) + 2 e− One point is earned for correct balancing. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 9. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 4 (15 points) (a) A barium nitrate solution and a potassium fluoride solution are combined and a precipitate forms. (i) Balanced equation: Two points are earned for the correct reactants (1 point each). Ba2+ + 2 F − → BaF2 One point is earned for the correct product. One point is earned for correctly balancing the equation for atoms and charge. (ii) If equimolar amounts of barium nitrate and potassium fluoride are combined, which reactant, if any, is the limiting reactant? Explain. According to the balanced chemical equation, twice as much potassium fluoride is required to completely react with the barium nitrate. Because there are equimolar One point is earned for a correct amounts of barium nitrate and potassium fluoride, there is answer that is consistent with part (i). not enough potassium fluoride to react with all of the barium nitrate, so potassium fluoride is the limiting reactant. (b) A piece of cadmium metal is oxidized by adding it to a solution of copper(II) chloride. (i) Balanced equation: One point is earned for both correct reactants. Cd + Cu2+ → Cd2+ + Cu One point is earned for both correct products. One point is earned for correctly balancing the equation for atoms and charge. (ii) List two visible changes that would occur in the reaction container as the reaction is proceeding. In the solution, the blue color of the copper(II) cation would decrease, and eventually the solution would become colorless. Two points are earned for correctly describing Reddish-brown (or black) copper metal would the changes (1 point each). plate out onto the piece of silvery cadmium metal. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 10. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 4 (continued) (c) A hydrolysis reaction occurs when solid sodium sulfide is added to distilled water. (i) Balanced equation: One point is earned for both correct reactants. Na2S + H2O → 2 Na+ + HS− + OH− One point is earned for any two correct products; 2 points are earned for all three correct products. OR Na2S + 2 H2O → 2 Na+ + H2S + 2 OH− One point is earned for correctly balancing the equation for atoms and charge. (ii) Indicate whether the pH of the resulting solution is less than 7, equal to 7, or greater than 7. Explain. The pH of the resulting solution is greater than 7. One point is earned for a correct The hydrolysis reaction of S2− produces the base answer that is consistent with part (i). OH −, thus raising the pH above 7. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 11. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 5 (9 points) Answer the following questions about nitrogen, hydrogen, and ammonia. (a) In the boxes below, draw the complete Lewis electron-dot diagrams for N2 and NH3. The correct structures are Two points are earned for the correct shown in the boxes above. Lewis electron-dot diagrams (1 point each). (b) Calculate the standard free-energy change, ΔG °, that occurs when 12.0 g of H2(g) reacts with excess N2(g) at 298 K according to the reaction represented below. → N2(g) + 3 H2(g) ← 2 NH3(g) ΔG298 = −34 kJ mol−1 One point is earned for 1 mol H 2 1 mol reaction -34 kJ the correct stoichiometry. 12.0 g H2 × × × = – 68 kJ 2.0 g H 2 3 mol H 2 1 mol reaction One point is earned for the correct answer. (c) Given that ΔH 298 for the reaction is −92.2 kJ mol−1, which is larger, the total bond dissociation energy of the reactants or the total bond dissociation energy of the products? Explain. ΔH 298 = Σ (bond energy of the reactants) − Σ (bond energy of the products) Based on the equation above, for ΔH 298 to be negative, the total bond One point is earned energy of the products must be larger than the total bond energy of for the correct answer the reactants. with the correct equation OR and explanation. More energy is released as product bonds are formed than is absorbed as reactant bonds are broken. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 12. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 5 (continued) (d) The value of the standard entropy change, ΔS298 , for the reaction is −199 J mol−1K−1. Explain why the value of ΔS298 is negative. All of the reactants and products in the reaction are in the gas phase, so the sign of the entropy change will depend on the number of moles of particles in the reactants and products. There are more moles of reactants One point is earned for (four) compared with moles of products (two), so there is a greater the correct explanation. number of microstates in the reactants than in the products. Therefore the entropy decreases as the reaction proceeds (fewer possible microstates), and the sign of the entropy change is negative. (e) Assume that ΔH ° and ΔS ° for the reaction are independent of temperature. (i) Explain why there is a temperature above 298 K at which the algebraic sign of the value of ΔG ° changes. ΔG° = ΔH° − TΔS° As the temperature increases |TΔS°| will at some point exceed |∆H°|. Because both ΔH° and ΔS° are One point is earned for the correct explanation. negative, the sign of ΔG° will then change from negative to positive. (ii) Theoretically, the best yields of ammonia should be achieved at low temperatures and high pressures. Explain. Low temperatures: The reaction is exothermic. By Le Chatelier’s principle, decreasing the temperature drives the reaction to the right to produce more heat energy, and thus more ammonia is One point is earned for explaining produced. increased yield at low temperatures. High pressures: For this reaction, higher pressure is achieved by decreasing the volume of the container. As pressure increases, the reaction equilibrium shifts in the direction that reduces the total number of particles (by Le Chatelier’s principle). In this case, the One point is earned for explaining product has fewer moles of particles than the reactants; thus increased yield at high pressures. product would be favored. Higher pressure therefore results in an increase in the amount of ammonia. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 13. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 6 (9 points) Answer the following questions about electrochemical cells. It is observed that when silver metal is placed in aqueous thallium(I) fluoride, TlF, no reaction occurs. When the switch is closed in the cell represented above, the voltage reading is +1.14 V. (a) Write the reduction half-reaction that occurs in the cell. Ag+ + e− → Ag One point is earned for the correct equation. (b) Write the equation for the overall reaction that occurs in the cell. Tl + Ag+ → Tl+ + Ag One point is earned for the correct equation. (c) Identify the anode in the cell. Justify your answer. The anode is where oxidation occurs. In the overall reaction Tl is One point is earned for the oxidized to Tl+, so the anode is the Tl electrode in the left cell. correct answer with justification. (d) On the diagram above, use an arrow to clearly indicate the direction of electron flow as the cell operates. The arrow should show electron flow in the direction from the Tl One point is earned electrode through the wire to the Ag electrode. for a correct arrow. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.
  • 14. AP® CHEMISTRY 2009 SCORING GUIDELINES (Form B) Question 6 (continued) (e) Calculate the value of the standard reduction potential for the Tl+/Tl half-reaction. Ecell = Ered − Eox One point is earned for the correct setup. +1.14 V = +0.80V − Eox One point is earned for the correct answer. Eox = −0.34 V The standard reduction potential, E° , of the reaction Pt2+ + 2 e− → Pt is 1.20 V. (f) Assume that electrodes of pure Pt, Ag, and Ni are available as well as 1.00 M solutions of their salts. Three different electrochemical cells can be constructed using these materials. Identify the two metals that when used to make an electrochemical cell would produce the cell with the largest voltage. Explain how you arrived at your answer. E°(V) Ni2+ + 2 e− → Ni −0.25 Ag+ + e− → Ag 0.80 Pt2+ + 2 e− → Pt 1.20 Ecell = Ered − Eox One point is earned for the correct answer with justification. The two metals that yield the largest Ecell are those with the biggest difference in E°, namely, Pt and Ni (see Ecell calculation below). Ecell = +1.20 − (−0.25) = +1.45 V (g) Predict whether Pt metal will react when it is placed in 1.00 M AgNO3(aq). Justify your answer. When Pt metal is added to 1.00 M AgNO3 , the only redox reaction that could occur would be for Pt to become oxidized One point is earned as Ag+ is reduced. for comparing E° values. Ecell = Ered − Eox = +0.80 V − (+1.20 V) = −0.40 V One point is earned for Because Ecell for that reaction is negative, no reaction will the correct interpretation. occur. © 2009 The College Board. All rights reserved. Visit the College Board on the Web: www.collegeboard.com.