AP Chemistry 2011 Free-Response Questions

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INFORMATION IN THE TABLE BELOW AND IN THE TABLES ON PAGES 3-5 MAY BE USEFUL IN ANSWERING THE QUESTIONS IN THIS SECTION OF THE EXAMINATION.

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STANDARD REDUCTION POTENTIALS IN AQUEOUS SOLUTION AT 25C Half-reaction

F2 ( g) + 2 e
Co
3+
3+

E (V)
2F Co
2+

+e

Au

+ 3e

Au(s) 2 Cl 2 H 2 O(l ) 2 Br Hg22+ Hg(l ) Ag(s) 2 Hg(l ) Fe 2+ 2 ICu(s) Cu(s) Cu+ Sn 2+ H 2S(g ) H2 (g) Pb(s) Sn(s) Ni(s) Co(s) Cd(s) Cr 2+ Fe(s) Cr(s) Zn(s) H 2 ( g ) + 2 OH Mn(s) Al(s) Be(s) Mg(s) Na(s) Ca(s) Sr(s)

Cl2 (g ) + 2 e Br2 (l ) + 2 e

O2 (g) + 4 H + + 4 e -

2 Hg2+ + 2 e Hg2+ + 2 e Ag + e
+ -

Hg2 Fe

2+

+ 2e
-

3+

+e

Cu+ + e Cu Cu
2+ 2+

I 2 (s) + 2 e + 2e +e
-

Sn 4+ + 2 e S(s) + 2 H + + 2 e 2H + 2e
+ -

Pb Sn Ni

2+ 2+

+ 2e + 2e + 2e

2+ 2+ 2+

Co Cd Cr Cr

+ 2e + 2e +e
-

3+

Fe 2+ + 2 e 3+ 2+

+ 3e

Zn

+ 2e

2 H 2 O(l ) + 2 e Mn 2+ + 2 e Al
3+ 2+

+ 3e

Be

+ 2e
-

Mg Ca Sr Ba

2+

+ 2e

Na + e
+ 2+ 2+

+ 2e + 2e
-

2+ +

+ 2e
-

Ba(s) Rb(s) K(s) Cs(s) Li(s)

Rb + e K +e
+ +

Cs + e Li + e
+

2.87 1.82 1.50 1.36 1.23 1.07 0.92 0.85 0.80 0.79 0.77 0.53 0.52 0.34 0.15 0.15 0.14 0.00 0.13 0.14 0.25 0.28 0.40 0.41 0.44 0.74 0.76 0.83 1.18 1.66 1.70 2.37 2.71 2.87 2.89 2.90 2.92 2.92 2.92 3.05

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ADVANCED PLACEMENT CHEMISTRY EQUATIONS AND CONSTANTS ATOMIC STRUCTURE

E = hv c = lv h l= p = mu mu -2.178 10 -18 En = joule n2 E v l p = = = = energy frequency wavelength momentum u = velocity n = principal quantum number m = mass

Speed of light, c = 3.0 108 m s-1 Plancks constant, h = 6.63 10 -34 J s Boltzmanns constant, k = 1.38 10 -23 J K -1 Avogadros number = 6.022 1023 mol -1 Electron charge, e = -1.602 10 -19 coulomb 1 electron volt per atom = 96.5 kJ mol -1

EQUILIBRIUM [H + ][A - ] Ka = [HA] [OH - ][HB+ ] Kb = [B] K w = [OH ][H + ] = 1.0 10 -14 @ 25C = K a Kb
pH = - log [H + ], pOH = - log[OH - ] 14 = pH + pOH pH = pK a + log pOH = pK b + log [A - ] [HA]

Equilibrium Constants K a (weak acid) K b (weak base) K w (water) K p (gas pressure) K c (molar concentrations)
S = standard entropy H = standard enthalpy G = standard free energy E T n m q c Cp = = = = = = = standard reduction potential temperature moles mass heat specific heat capacity molar heat capacity at constant pressure

[HB+ ] [B] pK a = - log K a , pK b = - log K b K p = K c ( RT )

Dn

where D n = moles product gas - moles reactant gas

THERMOCHEMISTRY/KINETICS

S products - S reactants DH = DHf products - DH f reactants

DS = DG =

DGf products - DGf reactants

DG = DH - T D S = - RT ln K = -2.303 RT log K
= -n E

DG = DG + RT ln Q = DG + 2.303 RT log Q q = mcDT DH Cp = DT

ln [A ] t - ln [A]0 = - kt 1 1 = kt [A] t [A]0 ln k = - Ea 1 + ln A R T

Ea = activation energy k = rate constant A = frequency factor Faradays constant, = 96,500 coulombs per mole of electrons Gas constant, R = 8.31 J mol -1 K -1 = 0.0821 L atm mol -1 K -1 = 62.4 L torr mol -1 K -1 = 8.31 volt coulomb mol -1 K -1

()

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GASES, LIQUIDS, AND SOLUTIONS

PV = nRT
n2 a P + 2 (V - nb) = nRT V PA = Ptotal X A , where X A =

Ptotal = PA + PB + PC + ... m n= M

moles A total moles

P V T n D m u

= = = = = = =
= = = = = = = = = = = = = = = =

pressure volume temperature number of moles density mass velocity

K = C + 273 PV PV 1 1 = 2 2 T1 T2 m D= V 3kT 3RT urms = = M m 1 2 KE per molecule = mu 2 3 KE per mole = RT 2 M2 r1 = M1 r2 molarity, M = moles solute per liter solution molality = moles solute per kilogram solvent DT f = iK f molality DTb = iK b molality p = iMRT A = abc

urms KE r M p i Kf Kb A a b c Q I q t

root-mean-square speed kinetic energy rate of effusion molar mass osmotic pressure vant Hoff factor molal freezing-point depression constant molal boiling-point elevation constant absorbance molar absorptivity path length concentration reaction quotient current (amperes) charge (coulombs) time (seconds)

E = standard reduction potential K = equilibrium constant

OXIDATION-REDUCTION; ELECTROCHEMISTRY

Gas constant, R = 8.31 J mol -1 K -1 = 0.0821 L atm mol -1 K -1 = 62.4 L torr mol -1 K -1 = 8.31 volt coulomb mol -1 K -1 Boltzmanns constant, k = 1.38 10 -23 J K -1 K f for H 2 O = 1.86 K kg mol -1 K b for H 2 O = 0.512 K kg mol -1 1 atm = 760 mm Hg = 760 torr STP = 0.00 C and 1.0 atm Faradays constant, = 96,500 coulombs per mole of electrons

Q= I =

[C] c [D] d [A] [B] q t

a b

, where a A + b B c C + d D

Ecell = Ecell

RT - 0.0592 log Q @ 25 C ln Q = Ecell n n

log K =

nE 0.0592

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS CHEMISTRY

Section II (Total time95 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.

1. Each of three beakers contains 25.0 mL of a 0.100 M solution of HCl, NH3 , or NH4Cl, as shown above. Each solution is at 25C. (a) Determine the pH of the solution in beaker 1. Justify your answer.

NH +(aq) + OH (aq) occurs. The value of K for (b) In beaker 2, the reaction NH3(aq) + H2O(l) 4 b 5 NH3(aq) is 1.8 10 at 25C.
(i) Write the Kb expression for the reaction of NH3(aq) with H2O(l). (ii) Calculate the [OH -] in the solution in beaker 2.

NH (aq) + H O+(aq) occurs. (c) In beaker 3, the reaction NH4+(aq) + H2O(l) 3 3

(i) Calculate the value of Ka for NH4+(aq) at 25C. (ii) The contents of beaker 2 are poured into beaker 3 and the resulting solution is stirred. Assume that volumes are additive. Calculate the pH of the resulting solution. (d) The contents of beaker 1 are poured into the solution made in part (c)(ii). The resulting solution is stirred. Assume that volumes are additive. (i) Is the resulting solution an effective buffer? Justify your answer. (ii) Calculate the final [NH4+] in the resulting solution at 25C.

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS

2. A student is assigned the task of determining the mass percent of silver in an alloy of copper and silver by dissolving a sample of the alloy in excess nitric acid and then precipitating the silver as AgCl. First the student prepares 50. mL of 6 M HNO3 . (a) The student is provided with a stock solution of 16 M HNO3 , two 100 mL graduated cylinders that can be read to 1 mL, a 100 mL beaker that can be read to 10 mL, safety goggles, rubber gloves, a glass stirring rod, a dropper, and distilled H2O. (i) Calculate the volume, in mL, of 16 M HNO3 that the student should use for preparing 50. mL of 6 M HNO3 . (ii) Briefly list the steps of an appropriate and safe procedure for preparing the 50. mL of 6 M HNO3. Only materials selected from those provided to the student (listed above) may be used. (iii) Explain why it is not necessary to use a volumetric flask (calibrated to 50.00 mL 0.05 mL) to perform the dilution. (iv) During the preparation of the solution, the student accidentally spills about 1 mL of 16 M HNO3 on the bench top. The student finds three bottles containing liquids sitting near the spill: a bottle of distilled water, a bottle of 5 percent NaHCO3(aq), and a bottle of saturated NaCl(aq). Which of the liquids is best to use in cleaning up the spill? Justify your choice. Then the student pours 25 mL of the 6 M HNO3 into a beaker and adds a 0.6489 g sample of the alloy. After the sample completely reacts with the acid, some saturated NaCl(aq) is added to the beaker, resulting in the formation of an AgCl precipitate. Additional NaCl(aq) is added until no more precipitate is observed to form. The precipitate is filtered, washed, dried, and weighed to constant mass in a filter crucible. The data are shown in the table below. Mass of sample of copper-silver alloy Mass of dry filter crucible Mass of filter crucible and precipitate (first weighing) Mass of filter crucible and precipitate (second weighing) Mass of filter crucible and precipitate (third weighing) (b) Calculate the number of moles of AgCl precipitate collected. (c) Calculate the mass percent of silver in the alloy of copper and silver. 0.6489 g 28.7210 g 29.3587 g 29.2599 g 29.2598 g

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS

3. Hydrogen gas burns in air according to the equation below. 2 H2(g) + O2(g) 2 H2O(l)
, for the reaction represented by the equation above. (a) Calculate the standard enthalpy change, H 298

(The molar enthalpy of formation, H f , for H2O(l) is 285.8 kJ mol1 at 298 K.) (b) Calculate the amount of heat, in kJ, that is released when 10.0 g of H2(g) is burned in air.
, for H O(l) is 44.0 kJ mol1 at 298 K, what is the (c) Given that the molar enthalpy of vaporization, H vap 2 , for the reaction 2 H (g) + O (g) 2 H O(g) ? standard enthalpy change, H 298 2 2 2

A fuel cell is an electrochemical cell that converts the chemical energy stored in a fuel into electrical energy. A cell that uses H2 as the fuel can be constructed based on the following half-reactions. Half-reaction 2 H2O(l) + O2(g) + 4 e 4 OH(aq) 2 H2O(l) + 2 e H2(g) + 2 OH(aq) (d) Write the equation for the overall cell reaction. (e) Calculate the standard potential for the cell at 298 K. (f) Assume that 0.93 mol of H2(g) is consumed as the cell operates for 600. seconds. (i) Calculate the number of moles of electrons that pass through the cell. (ii) Calculate the average current, in amperes, that passes through the cell. (g) Some fuel cells use butane gas, C4H10 , rather than hydrogen gas. The overall reaction that occurs in a butane fuel cell is 2 C4H10(g) + 13 O2(g) 8 CO2(g) + 10 H2O(l). What is one environmental advantage of using fuel cells that are based on hydrogen rather than on hydrocarbons such as butane?

E (298 K)
0.40 V 0.83 V

STOP
If you finish before time is called, you may check your work on this part only. Do not turn to the other part of the test until you are told to do so.

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS CHEMISTRY

Part B Time 40 minutes NO CALCULATORS MAY BE USED FOR PART B.

Answer Question 4 below. The Section II score weighting for this question is 10 percent. 4. For each of the following three reactions, write a balanced equation for the reaction in part (i) and answer the question about the reaction in part (ii). In part (i), coefficients should be in terms of lowest whole numbers. Assume that solutions are aqueous unless otherwise indicated. Represent substances in solutions as ions if the substances are extensively ionized. Omit formulas for any ions or molecules that are unchanged by the reaction. You may use the empty space at the bottom of the next page for scratch work, but only equations that are written in the answer boxes provided will be scored.

(a) Solid magnesium hydroxide is added to a solution of hydrobromic acid. (i) Balanced equation:

(ii) What volume, in mL, of 2.00 M hydrobromic acid is required to react completely with 0.10 mol of solid magnesium hydroxide? ______________________________________________________________________________________ ______________________________________________________________________________________

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS

(b) Excess hydrochloric acid is added to a solution of cobalt(II) nitrate to produce a coordination complex. (i) Balanced equation:

(ii) Which species in the reaction acts as a Lewis base? ______________________________________________________________________________________ ______________________________________________________________________________________

(c) A copper wire is dipped into a solution of silver(I) nitrate. (i) Balanced equation:

(ii) Describe what is observed as the reaction proceeds. ______________________________________________________________________________________ ______________________________________________________________________________________

YOU MAY USE THE SPACE BELOW FOR SCRATCH WORK, BUT ONLY EQUATIONS THAT ARE WRITTEN IN THE ANSWER BOXES PROVIDED WILL BE SCORED.

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS

Answer Question 5 and Question 6. The Section II score weighting for these questions is 15 percent each. Your responses to these questions will be scored on the basis of the accuracy and relevance of the information cited. Explanations should be clear and well organized. Examples and equations may be included in your responses where appropriate. Specific answers are preferable to broad, diffuse responses. 5. Hydrazine is an inorganic compound with the formula N2H4 . (a) In the box below, complete the Lewis electron-dot diagram for the N2H4 molecule by drawing in all the electron pairs.

(b) On the basis of the diagram you completed in part (a), do all six atoms in the N2H4 molecule lie in the same plane? Explain. (c) The normal boiling point of N2H4 is 114C, whereas the normal boiling point of C2H6 is 89C. Explain, in terms of the intermolecular forces present in each liquid, why the boiling point of N2H4 is so much higher than that of C2H6. (d) Write a balanced chemical equation for the reaction between N2H4 and H2O that explains why a solution of hydrazine in water has a pH greater than 7. N2H4 reacts in air according to the equation below. N2H4(l) + O2(g) N2(g) + 2 H2O(g) H = 534 kJ mol1

(e) Is the reaction an oxidation-reduction, acid-base, or decomposition reaction? Justify your answer. (f) Predict the sign of the entropy change, S , for the reaction. Justify your prediction. (g) Indicate whether the statement written in the box below is true or false. Justify your answer. The large negative H for the combustion of hydrazine results from the large release of energy that occurs when the strong bonds of the reactants are broken.

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2011 AP CHEMISTRY FREE-RESPONSE QUESTIONS

6. In an experiment, all the air in a rigid 2.0 L flask is pumped out. Then some liquid ethanol is injected into the sealed flask, which is held at 35C. The amount of liquid ethanol initially decreases, but after five minutes the amount of liquid ethanol in the flask remains constant. Ethanol has a boiling point of 78.5C and an equilibrium vapor pressure of 100 torr at 35C. (a) When the amount of liquid ethanol in the flask is constant, is the pressure in the flask greater than, less than, or equal to 100 torr? Justify your answer. (b) The flask is then heated to 45C, and the pressure in the flask increases. In terms of kinetic molecular theory, provide TWO reasons that the pressure in the flask is greater at 45C than at 35C. In a second experiment, which is performed at a much higher temperature, a sample of ethanol gas and a copper catalyst are placed in a rigid, empty 1.0 L flask. The temperature of the flask is held constant, and the initial concentration of the ethanol gas is 0.0100 M. The ethanol begins to decompose according to the chemical reaction represented below.
Cu CH3CH2OH(g) CH3CHO(g) + H2(g)

The concentration of ethanol gas over time is used to create the three graphs below.

(c) Given that the reaction order is zero, one, or two, use the information in the graphs to respond to the following. (i) Determine the order of the reaction with respect to ethanol. Justify your answer. (ii) Write the rate law for the reaction. (iii) Determine the rate constant for the reaction, including units. (d) The pressure in the flask at the beginning of the experiment is 0.40 atm. If the ethanol completely decomposes, what is the final pressure in the flask?

STOP END OF EXAM

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