Equilibrium FRQ - Acids and bases and Ksp etc.

2011 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.

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 25°C.

(a) Determine the pH of the solution in beaker 1. Justify your answer.

(b) In beaker 2, the reaction NH3(aq) + H2O(l) Æ̈ NH4+(aq) + OH −(aq) occurs. The value of Kb for
NH3(aq) is 1.8 × 10−5 at 25°C.
(i) Write the Kb expression for the reaction of NH3(aq) with H2O(l).

(ii) Calculate the [OH -] in the solution in beaker 2.

(c) In beaker 3, the reaction NH4+(aq) + H2O(l) Æ̈ NH3(aq) + H3O+(aq) occurs.

(i) Calculate the value of Ka for NH4+(aq) at 25°C.
(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 25°C.

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 2011 AP® CHEMISTRY FREE-RESPONSE QUESTIONS (Form B)

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 this booklet.

Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent.

1. Answer the following questions about the solubility and reactions of the ionic compounds M(OH)2 and MCO3 ,
where M represents an unidentified metal.

(a) Identify the charge of the M ion in the ionic compounds above.
(b) At 25°C, a saturated solution of M(OH)2 has a pH of 9.15.

(i) Calculate the molar concentration of OH-(aq) in the saturated solution.

(ii) Write the solubility-product constant expression for M(OH)2 .
(iii) Calculate the value of the solubility-product constant, Ksp , for M(OH)2 at 25°C.

(c) For the metal carbonate, MCO3 , the value of the solubility-product constant, Ksp , is 7.4 × 10-14 at 25°C.
On the basis of this information and your results in part (b), which compound, M(OH)2 or MCO3 , has the
greater molar solubility in water at 25°C ? Justify your answer with a calculation.

(d) MCO3 decomposes at high temperatures, as shown by the reaction represented below.

MCO3(s) Æ̈ MO(s) + CO2(g)

A sample of MCO3 is placed in a previously evacuated container, heated to 423 K, and allowed to come
to equilibrium. Some solid MCO3 remains in the container. The value of Kp for the reaction at 423 K
is 0.0012.
(i) Write the equilibrium-constant expression for Kp of the reaction.
(ii) Determine the pressure, in atm, of CO2(g) in the container at equilibrium at 423 K.
(iii) Indicate whether the value of ΔG° for the reaction at 423 K is positive, negative, or zero. Justify your
answer.

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 2011 AP® CHEMISTRY FREE-RESPONSE QUESTIONS (Form B)

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. A student is instructed to prepare 100.0 mL of 1.250 M NaOH from a stock solution of 5.000 M NaOH. The
student follows the proper safety guidelines.

(a) Calculate the volume of 5.000 M NaOH needed to accurately prepare 100.0 mL of 1.250 M NaOH solution.

(b) Describe the steps in a procedure to prepare 100.0 mL of 1.250 M NaOH solution using 5.000 M NaOH
and equipment selected from the list below.
Balance 25 mL Erlenmeyer flask 100 mL graduated cylinder 100 mL volumetric flask
50 mL buret 100 mL Florence flask 25 mL pipet 100 mL beaker
Eyedropper Drying oven Wash bottle of distilled H2O Crucible

(c) The student is given 50.0 mL of a 1.00 M solution of a weak, monoprotic acid, HA. The solution is titrated
with the 1.250 M NaOH to the endpoint. (Assume that the endpoint is at the equivalence point.)

(i) Explain why the solution is basic at the equivalence point of the titration. Include a chemical equation
as part of your explanation.
(ii) Identify the indicator in the table below that would be best for the titration. Justify your choice.

Indicator pKa

Methyl red 5
Bromothymol blue 7
Phenolphthalein 9

(d) The student is given another 50.0 mL sample of 1.00 M HA, which the student adds to the solution that had
been titrated to the endpoint in part (c). The result is a solution with a pH of 5.0.
(i) What is the value of the acid-dissociation constant, Ka , for the weak acid? Explain your reasoning.
(ii) Explain why the addition of a few drops of 1.250 M NaOH to the resulting solution does not
appreciably change its pH.

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 2012 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 this booklet.

Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent.

1. A 1.22 g sample of a pure monoprotic acid, HA, was dissolved in distilled water. The HA solution was then
titrated with 0.250 M NaOH. The pH was measured throughout the titration, and the equivalence point was
reached when 40.0 mL of the NaOH solution had been added. The data from the titration are recorded in the
table below.

Volume of 0.250 M NaOH pH of Titrated

Added (mL) Solution

0.00 ?
10.0 3.72
20.0 4.20
30.0 ?
40.0 8.62
50.0 12.40

(a) Explain how the data in the table above provide evidence that HA is a weak acid rather than a strong acid.
(b) Write the balanced net-ionic equation for the reaction that occurs when the solution of NaOH is added to the
solution of HA .
(c) Calculate the number of moles of HA that were titrated.
(d) Calculate the molar mass of HA .

The equation for the dissociation reaction of HA in water is shown below.

HA(aq) + H2O(l) Æ̈ H3O+(aq) + A−(aq) Ka = 6.3 × 10−5

(e) Assume that the initial concentration of the HA solution (before any NaOH solution was added) is 0.200 M.
Determine the pH of the initial HA solution.

(f) Calculate the value of [H3O+] in the solution after 30.0 mL of NaOH solution is added and the total volume
of the solution is 80.0 mL.
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2012 FRQ B

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 this booklet.

Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent.

CH3NH2(aq) + H2O(l) Æ̈ CH3NH3+(aq) + OH−(aq) Kb = 4.4 × 10 − 4

1. Methylamine, CH3NH2 , is a weak base that reacts with water according to the equation above. A student obtains
a 50.0 mL sample of a methylamine solution and determines the pH of the solution to be 11.77.

(a) Write the expression for the equilibrium constant, Kb , for methylamine.

(b) Calculate the molar concentration of OH - in the 50.0 mL sample of the methylamine solution.

(c) Calculate the initial molar concentration of CH3NH2(aq) in the solution before it reacted with water and
equilibrium was established.

The 50.0 mL sample of the methylamine solution is titrated with an HCl solution of unknown concentration.
The equivalence point of the titration is reached after a volume of 36.0 mL of the HCl solution is added. The pH
of the solution at the equivalence point is 5.98.

(d) Write the net-ionic equation that represents the reaction that takes place during the titration.

(e) Calculate the concentration of the HCl solution used to titrate the methylamine.
(f) Using the axes provided, sketch the titration curve that results from the titration described above. On the
graph, clearly label the equivalence point of the titration.

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 CaSO4⋅ 2H2O(s) Æ̈ CaSO4(s) + 2 H2O(g)

3. The hydrate CaSO4⋅ 2H2O(s) can be heated to form the anhydrous salt, CaSO4(s), as shown by the reaction
represented above.

(a) Using the data in the table below, calculate the value of ΔG °, in kJ/molrxn , for the reaction at 298 K.

Substance DG f at 298 K (kJ/mol)

CaSO4⋅ 2H2O(s) −1795.70

CaSO4(s) −1320.30
H2O(g) −228.59

(b) Given that the value of ΔH ° for the reaction at 298 K is +105 kJ/molrxn , calculate the value of ΔS ° for the
reaction at 298 K. Include units with your answer.

A sample of CaSO4⋅ 2H2O(s) is placed in a cylinder with a movable piston as shown in the diagram below. The
air above the solid is at 1.00 atm and is initially dry (partial pressure of H2O(g) = 0 atm).

(c) Write the expression for the equilibrium constant, Kp , for the reaction.

(d) Given that the equilibrium constant, Kp , is 6.4 × 10- 4 at 298 K, determine the partial pressure, in atm, of
water vapor in the cylinder at equilibrium at 298 K.

(e) If the volume of the system is reduced to one-half of its original volume and the system is allowed to
reestablish equilibrium at 298 K, what will be the pressure, in atm, of the water vapor at the new volume?
Justify your answer.

In the laboratory, the hydrate CaSO4⋅ 2H2O(s) can be heated in a crucible to completely drive off the water of
hydration to form the anhydrous salt, CaSO4(s).

(f) A 2.49 g sample of pure CaSO4⋅ 2H2O(s) is heated several times until the mass is constant. Calculate the
mass, in grams, of the solid that remains after the dehydration reaction is complete.

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 2013 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 this booklet.

Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent.

1. Answer the following questions about the solubility of some fluoride salts of alkaline earth metals.

(a) A student prepares 100. mL of a saturated solution of MgF2 by adding 0.50 g of solid MgF2 to 100. mL
of distilled water at 25’C and stirring until no more solid dissolves. (Assume that the volume of the
undissolved MgF2 is negligibly small.) The saturated solution is analyzed, and it is determined that [F ] in
the solution is 2.4 u 103 M.
(i) Write the chemical equation for the dissolving of solid MgF2 in water.
(ii) Calculate the number of moles of MgF2 that dissolved.
(iii) Determine the value of the solubility-product constant, Ksp , for MgF2 at 25qC.

(b) A beaker contains 500. mL of a solution in which both Ca2+(aq) and Ba2+(aq) are present at a concentration
of 0.10 M at 25qC. A student intends to separate the ions by adding 0.20 M NaF solution one drop at a time
from a buret. At 25qC the value of Ksp for CaF2 is 3.5 –1011; the value of Ksp for BaF2 is 1.8 – 106.

(i) Which salt will precipitate first, CaF2 or BaF2 ? Justify your answer.

For parts (b)(ii) and (b)(iii) below, assume that the addition of the NaF solution does not significantly affect
the total volume of the liquid in the beaker.
(ii) Calculate the minimum concentration of F (aq) necessary to initiate precipitation of the salt selected
in part (b)(i).
(iii) Calculate the minimum volume of 0.20 M NaF that must be added to the beaker to initiate
precipitation of the salt selected in part (b)(i).

(c) There are several ways to dissolve salts that have limited solubility. Describe one procedure to redissolve the
precipitate formed in part (b).

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2013 FRQ B

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 this booklet.

Answer Questions 1, 2, and 3. The Section II score weighting for each question is 20 percent.

 NH (g) + HCl(g)
NH4Cl(s) Ž 3

1. When solid ammonium chloride is heated, it decomposes as represented above. The value of Kp for the reaction
is 0.0792 at 575 K. A 10.0 g sample of solid ammonium chloride is placed in a rigid, evacuated 3.0 L container
that is sealed and heated to 575 K. The system comes to equilibrium with some solid NH4Cl remaining in the
container.

(a) Write the expression for the equilibrium constant for the reaction in terms of partial pressures (i.e., Kp ).

(b) Calculate the partial pressure of NH3(g), in atm, at equilibrium at 575 K.

(c) A small amount of NH3(g) is injected into the equilibrium mixture in the 3.0 L container at 575 K.
(i) As the new equilibrium is being established at 575 K, does the amount of NH4Cl(s) in the container
increase, decrease, or remain the same? Justify your answer.
(ii) After the new equilibrium is established at 575 K, is the value of Kp greater than, less than, or equal to
the value before the NH3(g) was injected into the container? Justify your answer.

(d) When the temperature of the container is lowered to 500 K, the number of moles of NH3(g) in the container
decreases. On the basis of this observation, is the decomposition of NH4Cl(s) endothermic or exothermic?
Justify your answer.

In another experiment, 20.00 mL of 0.800 M NH4Cl(aq) is prepared. The ammonium ion reacts with water
 NH (aq) + H O+(aq).
according to the equation NH4+(aq) + H2O(l) Ž 3 3

(e) Calculate the value of the equilibrium constant for the reaction of the ammonium ion with water. (At 25qC
the value of Kb for NH3 is 1.8 × 105.)

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 (f) A solution is prepared by mixing 20.0 mL of 0.800 M NH3(aq) with 20.0 mL of 0.800 M NH4Cl(aq).
Assume that volumes are additive.
(i) Is the solution acidic, basic, or neutral? Justify your answer.

2VFTUJPO
GJJ
EJE
OPU
BMJHO
XJUI
UIF
OFX
DPVSTF
BOE
IBT
CFFO
SFNPWFE

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 B B B B B B B B B B B B B B
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. A student is asked to prepare 100.0 mL of 1.000 × 102 M Na2SO4(aq) to use in a precipitation experiment. The
student first weighs out 0.1420 g of solid Na2SO4.

(a) The balance used to measure the mass of the Na2SO4(s) must have a certain minimum level of precision to
ensure that the concentration of the Na2SO4 solution can be known to four significant figures. If this
minimum level of precision of the balance is expressed as r x mg , what is the value of x ?

(b) Describe how the student can best prepare 100.0 mL of 1.000 × 102 M Na2SO4(aq) after the appropriate
mass of solid Na2SO4 has been measured. Circle each item used from the list below and describe the
essential steps in the procedure for preparing the solution.

50 mL buret 100 mL Erlenmeyer flask Distilled water

50 mL volumetric flask 100 mL volumetric flask Dropper
100 mL beaker 100 mL graduated cylinder
Squeeze bottle 10 mL volumetric pipet

The student is given 250 mL of a solution containing the following cations: Ba2+, Ca2+, Pb2+, and Sr2+. The
concentration of each of these cations in the solution is 1.0 M.
(c) In the first experiment, the student puts 10 mL of the Ba2+/Ca2+/Pb2+/Sr2+ solution in a test tube and then
adds 1.000 × 102 M Na2SO4(aq) one drop at a time, swirling the contents of the test tube after each drop is
added. Based on the information in the table below, which salt will be the first to precipitate in the test tube?
Justify your answer.

Salt BaSO4 CaSO4 PbSO4 SrSO4

Ksp at 25qC 1.5 × 109 6.1 × 105 1.3 × 108 3.2 × 107

(d) In a second experiment, the student electrolyzes the Ba2+/Ca2+/Pb2+/Sr2+ solution by putting 100 mL of the
solution in a beaker and immersing two platinum electrodes in the solution. The electrodes are connected to
a source of DC voltage, as shown in the following diagram. The voltage source has a dial that allows the
student to increase the voltage slowly. In doing so, the student observes that one of the metals is deposited
(plates out) on one of the electrodes.

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 B B B B B B B B B B B B B B

(i) On the diagram, circle the electrode on which the metal plates out. Justify your answer.
(ii) Identify the metal that plates out. Justify your answer.

2VFTUJPO
F
EJE
OPU
BMJHO
XJUI
UIF
OFX
DPVSTF
BOE
IBT
CFFO
SFNPWFE

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 CHEMISTRY
Section II
7 Constructed-Response Questions
(Time—90 minutes)
YOU MAY USE YOUR CALCULATOR FOR SECTION II

Directions: Questions 1, 2, and 3 are long constructed-response questions that should require about
20 minutes each to answer. Questions 4, 5, 6, and 7 are short constructed-response questions that should require
about seven minutes each to answer. Read each question carefully and write your response in the space provided
following each question. 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. Specific answers are preferable to broad,
diffuse responses. For calculations, 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.

1. A student performs an experiment in which the conductivity of a solution of Ba(OH)2 is monitored as the
solution is titrated with 0.10 M H2SO4 . The original volume of the Ba(OH)2 solution is 25.0 mL. A precipitate
of BaSO4 (Ksp = 1.0 × 10−10 ) formed during the titration. The data collected from the experiment are plotted in
the graph above.

(a) As the first 30.0 mL of 0.10 M H2SO4 are added to the Ba(OH)2 solution, two types of chemical reactions
occur simultaneously. On the lines provided below, write the balanced net-ionic equations for (i) the
neutralization reaction and (ii) the precipitation reaction.
(i) Equation for neutralization reaction: ___________________________________________________

(ii) Equation for precipitation reaction: ____________________________________________________

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42 Chemistry Practice Exam

(b) The conductivity of the Ba(OH)2 solution decreases as the volume of added 0.10 M H2SO4 changes from
0.0 mL to 30.0 mL.
(i) Identify the chemical species that enable the solution to conduct electricity as the first 30.0 mL of
0.10 M H2SO4 are added.
(ii) On the basis of the equations you wrote in part (a), explain why the conductivity decreases.

(c) Using the information in the graph, calculate the molarity of the original Ba(OH)2 solution.

(d) Calculate the concentration of Ba2+(aq) in the solution at the equivalence point (after exactly 30.0 mL of
0.10 M H2SO4 are added).

(e) The concentration of Ba2+(aq) in the solution decreases as the volume of added 0.10 M H2SO4 increases
from 30.0 mL to 31.0 mL. Explain.

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Chemistry Practice Exam 43

 SO2Cl2(g) Æ̈ SO2(g) + Cl2(g)

3. A 4.32 g sample of liquid SO2Cl2 is placed in a rigid, evacuated 1.50 L reaction vessel. As the container is
heated to 400. K, the sample vaporizes completely and starts to decompose according to the equation above.
The decomposition reaction is endothermic.

(a) If no decomposition occurred, what would be the pressure, in atm, of the SO2Cl2(g) in the vessel at 400. K ?

(b) When the system has reached equilibrium at 400. K, the total pressure in the container is 1.26 atm.
Calculate the partial pressures, in atm, of SO2Cl2(g), SO2(g), and Cl2(g) in the container at 400. K.

(c) For the decomposition reaction at 400. K,

(i) write the equilibrium-constant expression for Kp for the reaction, and
(ii) calculate the value of the equilibrium constant, Kp .

(d) The temperature of the equilibrium mixture is increased to 425 K. Will the value of Kp increase, decrease,
or remain the same? Justify your prediction.

(e) In another experiment, the original partial pressures of SO2Cl2(g), SO2(g), and Cl2(g) are 1.0 atm each at
400. K. Predict whether the amount of SO2Cl2(g) in the container will increase, decrease, or remain the
same. Justify your prediction.

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50 Chemistry Practice Exam

 HIn(aq) + H2O(l) Æ̈ In−(aq) + H3O+(aq)
yellow blue

7. The indicator HIn is a weak acid with a pKa value of 5.0. It reacts with water as represented in the equation
above. Consider the two beakers below. Each beaker has a layer of colorless oil (a nonpolar solvent) on top of a
layer of aqueous buffer solution. In beaker X the pH of the buffer solution is 3, and in beaker Y the pH of the
buffer solution is 7. A small amount of HIn is placed in both beakers. The mixtures are stirred well, and the oil
and water layers are allowed to separate.

(a) What is the predominant form of HIn in the aqueous buffer in beaker Y, the acid form or the conjugate base
form? Explain your reasoning.
(b) In beaker X the oil layer is yellow, whereas in beaker Y the oil layer is colorless. Explain these
observations in terms of both acid-base equilibria and interparticle forces.

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60 Chemistry Practice Exam

 2014 AP® CHEMISTRY FREE-RESPONSE QUESTIONS
 CH CH COO−(aq) + H O+(aq)
CH3CH2COOH(aq) + H2O(l) Ž 3 2 3

2. Propanoic acid, CH3CH2COOH, is a carboxylic acid that reacts with water according to the equation above. At
25’C the pH of a 50.0 mL sample of 0.20 M CH3CH2COOH is 2.79.

(a) Identify a Brønsted-Lowry conjugate acid-base pair in the reaction. Clearly label which is the acid and
which is the base.
(b) Determine the value of Ka for propanoic acid at 25’C.

(c) For each of the following statements, determine whether the statement is true or false. In each case, explain
the reasoning that supports your answer.
(i) The pH of a solution prepared by mixing the 50.0 mL sample of 0.20 M CH3CH2COOH with a
50.0 mL sample of 0.20 M NaOH is 7.00.
(ii) If the pH of a hydrochloric acid solution is the same as the pH of a propanoic acid solution, then the
molar concentration of the hydrochloric acid solution must be less than the molar concentration of the
propanoic acid solution.

A student is given the task of determining the concentration of a propanoic acid solution of unknown
concentration. A 0.173 M NaOH solution is available to use as the titrant. The student uses a 25.00 mL
volumetric pipet to deliver the propanoic acid solution to a clean, dry flask. After adding an appropriate indicator
to the flask, the student titrates the solution with the 0.173 M NaOH, reaching the end point after 20.52 mL of
the base solution has been added.

(d) Calculate the molarity of the propanoic acid solution.

(e) The student is asked to redesign the experiment to determine the concentration of a butanoic acid solution
instead of a propanoic acid solution. For butanoic acid the value of pKa is 4.83. The student claims that a
different indicator will be required to determine the equivalence point of the titration accurately. Based on
your response to part (b), do you agree with the student’s claim? Justify your answer.

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 2014 AP® CHEMISTRY FREE-RESPONSE QUESTIONS
 CaO(s) + CO (g)
CaCO3(s) Ž 2

4. When heated, calcium carbonate decomposes according to the equation above. In a study of the decomposition
of calcium carbonate, a student added a 50.0 g sample of powdered CaCO3(s) to a 1.00 L rigid container. The
student sealed the container, pumped out all the gases, then heated the container in an oven at 1100 K. As the
container was heated, the total pressure of the CO2(g) in the container was measured over time. The data are
plotted in the graph below.

The student repeated the experiment, but this time the student used a 100.0 g sample of powdered CaCO3(s). In
this experiment, the final pressure in the container was 1.04 atm, which was the same final pressure as in the
first experiment.

(a) Calculate the number of moles of CO2(g) present in the container after 20 minutes of heating.
(b) The student claimed that the final pressure in the container in each experiment became constant because
all of the CaCO3(s) had decomposed. Based on the data in the experiments, do you agree with this claim?
Explain.
(c) After 20 minutes some CO2(g) was injected into the container, initially raising the pressure to 1.5 atm.
Would the final pressure inside the container be less than, greater than, or equal to 1.04 atm? Explain
your reasoning.
(d) Are there sufficient data obtained in the experiments to determine the value of the equilibrium constant, Kp ,
for the decomposition of CaCO3(s) at 1100 K? Justify your answer.

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 2015 AP® CHEMISTRY FREE-RESPONSE QUESTIONS
3. Potassium sorbate, KC6H7O2 (molar mass 150. g/mol) is commonly added to diet soft drinks as a preservative.
A stock solution of KC6H7O2(aq) of known concentration must be prepared. A student titrates 45.00 mL of the
stock solution with 1.25 M HCl(aq) using both an indicator and a pH meter. The value of Ka for sorbic acid,
HC6H7O2, is 1.7 × 10−5.

(a) Write the net-ionic equation for the reaction between KC6H7O2(aq) and HCl(aq).

(b) A total of 29.95 mL of 1.25 M HCl(aq) is required to reach the equivalence point. Calculate [KC6H7O2] in
the stock solution.

(c) The pH at the equivalence point of the titration is measured to be 2.54 Which of the following indicators
would be the best choice for determining the end point of the titration? Justify your answer.

Indicator pKa
Phenolphthalein 9.3
Bromothymol blue 7.0
Methyl red 5.0
Thymol blue 2.0
Methyl violet 0.80

(d) Calculate the pH at the half-equivalence point.

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 2015 AP® CHEMISTRY FREE-RESPONSE QUESTIONS
(e) The initial pH and the equivalence point are plotted on the graph below. Accurately sketch the titration curve
on the graph below. Mark the position of the half-equivalence point on the curve with an X.

(f) The pH of the soft drink is 3.37 after the addition of the KC6H7O2(aq). Which species, HC6H7O2 or
C6H7O2− , has a higher concentration in the soft drink? Justify your answer.

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NaHCO3(s) + HC2H3O2(aq) → NaC2H3O2(aq) + H2O(l) + CO2(g)

2. A student designs an experiment to study the reaction between NaHCO3 and HC2H3O2 . The reaction is
represented by the equation above. The student places 2.24 g of NaHCO3 in a flask and adds 60.0 mL of
0.875 M HC2H3O2 . The student observes the formation of bubbles and that the flask gets cooler as the reaction
proceeds.

(a) Identify the reaction represented above as an acid-base reaction, precipitation reaction, or redox reaction.
Justify your answer.
(b) Based on the information above, identify the limiting reactant. Justify your answer with calculations.
(c) The student observes that the bubbling is rapid at the beginning of the reaction and gradually slows as the
reaction continues. Explain this change in the reaction rate in terms of the collisions between reactant
particles.
(d) In thermodynamic terms, a reaction can be driven by enthalpy, entropy, or both.
(i) Considering that the flask gets cooler as the reaction proceeds, what drives the chemical reaction
between NaHCO3(s) and HC2H3O2(aq) ? Answer by drawing a circle around one of the choices
below.
Enthalpy only Entropy only Both enthalpy and entropy

(ii) Justify your selection in part (d)(i) in terms of ΔG°.

(e) The HCO3− ion has three carbon-to-oxygen bonds. Two of the carbon-to-oxygen bonds have the same
length and the third carbon-to-oxygen bond is longer than the other two. The hydrogen atom is bonded to
one of the oxygen atoms. In the box below, draw a Lewis electron-dot diagram (or diagrams) for the HCO3−
ion that is (are) consistent with the given information.

(f) A student prepares a solution containing equimolar amounts of HC2H3O2 and NaC2H3O2 . The pH of
the solution is measured to be 4.7. The student adds two drops of 3.0 M HNO3(aq) and stirs the sample,
observing that the pH remains at 4.7. Write a balanced, net-ionic equation for the reaction between
HNO3(aq) and the chemical species in the sample that is responsible for the pH remaining at 4.7.

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→ C H O−(aq) + H O+(aq)
C6H5OH(aq) + H2O(l) ← Ka = 1.12 × 10−10
6 5 3

4. Phenol is a weak acid that partially dissociates in water according to the equation above.

(a) What is the pH of a 0.75 M C6H5OH(aq) solution?

(b) For a certain reaction involving C6H5OH(aq) to proceed at a significant rate, the phenol must be primarily
in its deprotonated form, C6H5O−(aq). In order to ensure that the C6H5OH(aq) is deprotonated, the reaction
must be conducted in a buffered solution. On the number scale below, circle each pH for which more than
50 percent of the phenol molecules are in the deprotonated form (C6H5O−(aq)). Justify your answer.

1 2 3 4 5 6 7 8 9 10 11 12 13 14

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Ba2+(aq) + EDTA4 −(aq) R Ba(EDTA)2−(aq) K = 7.7 × 107

6. The polyatomic ion C10H12N2O84− is commonly abbreviated as EDTA4−. The ion can form complexes with
metal ions in aqueous solutions. A complex of EDTA4− with Ba2+ ion forms according to the equation
above. A 50.0 mL volume of a solution that has an EDTA4 −(aq) concentration of 0.30 M is mixed with 50.0 mL
of 0.20 M Ba(NO3)2 to produce 100.0 mL of solution.

(a) Considering the value of K for the reaction, determine the concentration of Ba(EDTA)2−(aq) in the
100.0 mL of solution. Justify your answer.
(b) The solution is diluted with distilled water to a total volume of 1.00 L. After equilibrium has been
reestablished, is the number of moles of Ba2+(aq) present in the solution greater than, less than, or equal to
the number of moles of Ba2+(aq) present in the original solution before it was diluted? Justify your answer.

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 2 NaHCO3(s)  Na2CO3(s) + CO2(g) + H2O(g)

2. NaHCO3(s) (baking soda) decomposes upon heating to produce Na2CO3(s) and two gaseous products, as shown
by the equation above.

(a) A student claims that the reaction is an oxidation-reduction reaction because the oxidation number of carbon
changes. Do you agree with the claim? In your answer include the oxidation number of carbon in each of the
three carbon-containing species in the reaction.

The student conducts an experiment to determine the composition of a mixture of NaHCO3 (molar mass
84.01 g/mol) and Na2CO3 (molar mass 105.99 g/mol). The student places a sample of the mixture into a
preweighed test tube that is attached to a container that holds a drying agent. The student heats the test tube
strongly with a Bunsen burner for 10 minutes, during which time all of the water produced by the reaction is
captured by the drying agent. The following table shows the data the student recorded during the experiment.

Mass of empty test tube 15.825 g

Mass of test tube and mixture before heating 17.648 g
Mass of drying agent before reaction 2.134 g
Mass of drying agent and water after reaction 2.303 g

(b) Calculate the number of moles of NaHCO3(s) present in the mixture in the test tube before the reaction was
initiated.
(c) Determine the mass percent of NaHCO3(s) in the mixture.

(d) If the student spills some of the mixture out of the test tube after weighing the test tube and mixture and
before heating, how would this error affect the mass percent of NaHCO3 calculated in part (c) ? Justify your
answer.

When a sample of pure Na2CO3 is placed in distilled water, the student observes that the pH of the solution
increases significantly. This process is represented by the balanced net-ionic equation shown below.
CO32(aq) + H2O(l)  HCO3(aq) + OH(aq)

(e) The student prepares a 0.10 M Na2CO3(aq) solution and measures the pH of the solution to be 11.65.

(i) Calculate [OH] in the Na2CO3(aq) solution.

(ii) Write the expression for Kb for the carbonate ion.
(iii) Calculate the value of Kb for the carbonate ion.

The student adds some 1.0 M Sr(NO3)2(aq) to the 0.10 M Na2CO3(aq) and observes the formation of a
precipitate.
(f) Write the balanced net-ionic equation for the reaction between Sr(NO3)2 and Na2CO3 that produces the
precipitate.

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 CHEMISTRY
Section II
7 Questions
Time—1 hour and 45 minutes

YOU MAY USE YOUR CALCULATOR FOR THIS SECTION.

Directions: Questions 1–3 are long free-response questions that require about 23 minutes each to answer and are
worth 10 points each. Questions 4–7 are short free-response questions that require about 9 minutes each to answer
and are worth 4 points each.

Write your response in the space provided following each question. Examples and equations may be included in
your responses where appropriate. For calculations, clearly show the method used and the steps involved in arriving
at your answers. You must show your work to receive credit for your answer. Pay attention to significant figures.

→ H O+(aq) + C H O −(aq)
HC2H3O2(aq) + H2O(l) ← 3 2 3 2

1. The dissociation of ethanoic acid, HC2H3O2(aq) , is represented above. A student is given the task of
determining the value of Ka for HC2H3O2(aq) using two different experimental procedures.
(a) The student is first asked to prepare 100.0 mL of 0.115 M HC2H3O2(aq) using a 2.000 M standard solution.

(i) Calculate the volume, in mL, of 2.000 M HC2H3O2(aq) the student needs to prepare 100.0 mL of
0.115 M HC2H3O2(aq).
(ii) Describe the procedure the student should use to prepare 100.0 mL of 0.115 M HC2H3O2(aq) using
appropriate equipment selected from the list below. Assume that the student uses appropriate safety
equipment.

• 100 mL beaker • Eye dropper

• 100 mL graduated cylinder • 500 mL wash bottle filled with distilled water
• 100 mL volumetric flask • 2.000 M HC2H3O2(aq) in a 50 mL buret

(b) Using a pH probe, the student determines that the pH of 0.115 M HC2H3O2(aq) is 2.92.

(i) Using the pH value, calculate the value of Ka for HC2H3O2(aq).

(ii) Calculate the percent dissociation of ethanoic acid in 0.115 M HC2H3O2(aq).

In a separate experimental procedure, the student titrates 10.0 mL of the 2.000 M HC2H3O2(aq) with an
NaOH(aq) solution of unknown concentration. The student monitors the pH during the titration. The following
titration curve was created using the experimental data presented in the table.

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 (c) Write the balanced net ionic equation for the reaction that occurs when HC2H3O2(aq) and NaOH(aq) are
combined.
(d) Calculate the molar concentration of the NaOH(aq) solution.

(e) Explain how the student can estimate the value of Ka for HC2H3O2(aq) using the titration curve.

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6. Answer the following questions about the solubility of AgCl(s). The value of Ksp for AgCl(s) is 1.8 × 10−10.

(a) Calculate the value of [Ag+] in a saturated solution of AgCl in distilled water.
(b) The concentration of Cl−(aq) in seawater is 0.54 M.
(i) Calculate the molar solubility of AgCl(s) in seawater.
(ii) Explain why AgCl(s) is less soluble in seawater than in distilled water.

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 2018 AP® CHEMISTRY FREE-RESPONSE QUESTIONS

2 NO(g) + O2(g) → 2 NO2(g)

2. A student investigates the reactions of nitrogen oxides. One of the reactions in the investigation requires an
equimolar mixture of NO(g) and NO2(g), which the student produces by using the reaction represented above.
(a) The particle-level representation of the equimolar mixture of NO(g) and NO2(g) in the flask at the
completion of the reaction between NO(g) and O2(g) is shown below in the box on the right. In the box
below on the left, draw the particle-level representation of the reactant mixture of NO(g) and O2(g) that
would yield the product mixture shown in the box on the right. In your drawing, represent oxygen atoms
and nitrogen atoms as indicated below.

The student reads in a reference text that NO(g) and NO2(g) will react as represented by the equation below.
Thermodynamic data for the reaction are given in the table below the equation.

NO(g) + NO2(g) R N2O3(g)

D
DH D
DS D
DG

−40.4 kJ/molrxn −138.5 J/(K ⋅ molrxn) 0.87 kJ/molrxn

(b) The student begins with an equimolar mixture of NO(g) and NO2(g) in a rigid reaction vessel and the
mixture reaches equilibrium at 298 K.
(i) Calculate the value of the equilibrium constant, K, for the reaction at 298 K.
(ii) If both PNO and PNO 2 in the vessel are initially 1.0 atm, will PN 2O 3 at equilibrium be equal to
1.0 atm? Justify your answer.

(c) The student hypothesizes that increasing the temperature will increase the amount of N2O3(g) in the
equilibrium mixture. Indicate whether you agree or disagree with the hypothesis. Justify your answer.

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 2018 AP® CHEMISTRY FREE-RESPONSE QUESTIONS

N2O3(g) reacts with water to form nitrous acid, HNO2 (aq), a compound involved in the production of acid rain.
The reaction is represented below.
N2O3(g) + H2O(l) → 2 HNO2(aq)

(d) The skeletal structure of the HNO2 molecule is shown in the box below.
(i) Complete the Lewis electron-dot diagram of the HNO2 molecule in the box below, including any lone
pairs of electrons.

H O N O

(ii) Based on your completed diagram above, identify the hybridization of the nitrogen atom in the HNO2
molecule.

To produce an aqueous solution of HNO2 , the student bubbles N2O3(g) into distilled water. Assume that the
reaction goes to completion and that HNO2 is the only species produced. To determine the concentration of
HNO2(aq) in the resulting solution, the student titrates a 100. mL sample of the solution with 0.100 M KOH(aq).
The neutralization reaction is represented below.
HNO2(aq) + OH − (aq) → NO2−(aq) + H2O(l)

The following titration curve shows the change in pH of the solution during the titration.

(e) Use the titration curve and the information above to

(i) determine the initial concentration of the HNO2(aq) solution
(ii) estimate the value of pKa for HNO2(aq)

(f) During the titration, after a volume of 15 mL of 0.100 M KOH(aq) has been added, which species,
HNO2(aq) or NO2−(aq), is present at a higher concentration in the solution? Justify your answer.

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 2018 AP® CHEMISTRY FREE-RESPONSE QUESTIONS

HF(aq) + H2O(l) R F − (aq) + H3O+(aq)

5. The ionization of HF(aq) in water is represented by the equation above. In a 0.0350 M HF(aq) solution, the
percent ionization of HF is 13.0 percent.

(a) Two particulate representations of the ionization of HF molecules in the 0.0350 M HF(aq) solution are
shown below in Figure 1 and Figure 2. Water molecules are not shown. Explain why the representation of
the ionization of HF molecules in water in Figure 1 is more accurate than the representation in Figure 2.
(The key below identifies the particles in the representations.)

(b) Use the percent ionization data above to calculate the value of Ka for HF.

(c) If 50.0 mL of distilled water is added to 50.0 mL of 0.035 M HF(aq), will the percent ionization of HF(aq)
in the solution increase, decrease, or remain the same? Justify your answer with an explanation or
calculation.

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2. Answer the following questions relating to HCl, CH3Cl, and CH3Br.

(a) HCl(g) can be prepared by the reaction of concentrated H2SO4(aq) with NaCl(s), as represented by the
following equation.
H2SO4(aq) + 2 NaCl(s) → 2 HCl( g) + Na2SO4(aq)

(i) A student claims that the reaction is a redox reaction. Is the student correct? Justify your answer.
(ii) Calculate the mass, in grams, of NaCl(s) needed to react with excess H2SO4(aq) to produce 3.00 g of
HCl(g). Assume that the reaction goes to completion.

HCl(g) can react with methanol vapor, CH3OH(g), to produce CH3Cl(g), as represented by the following
equation.
CH3OH(g) + HCl(g)  CH 3Cl(g) + H2O(g) Kp = 4.7 × 103 at 400 K

(b) CH3OH(g) and HCl(g) are combined in a 10.00 L sealed reaction vessel and allowed to reach equilibrium at
400 K. The initial partial pressure of CH3OH(g) in the vessel is 0.250 atm and that of HCl(g) is 0.600 atm.

(i) Does the total pressure in the vessel increase, decrease, or remain the same as equilibrium is
approached? Justify your answer in terms of the reaction stoichiometry.
(ii) Considering the value of Kp , calculate the final partial pressure of HCl(g) after the system inside the
vessel reaches equilibrium at 400 K.
(iii) The student claims that the final partial pressure of CH3OH(g) at equilibrium is very small but not
exactly zero. Do you agree or disagree with the student’s claim? Justify your answer.

(c) The table below shows some data for the compounds CH3Cl and CH3Br .

Molar Mass Dipole Moment Boiling Point 

DHvaporization
Compound
(g/mol) (D) (K) (kJ/mol)
CH3Cl 50.5 1.87 249 18.9
CH3Br 94.9 1.81 277 22.8

(i) Identify all the types of intermolecular forces that exist among molecules in CH3Cl(l).
(ii) In terms of intermolecular forces, explain why the boiling point of CH3Br(l) is greater than that of
CH3Cl(l).

(d) A 2.00 mL sealed glass vial containing a 1.00 g sample of CH3Cl(l) is stored in a freezer at 233 K.
(i) Calculate the pressure in the vial at 298 K assuming that all the CH3Cl(l) vaporizes.
(ii) Explain why it would be unsafe to remove the vial from the freezer and leave it on a lab bench
at 298 K.

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 3 Cu+(aq) + Au3+(aq) → 3 Cu 2+(aq) + Au(s)

3. A student studying the reaction represented above constructs a voltaic cell as shown in the diagram below. The
cell contains an Au(s) electrode in a beaker containing 1.00 M Au(NO 3)3(aq) and a Pt(s) electrode in a beaker
containing 1.00 M CuNO 3(aq) and 1.00 M Cu(NO 3)2(aq).

The standard reduction potentials associated with the cell are given in the following table.

Half-reaction E° (V)
Cu2+(aq) + e− → Cu +(aq) 0.16

Au3+(aq) + 3 e− → Au(s) 1.50

(a) Calculate the value of the standard cell potential, E°.

(b) Does the mass of the Pt(s) electrode increase, decrease, or remain the same as the cell operates? Justify your
answer.

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 An expanded view of the Au half-cell before the reaction occurs is shown in box A below. An expanded view
of the Au electrode after the cell operates for a period of time is shown in box B below.

(c) Assuming that the representation in box A is accurate, explain what is wrong with the stoichiometry
represented in box B.

(d) After the cell has operated for 30.0 minutes, 0.185 g of Au(s) is deposited on the Au electrode.
(i) Calculate the number of moles of Au(s) deposited.
(ii) Calculate the average current that passed through the cell during the deposition of Au(s).

The student adds some NaCl(s) to the half-cell that contains Cu+(aq) and Cu2+(aq), and a precipitate forms.

(e) Based on the information in the following table, determine the identity of the precipitate. Justify your answer
with a calculation.

Compound Solubility (mol/L) Ksp

CuCl ? 1.7 × 10 −7
CuCl2 5.2 ?

(f) Write the net ionic equation for the formation of the precipitate.

(g) The student predicts that the cell voltage will increase after the precipitate forms. Do you agree with the
student’s prediction? Justify your answer.

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 Solution X 100 mL of 0.10 M NaOH(aq) is mixed with 100 mL of 0.10 M HBr(aq)

Solution Y 100 mL of 0.10 M NaBr(aq) is mixed with 100 mL of 0.10 M HBr(aq)

Solution Z 100 mL of 0.10 M HC2H3O2(aq) is mixed with 100 mL of 0.10 M NaC2H3O2(aq)

7. A student prepares three solutions, X, Y, and Z, as described in the table above. The values of Ka for the acidic
species in the solutions are given in the table below.

Species Ka

HBr(aq) >>1 (very large)

HC2H3O2(aq) 1.8 × 10−5

(a) Using the information above, write the letters of the solutions in the boxes below to rank the solutions in
order of increasing pH. Explain your reasoning for the ranking.

Lowest pH Highest pH
< <

(b) Does the pH of solution Y increase, decrease, or remain the same when 100 mL of water is added? Justify
your answer.

(c) The student adds 0.0010 mol of NaOH(s) to solution Y, and adds 0.0010 mol of NaOH(s) to solution Z .
Assume that the volume of each solution does not change when the NaOH(s) is added. The pH of
solution Y changes much more than the pH of solution Z changes. Explain this observation.

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