AP® CHEMISTRY

Question 1

Half-Reaction E ° (V)
2 CO2(g) + 12\ H+(aq) +/
12 e−
Æ C2H5OH(aq) + 3 H2O(l ) − 0.085
O2(g) + 4 H+(aq) + 4 e− Æ 2 H2O(l ) is
1.229

6 +20 >
-
1 + 12+ + 302
A student uses a galvanic cell to determine the concentration of ethanol, C2H5OH(aq), in an aqueous solution.
The cell is based on the half-cell reactions represented in the table above.

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

2 CO2 + 3H20 f CcHSOH + 302

(b) Calculate E ° for the overall reaction that occurs in the cell.

0 .
046

(c) A 10.0 mL sample of C2H5OH(aq) is put into the electrochemical cell. The cell produces an average
current of 0.10 amp for 20. seconds, at which point the C2H5OH(aq) has been totally consumed.
- -

④
(i) Calculate the charge, in coulombs, that passed through the cell.
-

0 1.
amp

&
(ii) Calculate the initial [C2H5OH] in the solution.

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2015 Free-Response Questions

Question 1 (continued)
An alternative approach to determine the concentration of C2H5OH(aq) in a solution is based on the reaction
represented below.

-
3 C2H5OH(aq) + 2 Cr2O72−(aq) + 16 H+(aq) Æ 4 Cr3+(aq) + 3 CH3COOH(aq) + 11 H2O(l )
orange blue-green

A solution has an initial Cr2O72−(aq) concentration of 1.0 ×10−3 M and an initial C2H5OH(aq) concentration
-

of 0.500 M. The solution contains enough strong acid to keep the pH essentially constant throughout the
reaction. The student places a sample of the solution in a cuvette that has a path length of 0.50 cm and places
it in a spectrophotometer set to measure absorbance at 440 nm. (Cr2O72−(aq) is the only species in the reaction
mixture that absorbs light at this wavelength.) The absorbance of Cr2O72−(aq) in the solution is monitored as
the reaction proceeds; the table below shows the absorbance as a function of time for the first trial.

Time (min) Absorbance at 440 nm

0.00 0.782
1.50 0.553
3.00 0.389
4.50 0.278
6.00 0.194

(d) Calculate the value of [Cr2O72−] at 1.50 min.

0 . 533 X2 =
1 106
.

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2015 Free-Response Questions

Question 1 (continued)
(e) The student runs a second trial but this time uses a cuvette that has a path length of 1.00 cm. Describe
how the experimental setup should be adjusted to keep the initial absorbance at 0.782. Justify your
-

answer with respect to the factors that influence the absorbance of a sample in a spectrophotometer.

the time should be adjusted

For the concentrations of reactants used in the experiment, the rate of the reaction can be written as follows.
Rate = kobserved[Cr2O72−]y, where kobserved = k[C2H5OH]

(f) Explain how the experimental data indicate that the reaction is first order with respect to Cr2O72−.

when graphed en concentration

13
and time the graph
linear
decreasing

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2015 SCORING GUIDELINES

Question 2
Answer the following questions about Fe and Al compounds.

(a) Fe2O3(s) and Al2O3(s) have similar chemical properties; some similarities are due to the oxides having
similar lattice energies. Give two reasons why the lattice energies of the oxides are similar.

they are both solid ; both have 03

Use the following reactions that involve Fe and Al compounds to answer parts (b) and (c).

In distilled water
Reaction 1: Fe2O3(s) + 3 H2O(l ) Æ 2 Fe(OH)3(s)
Reaction 2: Al2O3(s) + 3 H2O(l ) Æ 2 Al(OH)3(s)
In base
Reaction 3: Fe(OH)3(s) + NaOH(aq) Æ no reaction
Reaction 4: Al(OH)3(s) + NaOH(aq) Æ NaAl(OH)4(aq)
In acid
Reaction 5: Fe(OH)3(s) + 3 HCl(aq) Æ FeCl3(aq) + 3 H2O(l )
Reaction 6: Al(OH)3(s) + 3 HCl(aq) Æ AlCl3(aq) + 3 H2O(l )
Reaction 7: NaAl(OH)4(aq) + HCl(aq) Æ Al(OH)3(s) + NaCl(aq) + H2O(l )
When heated
heat
Reaction 8: 2 Fe(OH)3(s) æææ Æ Fe2O3(s) + 3 H2O(g)

Reaction 9: heat
2 Al(OH)3(s) æææ Æ Al2O3(s) + 3 H2O(g) Compound Ksp
Fe(OH)3 4 × 10−38
Al(OH)3 1 × 10−33

(b) The Ksp values for Fe(OH)3 and Al(OH)3 are given in the table above. A 1.0 g sample of powdered
Fe2O3(s) and a 1.0 g sample of powdered Al2O3(s) are mixed together and placed in 1.0 L of distilled
water.
(i) Which ion, Fe3+(aq) or Al3+(aq), will be present in the higher concentration? Justify your answer
with respect to the Ksp values provided. -

value
Alt because greater ksp

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Question 2 (continued)
(ii) Write a balanced chemical equation for the dissolution reaction that results in the production of the
ion that you identified in part (i).

AllOHn) AlT3
-

>
30H +
-

(c) Students are asked to develop a plan for separating Al2O3(s) from a mixture of powdered Fe2O3(s)
and powdered Al2O3(s) using chemical reactions and laboratory techniques.
(i) One student proposes that Al2O3(s) can be separated from the mixture by adding water to
the mixture and then filtering. Explain why this approach is not reasonable.

water
Alos is not soluble in

(ii) A second student organizes a plan using a table. The first two steps have already been entered in
the table, as shown below. Complete the plan by listing the additional steps that are needed to
recover the Al2O3(s). List the steps in the correct order and refer to the appropriate reaction by
-
number, if applicable.

Step Description Reaction(s)

1 Add NaOH(aq) to convert Al2O3(s) to Al(OH)3(s) and then to NaAl(OH)4(aq). 2 and 4

2 Filter out the solid Fe(OH)3 from the mixture and save the filtrate. −

3 use filtrate for reaction

4 heat reaction −

(iii) The second student recovers 5.5 g of Al2O3(s) from a 10.0 g sample of the mixture.
Calculate the percent of Al by mass in the mixture of the two powdered oxides.
(The molar mass of Al2O3 is 101.96 g/mol, and the molar mass of Fe2O3 is 159.70 g/mol.)

0 539 n
5 .

59
.
=
.

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2015 Free-Response Questions

Question 3

The structures of two compounds commonly found in food, lauric acid, C12H24O2 , and sucrose, C12H22O11 ,
are shown above.
(a) Which compound, lauric acid or sucrose, is more soluble in water? Justify your answer in terms of the
intermolecular forces present between water and each of the compounds.

sucrose is more soluble

acid has
because lauric

Stronger
I MF

(b) Assume that a 1.5 g sample of lauric acid is combusted and all of the heat energy released is transferred to
a 325 g sample of water initially at 25°C. Calculate the final temperature of the water if ∆Hcombustion of
-

lauric acid is −37 kJ/g and the specific heat of water is 4.18 J/(g⋅K).
-

-H =
M .

S .

&T
1 5
. x 4 18 .
+ T = -

37

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2015 Free-Response Questions

Question 3 (continued)

(c) In an attempt to determine ∆Hcombustion of lauric acid experimentally, a student places a 1.5 g sample of
-

lauric acid in a ceramic dish underneath a can made of Al containing 325 g of water at 25°C. The student
-

ignites the sample of lauric acid with a match and records the highest temperature reached by the water in
- -

the can.
&
(i) The experiment is repeated using a can of the same mass, but this time the can is made of Cu.
The specific heat of Cu is 0.39 J/(g⋅K), and the specific heat of Al is 0.90 J/(g⋅K). Will the final
temperature of the water in a
-

the can made of Cu be greater than, less than, or equal to the final
-

temperature of the water in the can made of Al? Justify your answer.
than of water
greater temp
Al because since
made of
can
in heat it can
lower specific
it has
more ecesily .
change temp
(ii) In both experiments it was observed that the measured final temperature of the water was less than
the final temperature calculated in part (b). Identify one source of experimental error that might
account for this discrepancy and explain why the error would make the measured final temperature
-

of the water lower than predicted.

-

in beaker
water
droplets
before experiment

(d) The experiment described above is repeated using a 1.5 g sample of sucrose. The combustion reaction for
sucrose in air is represented below.
C12H22O11(s) + 12 O2(g) Æ 12 CO2(g) + 11 H2O(g)
(i) Even though ∆G ° for the combustion of sucrose in air has a value of −5837 kJ/molrxn , the
combustion reaction does not take place unless it is ignited. Explain.
-

needs
combustion to take
with heat
place

(ii) Predict the sign of ∆S ° for the reaction and justify your prediction.

because the reaction

Positive
would be spontaneous

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2015 Free-Response Questions

Question 4

Boiling Point of Compound Dipole Moment Polarizability

Molecule
& (K) (debyes) (10−24 cm3)
HCl 188 1.05 2.63
HBr 207 0.80 3.61
HI 238 0.38 5.44

The boiling points, dipole moments, and polarizabilities of three hydrogen halides are given in
the table above.
(a) Based on the data in the table, what type of intermolecular force among the molecules HCl(l ), HBr(l ),
and HI(l ) is able to account for the trend in boiling points? Justify your answer.

molecules become more polar

as
because stronger
BP
increases
BP
IMF means increasing
bord between atomy
becourse stronger

(b) Based on the data in the table, a student predicts that the boiling point of HF should be 174 K.
The observed boiling point of HF is 293 K. Explain the failure of the student’s prediction in terms
of the types and strengths of the intermolecular forces that exist among HF molecules.

HE has bond
a hydrogen
So A would be stronger

than the students prediction

(c) A representation of five molecules of HBr in the liquid state is shown in box 1 below. In box 2,
draw a representation of the five molecules of HBr after complete vaporization has occurred.

00 .

00 .

.. & O

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Question 5
Answer the following questions about two isomers, methyl methanoate and ethanoic acid. The molecular
formula of the compounds is C2H4O2 .
(a) Complete the Lewis electron-dot diagram of methyl methanoate in the box below. Show all valence
electrons.

...

'
-

- - -
-

A student puts 0.020 mol of methyl methanoate into a previously evacuated rigid 1.0 L vessel at 450 K.
The pressure is measured to be 0.74 atm. When the experiment is repeated using 0.020 mol of ethanoic acid
instead of methyl methanoate, the measured pressure is lower than 0.74 atm. The lower pressure for ethanoic
acid is due to the following reversible reaction.
CH3COOH(g) + CH3COOH(g) ! (CH3COOH)2(g)

(b) Assume that when equilibrium has been reached, 50. percent of the ethanoic acid molecules have reacted.

(i) Calculate the total pressure in the vessel at equilibrium at 450 K.

-

Pro += 0 . 4&

(ii) Calculate the value of the equilibrium constant, Kp , for the reaction at 450 K.

Kp = IP (H) (00H]2
-
= I I
[P(H > 100 H)

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Question 6

Peak 1 Peak 2 Peak 3

4 3
6.72 × 10 kJ/mol 3.88 × 10 kJ/mol 1.68 × 103 kJ/mol

The complete photoelectron spectrum of an unknown element is shown above. The frequency ranges
of different regions of the electromagnetic spectrum are given in the table below.
-

Region of Electromagnetic Spectrum Frequency Range (s−1)

Infrared (IR) 1 × 1012 to 4 × 1014

Ultraviolet/visible (UV/vis) 4 × 1014 to 5 × 1016

X­rays 5 × 1016 to 1 × 1019

Gamma rays > 1 × 1019

(a) To generate the spectrum above, a source capable of producing electromagnetic radiation with an energy
of 7 × 104 kJ per mole of photons was used. Such radiation is from which region of the electromagnetic
spectrum? Justify your answer with a calculation.

infrared

(b) A student examines the spectrum and proposes that the second ionization energy of the element is
-
3.88 × 103 kJ/mol. To refute the proposed interpretation of the spectrum, identify the following.
(i) The subshell from which an electron is removed in the second ionization of an atom of the element

IS
(ii) The subshell that corresponds to the second peak of the photoelectron spectrum above

23
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2015 Free-Response Questions

Question 6 (continued)
(b) A student examines the spectrum and proposes that the second ionization energy of the element is
3.88 × 103 kJ/mol. To refute the proposed interpretation of the spectrum, identify the following.
(i) The subshell from which an electron is removed in the second ionization of an atom of the element

23

(ii) The subshell that corresponds to the second peak of the photoelectron spectrum above

31

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