2013 U.S.

NATIONAL
CHEMISTRY OLYMPIAD
NATIONAL EXAM - PART II
Prepared by the American Chemical Society Olympiad Examinations Task Force

OLYMPIAD EXAMINATIONS TASK FORCE

Arden P. Zipp, Chair, State University of New York, Cortland, NY
James Ayers, Mesa State College, Grand Junction, CO
Peter Demmin, Amherst HS, Amherst, NY (deceased)
Marian DeWane, Centennial HS, Boise, ID
Xu Duan, Holton-Arms School, Bethesda, MD
Valerie Ferguson, Moore HS, Moore, OK
Julie Furstenau, Thomas B. Doherty HS, Colorado Springs, CO
Kimberly Gardner, United States Air Force Academy, CO
Paul Groves, South Pasadena HS, South Pasadena, CA
Preston Hayes, Glenbrook South HS, Glenbrook, IL (retired)
Jeff Hepburn, Central Academy, Des Moines, IA
David Hostage, Taft School, Watertown, CT
Adele Mouakad, St. John's School, San Juan, PR
Jane Nagurney, Scranton Preparatory School, Scranton, PA
Ronald Ragsdale, University of Utah, Salt Lake City, UT
Peter Sheridan, Colgate University, Hamilton, NY (retired)
DIRECTIONS TO THE EXAMINER - PART II
Part II of this test requires that student answers be written in a response booklet with blank pages. Only this "Blue Book" is graded
for a score on Part II. Testing materials, scratch paper, and the "Blue Book" should be made available to the student only during the
examination period. All testing materials including scratch paper should be turned in and kept secure until April 15, 2013, after
which tests can be returned to students and their teachers for further study.
Allow time for the student to read the directions, ask questions, and fill in the required information on the "Blue Book". When the
student has completed Part II, or after one hour and forty-five minutes have elapsed, the student must turn in the "Blue Book", Part
II of the testing materials, and all scratch paper. Be sure that the student has supplied all of the information requested on the front of
the "Blue Book," and that the same identification number used for Part I has been used again for Part II.
There are three parts to the National Olympiad Examination. You have the option of administering the three parts in any order, and
you are free to schedule rest breaks between parts.
Part I
60 questions
single-answer multiple-choice
1 hour, 30 minutes
Part II
8 questions
problem-solving, explanations
1 hour, 45 minutes
Part III
2 lab questions
laboratory practical
1 hour, 30 minutes
A periodic table and other useful information are provided on page 4 for student reference. Students should be permitted to use nonprogrammable calculators.
DIRECTIONS TO THE EXAMINEE - PART II
DO NOT TURN THE PAGE UNTIL DIRECTED TO DO SO. Part II requires complete responses to questions involving
problem-solving and explanations. One hour and forty-five minutes are allowed to complete this part. Be sure to print your name,
the name of your school, and your identification number in the spaces provided on the "Blue Book" cover. (Be sure to use the same
identification number that was coded onto your Scantron sheet for Part I.) Answer all of the questions in order, and use both sides
of the paper. Do not remove the staple. Use separate sheets for scratch paper and do not attach your scratch paper to this
examination. When you complete Part II (or at the end of one hour and forty-five minutes) you must turn in all testing materials,
scratch paper, and your "Blue Book ". Do not forget to turn in your U.S. citizenship/ Green Card Holder statement before
leaving the testing site today.
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Distributed by the American Chemical Society, 1155 16th Street, N.W., Washington, DC 20036
All rights reserved. Printed in U.S.A.

1. [12] A compound contains only C, H, O and Cu. It is analyzed for its carbon and hydrogen content by combustion. The copper

content is obtained by reacting it with I according to equation (1),

2+
(1) 2 Cu (aq) + 5 I (aq) 2 CuI(s) + I3 (aq)

and reacting the I3 formed with standard thiosulfate, S2O32 according to equation (2).

(2) I3 (aq) + 2 S2O32 (aq) 3 I (aq) + S4O62 (aq)

a. The combustion of a 0.250 g sample of the compound produces 0.504 g of CO 2 and 0.0743 g of H2O. Determine the mass
percentages of carbon and hydrogen in the compound.
b. In the analysis for Cu2+, a 0.115 g sample of the compound is reacted with concentrated nitric acid, evaporated to dryness and

the residue is dissolved in H2O. The Cu2+ in the resulting solution is reacted with excess I and the resulting I3 is titrated

with 0.0320 M S2O32 , requiring 11.75 mL.

i. Name the indicator used for the titration of I3 with S2O32 and describe the color change observed.
2+
ii. Determine the moles of Cu and calculate the mass percentage of Cu in the compound.
c. Find the mass percentage of oxygen and write the empirical formula for the compound.
d. A solution prepared by dissolving 0.100 g of this compound in 15.00 g of benzene, C6H6, freezes at 5.436 C. Find the molar

mass and molecular formula of the compound. [C6H6 m.p. = 5.490 C, kf = 4.90 Cm 1]
2. [14] Some thermodynamic properties of liquid and gaseous benzene are given below.
C6H6(l)
C6H6(g)

Hf, kJmol
48.7
82.9

S, J mol 1 K
173.3
269.0

Hcombustion , kJmol
3273
NA

a. Calculate the vapor pressure of benzene at 25 C in mm Hg.

b. Calculate the enthalpy change associated with the hypothetical reaction: C 6H6(l) 6C(s) + 3H2(g) for 1.50 g of C6H6.
c. Write a balanced equation for the complete combustion of one mole of benzene.
d. Use the bond energies below to calculate an estimated bond energy of the carbon-carbon bonds in benzene.
Bond
Energy, kJ/mol

CH
414

CO
351

C=O
799

CO
1070

HO
464

OO
142

O=O
498

e. 1.50 g of benzene is burned in a bomb calorimeter with a heat capacity of 5.99 kJ/C submerged in 1.00 kg of water at

22.50 C. Determine the final temperature of the system. [Specific heat of H 2O (l) = 4.18 Jg 1C 1]
3. [10] The thermal decomposition of peroxynitric acid, HO 2NO2, has been studied and found to be first-order. The rate constant

was determined to be 2.1 10 1 s 1 at 331 K and 1.1 s 1 at 342 K.

a. Calculate the half-life of HO2NO2 at 331 K in seconds.

b. For a sample of HO2NO2 with an initial concentration of 7.1 10 8 molL 1, calculate the concentration of HO2NO2 after
0.40 minutes at 331 K.
c. Sketch a graph for the decomposition of HO2NO2 at 331 K for three half-lives and predict the fraction remaining after five
half-lives.
d. Calculate the activation energy of the reaction.
4. [14] A 0.0343 mol sample of XCl3(g) is added to an evacuated 1.50 L glass bulb. The bulb is sealed, heated to 100 C and the
following equilibrium is established: 2XCl3(g)
2X(g) + 3Cl2(g)
At equilibrium, the final pressure in the bulb is 0.800 atm.
a. Calculate the pressure of XCl3(g) in the bulb at 100 C if no reaction had occurred.
b. Calculate the equilibrium partial pressures of
i. XCl3(g),
ii. X(g),
iii. Cl2(g).
c. Determine the value at 100 C of:
i. Kp.

ii. G in kJmol 1.
d. Calculate the value of Kc at 100 C.
e. Write an expression that can be used to solve for the concentration of XCl 3 at equilibrium when 0.0500 mole of XCl3 is
placed in an evacuated 2.00 L glass bulb at 100 C. You need not solve this expression.

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Page 2

5. [12] Write net equations for each of the reactions below. Use ionic and molecular formulas as appropriate and omit formulas
for all ions or molecules that do not take part in a reaction. Write structural formulas for all organic substances. You need not
balance the equations or specify physical states.
a. Calcium sulfite is heated to a high temperature in a vacuum.
b. Solutions of sodium oxalate and acidified solution potassium permanganate are mixed.
c. Solutions of magnesium sulfate and barium hydroxide are mixed.
d. Gaseous dimethylamine and hydrogen chloride are mixed.
e. Toluene is reacted with chlorine in the presence of aluminum chloride.
f. Carbon-11 undergoes positron emission during a PET scan.
6. [13] Consider the highly reactive molecule SF3Cl.
a. Draw all of the possible structures of SF3Cl with S as the central atom.
b. Use VSEPR theory to predict the most stable structure in a. and justify your answer.
c. Recent calculations predict that the two structures that are lowest in energy differ by about 0.2 kJ/mol. Identify the second
lowest energy structure and justify your answer.
d. Nuclear magnetic resonance (NMR) spectroscopy can be used to distinguish between atoms in different environments in a
molecule. State and account for the number of unique F-19 signals if 19F NMR were carried out on SF3Cl at
i. a low temperature (e.g. 80 C)
ii. room temperature in solution.
e. While selenium and tellurium can potentially form SeF3Cl and TeF3Cl, an OF3Cl species is not known even though oxygen
has the same valence electron configuration. Account for this difference in the behavior of oxygen.
7. [10] Consider two solutions, each of which contains two volatile components. The vapor pressure of each of these components
at 25 C is given in the table below.
Substance
CCl4
CHCl3
CH3C(O)CH3
Vapor pressure at 25 C, torr
98.8
172.5
222
a. Solution 1 consists of chloroform and carbon tetrachloride, which form an ideal solution.
i. Describe an ideal solution in terms of the interactions of the component molecules and explain why CCl 4 and CHCl3 form
an ideal solution.
ii. Sketch a graph of vapor pressure vs. mole fraction CHCl3 for a CHCl3 CCl4 solution at 25 C and predict the vapor
pressure of a solution that is 0.30 mole fraction CHCl3.
iii. Describe how the composition of the vapor over this solution compares with the composition of the solution. Justify your
answer.
b. Propanone, CH3C(O)CH3, and chloroform mix with the release of heat.
i. Describe or sketch clearly the interaction between the propanone and chloroform molecules that is responsible for the heat
release.
ii. Use the axes from a. to sketch a graph of vapor pressure vs. mole fraction CHCl3 and account for its appearance.
8. [15] There are four isomeric alcohols with the formula C4H10O.
a. Write structural formulas for these four compounds.
b. One of the four alcohols is chiral (stereogenic). Write stereochemical structures for the two enantiomeric forms of this
compound. Comment on any differences in their chemical and physical properties.
c. Three of the alcohols in a. undergo oxidation to form aldehydes or ketones. Write structures for these products and account
for the fact that the fourth alcohol does not react in this way.
d. Several compounds exist with this formula but a different functional group. Name the functional group and write structures
for all the compounds with this functional group.

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Page 3

ABBREVIATIONS AND SYMBOLS

amount of substance
ampere
atmosphere
atomic mass unit
Avogadro constant
Celsius temperature
centi prefix
coulomb
density
electromotive force
energy of activation
enthalpy
entropy
equilibrium constant

n
A
atm
u
NA
C
c
C
d
E
Ea
H
S
K

Faraday constant
F
free energy
G
frequency

gas constant
R
gram
g
hour
h
joule
J
kelvin
K
kilo prefix
k
liter
L
measure of pressure mm Hg
milli prefix
m
molal
m
molar
M

CONSTANTS

molar mass
mole
Plancks constant
pressure
rate constant
reaction quotient
second
speed of light
temperature, K
time
vapor pressure
volt
volume

M
mol
h
P
k
Q
s
c
T
t
VP
V
V

R = 8.314 Jmol1K1
R = 0.0821 Latmmol1K1
1 F = 96,500 Cmol1
1 F = 96,500 JV1mol1
NA = 6.022 1023 mol1
h = 6.626 1034 Js
c = 2.998 108 ms1
0 C = 273.15 K
1 atm = 760 mm Hg

EQUATIONS

E Eo

1
1A
1
H

RT
ln Q
nF

k E 1 1
ln 2 a
k1 R T1 T2

H 1
ln K
constant
R T

PERIODIC TABLE OF THE ELEMENTS

18
8A
2
He

3
Li

2
2A
4
Be

13
3A
5
B

14
4A
6
C

15
5A
7
N

16
6A
8
O

17
7A
9
F

6.941

9.012

10.81

12.01

14.01

16.00

19.00

20.18

11
Na

12
Mg

13
Al

14
Si

15
P

16
S

17
Cl

18
Ar

22.99

24.31

26.98

28.09

30.97

32.07

35.45

39.95

19
K

31
Ga

32
Ge

33
As

34
Se

35
Br

36
Kr

1.008

4.003

10
Ne

20
Ca

3
3B
21
Sc

4
4B
22
Ti

5
5B
23
V

6
6B
24
Cr

7
7B
25
Mn

8
8B
26
Fe

9
8B
27
Co

10
8B
28
Ni

11
1B
29
Cu

12
2B
30
Zn

39.10

40.08

44.96

47.88

50.94

52.00

54.94

55.85

58.93

58.69

63.55

65.39

69.72

72.61

74.92

78.96

79.90

83.80

37
Rb

38
Sr

39
Y

40
Zr

41
Nb

42
Mo

43
Tc

44
Ru

45
Rh

46
Pd

47
Ag

48
Cd

49
In

50
Sn

51
Sb

52
Te

53
I

54
Xe

85.47

87.62

88.91

91.22

92.91

95.94

(98)

101.1

102.9

106.4

107.9

112.4

114.8

118.7

121.8

127.6

126.9

131.3

55
Cs

56
Ba

57
La

72
Hf

73
Ta

74
W

75
Re

76
Os

77
Ir

78
Pt

79
Au

80
Hg

81
Tl

82
Pb

83
Bi

84
Po

85
At

86
Rn

132.9

137.3

138.9

178.5

180.9

183.8

186.2

190.2

192.2

195.1

197.0

200.6

204.4

207.2

209.0

(209)

(210)

(222)

87
Fr

88
Ra

89
Ac

104
Rf

105
Db

106
Sg

107
Bh

108
Hs

109
Mt

110
Ds

111
Rg

112
Cn

113

114

115

116

117

118

(Uut)

(Uuq)

(Uup)

(Uuh)

(Uus)

(Uuo)

(223)

(226)

(227)

(261)

(262)

(263)

(262)

(265)

(266)

(281)

(272)

(285)

(284)

(289)

(288)

(293)

(294)

(294)

58
Ce

59
Pr

60
Nd

61
Pm

62
Sm

63
Eu

64
Gd

65
Tb

66
Dy

67
Ho

68
Er

69
Tm

70
Yb

71
Lu

140.1

140.9

144.2

(145)

150.4

152.0

157.3

158.9

162.5

164.9

167.3

168.9

173.0

175.0

90
Th

91
Pa

92
U

93
Np

94
Pu

95
Am

96
Cm

97
Bk

98
Cf

99
Es

100
Fm

101
Md

102
No

103
Lr

232.0

231.0

238.0

(237)

(244)

(243)

(247)

(247)

(251)

(252)

(257)

(258)

(259)

(262)

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Page 4

2013 U.S. NATIONAL

CHEMISTRY OLYMPIAD
NATIONAL EXAM PART II

1. a.
mol H
mol H

1.008 g = 8.317

Mass % C = (

103 g H

55.0 % C

Mass % H = (

b. i. Starch indicator. Blue solution turns colorless with excess I3.

ii.
(
(

) = 0.02389 g Cu

c. 55.0 % C + 3.33 % H + 20.77 % Cu = 79.1 % 100 79.1 = 20.9 % O

55.0 C 12.01 = 4.58 0.327 = 14
C14 H10 O4 Cu
3.33 H 1.008 = 3.30 0.327 = 10
FM
20.9 O 16.0 = 1.31 0.327 = 4.0
20.77 63.54 = 0.327 0.327 = 1
d. T = 5.436 C 5.490 C = 0.054 C

0.054 C
0.054 C = ( 4.90 C/m
m = 0.054 C /( 4.90 C/m
m = 0.011 mol/kg 0.015 kg
m = 1.65 104 mol
MM = 0.100 g/1.65 104 mol
MM = 605 g/mol
MM ~ 2 FM
Molecular Formula = C28H20O8Cu2

2. a. =

= 48700

298 K

= 82900

298

173.3

2943

80162 = 2738

269 = 82900

5681 J = 8.314
ln (K) = 2.293

K = 0.101 atm = 76.7 mmHg

b. 1.50 g C6H6
H = (0.0192 mol

48700 J/mol) = 935 J

c. C6H6 + 7 O2 6 CO2 + 3 H2O

Hcomb = 3273

d.

comb = 12 BEC=O + 6 BEHO + [6 BEC-H + 6 BEC-C + 7.5 BEO=O]

3273 = [12(799) + 6(464)] + [6(414) + 6 BEC-C + 7.5(498)]
3273 = [9588 + 2784] + [2484 + 3735 + 6 BEC-C]
3273 = 12372 + [6219 + 6 BEC-C]
3273 + 12372 6219 = 6 BEC-C
6 BEC-C = 2880
BEC-C = 480

e. 1.50 g C6H6
0.0192 mol
5.99

3273

+ 4.18

released
= 10.17

62.8 kJ
22.50

+ 6.18

3. a. ln ( )
b. ln

= 28.68
ln (2) =

) = 0.21 s1
0.21
24 s = 5.04
7.1
= 154.4
= 4.60
M
s-1

final T
=

= 3.3 s

c.
( )

Half lives

d. ln

ln

)
(

(8.314)
(8.314)

ln (5.24)
(1.66) =

4. a. PV = nRT

P=

b. P1 = Px Cl3 + Px + PCl2
0.800 = 0.70
+ x + 1.5
0.800 0.700 = 1.5x
= 0.067
PXCl3 = 0.700

0.067 = 0.633

Px = 0.067
PCl2 = 0.099
c. i.
ii.

d.

2 XCl3

2X

3 Cl2

e.

(0.0500 )

0
1.5
1.5

5. a. CaSO3 CaO + SO2

b. Na2C2O42 + H+ + M
Na+ + Mn2+ + CO2 + H2O
2+
2+
c. Mg +
+ Ba + OH- Mg(OH)2 + BaSO4
d. (CH3)2 NH + HCl (CH3)2 NH2+ Cl
e.

f.

6. a.

b.
Structure is correct for most stable. Lone pair of electrons and the
least electronegative atom (Cl) are in the equatorial plane at 120
degrees apart with very electronegative F atoms in axial positions,
drawing bonding pairs of electrons away from S.

c.
Structure is correct for second most stable. Cl is in an apical position
but the lone pair is still in the equatorial plane, minimizing its
repulsion of the bonding pairs of electrons.

d. i. At
there are 2 signals in a ratio of 2 (apical) to 1 (equatorial).
ii. At room temperature there will be 1 signal as the molecule reorganizes and the
signals average.
e. The central atomin :X F3 Cl has ten electrons around it. While S1 Se and Te can all
accommodate ten electrons, O (with fewer orbital available) cannot do so.
7. a. i. An ideal solution is one in which the forces between the molecules in the
individual components are comparable to the forces between the molecules of the
different components. The CCl4 4 attractions and CHCl3
3 attractions are
similar to the CCl4
attractions.
3
ii.

VP = (.30 172.5) + (0.70

VP = 51.75 + 69.16
VP = 120.9 mmHg

98.8)

iii. Vapor will be richer in CHCl3 than solution because CHCl3 has a higher VP.
b. i.

ii. The V.P. curve will lie below the straight line due to the greater interactions
between the different types of molecules than between similar ones.
8. a.

b.

Chemical properties are the same except for their interaction with chiral substrates.
The two forms will rotate plane polarized light in opposite directions.
c.

cannot be oxidized because C has 4 bonds.

d. ether