THE CANADIAN CHEMISTRY CONTEST 2017
for high school and CEGEP students
(formerly the National High School Chemistry Examination)
PART C: CANADIAN CHEMISTRY OLYMPIAD
Final Selection Examination 2017
Free Response Development Problems (90 minutes)
This segment has five (5) questions. While students are expected to attempt all questions for a
complete examination in 1.5 hours, it is recognized that backgrounds will vary and students will
not be eliminated from further competition because they have missed parts of the paper.
Your answers are to be written in the spaces provided on this paper. All of the paper, including
this cover page, along with a photocopy of Part A of the examination, is to be returned
IMMEDIATELY by courier to your Canadian Chemistry Olympiad Coordinator.
— PLEASE READ — PART A ( )
Correct Answers
1. BE SURE TO COMPLETE THE INFORMATION REQUESTED AT THE
BOTTOM OF THIS PAGE BEFORE BEGINNING PART C OF THE
EXAMINATION. 25 x 1.6 = ......... /040
2. STUDENTS ARE EXPECTED TO ATTEMPT ALL QUESTIONS OF
PART C
PART A AND PART C. CREDITABLE WORK ON A LIMITED
NUMBER OF THE QUESTIONS MAY BE SUFFICIENT TO EARN AN 1. .................... /012
INVITATION TO THE NEXT LEVEL OF THE SELECTION PROCESS.
2. .................... /012
3. IN QUESTIONS WHICH REQUIRE NUMERICAL CALCULATIONS, BE
SURE TO SHOW YOUR REASONING AND YOUR WORK.
3. .................... /012
4. .................... /012
4. ONLY NON-PROGRAMMABLE CALCULATORS MAY BE USED ON
THIS EXAMINATION. 5. .................... /012
5. NOTE THAT A PERIODIC TABLE AND A LIST OF SOME PHYSICAL
CONSTANTS WHICH MAY BE USEFUL CAN BE FOUND ON A DATA
SHEET PROVIDED AT THE END OF THIS EXAMINATION.
TOTAL ............ /100
Name _____________________________ School _____________________________
(LAST NAME, Given Name; Print Clearly)
City & Province _____________________________ Date of Birth __________________
E-Mail ____________________________ Home Telephone ( ) - _________________
Years at a Canadian high school ___ No. of chemistry courses at a Québec CÉGEP ___
Male Canadian Citizen Landed Immigrant Visa Student
Female Passport valid until February 2018 Nationality of Passport __________
Teacher __________________________ Teacher E-Mail ___________________________
GENERAL CHEMISTRY
1. Sulfur dioxide (SO2) is produced by volcanoes and in various industrial processes. Since coal
and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide.
Further oxidation of SO2, usually in the presence of a catalyst such as NO2, forms H2SO4, and
thus acid rain. This is one of the causes for concern over the environmental impact of the use of
these fuels as power sources.
(a). Draw the best two resonance structures for sulfur dioxide, SO2, which do not involve sulfur
using its d-orbitals in "hypervalency". Be sure to include all formal charges (should they exist)
and lone pairs of electrons in your structures.
4 marks
(b). Draw the best resonance form for sulfur dioxide in which sulfur does use its d-orbitals in
bonding. Be sure to include all formal charges (should they exist) and lone pairs of electrons in
your structure.
2 marks
(c). What is the hybridization of the sulfur atom in SO2?
2 marks
(d). Write a reaction involving SO2 which illustrates how its sulfur atom may act as a Lewis base
in reaction with a Lewis acid. In your reaction, designate the Lewis acid as “A”.
2 marks
-2-
(e). Write a reaction involving SO2 which illustrates how its sulfur atom may serve as a Lewis
acid in reaction with a Lewis base. In your reaction, designate the Lewis base as “B”.
2 marks
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PHYSICAL CHEMISTRY
2. Electrons moving back and forth in a one-dimensional box may only occupy discrete energy
levels given by the formula
h2 n = 1, 2, 3...
E = n2
2
8mL
in which n is the energy level, h is Planck’s constant, m is the mass of the electron, and L is the
length of the box.
(a). Calculate the energy of an electron in the second energy level of a box with length 1.00 nm.
1 mark
Pi electrons in a linear, conjugated molecule or section of a molecule can be modeled after the
one-dimensional box system.
(b). In the molecule 1,8-diphenyl-1,3,5,7-octatetratriene shown below, how many pi electrons are
part of the linear, conjugated system between the two phenyl groups?
number of pi electrons: ______
1 mark
(c). The linear, conjugated system in 1,8-diphenyl-1,3,5,7-octatetratriene can be modeled roughly
after a one-dimensional box. How many orbitals do the pi electrons in the system occupy when
the molecule is in the ground state?
1 mark
(d). The Highest Occupied Molecular Orbital, or “HOMO”, is the highest energy level orbital
that is occupied by electrons in ground state. Given a linear, conjugated system with N electrons,
what is the equation for the energy of the HOMO in terms of h, m, and L?
1 mark
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(e). The Lowest Unoccupied Molecular Orbital, or “LUMO”, is the lowest energy level orbital
that is not occupied by electrons in ground state. Given a linear, conjugated system with N
electrons, what is the equation for the energy difference between the HOMO and LUMO in
terms of h, m, and L?
2 marks
Retinal is a form of Vitamin A produced by oxidative cleavage of carotenoids. Retinal has the
following structure:
(f). The conjugated system in retinal can be roughly modeled as a one-dimensional box. Given
that the average length of a C – C bond in the system is 0.140 nm and the average length of a
C =O double bond is 0.123 nm, estimate the length of the box.
2 marks
(g). Calculate the wavelength of light that retinal can absorb to reach an excited state.
4 marks
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INORGANIC CHEMISTRY
3. Titanium is an economically important element used principally in the aerospace industry, but
also in medical prosthetics and as an industrial pigment. For example, the white lettering on
Skittles and M&M candies is made with titanium dioxide, which was recently declared a possible
carcinogen in humans by the International Agency for Research on Cancer (IARC).
(a). Among its minerals, titanium most commonly occurs with an oxidation number of +4. State
the complete electron configuration for titanium, corresponding to this oxidation number. Do not
use short-hand notation.
1 mark
(b). Ilmenite, FeTiO3, is one of the principal titanium-bearing minerals. An essential step in
producing high-purity titanium is the chloride process. Balance the chemical equation below for
the chloride process.
__FeTiO3(s) + __Cl2(g) + __C(s, graphite) __TiCl4(l) + __FeCl3(s) + __CO(g)
1 mark
(c). Write a balanced chemical equation for the complete hydrolysis of titanium tetrachloride.
1 mark
Though titanium metal can be produced from ilmenite by the sulfate process, a higher yield can
be obtained by refining the less common mineral rutile. The rutile unit cell (based upon a
body-centred tetragonal arrangement of titanium atoms) is shown below. The oxygen atoms are
dark-coloured spheres in the rutile unit cell.
(d). Name the localized geometries around oxygen and titanium.
O: _________________________ Ti: _________________________
1 mark
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(e). Given the dimensions of the unit cell, a = b = 0.4584 nm and c = 0.2953 nm, calculate the
density (in g cm-3) of the rutile form of titanium dioxide.
3 marks
(f). Titanium tetrachloride is a liquid at standard ambient temperature and pressure (SATP).
Given ∆Hvap of +37.5 kJ mol-1, a vapour pressure of 1.70 kPa at SATP and using the
Clausius-Clapeyron equation (below), calculate the boiling temperature of TiCl4. Assume no
change in external pressure.
2 marks
(g). High-purity titanium metal can be prepared industrially in a stainless-steel, high-pressure
reactor from titanium tetrachloride and magnesium metal, according to the Kroll process.
Assume the processing temperature is 900°C and a positive pressure (P > 100 kPa) is maintained
within the reactor by means of an inert gas. Using the data provided below, explain how titanium
metal could be produced by the Kroll process with the use of a diagram and a balanced chemical
reaction. If you were unable to obtain an answer from part (f), use 150°C for the boiling point of
TiCl4.
Substance Melting point (°C) Boiling point (°C) Density at 25°C (g cm-3)
TiCl4 -24 see part (f) 1.726
Mg 650 1091 1.584
Ti 1668 3287 4.506
MgCl2 714 1412 2.325
3 marks
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ORGANIC CHEMISTRY
4. GlaxoWellcome first marketed the pharmaceutical bupropion (structure below) in 1985 under
the trade-name Wellbutrin® as a treatment for depression. Many smokers taking the drug
reported that after one or two weeks their craving for tobacco ceased and they were able to quit
smoking with few withdrawal symptoms. Bupropion therefore began to be marketed in 1997
with a new name (Zyban®) for use as an aid in smoking cessation.
+
N Cl- Bupropion
Cl H H
Bupropion can be prepared from benzene according to the following scheme:
Q T
S V
R C9H10O U
O
Cl
Br2, H+ catalyst
X
Z C4H11N
Bupropion Y W
(a). Draw the structures of reagents Q, R, T, U, X and Z.
Q= R= T=
U= X= Z=
3 marks
(b). Draw the structures of intermediate compounds S, W and Y.
S= W= Y=
3 marks
(c). State how many stereoisomers of bupropion exist.
0.5 marks
-8-
(d). State whether you would expect bupropion to be soluble or insoluble in water, explaining
your reasoning IN LESS THAN TEN WORDS.
0.5 marks
(e). Draw the major organic product formed when intermediate compound V reacts with each of
the following five sets of reagents:
NaBH4, ethanol:
(1) CH3MgBr, ether, then (2) H3O+:
H2, Pt metal:
CH3NH2, H+ catalyst:
(CH3)2NH, H+ catalyst:
5 marks
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ANALYTICAL CHEMISTRY
5. The concentration of copper(II) ions in a dilute solution may be determined by a two-step
titration procedure as follows:
the sample is treated with excess potassium iodide, resulting in the formation of copper(I)
iodide and iodine
the iodine formed is titrated with sodium thiosulfate
(a). Balance the net ionic equation for the reaction of copper(II) with iodide.
_ Cu2+ (aq) + _ I– (aq) _ CuI (s) + _ I2 (aq)
1 mark
(b). Balance the net ionic equation for the reaction of iodine with thiosulfate.
_ I2 (aq) + _ S2O32– (aq) _ I– (aq) + _ S4O62– (aq)
1 mark
(c). Using these balanced equations, derive a relationship between the number of moles of
copper(II) nCu in the sample and the number of moles of thiosulfate nT required to reach the
stoichiometric equivalence point for the titration.
2 marks
(d). An excess of iodide is added to 50.00 mL of a solution containing copper(II). The solution
is then titrated with 0.1002 M thiosulfate, requiring 32.07 mL to reach the equivalence point.
Determine the initial concentration of copper(II) in the sample, making sure to show all steps in
your calculation.
2 marks
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(e). It is very important that an excess of iodide is used in the first step of this procedure. What
does the excess iodide do?
2 marks
(f). Suggest a suitable indicator that you could use for this titration. At what point in the
procedure would you add this indicator?
2 marks
(g). Titrations involving iodine require a number of precautions. Suggest two possible issues,
and the precautions you would take to deal with them.
2 marks
--END OF PART C--
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Data Sheet
Fiche de données
1 18
1 2
H He
1.008 2 13 14 15 16 17 4.003
Relative Atomic Masses (2012, IUPAC) Masses Atomiques Relatives (UICPA, 2012)
3 4 *For the radioactive elements the *Dans le cas des éléments radioactifs, la masse
5 6 7 8 9 10
Li Be atomic mass of an important isotope is given atomique fournie est celle d’un isotope important
B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.38 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.96 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
(223) (226) (227) (261) (262) (266) (264) (277) (268) (269) (272) (285) (284) (289) (288) (292) (294)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb 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 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.0 (231.0 (238.0) (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
Symbol Value
Symbole Quantité numérique
Atomic mass unit amu 1.66054 x 10-27 kg Unité de masse atomique
Avogadro’s number N 6.02214 x 1023 mol-1 Nombre d’Avogadro
Charge of an electron e 1.60218 x 10-19 C Charge d’un électron
Dissociation constant (H2O) Kw 1.00 x 10-14 (25ºC) Constante de dissociation de l’eau (H2O)
Faraday’s constant F 96 485 C mol-1 Constante de Faraday
Gas constant R 8.31451 J K-1 mol-1 Constante des gaz
0.08206 L atm K-1 mol-1
Mass of an electron me 9.10939 x 10-31 kg Masse d’un électron
Mass of a neutron mn 1.67493 x 10-27 kg Masse d’un neutron
Mass of a proton mp 1.67262 x 10-27 kg Masse d’un proton
Planck’s constant h 6.62608 x 10-34 J s Constante de Planck
Speed of light c 2.997925 x 108 m s-1 Vitesse de la lumière
Rydberg constant R∞ 1.097 x 107 m-1 Constante de Rydberg
1Å = 1 x 10-10 m STP/TPN SATP/TPAN
1 atm = 101.325 kPa 273.15 K 298 K
1 bar = 1 x 105 Pa 100 kPa 100 kPa
