THE CANADIAN CHEMISTRY CONTEST 2015

for high school and CEGEP students

(formerly the National High School Chemistry Examination)

PART C: CANADIAN CHEMISTRY OLYMPIAD

Final Selection Examination 2015
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 2016 Nationality of Passport __________
Teacher __________________________ Teacher E-Mail ___________________________ 
PHYSICAL CHEMISTRY

1. Chlorine in the atmosphere reacts readily with ozone. One of the many reaction pathways
between chlorine radicals and ozone in the troposphere occurs as follows:

Step 1: Cl + O3  ClO + O2

Step 2: ClO + O  Cl + O2

(a). Write a balanced equation for the overall reaction taking place in the troposphere.

1 mark

(b). What role do Cl atoms play in the overall reaction?

1 mark

Parts (c). and (d). refer to Step 1:

In an experiment measuring the reaction between ozone and atomic chlorine, the following data
were recorded at 298 K:

[Cl] [O3] Rate

(molecule cm-3) (molecule cm-3) (molecule cm-3 s-1)
4.80 x 1011 8.22 x 109 4.75 x 1010
9.60 x 1011 1.64 x 1010 1.91 x 1011
9.66 x 1011 3.25 x 1010 3.79 x 1011

(c). Write out the rate equation for this reaction.

1 mark

(d). Calculate the rate constant, k at 298K, and give its units.

1 mark

(e). At 200K, the rate constant for Step 1 is 66% of its value at 298K. Showing all work,
calculate the activation energy of this reaction.

3 marks
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(f). From the four reaction energy diagrams below for the breakdown of ozone by chlorine
atoms, which best represents the influence of chlorine? (circle one of (i), (ii), (iii) or (iv)).

(i) (ii)

(iii) (iv)

1 mark
(g). One way to measure the relative concentrations of atomic chlorine is using spectroscopic
methods, where the resonant fluorescence of Cl is monitored as it reacts with ozone. This
fluorescence signal arises predominantly from the (4s13p4)4P3/2  (3p5)2P3/2 transition in
chlorine, with an energy difference of 9.0 eV. What wavelength of light does this transition give
rise to? (the charge of one electron, 1.602 x 10-19 C = 1.0 eV).

1 mark
(h). Both ozone and molecular oxygen are susceptible to photolysis. Photolysis of O2 requires a
photon of no more than 240 nm, whereas photolysis of O3 requires a photon of no more than
320 nm. Draw Lewis structures of O2 and O3 including resonance structures and the locations of
lone pair electrons. Which molecule has stronger bonds and why?

3 marks
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INORGANIC CHEMISTRY

2. Lithium ion batteries are widely used as rechargeable energy sources in smartphones, tablets
and cordless power tools. Lithium ion batteries have distinct advantages over other rechargeable
energy sources, such as lighter weight, smaller size and higher energy density. However, their
disadvantages are well-documented: overheating lithium ion batteries caused fires that led to the
world-wide grounding of all Boeing 787 aircraft in 2013. Among the various cathode materials
used in these batteries is lithium iron disulfide, Li2FeS2.

(a). State the electron configuration of sulfide.

1 mark

(b). Determine the oxidation number of iron in Li2FeS2.

1 mark

(c). In the rechargeable cell, elemental lithium reacts with lithium iron disulfide to produce
elemental iron and lithium sulfide. Write a balanced chemical equation for this reaction.

2 marks

(d). Name the chemical process by which the iron in Li2FeS2 is transformed to elemental iron.

1 mark
(e). An essential chemical property of carbon is its ability to catenate, i.e. to form long chains of
carbon atoms bonded to one another. Similarly, sulfur will catenate, though to a lesser extent
than carbon. The standard state of sulfur is defined to be S8 (m.p. 119 °C), with the structure
shown below.

The average bond dissociation enthalpy for a sulfur-sulfur bond in S8 is +266 kJ mol-1 and the
enthalpy of sublimation for S8 is +100 kJ mol-1. Determine the enthalpy change when one mole
of sulfur in its standard state is decomposed into gaseous sulfur atoms.

2 marks
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Transition metal disulfides, MS2, occur in two broad classes of structure, depending on their
bonding. One class consists of two-dimensional metal ion layers sandwiched between sulfide
layers. For example, molybdenum – commonly occurring as Mo(IV) – forms MoS2, which is
used as a lubricant in high temperature and pressure applications. The other class consists of a
three-dimensional network structure of metal ions and discrete disulfide ions, S22-, such as the
iron compound, pyrite.

For the sake of clarity, iron and sulfur will be referred to as atoms in parts (f) and (g). The
crystal structure of pyrite reveals a unit cell with a face-centred cubic arrangement of iron atoms
(see below). In the unit cell, the centre of each iron atom is either located on one of the eight
vertices of the cube or in the centre of one of the six faces of the cube (the sulfur atoms have
been omitted for clarity).

(f). According to the chemical formula of pyrite and the unit cell above, determine the equivalent
number of iron atoms within the unit cell and the corresponding number of sulfur atoms that
must be located within the unit cell.

2 marks

(g). Within the unit cell, each iron atom has local octahedral geometry of surrounding sulfur
atoms. Each sulfur has local tetrahedral geometry, surrounded by one sulfur atom and the
remainder being iron atoms. Sketch each of these geometries below, clearly differentiating
between sulfur and iron and indicating relevant bond angles.

3 marks

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ORGANIC CHEMISTRY
3. Norethindrone (structure below) is the steroidal hormone that formed the basis of the first oral
contraceptive pill. In 1951, it was practically synthesized for the first time in Mexico by Carl
Djerassi and coworkers (Djerassi passed away on January 30th 2015 at the age of 91).

OH

norethindrone

(a). How many chirality centres (stereocentres) are present in norethindrone? What is the
absolute configuration of the carbon-carbon double bond? (use the descriptor R, Z, S or E).

Chirality centres: Configuration of alkene:

1 mark

(b). What is the numerical degree of unsaturation present in norethindrone?

1 mark

(c). State the names of the different functional groups found in norethindrone.

2 marks

(d). A similar substance (compound B, structure below) was of interest to researchers as an

alternative to norethindrone. Compound B is to be synthesized from compound A via three
reaction steps ((i), (ii) and (iii)). Two intermediate compounds (X and Y) are formed along the
pathway from A to B (note that “Ph” represents a benzene ring in compound B).

OH OH

A B
Ph
O HO

Draw structures of X and Y and state reagents needed to accomplish each of the three reaction
steps. Draw the structure of the compound formed (Z) when A is separately reacted with
pyridinium chlorochromate.

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(i) (ii) (iii)

X: Y: Z:

6 marks

(d). When compound B was synthesized in a research laboratory, a chemist left a sample of it
heating overnight in concentrated phosphoric acid. When he returned the next morning, a new
substance had formed (C). Draw a possible structure for compound C below.

2 marks

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ANALYTICAL CHEMISTRY

4. A salt is to be analysed for its bromide content. In one trial, a sample of 1.0273 g of the finely
ground salt is dissolved in water and treated with excess silver nitrate. Once reaction is
complete, the resulting silver bromide precipitate is separated by filtration, washed with cold
water, then dissolved in a solution of 0.3 g of K2[Ni(CN)4] in 1:1 ammonia/ammonium chloride
buffer. After diluting to ~150 mL and adding a suitable indicator, the resulting solution was
titrated with standard 0.1017 M EDTA, yielding a murexide indicator end-point volume of
14.76 mL.

(a). Write a balanced equation for the net reaction between solid silver bromide and the
[Ni(CN)4]2– anion, given that one of the products is [Ag (CN)2]–. What type of reaction is this?

2 marks

(b). What is the relationship between the number of moles of bromide precipitated by the silver
nitrate and the number of moles of EDTA used to reach the end-point in the titration, given that
metal cations form a 1:1 complex with EDTA?

1 mark

(c). Use this information to calculate the number of moles of bromide present in the mass of
sample analysed in this experiment. Show your calculation for full marks.

3 marks

(d). Express the amount of bromide in the sample as a percentage by mass (%w/w).

2 marks

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(e). Because the nickel–EDTA complex forms slowly, great care must be taken towards the end
of this titration in order to obtain an accurate and reproducible end-point. Zinc forms a more
stable complex with EDTA at a much faster rate than nickel, however the [Zn(CN)4]2– complex
is more stable than the [Ag(CN)2]–complex. Suggest a scheme by which the zinc–EDTA
reaction could be exploited to provide a better end-point than the nickel–EDTA one.

2 marks

(f). It has been noted that reducing species in the sample interfere in this titration. How might
this occur, and how would this affect the final result?

2 marks

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BIOLOGICAL CHEMISTRY

5. This question is about the enzymes that polymerize deoxyribonucleic acid. DNA is the basis
of heritable information transfer for living things. Information is transmitted through a code of
just four letters that represent four bases: G, C, A, and T. These letters are then combined with
dizzying proportions to build the genomes of different organisms. Below are the chemical
structures of the four bases.
O NH 2 NH 2 O
N NH N N H 3C
N NH
8 G C A T
N N NH 2 N O N N N O

(a). Consider that a single DNA polymerase enzyme is able to replicate a strand of B-form DNA
(3.4 nm per turn and about 10 base pairs per turn) at 800 nucleotides per second. How long in
minutes will it take for the polymerase to copy a specific chromosome (48,129,895 base pairs)?
How fast is it moving (in μm/s)?

2 marks
(b). In order to mitigate the impact of mistakes in replication, polymerases in higher organisms
have evolved proofreading mechanisms. The error rate for Taq, a commonly-used polymerase
that lacks proofreading capabilities, is about 3.0 x 10-4 per base. Consider the case where Taq is
responsible for copying your genome once. Assuming that all mutations are uniformly
distributed, that there are 19,000 human genes and that only about 2% of genomic DNA encodes
those proteins, how many mutations would each gene receive?

1 mark

(c). When people think about specificity for a DNA sequence they consider the Watson-Crick
base pairing as a mode of base-base recognition. Base-pairing between G and C involves three
hydrogen bonds. Draw a GC base pair in the space below, explicitly showing the hydrogen
bonds between the two bases.

3 marks

(d). Like other molecules, DNA is prone to chemical degradation. Unfortunately for us, since
DNA is the carrier of our heritable information, our cells must find a way to repair damage that
might otherwise cause information to be lost. One type of damage is the oxidation of guanosine
(G) to 8-oxoguanosine (OG) to form a lesion (abnormality).
O O
H
N [O] N NH OG
NH
G O
N N NH 2 N N NH 2

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In humans, an enzyme called hOGG1 is responsible for the recognition and removal of an OG
lesion. hOGG1 removes the damaged base and leaves an “abasic” site. It follows a somewhat
complex kinetic expression (below), for which the rate constants have each individually been
resolved (see table).
k1 k2 k3 k4 k5
E+S ES1 ES2 ES3 EP E+P
k-1 k-2 k-3

Rate constant (unit) Mean value

k1 (?) 2.6 x 108
k-1 (s-1) 130
k2 (s-1) 13.3
k-2 (s-1) 1.16
k3 (s-1) 0.012
k-3 (s-1) 0.07
k4 (s-1) 0.06
k5 (s-1) 0.0064

(e). What are the units of k1?

1 mark

(f). What is the rate-limiting step for the removal of an OG lesion by hOGG1 (state both the rate
constant and the physical event this corresponds to)?

2 marks
(g). A molecule, P2, was recently discovered as an inhibitor of hOGG1. If we simplify the
kinetic scheme to that shown below, we can try to understand the mechanism by which P2
functions.
k1 k 5*
E+S ES1 E+P
k-1

(h). Provide an expression for the reaction velocity (V) (i.e. the rate) in terms of [ES1]. In
addition, write the mass-balance equation for the total enzyme concentration, [E]total.

2 marks
(i). If the inhibitor P2 is a competitive inhibitor (whose binding is mutually exclusive with the
substrate S), would you expect to see a change in the maximal velocity (Vmax) for hOGG1 upon
addition of the inhibitor? Briefly explain.

1 mark
--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