NATIONAL HIGH SCHOOL CHEMISTRY EXAMINATION 2000

PART A – MULTIPLE CHOICE QUESTIONS (60 minutes)

227
1. When the unstable nuclide 89 Acundergoes β decay, the resulting nuclide is:
A. 223
87 Fr B. 227
89 Ac C. 227
88 Ra D. 227
90Th E. 231
91Pa

2. A sample of H 2 (2.0 g) was burnt in Cl2 (75.0 g) containing a naturally occurring mixture of
isotopes. The resulting gas mixture was analyzed by mass spectrometry. The biggest peak
was found at which of the following mass numbers?
A. 36 B. 38 C. 70 D. 72 E. 74

3. Which of the following species has the greatest number of parallel spin electrons in the
ground state?
A. Cr B. Mn C. Fe3+ D. Co2+ E. Cu+

4. Which of the following species contains an element in an oxidation state that is not a whole
number?
A. VO43– B. Mn2O3 C. S4O62– D. Cl2O7 E. Cr2O72–

5. A certain substance contains 54.50% carbon and 9.09% hydrogen by mass. It molecular
formula could be:
A. CH 2 B. C2H4 C. C2H5OH D. C3H7CHO E.C3H7CO2H

6. Which one of the following species has the largest radius?

A. Cl– B. Ar C. K D. Ca E. Cu+

7. Which of the following molecules has the smallest bond angle between its atoms?
A. H 2O B. NH 3 C. SO3 D. CH 4 E. XeF4

8. The following sequence of reactions may be used to extract zinc from its sulfide ore:
2ZnS + 3O 2 → 2ZnO + 2SO 2
ZnO + C → Zn + CO
How many tonnes of zinc can be obtained from 20 tonnes of zinc sulphide, assuming that the
yield is 75%?
A. 5 B. 10 C. 12 D. 15 E. 20

9. Which one of the following substances in their standard state are held together by covalent
bonds ONLY?¤
A. C B. AgBr C. SiO2 D. NaOH E. C6H12O6

10. Which one of the following substances has the highest boiling point?
A. CH 3COCH 3 B. CH3CO2CH3 C. CH3(CH2)2OH
D. CH 3(CH2)2CH3 E. CH3CHOHCH3
11. A solution of iodine was prepared by dissolving 12.70g of I2 and 20g of KI in water, and
making the volume up to 1 L. A 10.00 mL aliquot of this solution was titrated with standard
0.0500 M sodium thiosulphate solution, according to the following equation;
I2 + 2Na2S2O3 → Na2S4O6 + 2NaI
The volume of sodium thiosulphate used was 18.34mL. The molarity of the I2 solution in
mol/L was therefore:
A. 0.04585 B. 0.05004 C. 0.05453 D. 0.1001 E. 0.1205

12. Which one of the following compounds gives the highest pH when dissolved in water?
A. CH 3NH 2 B. CH3CO2H C. CH3CONH 2
D. CH 3CO2NH 4 E. CH3NH 2CO2H

13. A concentrated aqueous solution of H2SO4 is 86% by mass and has a density of 1.78 g/mL.
50 mL of this solution is diluted to 1 L with water. What is the H+ ion concentration of the
dilute solution in mol/L? (All measurements are made at 25°C.)
A. 0.15 B. 0.51 C. 0.78 D. 1.01 E. 1.56

14. A container of 250 mL capacity contains 0.374 g of a particular gas at a temperature of

22.5°C and pressure of 1.006 bar. The gas could be:
A. H 2 B. He C. HCl D. H 2S E. CH4

15. One Spring day the atmospheric temperature and pressure are 15.0°C and 101.23 kPa
respectively, and the air contains 2% by volume of water vapour. The next day the
temperature is still 15.0°C, but the pressure has dropped to 100.47 kPa. Given that the
average relative molecular weight of the gases in dry air is 28.94, the water vapour content of
the air is now:
A. 0% B. 1% C. 3% D. 4% E. 5%

16. All of the following reactions occur in the Earth’s stratosphere. Which one protects us most
from U-V radiation?
A. O 2 → O + O B. O3 → O2 + O C. O + O → O2
D. O + O2 → O3 E. O + O 3 → 2O2

17. Which of the following combustion reactions would give the maximum energy output per unit
mass of fuel plus oxidant when used to propel a rocket?
A. C(s) + O2(g) → CO2(g) ∆H = –393.5 kJ/mol
1
B. H2(g) + O2(g) → H2O(g) ∆H =–285.8 kJ/mol
2
1 1
C. H2(g) + F2(g) → HF(g) ∆H = –271.1 kJ/mol
2 2
D. CH 4(g) + 2O2(g) → CO2(g) + 2H2O(g) ∆H = –890.3 kJ/mol
E. C2H5OH(g) + 3O2(g) → 2CO(g) + 3H2O(g) ∆H = –1367.3 kJ/mol
18. Hydrogen is obtained industrially by the reaction of natural gas (methane) with steam in a
continuous flow system. The equation for the reaction is:
CH4(g) + H2O(g) → CO(g) + 3H2(g) ∆H = +206.1 kJ/mol
Which of the following would NOT increase the yield of hydrogen?
A. Increasing the pressure
B. Increasing the temperature
C. Removing the hydrogen as it is produced
D. Increasing the proportion of methane in the mixture
E. Increasing the proportion of water vapour in the mixture

19. What is the equilibrium law expression in terms of partial pressure for the following reaction?
C(s) + 2H 2O(g) → CO2(g) + 2H2(g) ∆H = +90.0 kJ/mol
1
( ) ( ) ( )
2 2
pCO 2 2 • pH 2 pCO 2 • p H2 pCO 2 • p H2
A. B.. C.
(pH 2 O) pC • (pH 2O )
p H2O 2 2

)( pC • ( pH 2O )
2 2
pCO 2 • 2pH2
D. E.
pC • (2pH 2 O ) pCO 2 • (p H 2 )
2 2

20. Ethyl ethanoate (0.20 mol) and water (0.6 mol) are mixed and left for several days to
equilibrate in the presence of an acid catalyst. At the end of this time 0.11 mol of ethanoic
acid is found to be present in the mixture. The equation for the reaction is:
CH3COOC 2H5 + H 2O → CH3COOH + C2H5OH
The equilibrium constant, Kc for the reaction is therefore:
A. 0.10 B. 0.27 C. 3.6 D. 4.0 E. 9.9

21. A group of students left a mixture of calcium hydroxide and water to equilibrate at 20°C.
They titrated the resulting saturated solution and found that it contained 0.040 mol/L of OH–
ions. The solubility product constant, Ksp{Ca(OH) 2} at this temperature is therefore:
A. 8.0 x 10–6 B. 1.6 x 10–5 C. 3.2 x 10–5 D. 6.4 x 10–5 E. 1.3 x 10–4

22. Hydrogen carbonate ions act as a buffer in blood. When acid comes in contact with hydrogen
carbonate ions, which of the following species is formed as the conjugate acid?
A. H 2O B. H3O+ C. CO32– D. HCO 3– E. H2CO3

23. The base dissociation constant, Kb, of NH 3 is 1.8 x 10–5 at 25°C. The pH of a 0.1M solution
of NH 3 at this temperature is therefore:
A. 2.9 B. 4.8 C. 9.3 D. 11.1 E. 11.6
24. Two students performed a series of experiments to investigate the rate of the reaction
between magnesium and hydrochloric acid at room temperature. In each experiment they used
the same mass of magnesium but with different concentrations of acid (the acid always being
in excess). They measured the time taken for all the magnesium to react. Here are their
results:
Expt Concentration of HCl, Time taken for all the
# mol/L Mg to react, s
1 2.00 25
2 1.50 30
3 1.00 100
4 0.50 400
The rate expression for this reaction is:
A. k[H+] B. k[H+ ]2 C. k[Mg][HCl] D. k[H+ ]–1 E. k[H+ ]–2

25. All of the following metals are used as protective coatings for iron and steel. Which one is
most likely to promote the rusting process? (E°(Fe 2+ /Fe) = –0.44 V)¤
A. Cadmium (E°(Cd2+ /Cd) = –0.40 V)
B. Chromium (E°(Cr3+ /Cr) = –0.74 V)
C. Nickel (E°(Ni2+ /Ni) = –0.25 V)
D. Tin (E°(Sn2+ /Sn) = –0.14 V)
E. Zinc (E°(Zn 2+ /Zn) = –0.76 V)
 THE CHEMICAL INSTITUTE OF CANADA
INSTITUT DE CHIMIE DU CANADA
“Chemists, engineers and technologists working together.”
“Les chimistes, les ingénieurs et les technologistes travaillant ensemble.”

_____________________________________________________________________

NATIONAL HIGH SCHOOL CHEMISTRY EXAMINATION 2000

PART B – ESSAY QUESTIONS (90 minutes)

Answer TWO questions only in the form of scientific essays, including any appropriate
equations, formulae and diagrams. Each question is of equal value. The judging of the essays will
be based on both factual accuracy and presentation. A clear, concise and well-organized essay
will be rated more highly than a long rambling one that contains the same information.

1. The Periodic Table and Periodicity

In this essay you might like to consider: (a) the history of the classification of the elements and
the development of the periodic table, especially the contribution of Mendeleev, (b) the
periodicity of physical properties on the macro scale, such as the “atomic volume”, density,
melting and boiling points, and structure and bonding of the elements, (c) the periodicity of
atomic scale properties, such as atomic and ionic radii, ionisation energies and electron affinities,
electronegativity, and oxidation number, and (d) the periodicity of the chemical properties of the
elements and their hydrides, oxides and chlorides. Note that you are not expected to have
memorized the values of the physical properties but you should discuss the trends across the
periods, and the reasons for these trends.

2. Water
In this essay you might like to consider: (a) the bonding and structure of water, (b) the phase
diagram of water, (c) the anomalous properties of water, and (d) its solvent properties. In each
case you should relate the properties of water with its importance in nature, eg. in the water
cycle and the weathering of rocks, and in living organisms and their habitats.

3. Petroleum
In this essay you might like to consider: (a) the way in which petroleum (crude oil) was formed,
(b) the chemical composition of petroleum, (c) the way in which petroleum is processed
industrially, (d) the uses of petroleum fractions, (e) the environmental problems of burning
petroleum products and how to limit these problems, and (f) the likelihood of all the petroleum
reserves being used up in the near future, and how we can replace petroleum as a raw material.
 CHEMICAL INSTITUTE OF CANADA
and
CANADIAN CHEMISTRY OLYMPIAD
Final Selection Examination 2000
PART C: Free Response Development Problems 60%
Time: 1.5 hours
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, is to be returned promptly to your Canadian Chemistry Olympiad Coordinator.

— PLEASE READ — PART A ( )

correct numbers
1. BE SURE TO COMPLETE THE INFORMATION REQUESTED AT THE
BOTTOM OF THIS PAGE BEFORE BEGINNING PART C OF THE 25 x 1.6 = ....... /040
EXAMINATION.
PART C
2. STUDENTS ARE EXPECTED TO ATTEMPT ALL QUESTIONS OF
PART A AND PART C. CREDITABLE WORK ON A LIMITED 1. ............... /012
NUMBER OF THE QUESTIONS MAY BE SUFFICIENT TO EARN AN
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. ONLY NON-PROGRAMMABLE CALCULATORS MAY BE USED ON 4. ............... /012

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 THE
DATA SHEET PROVIDED WITH THIS EXAMINATION.

TOTAL ......... /100

NAME _______________________________ SCHOOL ___________________________

(Print Clearly)
CITY ______________________________ PROVINCE _________________________

Date of birth: Exam Supervisor _____________________

Home Telephone number: ( ) - _____________ Years at a Canadian high school _____

Male ❐
Canadian Citizen ❐ Landed Immigrant ❐ Visa Student ❐
Female ❐
 Part C of Final Selection Examination (IChO 2000)

1. a) In 1828 Friedrich Wöhler found that the organic compound urea could be made by
evaporating an aqueous solution containing the inorganic compound ammonium cyanate,
thus repudiating the concept of "vitalism" which had held that organic compounds could
only be formed by living systems. The rate of this reaction has now been examined in an
aqueous solution containing 22.9 g of ammonium cyanate in 1.00 L of solution.
NH 4 CNO → CO(NH2 )2
Given the following data, what is the order of the reaction and the mass of ammonium
cyanate left after 200 min?
T/min 0 20 50 65 150
NH 4 CNO /g 22.9 15.9 10.8 9.1 5.2

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 Part C of Final Selection Examination (IChO 2000)

1. b) A typical urine sample contains 2.3% by mass of the base urea, CO(NH2 )2 . Urea is a
monoprotic base with a base dissociation constant, K b , equal to 1.5 x 10 –14 mol L–1 at
25°C. If, at 25°C, the density of a urine sample is 1.06 g cm–3 and the pH of the sample is
6.35, calculate the concentration of CO(NH2 )2 and of its conjugate acid CO(NH2 )NH 3 + in
the sample.

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 Part C of Final Selection Examination (IChO 2000)

2. HYDROLYSIS OF UREA

Urea, CO(NH 2 )2 , reacts with water to produce carbon dioxide and ammonia. Thermodynamic
data for the possible reactants and products are given below (neglect the solubility of carbon
dioxide and ammonia in liquid water).

Compound ∆H fo (kJ mol –1 ) S o (J K –1 mol –1 )

CO(NH2 )2 (s) -333.51 104.60

H2 O (l) -285.83 69.91
H2 O (g) -241.82 188.83
CO2 (g) -393.51 213.74
NH 3 (g) -46.11 192.45

a) Consider the hydrolysis of urea with H2 O (l) (Reaction A) and H2 O (g) (Reaction B)
respectively. Calculate ∆Ho , ∆S o , and ∆Go at 25o C for each reaction and specify whether
or not the reaction is spontaneous.

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 Part C of Final Selection Examination (IChO 2000)

2. b) Assuming that both ∆Ho and ∆S o are independent of temperature, find the temperature
above which Reaction A shall be spontaneous.

c) What major driving force favors both reactions in the forward direction? Justify your
answer.

d) Calculate K p at 25o C for each reaction and express these values with the proper units.

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 Part C of Final Selection Examination (IChO 2000)

3. COMPLEX IONS

PART I: Zinc Complex Ion

Zinc hydroxide is not very soluble in water, but in basic solution, it may dissolve as the
tetrahydroxozinc complex ion: Zn(OH)4 2-.

The solubility product constant of zinc hydroxide is K sp = 2.1 x 10-16 .

The formation constant (or stability constant) of Zn(OH)4 2- is K f = 2.8 x 1015 .

a) If 150.0 mg of zinc hydroxide crystals are mixed with 250.0 mL of pure water, what
mass of crystals will remain undissolved and what will be the pH of the resulting solution.
Justify your answer by showing your calculations.

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 Part C of Final Selection Examination (IChO 2000)

b) If 150.0 mg of zinc hydroxide crystals are mixed with 250.0 mL of a 0.100 mol/L NaOH
solution, what mass of crystals will remain undissolved. Justify your answer by showing
your calculations.

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 Part C of Final Selection Examination (IChO 2000)

3. COMPLEX IONS

PART II: Nickel Complex Ions

Several examples of Ni(II) complex ions appear below. They all possess an octahedral three-
dimensional structure.

Complex Ion A: Ni(NH 3 )3 (H2 O)3 2+

Complex Ion B: Ni(en)2 (NH 3 )2 2+ where “en” = H2 N-CH 2 -CH2 -NH 2
Complex Ion C: Ni(NH 3 )6 2+

a) Draw the possible structural isomers of complex ions A and B. Specify if any one
shows optical isomerism.

b) Complex ion C possess a pure octahedral geometry. Using crystal field theory, sketch the
energy-level diagram for the “d” orbitals of a metal atom in a pure octahedral field. Then,
fill in the d-electrons of the nickel ion using arrows to specify their spin. Label all the
orbitals in the diagram with the corresponding “d” notation (e.g. dxy ).

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 Part C of Final Selection Examination (IChO 2000)

4. Consider the half reactions shown below

Half reaction E° (V)

Ce4+ (aq) + e– → Ce3+ (aq) +1.61
Cu2+ (aq) + 2 e– → Cu(s) +0.34
Sn2+ (aq) + 2 e– → Sn(s) –0.14
Ni2+ (aq) + 2 e– → Ni(s) –0.25
Al3+ (aq) + 3 e– → Al(s) –1.66

a) From the list above, identify

i) the strongest reducing agent

ii) the strongest oxidizing agent

iii) which metallic ion(s) can be reduced by Sn?

b) An electrochemical cell with a potential difference of 1.59 V is prepared with aluminum

and nickel electrodes in their respective ionic solutions.

i) Calculate the standard cell potential for the spontaneous reaction.

ii) Given that the observed cell potential is 1.59 V, determine the
concentration of the aluminum ion if the concentration of the nickel ion is 2.0 M.

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 Part C of Final Selection Examination (IChO 2000)

c) A small piece of freshly cleaned aluminum metal is placed in a solution of 1.0 M copper
nitrate, Cu(NO3)2, solution. After some time the blue colour of this solution decreases
considerably or disappears.

i) Describe what is happening, including any other observations that might be expected.

ii) Determine the free energy change, ∆G°, for this reaction.

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 Part C of Final Selection Examination (IChO 2000)

5. A) Complete the structural formulas located to the right of compound A in order to illustrate,
respectively, a diastereoisomer of A and the enantiomer of A.

O O O
C C C
H3 C C Br C C
CH2 CH2 CH2
Cl
C C C C C C
H CH2 OH
Compound A Diastereoisomer of A Enantiomer of A

Circle the most appropriate choices regarding Compound A:

i) The stereochemistry assignments are: R S as well as E Z

ii) The number of lone pairs of electrons is: 2 4 6 8 10 12 14 16

iii) The degree of unsaturation is: 1 2 3 4 5 6 7 8

B)

i) Nuclear magnetic resonance (NMR) spectroscopy is a technique that can probe the structural
differences of various hydrogen atoms in a molecule. Assuming that free rotation is occurring
about all bonds and thus equivalent hydrogens are able to interconvert, indicate how many
different NMR signals you would expect to see in each of the following isomeric compounds.

Br Br CH3
H3 C C CH3 H3 C CH2 C CH3 H3 C C CH2 Br
CH3 H H

iii) Circle the structure that represents a positively charged species and underline the negatively
charged species.

H2 C CH2 O
H3 CO O C H2 C N N
H2 N H
H

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 Part C of Final Selection Examination (IChO 2000)

ii) Draw the structures of the major organic products necessary to complete the following
reactions. Pay close attention to stereochemistry. Indicate whether the product is achiral,
racemic or enantiomerically pure. In cases where a racemic mixture will be formed, draw
only one of the two possible enantiomers, but indicate that the product is racemic.

HBr
(concentrated)

HO H
+
1) NaNH 2 K2 Cr2 O7 /H
CH3
D B
2) CH3 CH2 Br

+
H /Heat

(End of Part C Examination)

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