AUSTRALIAN CHEMISTRY OLYMPIAD

QUALIFYING EXAMINATION

1992

General Instructions

(1) This paper is in two sections and you must answer each section according to the instructions.
ie. Section A: Answer ALL questions
Section B: Question 16 is compulsory
Answer any two of Questions 17, 18 or 19

(2) All answers must be written in the space provided in the answer book.

(3) Use blue or black pen to write your answers, pencil is not acceptable.

(4) Rough working must be done only in the indicated areas of the answer book.

(5) You are not permitted to refer to books or periodic tables and the only permitted aid is a
non-programmable electronic calculator.

(6) You are permitted 15 minutes to read the paper and supply the requested information on the cover of
the answer book, followed by 120 minutes to work the questions.

(7) Relevant data that may be required for a question will be found on page 2.
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DATA

Avogadro constant 6 x 1023 mol-1

1 faraday 96,486 coulombs

1 coulomb 1 amp sec

Universal gas constant (R) 8.314 J K-1 mol-1

8.206 x 10 -2 L atm K-1 mol-1

Standard temperature and pressure (STP) 273 K and 101.3 kPa

0 ° C and 101.3 kPa
0 ° C and 1 atm

Molar volume of ideal gas at STP 22.4 L

Ionic molar conductivities λH+ = 35.0 x 10 - 3 ohm-1 m2 mol- 1

λ = 4.45 x 10 - 3 ohm-1 m2 mol- 1

HCO-3

Dissociation constants for carbonic acid pKa1 = 6.35

pKa2 = 10.33

Relative atomic masses: Ag 107.87 Al 26.98 Br 79.90

C 12.01 Ca 40.08 Cl 35.45
Cr 52.00 Cu 63.55 F 19.00
H 1.008 He 4.003 I 126.90
Mg 24.31 Mo 95.94 N 14.01
Na 22.99 Ne 20.18 O 16.00
P 30.97 S 32.06 Si 28.09
Ta 180.95 U 232.03 Zr 91.22
 3

SECTION A
It is intended that candidates devote not more than 30 minutes to this section. Answer ALL fifteen (15)
questions in this section. Only one choice is allowed per question and this should be made by clearly crossing
the chosen answer box in the answer book. If you make a mistake, correct it clearly so that the examiners
can read your answer.

Q1 In the nineteenth century, there was considerable doubt over the formula of zirconium oxide. The relative
atomic mass of zirconium (Zr) was thought to be about 90. The relative molecular mass of the volatile
chloride was found to be 236 (Cl = 35.5). This evidence suggests that the most likely formula for the oxide
of zirconium is
A ZrO
B ZrO2
C ZrO3
D Zr2O3
E Zr2O5

Q2 What is the particle X in the following nuclear reaction?

27 1n 4
13Al + → X + 2He
0

24
A 11Na

24
B 10Ne

24
C 12Mg

24
D 14Si

23
E 11Na

Q3 A student set up the following apparatus to determine the hydrogen ion concentration of solution X .

High impedance voltmeter

Hydrogen gas
Bridge
Copper elctrode

Electrode M

Solution X of unknown [H+ ] 1.0M copper(II)sulfate

The cell is: M [H2(g)] | 2H+(aq) || Cu2+(aq) | Cu(s)

The potential for the cell was found to be +0.43 volts. From tables the potential for the copper electrode
was found to be +0.34 volts.

The potential of the hydrogen electrode was

A +0.76 V
B +0.09 V
C zero (since the hydrogen electrode is the standard)
D -0.09 V
E -0.76 V
4

Q4 The ground-state electronic configurations of five elements are shown below. For which element would
you expect the value of the first ionisation energy to be the greatest?

1s 2s 2p

Q5 Which change would have a negative ∆ H value?

A Na(s) → Na (g)
B Na(g) → Na+(g) + e-
C Na+Cl-(s) → Na +(g) + Cl-(g)
D Cl2(g) → 2Cl(g)
E Cl(g) + e- → Cl-(g)

Q6 The data below refer to eight elements, lettered M to T (these letters are NOT chemical symbols).

Element M N O P Q R S T
Atomic number Z Z+1 Z+2 Z+3 Z+4 Z+5 Z+6 Z+7
Molar enthalpy of vaporisation
2.8 3.4 3.3 1.8 89 129 294 377
(kJmol-1)

Boiling point (K) 73 93 83 23 1163 1373 2673 2973

From these data, it can be deduced that

A T is in the same group of the periodic table as helium

B the elements are all in the same period of the periodic table

C N is a metallic element

D S could be described as a giant structure or a molecular network

E M is a group 1 element in the periodic table

Q7 The solubility product of silver chromate is 1 x 10-12 mol 3L - 9. In a solution in which [CrO2- ] is 1 x 10- 4
4
molL - 3, the maximum [Ag+], in molL- 3, is
A 0.5 x 10 - 8
B 1 x 10-8
C 1 x 10-6
D 0.5 x 10 - 4
E 1 x 10-4
 5

Q8 When aqueous sodium hydroxide is added to an aqueous solution of chromium(III) ions, a green-blue
precipitate is first formed which re-dissolves to give a green solution. This green colour could be due to
A [Cr(H2O)6]3+
B [CrO4]2-
C [Cr(OH)4]-
D [Cr(OH)3(H 3O)3]
E [Cr2O7]2-

Q9 The compound

H H NH2 H

H C C C C OH

H H H
H C H

H C H

H
is called
A 2-ethyl-3-aminobutan-4-ol
B 3-amino-2-ethylbutan-4-ol
C 3-methyl-4-aminopentan-5-ol
D 4-amino-3-methylpentan-1-ol
E 2-amino-3-methylpentan-1-ol

Q10 The experimentally determined melting point of a compound is lower than expected. If each of the
following procedures is applied to separate samples of the prepared compound, which is likely to NOT
change the melting point?
A Drying to remove solvent
B Mixing with pure compound
C Grinding to a finer powder
D Recrystallising from a solvent
E Adsorbing impurities on charcoal

4- 3- 4-
Q11 The species Mo(CN) , TaF and U(NCS) all contain metal ions with a coordination number of
8 8 8
eight (8) even though their geometries are different. Various sets of hybrid orbitals have been proposed to
account for the bonding in one or other of these complex ions. Of the sets of hybrids listed below which
cannot be considered in discussing the bonding in one or more of the species above.
1 d 4sp 3
2 d 5sp
3 d 4sp 2
4 d 5p 3
5 d 3fsp3

A 2 and 3
B 4 alone
C 4 and 5
D 1 and 4
E 5 alone
6

Q12 Which diagram could represent the variation in the concentration of X and Y with time in the reversible
reaction X Y which comes to equilibrium after time t.

Concentration

Concentration
Concentration

X X
X

Y Y
Y

A t Time B t Time
C t Time

X X
Concentration

Concentration
Y
Y

D t Time
E t Time

Q13 The electron configuration of atoms of a certain element is 1s2 2s2 2p6 3s2 3p6 3d 3 4s2. The maximum
oxidation number of the element is
A +2
B +3
C +4
D +5
E +6

Q14 Ozone is a form of oxygen in which the molecules are triatomic. Ozone reacts with compounds containing
carbon to carbon double bonds thus:

H H H H

X C C Y + O3 X C O C Y

O O

The product of this reaction can be carefully hydrolysed as shown:

H H H H

X C O C Y + H2 O X C + H2 O2 + C Y
O O O O

Which of the following would be reasonable uses of either or both of these reactions?
1 To find out if a compound contains a carbonyl group.
2 To find the percentage of ozone in a sample of partially ozonised oxygen.
3 To promote polymerisation of compounds containing double bonds.
4 Determining the location of double bonds in suitable compounds.

A 1, 2, 3 only correct
B 1, 3 only correct
C 2, 4 only correct
D 4 only correct
E 1, 2, 3, 4 are all correct
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Q15 Consider the following reaction (assume an IDEAL gas mixture)

2NOBr (g) 2NO(g) + Br 2(g)

A 1.0 L vessel was initially filled with pure NOBr, at a pressure of 4.0 atm, at 300 K. After equilibrium was
established, the partial pressure of NOBr was 2.5 atm. What is K p for the reaction?
A 0.27
B 0.45
C 0.18
D 0.75
E none of these

SECTION B
Candidates are advised that the corect use of significant figures will be taken into consideration when marking
answers to these problems. Candidates are also advised that steps to the solution of problems must be clearly
explained. Marks will be deducted for untidy and poorly explained answers.
Question 16 is compulsory. You have a choice of answering any two questions of the remaining three questions.

Compusory question

Q16 (a) Diatoms, microscopic organisms that can be considered to be carbohydrate, are an abundant
food source in oceans producing carbohydrates from carbon dioxide and water by
photosynthesis.

6CO 2 + 6H2O + solar energy → C6H12O6 + 6O2

During their first five years of life blue whales gain 75.0 kg of mass per day by feeding on krill.
The blue whale must consume ten times this mass of krill each day. The krill must consume
10.0 kg of diatoms to produce 1.0 kg of krill. Assuming that the mass gain in the first five years
of a blue whale’s life is due to the consumption of carbohydrates (C6 H 12 O6), calculate the
volume of CO2 at STP that must be used by the diatoms to produce the carbohydrates
consumed by a blue whale in its first five years of life.

(b) (i) There is 0.23mL of dissolved CO2 per L of sea water (at 24°C and 1.0 atm). If diatoms can
completely remove carbon dioxide from the water they process, what volume of water would
they process to produce the carbohydrates required by a blue whale during the first five years of
life?

(ii) What fraction of the total volume of the oceans will be needed to supply the carbon dioxide for
the first five years of growth of 1000 blue whales? The volume of the oceans is 1.37 x 1018 m3.

(c) Consider the mass of an adult blue whale to be 9.1 x 10 4 kg. Three percent of the mass of an
adult blue whale is nitrogen, when such a blue whale dies, what is the maximum mass of NH + 4
that can become available to marine organisms?

(d) Eighteen percent of an adult blue whale’s mass is carbon. Carbon can be returned to the
atmosphere as carbon dioxide, and then removed from the atmosphere by weathering of rocks
containing calcium silicate.
CaSiO3(s) + 2CO2(g) + 3H2O(l) → Ca2+(aq) + 2HCO - (aq) + H4SiO 4(aq)
3

What are the maximum number of grams of CaSiO3 that can be weathered by the carbon
dioxide produced from the decomposition of 1000 adult blue whales, the number estimated to
die annually?
8

Answer any two of the remaining three questions.

Q17 (a) The arrangement of valence electrons in atoms in molecules can be represented using Lewis
structures. Lewis structures of molecules are constructed by using the following rules:
(1) Sum the valence electrons from all the atoms.
(2) Use a pair of electrons to form a bond between each pair of bound atoms.
(3) Arrange the remaining electrons such that each atom achieves a noble gas
configuration of valence electrons as, in general, the most stable compounds are those
in which the atoms have such a configuration.
(4) Third row elements in molecules sometimes exceed the octet rule. When it is necessary
to exceed the octet rule the extra electrons are placed on the central atom.

Before proceeding further you should be aware that additional information is available at the
end of the problem if required.

Write Lewis structures for each of the following species:

(i) CH4
(ii) NH3
(iii) SF6
(iv) CO2
(v) SO3 (This molecule has more than one valid Lewis structure.)

(b) The valence shell electron pair repulsion (VSEPR) model is used by chemists to predict the
shapes of molecules. The underlying idea is that the electron pairs surrounding an atom in a
molecule arrange themselves so as to minimise electron pair repulsions. Consider the following
table:-

Molecule Effective* electron Electron Pair** Molecular** Bond Angle

pairs around Geometry Structure
central atom
CO2 2 linear linear 180 o
SO3 3 trigonal planar trigonal planar 120 o
CH4 4 tetrahedral tetrahedral 109.5o
NH3 4 tetrahedral trigonal 107 o
pyramidal
H2O 4 tetrahedral angular 104.5o
PCl5 5 trigonal trigonal see below***
bipyramidal bipyramidal
SF6 6 octahedral octahedral 90o
* Multiple bonds count as one effective pair of electrons. ***
90° Cl
** The electron pair geometry refers to the arrangement of Cl
the electron pairs about a central atom, whereas the Cl P 120°
molecular structure refers to the arrangement of atoms in
the molecules. Cl
Cl

Write the Lewis structure and describe the electron pair geometry and molecular structure for
each of the following species:

(i) CCl 4
(ii) SCl2
(iii) ICl-
4

(c) From the above table it is clear that CH 4 , NH 3 and H 2O all have a tetrahedral electron pair
geometry, however, the bond angle decreases from left to right. This is because lone pairs of
electrons are considered to occupy more space than bonding pairs of electrons. Electron pair
interactions decrease in the following manner:
lone pair - lone pair > lone pair - bonding pair > bonding pair - bonding pair.

With this in mind, predict the molecular structures of the following species:
 9

(i) Br-
3
(ii) BrF3
(iii) SF4

(d) The bond angle in SO3 and SO 2 is 120o. Can you offer a suggestion as to why the bond angle
in O3 and NO - is less than 120o.
2

Additional information: C is in Group IV, N and P are in Group V, O and S are in Group VI,
and the halogens are in Group VII of the Periodic Table.

Q18 (a) Standard solutions of sodium thiosulphate are employed in volumetric determination of iodine.
Unfortunately crystalline sodium thiosulfate (Na2S 2O3.5H 2 O) is not a satisfactory primary
standard and the analyst must first standardise solutions of thiosulfate before using them. One
way of achieving this is to stoichiometrically liberate iodine by oxidising Iodide ion in acidic
solution with bromate ion (BrO- ). The iodine liberated can then be used to determine the exact
3
strength of the thiosulfate solution.

(i) Write half equations for the reduction of bromate to bromide and the oxidation of iodide to
iodine.

(ii) Using you answer to part (i) construct a balanced ionic equation of the reaction of bromate with
iodide in acidic solution.

(iii) Given that iodine converts thiosulfate ion (S 2O32- ) to the S4O62- ion and is itself reduced to
iodide. Write a balanced equation for the reaction of sodium thiosulfate with iodine.

(iv) In standardising a solution of sodium thiosulfate a chemist found that on average 19.52 mL of
solution was required to react with the iodine liberated from 0.05568g of potassium bromate and
excess potassium iodide in acidic solution. What was the molarity of the sodium thiosulfate
solution?

(v) Which indicator might the chemist have used to detect the end point of the titration?

(b) Carbon monoxide is a toxic gas produced by the incomplete combustion of hydrocarbons, and
the estimation of carbon monoxide concentration in flue gases and exhausts is of considerable
environmental interest. One way of determining carbon monoxide concentration is to react the
gas with iodine pentoxide (I 2O5 ), a process which stoichiometrically oxidises the CO and
reduces the I2O5 to elemental iodine. The latter can be trapped and estimated by titration with
standard sodium thiosulfate solution
In one such estimation 1.092L (at STP) of a gas mixture was reacted with I 2O5. Subsequent
titration of the iodine with standard sodium thiosulfate showed that 17.92 mL was required to
reach an end point. The standard solution used was prepared by taking 10 mL of the solution
prepared in part (a) of this question and diluted to a total volume of 1L in a volumetric flask.

(i) What was the percentage by volume of CO in the gas sample?

(ii) What was the concentration of CO in ppm (to the nearest whole number) in the gas sample?

(iii) What sort of compound present in the gas sample might cause this result to be in error.
10

Q19 It might come as a bit of a surprise but the pH of distilled water is not really 7 (neutral), but is
actually about 5.6 (acidic). Upon standing, left open to the air, gases readily dissolve back into
freshly distilled water. The amount of gas that dissolves can be shown to be directly proportional
to the partial pressure of that particular gas above the solution, this is Henry’s law. The most
common gas that can change the pH of water is carbon dioxide. Once dissolved the carbon
dioxide reacts to a tiny degree to form an equilibrium with carbonic acid, a diprotic acid. The
carbonic acid is a weak acid and dissociates into ionic products.

(a) Write down the equilibrium equations and develop expressions for the dissociation constants
(ka1 and ka2) for carbonic acid.

(b) Assuming that the final dissociation to yield the carbonate anion can be ignored, write an
expression for the pH dependency of the solution in terms of the concentration of carbonic acid.

(c) Electricity conducts quite well through ionic solutions. How well depends upon the concentration,
the valency and the identity of the dissolved ions. For example, a 10- 2M KCl solution conducts
slightly better than a 10- 2M NaCl solution, the difference arising from the difference in the size
of the two cations. At low concentrations, say less than 10-4 M, it can be said that the total
solution conductivity (Λ) is the sum of the products of the molar conductivities of the individual
ionic species (λ) by their concentrations.

Λ = λcation [cation] + λanion [anion]

It should be noted that the electrical resistance of a solution is inversely proportional to the
solutions conductivity.

Knowing all this an environmental chemist decided that she would try and determine the
concentration of atmospheric carbon dioxide, also knowing that CO2 is the only atmospheric gas
that gives an appreciable concentration of ions in aqueous solution. By bubbling air through a
conductance cell, she was able to measure the resistance of the solution, (which was readily
saturated with CO2). Given that the partial pressure of CO2 in air is about 300Pa and that she
can measure resistances to within 0.1%, what is the smallest change in CO2 that she can
determine?.