AUSTRALIAN CHEMISTRY OLYMPIAD

QUALIFYING EXAMINATION

1990

General Instructions

(1) This paper is in two sections and candidates must answer each section according to the instructions.
ie. Answer ALL questions in section A and any three (3) in section B.

(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 on left-hand pages of the answer book.

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

(6) Make sure your NAME, HOME ADDRESS and HOME TELEPHONE NUMBER are written on the
cover sheet. Your teacher will fill in the other information.

(7) You are permitted 10 minutes to read the paper followed by 120 minutes to work the questions.

(8) Data relevant to a question will be found at the end of the question.
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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 20 cm3 of a gaseous element X reacts with excess of an element Y to form 40 cm 3 of a gaseous

compound of X and Y. All volumes are measured under the same conditions of temperature and
pressure.

From this information it can be deduced that:

A The molecule of X contains at least two atoms of X.

B The formula of the compound formed is XY.
C Molecules of X cannot consist of more than two atoms.
D X is less dense than the compound of X and Y.
E X is more dense than the compound of X and Y.

Q2 Benzamide (2) may be prepared by the action of concentrated ammonia upon benzoyl chloride (1)

C6H5COCl + 2NH3 → C6H5CONH2 + NH 4Cl

(1) (2)

In one such reaction 65 cm3 of concentrated ammonia (an excess) was reacted with 15.0g of benzoyl
chloride to give 11.1g of pure benzamide.

The percentage yield of benzamide is:

11.1
A x 100
15.0
(15.0 - 11.1)
B x 100
15.0
11.1
C x 100
65
121
D x 100
141
11.1 x 141
E x 100
121 x 15.0

Data
Relative molecular masses: benzoyl chloride (1) 141; benzamide(2) 121.
Density of benzoyl chloride (1) 1.21 gcm-3.

Q3 The dissociation constant Ka of a weak monobasic acid is 10- 7. What is the approximate pH of a 0.1M
solution of the acid?

A 1
B 2
C 3
D 4
E 5
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Q4 An oxyacid of phosphorus has the following properties.

Complete neutralisation of the acid with sodium hydroxide solution gives an aqueous solution of sodium
ions and oxyacid anions in the ratio 2:1. When a solution of the acid is warmed with silver nitrate solution
metallic silver is deposited.

What is the structure of the oxyacid?

OH OH H OH
HO P OH H P OH HO P O HO P O
••
H OH
O
1 2 3 4

A 1
B 2
C 3
D 4
E 2 or 3

Q5 Ustic acid (3) is a natural compound found in lichens.

Which statement correctly represents four of the functional groups present in ustic acid?

H 3C O
C
H C OH
CH 3O CO 2H (3)

HO OH
H

A carboxylic acid ketone aldehyde alcohol

B ether ketone alcohol aldehyde
C carboxylic acid ketone phenol alcohol
D ester phenol carboxylic acid ketone
E alcohol phenol ester ketone

Q6 A solution of a trivalent metal ion is electrolysed by a current of 5.0A for 10 minutes during which time
1.18g of metal was plated out. The identity of the metal is:

A cobalt
B chromium
C indium
D gallium

E bismuth

Data
Relative atomic masses: Co 58.93; Ga 69.72; In 114.82; Bi 208.98; Cr 52.00.
1 faraday = 96,486 coulombs.
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Q7 Which of the following does not represent a detergent molecule?

A
CH3(CH2)11CH2 OCH2(CH2)12CH3

B
-+
CH3(CH2)11CH2 SO3 Na

C
CH3(CH2)9CH2 O(CH2)2O(CH2)2O(CH2)2OH

D -+
CH3(CH2)12CH2CO2 Na
E - +
Cl NH2CH2(CH2)11CH3

Q8

x
Energy

REACTANTS

PRODUCTS

Reaction path

The energy profile shown above relates to the reaction:

CO(g) + NO 2(g) -_ CO2(g) + NO(g)

Which of the following statements follow from this?

A The activation energy of the forward reaction is (x + y).

B ∆H for the reverse reaction is x.
C The forward reaction is exothermic.
D Both forward and reverse reactions are second order overall.
E The activation energy for the reverse reaction is (x - y).
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Q9 For a certain temperature the chemical reaction represented by the following equation has an equilibrium
constant of 4.

CO(g) + H2O(g) -_ CO 2(g) + H2(g)

A mixture initially containing one mole of each of carbon monoxide and steam is allowed to reach
equilibrium. How many moles of carbon monoxide are now present?
1
A 4

1
B 3

1
C 2

2
D 3

3
E 4

Q10 A coloured solution, known to contain two metal ions, was treated with excess cold sodium hydroxide
solution. When filtered a whitish solid, slowly changing to brown, was retained on the filter paper and a
colourless solution collected as the filtrate. Dropwise addition of hydrochloric acid to the filtrate produced
a white precipitate which dissolved in excess acid. Treatment of the residue from the filter paper with a
solution of a strong oxidiser produced a reddish-violet solution.

Indicate any pairs of ions which on testing as above leads to the observed changes.

A Zn 2+ and Mn2+ ions

B Mg2+ and Zn2+ ions
C Mn2+ and Mg2+ ions
D Fe 2+ and Zn2+ ions
E Mn2+ and Fe 2+ ions

Q11 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

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

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

The best material for electrode M would be:

A Polished copper metal.

B Platinum metal coated with platinum oxide.
C Copper metal coated with oxide.
D Platinum metal coated with finely divided platinum.
E Polished platinum.
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Q12 The following partial equations focus on chlorine containing species.

1 Cl2 → OCl-
2 Cl2 + I2 → 2ICl
3 OCl- → ClO3-
4 OCl- → Cl-

Is the chlorine oxidised in:

A Reaction 2, 3 and 4.
B Reaction 1 only.
C Reaction 1 and 3.
D Reaction 4 only.
E Reactions 2 and 4 only.

Q13 The following graphs show the change in pH of 20 cm3 of 1M alkali solution when 1M acid solution is
added.

Which of the graphs shown below correspond to a titration of aqueous ammonia with nitric acid?

14 14 14
1 2 3

pH 7 pH 7 pH 7

0 0 0
0 10 20 30 0 10 20 30 0 10 20 30
Volume of acid added Volume of acid added Volume of acid added
(cm3) (cm3) (cm3)

14 4 14 5

pH 7 pH 7

0 0
0 10 20 30 0 10 20 30
Volume of acid added Volume of acid added
(cm3) (cm3)

A 1
B 2
C 3
D 4
E 5
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Q14 Consider the following changes:

1 M(s) → M(g)
2 M(s) → M2+(g) + 2e-
3 M(g) → M+(g) + e-
4 M+(g) → M 2+(g) + e-
5 M(g) → M2+(g) + 2e-

The second ionisation energy of M could be calculated from the energy values associated with:

A 1+5
B 2+4
C 5-3
D 2-1+3
E 1+3

Q15 The figure below refers to the preparation of dibromoethane.

Dropping funnel

To fume cupboard

Water

Bromine
Ethanol and
concentrated Freezing mixture
sulfuric acid
Sodium hydroxide solution

Heat

The mixture in the flask was heated to about 170° C. Ethene (ethylene) was formed and reacted with the
bromine in the second test tube to form 1,2-dibromoethane.

H 2C CH 2 + Br2 → CH 2 BrCH 2 Br

Which answer pair best fits the two questions related to this synthesis?

The main purpose of surrounding the The 1,2-dibromoethane is usually

second test tube with freezing mixture was contaminated with excess bromine. This
to… can be removed by washing with…

A increase the rate of reaction hot concentrated aqueous

between ethene and bromine. NaOH.
B solidify any ethanol which has cold dilute aqueous NaOH
distilled from the flask
C minimise the vaporisation of dilute aqueous NaCl
bromine
D prevent hot ethene from cracking concentrated H2SO4
the test tube
E minimise the vaporisation of cold dilute aqueous NaOH
bromine
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SECTION B
Candidates should answer any three (3) of the four questions in this section. Be sure that ALL relevant working
is shown in your answers to numerical questions. You should devote 90 minutes to this section.

Q16 Dinitrogen monoxide, "laughing gas", is used as an anaesthetic during, for instance, childbirths.
It is important that the dinitrogen monoxide is free from other oxides of nitrogen, which are
poisonous. The nitrogen monoxide, NO, content can be determined in the following way.

1.000 L of the mixture of dinitrogen monoxide and nitrogen monoxide at 19°C and 98.2kPa is
bubbled through 100.0 mL of acidified potassium permanganate solution. The nitrogen
monoxide is oxidised to nitrate ions, while dinitrogen monoxide does not react at all. The
permanganate solution is then titrated with a 0.1000 M iron(II)sulfate solution, of which 39.0 mL
are required. A "fresh" 100.0 mL portion of the same permanganate solution requires 50.0 mL of
the iron(II)sulfate solution.

(a) Write the chemical equation for the reaction between iron(II) ions and permanganate ions.

(b) Write the chemical equation for the reaction between nitrogen monoxide and permanganate
ions.

(c) Calculate the nitrogen monoxide content of the original gas mixture as percentage by volume.

Data
Relative atomic masses: N 14.01; O 16.00; Mn 54.94; Fe 55.85.
Standard temperature and pressure (STP): 0° C and 101.3 kPa.

Q17 Quantitative analysis for carbon and hydrogen was originally carried out using a technique and
apparatus (see diagram) originally developed in 1831 by the famous chemist Justus Liebig.

C D F G

oxygen B E
A

A carefully weighed sample of the organic compound (C) is placed in a combustion tube (A)
and vaporised by heating in a furnace (B). The vapours are swept by a stream of oxygen
through a heated copper oxide packing (D) and through another furnace (E), which ensures the
quantitative oxidation of carbon and hydrogen to carbon dioxide and water. The water vapour is
absorbed in a weighed tube (F) containing magnesium perchlorate and the carbon dioxide is
absorbed in another weighed tube (G) containing asbestos impregnated with sodium hydroxide.

(a) (i) 0.04079 g of a pure liquid sample of compound (C) containing only carbon, hydrogen and
oxygen when combusted produced 0.03357 g of water and 0.08155 g of carbon dioxide.
Calculate the percentage by mass of C, H and O present in the compound.

(ii) Derive the empirical formula of the compound (C).

(b) (i) To estimate the molar mass of the compound (C), 1.0045 g was gasified. The volume,
measured at a temperature of 350 K and a pressure of 35.0 kPa, was 0.95 L. What is the molar
mass of the compound?

(ii) What is the molecular formula of the compound (C)?

(iii) Draw ten possible structures corresponding to the molecular formula, exclude cyclic structures,
stereo isomers, peroxides and unsaturated compounds. There are 18 possible structures.
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(c) When the compound (C) is heated with sodium hydroxide solution two products are formed.
Fractional distillation of the reaction mixture yields one of the substances. The other substance
is purified by distillation after acidification and appears to be an acid (L). What structures are
possible for compound (C)?

(d) 0.1005 g of the acid (L) was dissolved in water and titrated with 0.1000 M sodium hydroxide
solution. 16.75 mL of the sodium hydroxide solution were needed to neutralise the acid. What is
the formula of the original compound (C)?

Data
Relative atomic masses: C 12.01; H 1.01; O 16.00.
Standard temperature and pressure (STP): 0° C and 101.3 kPa.
Molar volume of ideal gas at STP: 22.4 L.

Q18 Many reactions between aqueous salt solutions result in a precipitated product. For example
the combination of a silver nitrate solution with a sodium chloride solution yields white
"insoluble" silver chloride. As insoluble as AgCl may seem, a tiny fraction is able to firstly
dissolve and then dissociate back to aquated Ag+ and Cl- ions. An equilibrium is established
between the solid AgCl and the solution as shown in the following equation.

AgCl (s) AgCl (aq) Ag+(aq) + Cl - (aq)

This equilibrium produces a corresponding reaction quotient.

[Ag+] [Cl- ]
K=
[AgCl(aq)]

However as the dissolved AgCl is also in equilibrium with the solid AgCl its concentration is
constant and the new reaction quotient, now called solubility product and shown below, may be
described only in terms of the concentration of both ions.

K SP = [Ag +] [Cl- ]

It can be seen that if an excess of Ag+ or Cl- ions are added then by Le Chatelier's principle the
K SP is exceeded and AgCl is precipitated to restore the equilibrium. Note that KSP, like all
reaction quotients is without units.

The concept of solubility products is important in the purification of metals. For example pure
manganese metal may be obtained electrolytically but often nickel, present as an impurity, will
interfere with this process. Nickel ions may be selectively removed as NiS prior to electrolysis
by firstly acidifying the solution and then saturating the solution (at STP) with H2S. In the correct
pH range only NiS precipitates leaving the manganese ions in solution.

(a) Given that H 2S behaves as a weak diprotic acid in aqueous solution, derive an expression for
the pH of a solution of H2S in terms of its pKa1, pKa2 , [H2S] and [S2-].

(b) If prior to saturation with H2S a solution has [Mn 2+] = 0.50M and [Ni2+] = 0.01M, what will be
the pH range in which only NiS precipitates?

Data
Relative atomic masses: S 32.06; H 1.01.
Standard temperature and pressure (STP): 0° C and 1 atm.
Solubility of H2S(g) (STP): 0.338g/100g H2O.
Acid dissociation products for H2S: pKa1 = 7.02; pKa2 = 12.9.
Solubility products (KSP): MnS = 3 x 10 - 13; NiS = 3 x 10 - 19 .
Density of H2O at STP: 1.00g/mL.
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Q19 (a) A molecule is said to have SYMMETRY if certain parts can be interchanged with others without
altering the appearance of the molecule. For example, the water molecule has a bent structure
as shown below.

180°
O O
Ha Hb Hb Ha

Rotation of the molecule 180° about an axis which bisects the HOH angle interchanges the two
H atoms (labelled Ha and Hb) but does not alter the appearance of the molecule. This action
of rotation through a certain angle leaves the molecule apparently unchanged is called a
S YMMETRY OPERATION. The axis about which the operation was performed is known as an
AXIS OF SYMMETRY and is said to be two fold, written C2, as the operation must be performed
twice in order to return Ha ( or Hb) to its original position —

180° 180°
O O O
Ha Hb Hb Ha Ha Hb

C2 C2

In general, if the molecule has to be rotated n times to return it to its original position then the
axis of symmetry is designated Cn.

How many axes of symmetry do each of the following three molecules possess? Show them on
a clearly labelled diagram.

(1) (2) (3)

F
F F
S B Xe
H H F F
F F

(b) (i) A second type of symmetry operation involves reflection of all the atoms through a mirror plane
which passes through the molecule. For example, a mirror plane lying along the C2 axis of our
water molecule and perpendicular to the HOH plane interchanges H a and H b without altering
the appearance of the molecule —

C2

mirror plane

reflection
O O
Hb Ha

Ha Hb
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A mirror plane also exists in the HOH plane which upon reflection generates the same water
molecule —

C2 mirror plane

O reflection
Ha O
Hb Ha Hb

Hence the water molecule has symmetry which is characterised by a C2 axis of symmetry and
two PLANES OF SYMMETRY.

How many planes of symmetry do molecules (1), (2) and (3) possess?

(ii) How many axes of symmetry and planes of symmetry do each of the following molecules
possess?

(4) (5) F (6) H

S B C
H D F Cl Cl
H Cl
(Note: Example (6) is not planar but has a tetrahedral structure.)

(c) (i) The tetrahedral molecule bromochloroiodomethane (7) exists as mirror image isomers which
are not superimposable.

Draw clearly the mirror image forms of (7) using to designate a bond coming out of the
plane of the paper and a for a bond going into the plane of the paper (see (6) above for the
uses of these bond representations).

(ii) How many planes of symmetry does (7) possess?

(iii) Can you suggest a possible criterion based on planes of symmetry which would determine
whether or not a molecule could exist as two superimposable mirror image isomers. [Hint: look
carefully at your answers for (6) and (7)]