2019 Asoe Chemistry Exam Answers

2019 AUSTRALIAN SCIENCE OLYMPIAD EXAM
CHEMISTRY
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2019 AUSTRALIAN SCIENCE OLYMPIAD EXAM
CHEMISTRY
Time Allowed:
Reading Time: 10 minutes
Examination Time: 120 minutes
INSTRUCTIONS
• Attempt ALL questions in ALL sections of this paper.
• Permitted materials: Non-programmable, non-graphics calculator, pens, pencils, erasers and a ruler.
• Answer SECTION A on the Multiple Choice Answer Sheet provided. Use a pencil.
• Answer SECTION B in the spaces provided in this paper. Write in pen and use a pencil only for graphs.
• Ensure that your diagrams are clear and labelled.
• All numerical answers must have correct units.
• Marks will be awarded for correct answers, not deducted for incorrect answers.
• Note that it may be possible to complete some later parts of short answer questions without having
completed earlier parts.
• Rough working may be done on page 33 and 34 of this booklet.
• Data that may be required for a question may be found on page 3.
• Do not staple the multiple choice answer sheet to this booklet.
MARKS
SECTION A 15 multiple choice questions 30 marks
SECTION B 3 short answer questions 30 marks each
Total marks for the paper 120 marks
Page 2 of 34
2019 Australian Science Olympiad Exam - Chemistry
©Australian Science Innovations ABN 81731558309
Avogadro constant (N) = 6.022  1023 mol–1 Velocity of light (c) = 2.998  108 m s–1
1 faraday = 96 485 coulombs Density of water at 25 °C = 0.9971 g cm–3
1 coulomb = 1 A s–1 Acceleration due to gravity = 9.81 m s–2
Universal gas constant (R) 1 newton (N) = 1 kg m s–2
8.314 J K–1 mol–1
8.206  10–2 L atm K–1 mol–1
Planck’s constant (h) = 6.626  10–34 J s 1 pascal (Pa) = 1 N m–2
Molar volume of ideal gas pH = log10[H+]
 at 0 °C and 100 kPa = 22.71 L pH + pOH = 14.00 at 25°C
 at 25 °C and 100 kPa = 24.79 L Ka = {[H+] [A–]} / [HA]
 at 0 °C and 101.3 kPa = 22.41 L pH = pKa + log10{[A–] / [HA]}
 at 25 °C and 101.3 kPa = 24.47 L PV = nRT
E = h
Surface area of sphere A = 4r2 c = 
Page 3 of 34
SECTION A: MULTIPLE CHOICE
USE THE ANSWER SHEET PROVIDED
1. What is the formula for the compound formed by barium and nitrogen?
(a) BaN
(b) Ba2N
(c) BaN2
(d) Ba2N3
(e) Ba3N2
2. Which of the following compounds exists as linear molecules at room temperature and
pressure?
(a) CO2
(b) SiO2
(c) NaCl
(d) OF2
(e) H2O
3. When liquid methane (CH4) is vapourised, which bonds or forces are broken?
(a) covalent bonds

(b) dipole-dipole interactions
(c) dispersion forces
(d) hydrogen bonds
(e) ionic bonds
4. The molar masses of C2H6, CH3OH and CH3F are similar. Which of the following lists these
compounds in order of increasing boiling point?
(a) C2H6 < CH3OH < CH3F

(b) CH3F < CH3OH < C2H6
(c) CH3OH < CH3F < C2H6
(d) C2H6 < CH3F < CH3OH
(e) CH3F < C2H6 < CH3OH
Page 4 of 34
5. Which of the following species contains 21 neutrons and 19 electrons?
41 2+
(a) 20Ca
41 +
(b) 20Ca
40 +
(c) 19K
40 2+
(d) 21Sc
38 −
(e) 17Cl
6. Which of the following elements has the highest fourth ionisation energy?
(a) helium
(b) lithium
(c) boron
(d) carbon
(e) nitrogen
7. Jarosite is a white mineral of formula KAl3X2(OH)6, where X is an unspecified species. Which

of the following could X be?
(a) HCO3–
(b) Ca2+
(c) Ag+
(d) SO42–
(e) PO43–
8. How many atoms are present in a 1.0 g sample of the dimethylaminoxyl radical, (CH3)2NO?
(a) 1.0  1022

(b) 6.0  1022
(c) 1.0  1023
(d) 6.0  1023
(e) 6.0  1024
Page 5 of 34
9. Silver oxide (Ag2O) decomposes to silver and oxygen upon heating. The molar mass of silver
oxide is approximately 232 g mol–1.
What amount of oxygen gas is produced when 4.64 g of silver oxide decomposes?
(a) 0.005 mol

(b) 0.01 mol
(c) 0.02 mol
(d) 0.04 mol
(e) 0.08 mol
10. Iron can be produced by reducing iron(III) oxide with carbon monoxide, as described by the
following balanced chemical equation:
Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)
What mass of carbon dioxide is produced by the complete reduction of 16.0 g of iron(III) oxide?
(a) 1.5 g
(b) 4.4 g
(c) 6.6 g
(d) 8.8 g
(e) 13.2 g
11. The following diagram shows the relative atomic radii of two elements, X and Y.
Elements X and Y are non-metals and are in the same group of the Periodic Table
Which of the following statements must be true?
(a) Element X has a higher first ionisation energy than element Y.

(b) Element X is more reactive than element Y.
(c) Element Y has greater electron shielding than element X.
(d) Element Y has a higher electronegativity than element X.
(e) Element X has a higher effective nuclear charge than Y.
Page 6 of 34
12. A mixture of calcium carbonate and sodium chloride contains 10% carbon by mass. What is the
percentage by mass of sodium chloride in the sample?
(a) 10%
(b) 17%
(c) 50%
(d) 83%
(e) 90%
13. When the following unbalanced equation is balanced, how many O2(g) molecules are consumed
for every CO2(g) produced?
C3H7OH(l) + O2(g) → CO2(g) + H2O(l)
(a) 0.67
(b) 0.75
(c) 1.00
(d) 1.33
(e) 1.5
14. When aluminium reacts with hydrochloric acid, aluminium chloride and hydrogen gas are
produced. The volume of one mole of hydrogen gas at 25 °C and 100 kPa is 24.79 L.
When 2.70 g of aluminium reacts with 50.0 mL of 5.00 mol L−1 hydrochloric acid, what volume
of hydrogen gas is produced, when measured at 25 °C and 100 kPa?
(a) 2.48 L
(b) 3.10 L
(c) 3.72 L
(d) 4.96 L
(e) 6.20 L
15. A nucleophile is a chemical species that forms a covalent bond by donating a pair of electrons to
another species. Which of the following would you expect to be the best nucleophile?
(a) Na+
(b) I–
(c) Ca
(d) Ca2+
(e) CH4
END OF SECTION A
SECTION B COMMENCES OVERLEAF
Page 7 of 34
SECTION B
ANSWER IN THE SPACES PROVIDED
Question 16
Intermolecular forces and bonding affect many bulk properties of chemicals, including melting
point, freezing point and solubility. There are a range of units used for solubility, including molarity
(moles of solute per litre of solution, mol L−1), g/100 mL (grams of solute per 100 mL of solution)
and molality (moles of solute per kilogram of solvent, mol kg−1).
A sample of 15.0 g of caffeine was partially dissolved in water and the remaining solid was filtered
off, leaving 500 mL of solution. The water from the resulting saturated caffeine solution was boiled
off and the dissolved caffeine was recovered and weighed. 4.5 g of caffeine was recovered.
(a) Calculate the solubility of caffeine in water, in g/100 mL.
m(caffeine dissolved) = 15.0 g – 4.5 g = 10.5 g
Solubility = 10.5 g / 5 = 2.10 g/100 mL
Hansen solubility parameters (HSPs) can be used to predict if a solute will dissolve in a solvent.
Each molecule is given three parameters:
 δD is related to the dispersion forces between molecules. These come from the rearrangement of
electrons forming instantaneous dipoles.
 δP is related to the dipole-dipole forces between molecules. These come from the static dipoles
in polar molecules.
 δH is related to the hydrogen bonding between molecules. These come from the interaction of
highly polarised bonds to hydrogen and lone pairs.
Larger values for these parameters correspond to stronger forces.
(b) Explain why the values for δP and δH for hexane (C6H14) are zero.
Hexane is non-polar, so has no dipole-dipole forces or hydrogen bonding between its molecules.
Accordingly, δP and δH are zero.
Page 8 of 34
HSPs for caffeine and water are shown in the table below:
δD δP δH
Caffeine 19.5 10.1 13
Water 15.5 16 42.3
We can predict the solubility from the HSPs by computing the parameter R, using the following
formula:
𝑅 2 = 4(𝛿𝐷,1 − 𝛿𝐷,2 )2 + (𝛿𝑃,1 − 𝛿𝑃,2 )2 + (𝛿𝐻,1 − 𝛿𝐻,2 )2
R is a measure of how different the two molecules are. The smaller the value of R for a
solute-solvent pair, the more likely the solute is soluble in the solvent. From experimental evidence,
R < 7 generally means the solute is soluble in the solvent.
(c) Calculate the value of R for caffeine in water.
𝑅 2 = 4(𝛿𝐷,1 − 𝛿𝐷,2 )2 + (𝛿𝑃,1 − 𝛿𝑃,2 )2 + (𝛿𝐻,1 − 𝛿𝐻,2 )2
𝑅 2 = 4(19.5 − 15.5)2 + (10.1 − 16)2 + (13 − 42.3)2 = 957.3
𝑅 = 30.9
(d) The same experiment as in a) was conducted with using dichloromethane instead of water. The
solubility of caffeine in dichloromethane was found to be 140 mg mL−1 and the corresponding R
value was calculated to be 8.22. Do the values of R agree with the observed solubilities for
dichloromethane and water?
140 mg mL−1 = 14 g/100 mL.
Thus caffeine is more soluble in dichloromethane (14 g/100 mL) than it is in water
(2.1 g/100 mL, from part (a)).
R for caffeine in dichloromethane is 8.22, which is smaller than R for caffeine in water (30.9,
from part (b)).
Accordingly, caffeine should be more soluble in dichloromethane than in water, which agrees
with the observed solubilities.
Page 9 of 34
Hansen solubility parameters can also be used to understand the properties of mixed solvents. The
HSPs for a solvent mixture are the weighted averages of the HSPs for the pure components.
(e) Using the information in the table below:
δD δP δH
Nitromethane 15.8 18.8 6.0
Benzene 18.4 0 2.0
PMMA 18.6 10.5 5.1
i. Calculate the Hansen solubility parameters for a 1:1 mixture of nitromethane and benzene.
δD = (15.8 + 18.4)/2 = 17.1
δP = (18.8 + 0)/2 = 9.4
δH = (6.0 + 2.0)/2 = 4.0
ii. Calculate R for PMMA in 1:1 nitromethane/benzene.
𝑅 2 = 4(18.6 − 17.1)2 + (10.5 − 9.4)2 + (5.1 − 4.0)2 = 11.4
𝑅 = 3.38
iii. R for PMMA in benzene is 10.96 and for PMMA in nitromethane is 10.06. Based off
these R values, would PMMA be most likely to dissolve in benzene, nitromethane or 1:1
nitromethane/benzene?
The 1:1 nitromethane/benzene mixture (R for the mixture is lowest).
Page 10 of 34
Colligative properties of solutions are properties that depend upon the concentration of solute
molecules or ions but not upon the identity of this solute. One such property is freezing-point
depression.
The freezing point of a liquid decreases when a solute is added. Historically, molecular weights
were calculated empirically by using this property.
Freezing-point depression is directly proportional to the molality of the solute. Molality (moles of
solute per kilogram of solvent, mol kg−1) should not be confused with molarity (moles of solute per
litre of solution, mol L−1).
106.5 g of urea (CH4N2O, molar mass 60.062 g mol−1) is dissolved in 195.4 mL of water at 60 ºC.
The density of water at 60 ºC is 0.9832 g mL−1.
(f) What is the molality (in mol kg−1) of the solution?
106.5 g
𝑛(𝑢𝑟𝑒𝑎) = = 1.773 mol
60.062 g mol−1
𝑚(𝐻2 𝑂) = 0.1954 L × 0.9832 kg L−1 = 0.1921 kg
1.773 mol
𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦 = = 9.230 mol kg −1
0.1921 kg
(g) A saturated solution of glucose (C6H12O6) in water at 60 ºC has a molarity of 8.25 mol L−1 and a
density of 2.47 g mL−1. What is the molality of a saturated solution of glucose in water at 60 ºC?
𝑛(𝑔𝑙𝑢𝑐𝑜𝑠𝑒 𝑝𝑒𝑟 L) = 8.25 mol
𝑚(𝑔𝑙𝑢𝑐𝑜𝑠𝑒 𝑝𝑒𝑟 L) = 8.25 mol × 180.156 g mol−1 = 1486 g = 1.49 kg
𝑚(1 L solution) = 2.47 g mL−1 × 1000 mL = 2470 g = 2.47 kg
𝑚(𝑤𝑎𝑡𝑒𝑟 𝑝𝑒𝑟 L) = 2.47 kg − 1.49 kg = 0.98 kg
8.25 mol
𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦 = = 8.4 mol kg −1
0.98 kg
Page 11 of 34
The change in freezing point of the solution can be calculated using the following equation:
𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) − 𝑇𝐹 (𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡) = ∆𝑇𝐹 = −𝑖𝐾𝐹 𝑚
 TF is the freezing temperature in K

 ∆TF is the change in freezing temperature in K
 i is the van’t Hoff factor (more information below)
 Kf is the cryoscopic constant equal to 1.86 K kg mol−1
 m is the molality of the solution in mol kg−1.
The van’t Hoff factor, i, is the number of discrete particles (e.g. molecules, ions) released into
solution per formula unit. For species that do not dissociate, such as urea, i = 1.
A particularly useful application of freezing point depression is in making ice baths that are colder
than 0 ºC whilst still using ice and water. One such salt used is sodium chloride, which dissolves as
follows:
NaCl(s) → Na+(aq) + Cl−(aq)
(h) What is the theoretical van’t Hoff factor for sodium chloride?
(i) Sodium chloride is added to ice (freezing point 0.0 ºC) to make a bath with a freezing point of
−20.0 ºC. If 2.457 kg of ice is used, what mass of sodium chloride must be added?
−∆𝑇f 20.0 K
𝑚= = = 5.38 mol kg −1
𝑖𝐾f 2 × 1.86 K kg mol−1
𝑛(𝑁𝑎𝐶𝑙) = 5.38 mol kg −1 × 2.457 kg = 13.2 mol
𝑚(𝑁𝑎𝐶𝑙) = 13.2 mol × 58.44 g mol−1 = 772 g
Page 12 of 34
In winter, salts are often spread on top of icy roads to melt ice and make driving safer. Calcium
chloride hexahydrate is often used for this purpose as it is very cheap and effective.
(j) The concentration of a saturated solution of calcium chloride in water at 0 °C is 60.93 g/100 mL,
the density of this solution is 1.366 g mL−1 and the density of water at 0 °C is 1.000 g mL−1.
i. What is the freezing point of saturated calcium chloride solution?
m(100 mL saturated CaCl2 solution) = 100 × 1.366 = 136.6 g = 0.1366 kg
m(water in 100 mL saturated CaCl2 solution) = 136.6 g − 60.93 g = 75.67 g = 0.07567 kg
60.93 60.93
n(CaCl2 in 100 mL solution) = = = 0.5490 mol
40.08 + 2 × 35.45 110.98
0.5490 mol
molality(saturated CaCl2 solution) = = 7.255 mol kg −1
0.07567 kg
𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) = 𝑇𝐹 (𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡) − 𝑖𝐾𝐹 𝑚
𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) = 0 − 3 × 1.86 × 7.255 = −40.5 ℃
Page 13 of 34
ii. What mass of calcium chloride hexahydrate (CaCl2·6H2O) needs to be added to 100 mL
of water to make a saturated solution? (Hint: consider the water present in the added solid.)
1 mol of CaCl2·6H2O liberates 6 mol of H2O, i.e. 6 × 18.016 = 108.096 g of H2O
From (j), the molality of saturated CaCl2 solution is 7.255 mol kg−1.
Dissolving 7.255 mol of CaCl2·6H2O liberates 7.255 × 108.096 = 784 g of H2O
So to prepare a saturated CaCl2 solution, we need to add 7.255 mol of CaCl2·6H2O to

1000 – 784.3 = 215.7 g H2O.
From (j), m(100 mL water) = 100 g.We can prepare a saturated CaCl2 solution by dissolving
100
7.255 mol of CaCl2·6H2O in 215.7 g of H2O, so if we have 100 g H2O, we need: 215.7 ×
7.255 mol = 3.363 mol
So m(CaCl2·6H2O required) = 3.36 × 219.076 = 737 g
Page 14 of 34
Question 17
The properties of different compounds can be used to separate or distinguish them in a mixture.
These properties can often be predicted by looking at molecular structures.
An example of a Lewis structure is shown below for water.
O
H H
(a) Draw Lewis structures for the following molecules:
(i) hydrogen gas (H2) H H
(ii) nitrogen gas (N2) N N
H N H
(iii) ammonia (NH3)
Page 15 of 34
The structural formula of organic (carbon-based) molecules can be represented by skeletal formula
notation. In this notation, bonds are represented by lines, with carbon atoms located at the end of
each line segment or meeting point of line segments. Hydrogen atoms connected to carbon atoms
are implied rather than explicitly shown. For example, the two drawings below represent the same
molecule.
(b) Draw the skeletal formula for the following structure:
Page 16 of 34
When a compound is in a liquid state, at any given time, some fraction of the molecules have
enough kinetic energy to evaporate into the gas phase. The pressure of this gas phase at a given
temperature is known as vapour pressure.
The boiling point is the temperature at which the vapour pressure of the compound is equal to
atmospheric pressure. The graph below shows the relationship between vapour pressure and
temperature for water and diethyl ether.
(c) If water boils at 100 °C under normal pressure, what is the boiling point of diethyl ether under
the same conditions?
36 °C
Page 17 of 34
The structures of some simple compounds are shown below.
O O
H OH H H
acetaldehyde butane ethanol formaldehyde
H H
OH O
propane propan-1-ol water
Substances that have lower boiling points tend to have higher vapour pressures at any given
temperature.
(d) For each of the following pairs of compounds, tick the one with the higher vapour pressure at
20 °C. Explain your reasoning, identifying the relevant intermolecular forces involved.
i. Higher vapour pressure: ☐ butane ☐ propane
Reasoning:
The dispersion forces between propane molecules are weaker than the dispersion forces between
butane molecules, hence propane has a higher vapour pressure than butane.
ii. Higher vapour pressure: ☐ acetaldehyde ☐ ethanol
Reasoning:
The dipole-dipole interactions between acetaldehyde molecules are weaker than the hydrogen
bonds between ethanol molecules, hence acetaldehyde has a higher vapour pressure than ethanol.
Page 18 of 34
The differences in vapour pressure of different compounds can be used to separate them. One such
technique that uses this is gas chromatography.
(e) Rank the above compounds from the previous figure in terms of their vapour pressure at 20 °C.
Three boxes have been filled out for you.
(high vapour pressure)

propane
1
2 formaldehyde
3 butane
4 acetaldehyde
5 ethanol
6 propan-1-ol
7
water
(low vapour pressure)
Page 19 of 34
To analyse a sample by gas chromatography, the sample is first heated, and the vapours produced
are transferred to one end of a tube known as the column. The column is lined with a liquid solvent,
and a carrier gas flows through the tube. This allows compounds to travel through the column in the
gaseous phase, eventually reaching a detector at the other end.
The length of time a substance spends in the column is known as its retention time.
The higher a substance’s vapour pressure, the longer it spends in the gas phase (rather than
dissolved in the liquid solvent), so the faster it proceeds through the column.
(f) If a sample of butane and formaldehyde were run in gas chromatography, which sample would
have the longer retention time, assuming that they interact identically with the liquid solvent?
☐ butane ☐ formaldehyde
(g) For each row, select the class of compound expected to have the longer retention time with the
given liquid solvent, assuming that we are comparing polar and non-polar compounds with similar
vapour pressures.
Liquid solvent polarity Longer retention time
i. Polar solvent ☐ Polar compound ☐ Non-polar compound ☐ Neither
ii. Non-polar solvent ☐ Polar compound ☐ Non-polar compound ☐ Neither
Page 20 of 34
The detector produces a signal when the gaseous compounds pass by. The resulting graph is called
a chromatogram, showing the time and size of the signals from the detector.
Gas chromatography of a sample containing the following four compounds was performed using a
polar liquid solvent. The resulting chromatogram is shown on the next page.
O O
- +
O Na
hexane pentane pentan-2-one sodium acetate
(h) Assign the compounds to the peaks observed. Note: one of the four compounds does not
appear.
Peak 1 Peak 2 Peak 3
Compound pentane hexane pentan-2-one
(i) Which of the four compounds did not appear on the chromatogram? Why?
Sodium acetate. There are strong electrostatic interactions between the sodium and acetate ions
in its crystal lattice, hence sodium acetate has a much smaller vapour pressure than the other
(molecular) compounds.
Page 21 of 34
(j) If the liquid solvent was non-polar, can the order of compound peaks still be predicted? If yes,
what would the order be? If no, why not?
No. The non-polar substances (with the lowest vapour pressures and shortest retention times)
will now have increased retention times due to increased interaction with the non-polar solvent.
The retention time for each molecule will depend on which of these factors is more important.
The conditions under which gas chromatography is performed can be optimised to improve the
quality of the chromatogram. For example, one common issue is peak separation in the
chromatogram, which is important to differentiate compounds. Peak separation is defined as the
difference in retention time between two peaks.
(k) Tick the box corresponding to the conditions which would change peak separation.
Condition Peak separation
a) Increased flow rate of carrier gas ☐ Decrease ☐ No change ☐ Increase

b) Increased temperature ☐ Decrease ☐ No change ☐ Increase
c) Increased column length ☐ Decrease ☐ No change ☐ Increase
Page 22 of 34
In addition to separating and identifying compounds, gas chromatography can be used to determine
the concentration of a compound in an unknown sample. In general, the area of the peak
corresponding to a particular compound in a chromatogram is proportional to the concentration of
that compound in the sample.
To do this, a calibration curve must first be produced by analysing a series of solutions of known
concentration. A calibration curve for aqueous solutions of ethanol is shown below, including the
equation of the line of best fit.
Calibration curve
for ethanol
12 000 000
10 000 000
Peak Area
8 000 000
6 000 000 y = 356937x
4 000 000
2 000 000
0
0 5 10 15 20 25 30 35
Concentration of ethanol (%v/v)
An ethanol-water mixture of unknown concentration is analysed, and the corresponding

chromatogram has a single peak with an area of 5.31 × 106.
(l) Determine the percentage by volume of ethanol in the unknown sample.
5.31 × 106
%(𝑣/𝑣) = = 14.9%
356937
(m) Given that ethanol has a density of 0.789 g mL-1, calculate the concentration of ethanol (in
mol L−1) in the unknown ethanol-water mixture. (If you do not get an answer to the previous
question, assume that the percentage by volume of ethanol in the unknown sample is 14.0%(v/v)).
𝑚(𝑒𝑡ℎ𝑎𝑛𝑜𝑙 𝑖𝑛 1 L) = 0.789 g mL−1 × 14.9 g/100 mL × 10 = 117 g
117 g
𝑛(𝑒𝑡ℎ𝑎𝑛𝑜𝑙) = = 2.55 mol
46.068 g mol−1
So [ethanol] = 2.55 mol L−1
Page 23 of 34
Often, samples contain many different compounds besides the compound being analysed. These
additional compounds are termed the matrix. The matrix can have a significant effect on gas
chromatography, and using standard solutions with a different matrix to the sample being analysed
can lead to errors. One strategy for overcoming these “matrix effects” is standard addition. The
premise of this technique involves ensuring that the standard solutions contain the same matrix
present in the sample to be analysed.
Petrol is a complex mixture of non-polar hydrocarbons, and ethanol is sometimes added to improve
combustion. Standard addition can be used to determine the concentration of ethanol by gas
chromatography.
Five samples of petrol are taken, and a different volume of ethanol is added to each, as shown in the
following table. Each sample is then diluted with hexane to a final volume of 1.2 mL.
Sample Code Volume petrol Volume ethanol Concentration of
(mL) (mL) added ethanol
(%(v/v))
A 1.00 0.00 0.00
B 1.00 0.05 4.17
C 1.00 0.10 8.34
D 1.00 0.15 12.5
E 1.00 0.20 16.7
(n) Complete the table by calculating the concentration of ethanol added to sample C (working
space is provided below).
(o) Explain why each sample is diluted to constant volume.
 makes calculations easier

 allows for the samples to be compared directly, since the unknown is of constant
concentration across them
Page 24 of 34
(p) Would water be an appropriate solvent to dilute the samples with, instead of hexane? Explain
why or why not.
No, as water is not miscible with the non-polar hydrocarbons in petrol.
Samples A – E are analysed by gas chromatography as before, and the ethanol peak areas are
plotted against the concentration of added ethanol. The plot is shown below, again including the
equation of the line of best fit.
Standard addition plot for ethanol

5 000 000
y = 191915x + 1027100
4 000 000
Peak Area
3 000 000
2 000 000
1 000 000
0 5 10 15 20
Added ethanol concentration (%v/v)
(q) Calculate the percentage by volume of ethanol in the petrol sample.
Peak area for 0% added ethanol = 1027100
1027100 1.2
[𝑒𝑡ℎ𝑎𝑛𝑜𝑙] = × = 5.35%
191915 1.0
Page 25 of 34
Question 18
The energy of a photon of light is given by the following equation:

ℎ𝑐
𝐸=
𝜆
 E is the energy of the photon (in J)
 λ is the wavelength of light (in m)
 h is Planck’s constant (6.626 × 10−34 J s)
 c is the speed of light (2.998 × 108 m s−1)
(a) Calculate the energy of a photon of light with wavelength 500.0 nm (500.0 × 10−9 m).
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝐸= = = 3.973 × 10−19 J
𝜆 500.0 × 10−9
The Bohr Model of the atom describes the different discrete energy levels that electrons can
occupy. For example, the energy levels of the hydrogen atom are shown in the diagram below. An
electron can change energy levels by absorbing or emitting a photon of light that has the same
energy as the energy difference between the two levels. Atoms fluoresce when they move from an
excited energy level to the ground state (i.e. lowest) energy level, releasing energy in the form of
light.
(b) In the hydrogen atom, an electron absorbs a photon and moves from the 𝑛 = 2 to 𝑛 = 3 energy
level, and then fluoresces. Draw an arrow that represents the transition of the electron during
fluorescence on the energy diagram below.
Page 26 of 34
(c) Will the wavelength of the photon emitted by fluorescence be higher, lower or the same as the
photon absorbed by the electron initially? Briefly explain your answer.
The energy difference is greater for fluorescence, so the wavelength will be lower.
Atoms are not the only species that can fluoresce. Molecules can fluoresce as well, however their
energy diagrams are far more complex than for atoms:
 Molecules contain both electronic energy levels (like those in the hydrogen atom examined
above) and vibrational energy levels.
 The overall energy of the molecule is the sum of the electronic and vibrational energies.
 The energy gap between vibrational energy levels is much smaller than the gap between
electronic energy levels.
 A molecule can be in any combination of excited electronic and vibrational states.
Each of these energy levels can be represented as a line on a Jablonski diagram, shown below, and
is labelled based on the electronic energy level (labelled from the ground state up by 𝑛 = 1, 2, 3, …)
and the vibrational energy level (labelled from the ground state up by 𝜈 = 0, 1, 2, …).
For example, in the diagram below, the bold lines represent the electronic energy levels (𝑛 =
1, 2, 3, …) in the lowest vibrational energy level (𝜈 = 0). The ground state of the entire system is
labelled 𝑛 = 1, 𝜈 = 0.
(d) Write the corresponding 𝑛 and 𝜈 numbers next to the energy level labelled ∗ below. Some other
energy levels have been labelled for your convenience.
𝑛 = 2, 𝜈 = 3
Page 27 of 34
Molecules can also move between different vibrational energy levels by emitting energy as heat,
without emitting photons. Typically, if a molecule is in a state with 𝜈 ≠ 0, it will quickly release
heat through this process to reach the 𝜈 = 0 state. After this, a molecule can fluoresce by releasing a
photon of light, ending up in a state with 𝑛 = 1, before again releasing heat to return it to the 𝑛 =
1, 𝜈 = 0 state.
(e) One of the following transitions on the Jablonksi diagram below corresponds to the release of a
photon from a molecule that is fluorescing, as described in the paragraph above. Circle the letter
corresponding to this transition.
A molecule initially in the ground state absorbs a photon of light with a wavelength of 350.0 nm
(350.0 × 10−9 m) and undergoes fluorescence. In the process, it releases 1.351 × 10−19 J of heat to
the environment.
(f) Calculate the wavelength of the emitted photon of light.
Recall from (a) that the energy of a photon of light is given by the following equation:
ℎ𝑐
𝐸=
𝜆
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝐸= = = 5.676 × 10−19 J
𝜆 350.0 × 10−9
𝐸𝑓𝑙𝑢𝑜𝑟𝑒𝑠𝑐𝑒𝑛𝑐𝑒 = 5.676 × 10−19 J − 1.351 × 10−19 J = 4.325 × 10−19 J
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝜆= = = 4.593 × 10−7 m = 459.3 nm
𝐸 4.325 × 10−19
Page 28 of 34
Another process that a molecule can undergo is internal conversion, which allows the molecule to
decay from the 𝑛 = 2, 𝜈 = 0 energy level to the 𝑛 = 1, 𝜈 = 0 energy level by emitting energy only
as heat, without releasing a photon. This process occurs more frequently when the molecule
concerned collides more frequently with other molecules. We define the quantum yield, Φ, of a
molecule as the number of photons emitted in fluorescence divided by the number of photons
absorbed.
(g) What is the range of possible values for Φ?
0-1
(h) As temperature increases, will Φ increase or decrease? Briefly explain your answer.
As temperature increases, the molecules will collide more frequently with each other, so the rate
of internal conversion increases. Accordingly, Φ decreases.
(i) 200.0 J of light with wavelength 700 nm (700.0 × 10−9 m) is shone onto a material. Calculate
the number of photons in the light.
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝐸= = = 2.838 × 10−19 J
𝜆 700.0 × 10−9
200 J
Number of photons = = 7.048 × 1020 photons
2.838 × 10−19 J
(j) The quantum yield of the event is 0.993954. Calculate the number of photons emitted by
fluorescence.
Number of photons = 0.993954 × 7.048 × 1020 = 7.005 × 1020 photons
Page 29 of 34
The fluorescence of a molecule or atom can be measured by exciting a sample with light of a
wavelength 𝜆excite and detecting the intensity of light that the sample emits by fluorescence at
wavelength 𝜆detect .
There are two different ways of displaying this data: in an excitation spectrum, the excitation
wavelength 𝜆excite is varied and the detection wavelength 𝜆detect is held constant; in an emission
spectrum, the excitation wavelength is 𝜆excite held constant and the detection wavelength 𝜆detect is
varied. In each case, the spectrum is presented as a graph of intensity (on the 𝑦-axis) vs varied
wavelength (𝜆excite or 𝜆detect ) on the 𝑥-axis.
The emission and excitation spectra of a molecule are provided below (1 nm = 1 × 10−9 m).
Page 30 of 34
(k) On the Jablonski diagrams below, draw the transition corresponding to the following peaks:
i. 380 nm in Spectrum A. ii. 380 nm in Spectrum B.
iii. 329 nm in Spectrum B.
Page 31 of 34
(l) The emission spectrum of the molecule as shown above was produced at an excitation
wavelength of 𝜆excite = 380 nm. What would happen to the emission spectrum if the excitation
wavelength was changed to 𝜆excite = 329 nm? (Circle all that apply)
A. The spectrum will be shifted towards larger wavelengths.
B. The spectrum will be shifted towards shorter wavelengths.
C. The spectrum will be shifted to higher intensities.
D. The spectrum will be shifted to lower intensities.
E. There will be no change to the spectrum.
(m) Calculate the energy difference between 𝑛 = 1, 𝜈 = 1 and 𝑛 = 2, 𝜈 = 3 energy levels.
The 𝑛 = 1, 𝜈 = 0 to 𝑛 = 2, 𝜈 = 3 transition occurs at 303 nm

in Spectrum B. E
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝐸= = = 6.556 × 10−19 J
𝜆 303.0 × 10−9
The 𝑛 = 2, 𝜈 = 0 to 𝑛 = 1, 𝜈 = 1 transition occurs at 401 nm 𝑛 = 2, 𝜈 = 3

in Spectrum A.
𝑛 = 2, 𝜈 = 0
ℎ𝑐 6.626 × 10−34 × 2.998 × 108
𝐸= = −9
= 4.954 × 10−19 J
𝜆 401.0 × 10
The 𝑛 = 1, 𝜈 = 0 to 𝑛 = 2, 𝜈 = 0 transition occurs at 380 nm

in Spectrum A.
ℎ𝑐 6.626 × 10−34 × 2.998 × 108

𝐸= = = 5.228 × 10−19 J
𝜆 380.0 × 10−9
𝑛 = 1, 𝜈 = 1
𝑛 = 1, 𝜈 = 0
So for the 𝑛 = 1, 𝜈 = 1 to 𝑛 = 2, 𝜈 = 3 transition:
𝐸 = 6.556 × 10−19 J + 4.954 × 10−19 J − 5.228 × 10−19 J = 6.282 × 10−19 J
Page 32 of 34
BLANK WORKING PAGE
Page 33 of 34
BLANK WORKING PAGE
Integrity of Competition
If there is evidence of collusion or other academic dishonesty, students will be

disqualified. Markers’ decisions are final.
Page 34 of 34

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2019 AUSTRALIAN SCIENCE OLYMPIAD EXAM

First Name: ………………...…..………… Last Name………………………………….

Name of School: ………………………………………….………………..State: ……...

Examiners Use Only:

• Attempt ALL questions in ALL sections of this paper.

• Ensure that your diagrams are clear and labelled.

• All numerical answers must have correct units.

• Rough working may be done on page 33 and 34 of this booklet.

• Data that may be required for a question may be found on page 3.

• Do not staple the multiple choice answer sheet to this booklet.

(a) covalent bonds

(a) C2H6 < CH3OH < CH3F

7. Jarosite is a white mineral of formula KAl3X2(OH)6, where X is an unspecified species. Which

(a) 1.0  1022

(a) 0.005 mol

Fe2O3(s) + 3CO(g) → 2Fe(s) + 3CO2(g)

Which of the following statements must be true?

(a) Element X has a higher first ionisation energy than element Y.

C3H7OH(l) + O2(g) → CO2(g) + H2O(l)

(a) Calculate the solubility of caffeine in water, in g/100 mL.

m(caffeine dissolved) = 15.0 g – 4.5 g = 10.5 g

Solubility = 10.5 g / 5 = 2.10 g/100 mL

Larger values for these parameters correspond to stronger forces.

Caffeine 19.5 10.1 13

Water 15.5 16 42.3

(c) Calculate the value of R for caffeine in water.

𝑅 2 = 4(𝛿𝐷,1 − 𝛿𝐷,2 )2 + (𝛿𝑃,1 − 𝛿𝑃,2 )2 + (𝛿𝐻,1 − 𝛿𝐻,2 )2

𝑅 2 = 4(19.5 − 15.5)2 + (10.1 − 16)2 + (13 − 42.3)2 = 957.3

140 mg mL−1 = 14 g/100 mL.

(e) Using the information in the table below:

Nitromethane 15.8 18.8 6.0

Benzene 18.4 0 2.0

PMMA 18.6 10.5 5.1

δD = (15.8 + 18.4)/2 = 17.1

δP = (18.8 + 0)/2 = 9.4

δH = (6.0 + 2.0)/2 = 4.0

ii. Calculate R for PMMA in 1:1 nitromethane/benzene.

𝑅 2 = 4(18.6 − 17.1)2 + (10.5 − 9.4)2 + (5.1 − 4.0)2 = 11.4

The 1:1 nitromethane/benzene mixture (R for the mixture is lowest).

(f) What is the molality (in mol kg−1) of the solution?

𝑚(𝐻2 𝑂) = 0.1954 L × 0.9832 kg L−1 = 0.1921 kg

𝑛(𝑔𝑙𝑢𝑐𝑜𝑠𝑒 𝑝𝑒𝑟 L) = 8.25 mol

𝑚(𝑔𝑙𝑢𝑐𝑜𝑠𝑒 𝑝𝑒𝑟 L) = 8.25 mol × 180.156 g mol−1 = 1486 g = 1.49 kg

𝑚(1 L solution) = 2.47 g mL−1 × 1000 mL = 2470 g = 2.47 kg

𝑚(𝑤𝑎𝑡𝑒𝑟 𝑝𝑒𝑟 L) = 2.47 kg − 1.49 kg = 0.98 kg

𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) − 𝑇𝐹 (𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡) = ∆𝑇𝐹 = −𝑖𝐾𝐹 𝑚

 TF is the freezing temperature in K

𝑛(𝑁𝑎𝐶𝑙) = 5.38 mol kg −1 × 2.457 kg = 13.2 mol

𝑚(𝑁𝑎𝐶𝑙) = 13.2 mol × 58.44 g mol−1 = 772 g

m(100 mL saturated CaCl2 solution) = 100 × 1.366 = 136.6 g = 0.1366 kg

m(water in 100 mL saturated CaCl2 solution) = 136.6 g − 60.93 g = 75.67 g = 0.07567 kg

𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) = 𝑇𝐹 (𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡) − 𝑖𝐾𝐹 𝑚

𝑇𝐹 (𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛) = 0 − 3 × 1.86 × 7.255 = −40.5 ℃

1 mol of CaCl2·6H2O liberates 6 mol of H2O, i.e. 6 × 18.016 = 108.096 g of H2O

Dissolving 7.255 mol of CaCl2·6H2O liberates 7.255 × 108.096 = 784 g of H2O

So to prepare a saturated CaCl2 solution, we need to add 7.255 mol of CaCl2·6H2O to

7.255 mol = 3.363 mol

So m(CaCl2·6H2O required) = 3.36 × 219.076 = 737 g

An example of a Lewis structure is shown below for water.

(i) hydrogen gas (H2) H H