40th Austrian Chemistry Olympiad

National Competition

Solution
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

Task 1 15 points
Titanium and other metals

A. From the ore to the element

1.1. Calculate the empirical formula of titanite.

formula: CaTiSiO5
calculations:

24.42 20.44 14.33 40.81

Ti: = 0.5101 Ca: = 0.5100 Si: = 0.5101 O: = 2.5506
47.87 40.08 28.09 16.00
proportion 1:1:1:5

1.2. Write down balanced equations for the reactions in the scheme and derive from them an overall
equation for the depicted process.
A: FeTiO3 + C → Fe + CO + TiO2
B: TiO2 + 2 C + 2 Cl2 → TiCl4 + 2 CO
C: TiCl4 + 2 Mg → Ti + 2 MgCl2

D: MgCl2 → Mg + Cl2
overall: FeTiO3 + 3 C → Fe + 3 CO + Ti

1.3. 1000 kg of the reaction mixture according to the overall equation were used. Which maximum
mass of titanium may be generated starting from these 1000 kg?
mass of Ti: 255 kg Ti
calculations:

M(FeTiO3) = 151.72 g/mol

n·151,72 + 3n·12,01 = 106 g therefore n = 5326 mol
m(Ti) = 5326·47.87 = 255 kg Ti

1.4. Which process is used to execute reaction D?

electrolyis, fused-salt electrolysis

1.5. Complete the equation for the synthesis of barium titanate(IV) from TiO2:
BaCO3 + TiO2 → BaTiO3 + CO2

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

1.6. Write down the complete equation for the radioactive decay of 45Ti.
45 45
22Ti → 21Sc + 𝑒𝑒 + + 𝜈𝜈𝑒𝑒

1.7. What was the specific activity of the sample put aside after 3.0 hours?
specific activity after 3.0 hours: 33.54 Bq/g
calculations:

ln 2 ln 2
𝜆𝜆 = = = 0.2252 h−1 𝐴𝐴(𝑡𝑡) = 65.91 ⋅ 𝑒𝑒 −0.2252⋅3 = 33.54
𝑡𝑡1� 3.078 h
2

1.8. Calculate the overall yield of Ti of the reaction sequence (A,B,C,D) based on the starting amount
of FeTiO3.
yield in %: 80.0 %
calculations:

total activity at the beginning: 82.6 g · 65.91 = 5681.4 Bq

After some time – activity after 210 min (3.5h) 𝐴𝐴(𝑡𝑡) = 5681.4 ⋅ 𝑒𝑒 −0.2252⋅3.5 = 2584.4 Bq
2068
yield: = 0.8002
2584.4

B. Other Ti-compounds – crystal lattice

1.9. Write down the electron configuration of Ti3+.

1s2 2s2 2p6 3s2 3p6 3d1

1.10. Calculate the ionic radius of N3− using the Kapustinskii-equation. Show your calculations.
(d* = 34.5 pm; κ = 1.21·105 kJ·pm/mol)
Ionic radius of nitride N3−: 1.64Å
calculations:
𝑁𝑁𝑖𝑖𝑖𝑖𝑖𝑖 |𝑧𝑧− 𝑧𝑧+ |𝜅𝜅 𝑑𝑑 ∗
𝛥𝛥𝛥𝛥 = − (1 − 𝑟𝑟 )
𝑟𝑟0 0
𝑁𝑁𝑖𝑖𝑖𝑖𝑖𝑖 |𝑧𝑧− 𝑧𝑧+ |𝜅𝜅 2⋅3⋅3⋅1.21⋅105 l
𝐵𝐵 = − =− = 2.711 ⋅ 102 𝑝𝑝𝑝𝑝
𝛥𝛥𝛥𝛥 −8033
1 1 𝑑𝑑 ∗ 𝑟𝑟 2
= − 𝑟𝑟 ⇒ 𝐵𝐵0 = 𝑟𝑟0 − 𝑑𝑑∗ ⇒ 𝑟𝑟02 − 𝐵𝐵𝑟𝑟0 + 𝑑𝑑∗ 𝐵𝐵 = 0
𝐵𝐵 𝑟𝑟0 0

𝐵𝐵 𝐵𝐵2
𝑟𝑟0 = + � 4 − 𝑑𝑑∗ 𝐵𝐵
2
r0 = 2.31Å = rTi + rN therefore rN = 1.64Å

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

1.11. Calculate the lengths of x and y using this information.

x = 3,562 Å y = 3,548 Å
calculations:

180−118.4
Looking at the front plane: ∠(𝑇𝑇𝑇𝑇 − 𝑇𝑇𝑇𝑇 − 𝐶𝐶) = = 30.8°
2
𝑥𝑥
and = (𝐶𝐶 − 𝑇𝑇𝑇𝑇) ⋅ cos 30.8° = 2.074 Å ⋅ 0.85896 = 1.781Å ⇒ 𝑥𝑥 = 3.562Å
2

𝑦𝑦 = 2 ⋅ (𝐶𝐶 − 𝑇𝑇𝑇𝑇) ⋅ sin 30.8° + (𝐶𝐶 − 𝐶𝐶) = 2.124 + 1.424 = 3.548 Å

C. Complexes of chromium and cobalt

1.12. Write down the missing name or formula respectively for each of the compounds (a) to (e).
(a) pentaamminbromidocobalt(III)-sulfate
(b) pentaamminsulfatocobalt(III)-bromide

(c) [CrCl2(OH2)4]Cl · 2 H2O

(d) [CrCl(OH2)5]Cl2 · H2O
(e) potassium hexafluoridocobaltat(III)

1.13. Assign (a) to (e) with the roman numbers I to V.

I: (a) II: (e) III: (c) IV: (b) V: (d)
Give your reasoning for the classification using either calculations or chemical equations.

Vessels III, IV and V must contain bromide, and twice chloride respectively.
Vessel I: SO42- + Ba2+ → BaSO4
𝑚𝑚 3.28
M(c) = M(d) = 266.47 g/mol 𝑛𝑛 = = = 0.123 mol ⇒ corresponds to 1.76 g AgCl
𝑀𝑀 266.47
→ vessel III contains (c)
Mass loss by drying → crystal water → have only (c) and (d) → vessel V must (d).
molar mass 290.23 g/mol → (e)

1.14. How do you call the constitution isomerism of (a) and (b)?

ionisation isomersm

1.15. How many diastereomeres may occur in the case of the cation of (c)? Give also the prefixes
which you use in naming them.

two -- cis and trans

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

1.16. Calculate ΔO in kJ/mol.

ΔO = 156.7 kJ mol-1
calculation:

𝑐𝑐
𝐸𝐸 = ℎ = ℎ𝑐𝑐𝜈𝜈� = 6.6262 ⋅ 10−34 ⋅ 2.9979 ⋅ 108 ⋅ 13100 ⋅ 100 = 2.6022 ⋅ 10−19 J
𝜆𝜆
E = 2.6022 ⋅ 10−16 ⋅ 6.0221 ⋅ 1023 = 156.7 kJ mol-1

1.17. Sketch a d-orbital scheme for the complex in (e)

1.18. Calculate the magnetic moment in units of μB.

μ = 4.90𝜇𝜇𝐵𝐵
calculation:

𝜇𝜇 = �𝑛𝑛(𝑛𝑛 + 2)𝜇𝜇𝐵𝐵 = �4(6)𝜇𝜇𝐵𝐵 = 4.90𝜇𝜇𝐵𝐵

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

Task 2 13 points
Some Equilibria

A. Electrochemical Equilibria – Alkaline Cell

2.1. Write down the reaction equations for the generation of MnOOH and Mn(OH)3 respectively,
starting from Mn2O3 using water as reaction partner.
Mn2O3 + H2O ⇌ 2 MnOOH
Mn2O3 + 3 H2O ⇌ 2 Mn(OH)3

2.2. Calculate the free standard reaction enthalpy for the reaction Mn2O3 → Mn(OH)3.
ΔG0= 77 kJ
calculation:
2 Mn(OH)3 + 2e- ⇌ 2 Mn(OH)2 + 2 OH- E03 = 0.15 V
Mn2O3 + 3 H2O + 2e- ⇌ 2 Mn(OH)2 + 2 OH- E04 = -0.25 V
Mn2O3 + 3 H2O ⇌ 2 Mn(OH)3 E07 = E04 – E03 = -0.40 V
ΔG07 = -z·F·E07 = 77 k

2.3. Calculate the free standard reaction enthalpy for the reaction Mn2O3 → MnOOH.
ΔG0= 5.8 kJ
calculation:
2 MnOOH + H2O + Zn ⇌ 2 Mn(OH)2 + ZnO E02 = 1.06 V
Zn + 2 OH- ⇌ ZnO + H2O + 2e- E01 = 1.28 V
2 MnOOH + 2 H2O + 2e- ⇌ 2 Mn(OH)2 + 2 OH- E08 = E02 – E01 = -0.22 V
Mn2O3 + 3 H2O + 2e- ⇌ 2 Mn(OH)2 + 2 OH- E04 = -0.25 V
Mn2O3 + H2O ⇌ 2 MnOOH E09 = E04 – E08 = -0.03 V
ΔG09 = -z·F·E09 = 5.8 kJ

2.4. Calculate the solubility product of Mn(OH)2.

KL = 1.42·10-13
calculation:
Mn2+ + 2e- ⇌ Mn E05 = -1.18 V ΔG05 = -z·F·E05 =228 kJ
Mn(OH)2 + 2e- ⇌ Mn + 2 OH- E06 = -1.56 V ΔG06 = -z·F·E06 =301 kJ
Mn(OH)2 ⇌ Mn2+ + 2 OH- ΔG010 = ΔG06 - ΔG05 = 73.3 kJ
𝛥𝛥𝐺𝐺0
10
𝐾𝐾𝐿𝐿 = 𝑒𝑒 −𝑅𝑅·𝑇𝑇 = 1.42 · 10−13

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

B. The coral reef

2.5. Calculate the minimum concentration of carbonate ions in sea water in order to build the lime
frame.
[𝐶𝐶𝑂𝑂32− ] = 8.3·10-7 mol/L

calculation:
0.42
[𝐶𝐶𝑎𝑎2+ ] = = 0.0105 𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿
40.08
8.7·10−9 8.7·10−9
[Ca2+]·[CO32-] = 8.7·10-9 ⟶ [𝐶𝐶𝑂𝑂32− ] = = = 8.3 · 10−7 𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿
[𝐶𝐶𝑎𝑎 2+ ] 0.0105

2.6. Calculate the highest pH, where the lime frame dissolves.
pH = 6.92
calculation:

�𝐶𝐶𝑂𝑂32− �·[𝐻𝐻3 𝑂𝑂 + ]
[𝐻𝐻𝐻𝐻𝑂𝑂3− ]
= 5.6 · 10−11 ⟶
�𝐶𝐶𝑂𝑂32− �·[𝐻𝐻3 𝑂𝑂 + ] 8.302·10−7
[𝐻𝐻𝐻𝐻𝑂𝑂3− ] = = · [𝐻𝐻3 𝑂𝑂+ ] = 14826 · [𝐻𝐻3 𝑂𝑂+ ]
5.6·10−11 5.6·10−11

[𝐻𝐻2 𝐶𝐶𝑂𝑂3 ] + [𝐻𝐻𝐻𝐻𝑂𝑂3− ] + [𝐶𝐶𝑂𝑂32− ] = 2.3 · 10−3 𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿 ⟶

[𝐻𝐻2 𝐶𝐶𝑂𝑂3 ] = 2.3 · 10−3 − 14826 · [𝐻𝐻3 𝑂𝑂+ ] − 8.302 · 10−7
[𝐻𝐻𝐻𝐻𝑂𝑂3− ]·[𝐻𝐻3 𝑂𝑂 + ] 14826·[𝐻𝐻 𝑂𝑂 + ]2
[𝐻𝐻2 𝐶𝐶𝑂𝑂3 ]
3
= 2.299·10−3 −14826·[𝐻𝐻 +] = 4.3 · 10−7 ⟶ [H3O+] = 1.21·10-7
3 𝑂𝑂

⟶ pH = 6.92

C. A mixture of acids

2.7. Calculate the pH of this solution. Neglect the autoprotolysis of water.

pH = 2.88
calculation:
𝑝𝑝𝑝𝑝 = 0.5 · (4.76 − 𝑙𝑙𝑙𝑙𝑙𝑙(0.1)) = 2.88

2.8. Give for the concentrations of all particles in this mixture numbers or terms with variables,
whereby you should show reasonable assumptions about negligible species.
[HAc] ≈ 0.05 [Ac-] = x [H2SO4] ≈ 0 [HSO4-] = a [SO42-] = b

[H3O+] = 10-(2.88-0.300) = 10-2.58 = 0.00263 mol/L

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

2.9. Calculate the concentration of the diluted sulphuric acid, which is added to the acetic acid
solution.
c = 0.00251 mol/L
calculation:

𝑥𝑥·0.00263
= 10−4.76 ⟶ x = 0.0003303 mol/L
0.05

[H3O+] = x + a + 2b ⟶ 0.00263 = 0.0003303 + a + 2b

𝑏𝑏·0.00263 10−1.92 ·𝑎𝑎
= 10−1.92 ⟶ 𝑏𝑏 = = 4.571 · 𝑎𝑎
𝑎𝑎 0.00263

⟶ 0.00263 = 0.0003303 + a + 2·4.571·a

⟶ a = 0.000227 mol/L
⟶ b = 0.00104 mol/L
𝑐𝑐𝐻𝐻𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
2 𝑆𝑆𝑂𝑂4
= 𝑎𝑎 + 𝑏𝑏 = 0.001253 𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿

Before dilution: c = 0.00251 mol/L

2.10. Give reasoning for your assumptions in 2.8.

[HAc] = 0.05 – x x = 0.0003303 mol/L

⟶ assumption [HAc] ≈ 0.05 true

[𝐻𝐻𝐻𝐻𝑂𝑂4− ] · [𝐻𝐻3 𝑂𝑂+ ] 0.0002237 · 0.002613

[𝐻𝐻2 𝑆𝑆𝑂𝑂4 ] = = = 5.85 · 10−9 𝑚𝑚𝑚𝑚𝑚𝑚/𝐿𝐿
𝐾𝐾𝐴𝐴1 102
⟶ assumption [H2SO4] ≈ 0 true

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

Task 3 15 points
Kinetics and Thermodynamics

A. Two kinetic problems

3.1. Write down the differential rate law for reaction (1) and give proof by a short calculation.
rate law: 𝑣𝑣 = 𝑘𝑘 ∙ [𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵]
calculation:

𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵: 𝑉𝑉 ∝ 𝑚𝑚 ∝ 𝑛𝑛 ∝ 𝑐𝑐 ; 𝑉𝑉(𝐴𝐴𝐴𝐴𝐴𝐴𝑂𝑂3 ) ∝ 𝑣𝑣

𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵(𝐸𝐸𝐸𝐸𝐸𝐸1 − 𝐸𝐸𝐸𝐸𝐸𝐸2): 𝑐𝑐(2): 𝑐𝑐(1) = 1.5: 1 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉(2): 𝑉𝑉(1) = 1,5: 1 ⇒ 1st order

𝐻𝐻2 𝑂𝑂(𝐸𝐸𝐸𝐸𝐸𝐸3 − 𝐸𝐸𝐸𝐸𝐸𝐸2): 𝑐𝑐(3): 𝑐𝑐(2) = 1: 0.75 𝑎𝑎𝑎𝑎𝑎𝑎 𝑉𝑉(3): 𝑉𝑉(2) = 1: 1 ⇒ zero order

3.2. Calculate the initial concentration of t-butyl bromide.

exp1: c0 (t-BuBr) = 0.212 mol/L exp2: c0 (t-BuBr) = 0.318 mol/L
calculation for one example:

𝑚𝑚 = 𝜌𝜌 ∙ 𝑉𝑉 = 1.20 ∙ 1.21 = 1.452 g

𝑚𝑚 1.452
𝑛𝑛 = = = 0.0106 mol
𝑀𝑀 137
𝑛𝑛 0.0106
𝑐𝑐 = = = 0.212 mol/L
𝑉𝑉 50

3.3. Calculate the concentration of t-butyl bromide after one hour for experiment (1) and (2).
ct (1) = 0.201 mol/L ct (2) = 0,302 mol/L
calculation for one example:

𝑛𝑛(𝐴𝐴𝑔𝑔+ ) = 𝑛𝑛(𝐵𝐵𝑟𝑟 − ) = 𝑉𝑉(𝐴𝐴𝑔𝑔+ ) ∙ 𝑐𝑐(𝐴𝐴𝑔𝑔+ ) = 10.6 ∙ 0.05 = 0.530 mmol

𝑛𝑛𝑡𝑡 (𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) = 𝑛𝑛0 (𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) − 𝑛𝑛(𝐵𝐵𝑟𝑟 − ) = 10.6 − 0.53 = 10.07 mmol
𝑛𝑛𝑡𝑡 10.07
𝑐𝑐𝑡𝑡 = 𝑉𝑉
= = 0.2014 mol/L
50

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

3.4. Calculate the rates in experiment 1 and 2 using the differential rate law, and thereby find also a
mean value for the rate constant.
v(1) = 0.0106 mol/L·h v(2) = 0,0159 mol/L·h

k = 5.00·10-2 h-1
calculation:
𝑐𝑐0 (𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) − 𝑐𝑐𝑡𝑡 (𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) 0.212 − 0.2014
𝑣𝑣 = = = 0.0106 mol/L ∙ h
∆𝑡𝑡 1
𝑣𝑣 0.0106
𝑘𝑘 = = = 5.00 · 10−2 h−1
𝑐𝑐0 (𝑡𝑡 − 𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) 0.212

Concerning reaction (2):

3.5. Which reaction order do you suppose based on the chemical system in question?
reaction order: 2nd order

3.6. Calculate the initial concentrations of the starting products.

c0(methyl bromide) = 1.00 mol/L c0(sodium methylate) = 1,00 mol/L
calculation:
𝑚𝑚 94.9
𝑐𝑐(𝐶𝐶𝐻𝐻3 𝐵𝐵𝐵𝐵) = = = 1.00 mol/L
𝑀𝑀∙𝑉𝑉 94.9∙1
𝑚𝑚 54.0
𝑐𝑐(𝐶𝐶𝐻𝐻3 𝑂𝑂− ) = = = 1.00 mol/L
𝑀𝑀∙𝑉𝑉 54.0∙1

3.7. Calculate the concentrations of methyl bromide and sodium methylate respectively after 30, 60,
90, 120 and 150 minutes.
ct(30) = 0.984 mol/L ct(60) = 0.968 mol/L ct(90) = 0.953 mol/L

ct(120) = 0.938 mol/L ct(150) = 0.923 mol/L

calculation for one example:

𝑉𝑉(𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚)−𝑐𝑐(𝐴𝐴𝑔𝑔+ )∙[𝑉𝑉(𝐴𝐴𝑔𝑔+ )−𝑉𝑉(𝑆𝑆𝑆𝑆𝑁𝑁 − )]

𝑐𝑐𝑡𝑡 = 𝑉𝑉(𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚)
50−0.1∙[50−𝑉𝑉(𝑆𝑆𝑆𝑆𝑁𝑁 − )] 45+0.1∙𝑉𝑉(𝑆𝑆𝑆𝑆𝑁𝑁 − )
𝑐𝑐𝑡𝑡 = =
50 50
45+0.1∙33.9
𝑐𝑐𝑡𝑡 (60) = = 0.9678 mol/L
50

9
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

3.8. Proof your assumption in part 2.7. by a calculation and find a mean value of the rate constant.
k (30) = 5.56·10-4 L/mol·min k (60) = 5.55·10-4 L/mol·min k (90) = 5.53·10-4 L/mol·min

k (120) = 5.53·10-4 L/mol·min k (150) = 5.55·10-4 L/mol·min kM = 5.54·10-4 L/mol·min

calculation for one example:
1 1 1
𝑘𝑘 = ∙� − �
𝑡𝑡 𝑐𝑐𝑡𝑡 𝑐𝑐0
1 1
𝑘𝑘(60) = ∙� − 1� = 5.55 ∙ 10−4 L/mol ∙ min
60 0.9678

k remains constant ⇒ 2nd order

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 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

B. Four (extraordinary?) compounds

3.9. What is element X?

X: Fluorine, F2

[Link] the formulae of A, B, C, and D. Show your calculations, if this is possible.

A: CF4 B: PF3

C: XeF4 D: SF4
Calculation:
𝑚𝑚 𝑚𝑚 𝜌𝜌∙𝑅𝑅∙𝑇𝑇
A: 𝑓𝑓𝑓𝑓𝑓𝑓𝑓𝑓 𝑝𝑝𝑝𝑝 = 𝑛𝑛𝑛𝑛𝑛𝑛 𝑎𝑎𝑎𝑎𝑎𝑎 𝑛𝑛 = 𝑀𝑀 𝑎𝑎𝑎𝑎𝑎𝑎 𝜌𝜌 = 𝑉𝑉
𝑤𝑤𝑤𝑤 ℎ𝑎𝑎𝑎𝑎𝑎𝑎: 𝑀𝑀 =
𝑝𝑝
3570∙8.314∙300
𝑀𝑀(𝐴𝐴) = = 87.9 g/mol
101300

3 fluorine: M(element) = 87.9 − 57 = 30.9 ⇒ P

4 fluorine: M(element) = 87.9 − 76 = 11.9⇒ C

PF3 or CF4, the description of properties and the fact that B obviously is PF3, lead to CF4.

C: 207 - 3·19 = 150 g/mol, could be M of samarium, SmF3 possible, but not a molecule!

207-4·19 = 131, is M of Xe, therefore XeF4

3∙19
D: 𝑀𝑀(𝐷𝐷) = 0.704 = 81.0 g/mol 𝑀𝑀(𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒) = 81.0 − 57 = 24.0 g/mol could be Mg, but MgF3 does not

exist
4∙19 g
𝑀𝑀(𝐷𝐷) =
0.704
= 108 g/mol . 𝑀𝑀(𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒𝑒) = 108 − 76 = 32
mol
, sulphr, SF4 makes sense

[Link] first sight, A and C have very similar fornulae. In fact, their three dimensional structures are
quite different. Sketch the three dimensional structures of both molecules using the VSEPR-
theory, and find for both structures the point groups.

C F F
F Xe
F F F
F
TD D4h
3.12. Write down a balanced equation for this synthesis.
P4 + 6 H2 ⇄ 4 PH3

11
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

[Link] the standard reaction enthalpy of process 3.12., and consequently the standard
formation enthalpy of phosphane at 298 K.
𝑂𝑂
∆𝐵𝐵 𝐻𝐻298 = 1.25 kJ/mol

Calculation:
The equation in 3.6. follows from: (a) + (b) + 3×(c) - 4×(d)
-2984 – 415 - 3·572 + 4·1280 = 5.0 kJ for 4 mol ⇒ 1.25 kJ/mol

[Link] the equilibrium constant of the phosphane synthesis at 300°C.

K = 4,9·10-9
Calculation:

∆𝑋𝑋 = ∑𝑖𝑖 𝑋𝑋𝑖𝑖 (𝑒𝑒𝑒𝑒𝑒𝑒) − ∑𝑖𝑖 𝑋𝑋𝑖𝑖 (𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠)

𝑇𝑇
∆𝐻𝐻(𝑇𝑇2 ) = ∆𝐻𝐻(𝑇𝑇1 ) + ∆𝐶𝐶𝑃𝑃 ∙ ∆𝑇𝑇 ∆𝑆𝑆(𝑇𝑇2 ) = ∆𝑆𝑆(𝑇𝑇1 ) + ∆𝐶𝐶𝑃𝑃 ∙ 𝑙𝑙𝑙𝑙 𝑇𝑇2 ∆𝐺𝐺 = ∆𝐻𝐻 − 𝑇𝑇 ∙ ∆𝑆𝑆
1

∆𝐶𝐶𝑃𝑃 = 4 ∙ 37 − 6 ∙ 29 − 21 = −47 J/K

𝑂𝑂 𝑂𝑂
∆𝑅𝑅 𝐻𝐻298 = 5 − 59 = −54 kJ ∆𝑅𝑅 𝐻𝐻573 = −54 + (573 − 298) ∙ (−0.047) = −66.925 kJ
𝑂𝑂 𝑂𝑂 573
∆𝑅𝑅 𝑆𝑆298 = 4 ∙ 210 − 6 ∙ 131 − 280 = −226 J ∆𝑅𝑅 𝑆𝑆573 = −226 + (−47) ∙ 𝑙𝑙𝑙𝑙 = −256.73 J
298

𝑂𝑂
∆𝑅𝑅 𝐺𝐺298 = −66925 − 573 ∙ (−256.73) = 80181 J
∆𝐺𝐺𝑂𝑂 80181
𝐾𝐾 = 𝑒𝑒 − 𝑅𝑅𝑅𝑅 = 𝑒𝑒 −8.314∙573 = 4.9 ∙ 10−9

12
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

Task 4 17points
Nitrogen-Heterocycles

Cimetidin, an antagonist for histamine receptors

4.1. Draw the constitutional formulae of A, B, D, E, and F.

N NH2 H
OH HS N
N B
H
F
A

S CN
N N N
S S
N N N N S
H H H N
H H
D E

4.2. Which type of reaction is meant by the conversion from C to E, and from E to cimetidine (Look at
the –CN-group!)
1,4-nucleophilic addition to a conjugated system, then elimination

4.3. Draw the mechanism of the reaction C→E. Use for C R-NH2, and arrows to show the positions of
the respective attacks.

S S H S H
- H+ N S N N
R R
N
R-NH2 N - CH3S- N
N
- N
N

13
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

B: Ketorolac, an inflammation inhibitor

4.4. Draw the structural formulae of U, V, X, and Y.

N N
O O
COOH COOCH3

U V

N I COOCH3
N
O
COOCH3 O
X Y

4.5. What is the mechanism of the reaction X →Y? Think about AIBN.
radical cyclisation

Ketorolac appears as racemic mixture, whereby only the (S)-enantiomere has a medical effect.

4.6. Draw the structure of the (S)-enantiomere of ketorolac.

COOH
N
O

C. Norflurazon and Diclomezin, two herbicides belonging to the pyridazinon-type

4.7. Draw the structural formulae of G, H, and J.

+ NH-NH2
N2 Cl-

CH3NH2
J
CF3 CF3

G H

4.8. Write down the formula of the reaction product of a carboxylic acid RCOOH with hydrazine.
How do you call this class of substances?
formula: name:
RCONHNH2 acid hydrazides, hydrazides

14
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

4.9. Write down the formula of the reaction product of an aldehyde RCHO with hydrazine.
How do you call this class of substances?
formula: name:
RCH=NNH2 hydrazone

4.10. Allocate the two N-atoms in compound I to the classes of compounds from above.
Hydrazon
CF3
N
N Cl

O Cl
Hydrazid

In reaction H →I, mucochloro acid is involved. Some sub-tasks for this issue:

4.11. Draw the possible stereo isomers of mucochloro acid.

H
Cl Cl O Cl

O O Cl O
H OH OH
(Z) (E)

4.12. Write down a balanced equation for this reaction.

C5H4O2 + 5 Cl2 + 3 H2O → C4H2Cl2O3 + CO2 + 8 HCl

4.13. Mucochloro acid may also occur in a tautomeric cyclic form K.

Draw the structural formulae of K.
Cl Cl

HO
O
H O
K

4.14. Write down the molecular formula for the particle which causes the peak at 126 m/e.
[C3H235Cl37ClO]+

15
 40th Austrian Chemistry Olympiad
National Competition - Deutschlandsberg
Theoretical Part - solution
June 12th, 2014

4.15. Draw the structure formulae of the compounds L, M, N, and O.

COOH

O O O
O
L
M
COOH Cl
Cl
O
N N
O H
Cl
Cl
N O

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