42nd Austrian Chemistry Olympiad

National Competition

SOLUTIONS
Theoretical Competition
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Task 1 41.5 bp ≙ 11 rp; 𝒇𝒇 =

𝟏𝟏𝟏𝟏
𝟒𝟒𝟒𝟒.𝟓𝟓

Some antibiotics

A. Prontosil

1.1. Draw the constitutional formulae of the compounds B, C, D, E , F and benzene-1,3-

diamine.
B C
SO 2 Cl SO 2 NH 2
O O

N N
H H

2bp 1.5bp
D E
SO 2 NH SO 2
NH 2
2

+
N2
H 2N Cl-

1.5bp 2bp
F benzene-1,3-diamine
SO 2 NH 2

N N

H 2N N H 2
H 2N N H 2

2bp 0.5bp

1.2. Why is the step E→F impossible when benzene is used instead of benzene-1,3-diamine?
verbal justification:
diazonium ion is a weak electrophile, benzenediamine is more reactive than benzene,
caused by the +M-effect of the amino groups of benzenediamine;
1.5bp

1.3. What type of stereoisomerism can occur in F?

diastereomerism 1bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

B. Chloramphenicol

1.4. Draw the constitutional formulae of the compounds A and B and the configurational
formulae of C and E.
A B NO 2
O H
HO

O H

0.5bp 2bp
C E
N H 2 O H Cl

HO H
N
Cl
O H
O
O 2N O H

2bp 2bp

1.5. Draw the structural formulae of the reactive species in the reaction A→B and D→E and
name the respective reaction mechanism of each.
A→B D→E
H

+
C – O H
O N O
O 2N

1.5bp 1.5bp
reaction mechanism: AN 1bp reaction mechanism: SE 1bp

1.6. Name substance C according to IUPAC.

(2R, 3R) - 2-amino-3-phenylpropane-1,3-diol 1.5bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

C. Trimethoprim

1.7. Draw the constitutional formulae of the compounds B, C, D and E and write down the
molecular formula of X.
A B
COCl CO 2
Me

HO O H HO O H

O H O H
1.5bp 1bp
C D O H
O H

H 3 CO OCH 3
HO O H
OCH 3
O H
2bp 1.5bp
E X
CN
CH3OH 0.5 bp

OEt

H 3 CO OCH 3

OCH 3

2 bp

1.8. Which effect in protonated guanidine is responsible for this? Draw at least two
structural formulae in order to show this.
H N N H H N N H
2 2 2 2
+

N H NH 2
2
+

mesomeric effect 0.5 bp etc.

structural formulae: 1.5bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

D. Penicillin V

1.9. Draw the configurational formulae of the compounds A and B.

A B H
H H H H H
N N S
S
C H PhO CH
PhO 3 3

H N N
O O C H O CH 3
–
3 O
O

CO 2 H CO 2 K
K+

1 bp 2bp

1.10. Write the mechanism of the reaction A→B with structural formulae and „arrows“ for
the attacking species. Draw only the parts of the molecules that are involved in this
step. For all other parts write „R“ for rest in the usual way.
O
O N
N
+
R C R
+ N
O
- R C R
N
O H +
H

O NR Acylsubstitution
O O
+
O NHR
+ RNH2 NH 2
RHN NHR

2.5bp

1.11. Write down the name of the functional group that is formed in reaction A→B.
lactam 0.5bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

𝟒𝟒
Task 2 16 bp ≙ 4 rp; 𝒇𝒇 = 𝟏𝟏𝟏𝟏

Birch sugar

2.1. Draw the structural formulae of A – F in Fischer projection.

A CHO
B
CH 2
OH

H O H
H O H

H O H
H O H

H O H
H O H

CH 2
OH CH OH
2

1bp 1.5bp
C D
CN CN

H O H H O H

H O H H O H

H O H H O H

H O H H O H

CH 2
OH CH OH
2

1bp 1bp
E F
CHO CHO

H O H H O H

H O H H O H

H O H H O H

H O H H O H

CH 2
OH CH OH
2

1bp 2bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

2.2. Draw the two formed pyranose sugars F1 and F2 in the Haworth projection and name
both monosaccharides.
F1 F2
CH 2
OH
CH 2
OH
OH O OH
OH O
OH OH

OH
OH OH

α-D-idopyranose 1.5bp β-D-idopyranose 1.5bp

2.3. Name the special isomeric relationship between F1 and F2.

epimers / anomers 1bp

2.4. Draw the structural formula of the disaccharide in the Haworth projection that is
formed through the combination of F1 and F2. This substance shows a negative reaction
with Fehling’s solution.
2.5bp
CH OH O H
2

O H O
O H
O H

O
O H
O
O H CH 2
OH

2.5. How many stereoisomers exist for B?

4 (32) 2bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Task 3 33 bp ≙ 9 rp; 𝒇𝒇 =
𝟗𝟗
𝟑𝟑𝟑𝟑
A journey through the world of metals

3.1. Determine which metal the mentioned metal Y is and provide your calculation below.

Supposing 100g:
69.75g O n = m/M =4.359 mol
30.25g Y 1:1 ⇒ n = 4.359 mol
M(Y) = 30.25/4.359 = 6.94 g∙mol-1 ⇒ Li 2bp

3.2. Write down the exact total formula of substance Z.

Li2O2 1bp

3.3. Calculate into which cubic lattice the metal Y crystallises.

𝑚𝑚𝐸𝐸𝐸𝐸 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎/𝐸𝐸𝐸𝐸∙𝑀𝑀
𝜌𝜌 = = 𝑁𝑁𝐴𝐴 ∙𝑎𝑎3
𝑉𝑉𝐸𝐸𝐸𝐸
𝜌𝜌∙𝑁𝑁𝐴𝐴 ∙𝑎𝑎3
Atoms/EC = 𝑀𝑀
Atoms/EC = 2

⇒ cubic body centred 3bp

3.4. Write down balanced reaction equations for the four discussed processes. 1 bp each
BaSO4 + 2C → BaS + 2CO2
BaS + H2O + CO2 → BaCO3 + H2S
BaCO3 → BaO + CO2
3 BaO + 2Al → 3 Ba + Al2O3

3.5. Specify the coordination numbers of the metal and oxide ions in the crystal structure.
CN = 6 for both 1bp

3.6. Write down balanced reaction equations for the formation of the three metal oxides
from their elements. 0.5 bp each
Ba + O2 → BaO2
2 Ba + O2 → 2 BaO

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Ba + 2 O2 → Ba(O2)2
3.7. Write down the balanced reaction equation for the reaction of the ozonide ions with
water. Assign oxidation states to all atoms.

−1�3 −II 0 −II

�3− + 2 H2 O
4 O ⏞ 5O
⏞2 + 4 O
⏞ H- 1,5bp for ON
4bp for RE

3.8. Calculate the amount of hydrogen in Mg2NiH4 in percent by mass.

mass content = (4∙ 1.01)/(2∙24.31+58.69+4∙ 1.01) = 0.03628 = 3.628 % 1bp

3.9. Draw all nickel atoms (without H atoms) as coloured balls, and one magnesium ion,
which you can choose freely, as a triangle into the given unit cell. Indicate the
tetrahedron for the chosen magnesium ion with dashed lines.

4bp

3.10. How many tetrahedron gaps and how many octahedron gaps are there per unit cell?
tetrahedron gaps: 8 1bp octahedron gaps: 4 1bp

3.11. Write down the amount of formula units of Mg2NiH4 in one unit cell.

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

1 1
8∙ 8 + 6∙2 = 4 1bp
3.12. Calculate the lattice parameter a0 of the unit cell.

𝑛𝑛 ∙ 𝜆𝜆 = 2𝑑𝑑 ∙ 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
with n = 1. λ = 1.542 Å. 𝜃𝜃 = 11.92°
1∙1.542∙10−10
𝑑𝑑 = = 3.733 ∙ 10−10 𝑚𝑚
2∙sin (11.92°)
d is the distace between the planes, 3d the leghth of the body diagonal in the cell
𝑎𝑎 ∙ √3 = 3𝑑𝑑
3∙3.733∙10−10
𝑎𝑎 = 𝑚𝑚 = 6.465 ∙ 10−10 𝑚𝑚 4bp
√3

3.13. Calculate the density of Mg2NiH4 powder in g/cm3.

𝑚𝑚𝐸𝐸𝐸𝐸 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎/𝐸𝐸𝐸𝐸∙𝑀𝑀
𝜌𝜌 = = 𝑁𝑁𝐴𝐴 ∙𝑎𝑎3
𝑉𝑉𝐸𝐸𝐸𝐸

4∙111.34 g∙𝑚𝑚𝑚𝑚𝑚𝑚−1
𝜌𝜌 =
6.022∙1023 𝑚𝑚𝑚𝑚𝑚𝑚 −1 ∙(6.465∙10−8 𝑐𝑐𝑐𝑐)3

𝜌𝜌 = 2.737 𝑔𝑔 ∙ 𝑐𝑐𝑐𝑐−3 3 bp

𝟔𝟔
Task 4 24 bp ≙ 6 rp; 𝒇𝒇 = 𝟐𝟐𝟐𝟐
Something „Gschmackig’s“(= tasty) from Tyrol

A. The „Tiroler Zelten“

4.1. Calculate the exact total formula of substance W.

m(C) = 70.56g ⟶ n(C) = 5.875 mol
m(H) = 5.93g ⟶ n(H) = 5.871 mol
m(O) = 23.51g ⟶ n(O) = 1.469 mol
⟶ empirical formula: C4H4O MS ⟶ total formula: C8H8O2 2bp

4.2. Draw the exact structural formula of substance W.

O

7.88
9.88
7.18

3.83
7.88
O
7.18
2bp

4.3. Calculate the exact total formula of substance X.

m(C) = 2.4020g ⟶ 81.03% C ⟶ n(C) = 6.7468 mol
m(H) = 0.2424g ⟶ 8.17% H ⟶ n(H) = 8.0891 mol

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

m(O) = 0.3200g ⟶ 10.80% O ⟶ n(O) = 0.6750 mol

⟶ total formula: C10H12O 3bp

4.4. Draw the structural formula of substance X and mark which H atom is responsible for
the signal at 6.06 ppm with an arrow.
6.06
7.62
6.94
O 2.5bp
H 3.83

6.94
2.05 7.62

H
6.44

4.5. Write down the IUPAC name of substance X without stereo descriptors.
1-methoxy-4-(prop-1-enyl)-benzene 2bp

4.6. Denote the both configurations of X by drawing their structural formulae in the boxes
provided below and indicate eventual stereo descriptors.

E-form: 0.5bp Z-form: 0.5bp

4.7. Draw the structural formula of estragole and mark which H atom(s) are responsible for
the signal at 3.21 ppm.
6.87

7.12
O
2.5bp
3.83

6.87
3.21
7.12

H 5.00
5.92 H

H
4.98

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

B. A mug of mulled wine

4.8. Mark all chiral centres with an asterisk (*) in the corilagin molecule depicted below and
precisely indicate their absolute configuration by labelling the atoms with their stereo
descriptors.

R S

R S
R

marking 1bp
configuration: 5bp
picture: corilagin

4.9. Provide a drawing of the heterocyclic compound of corilagin in the Haworth projection.
Simplify the structure as depicted below.

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

3bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Task 5 35 bp ≙ 10 rp; 𝒇𝒇 =
𝟏𝟏𝟏𝟏
𝟑𝟑𝟑𝟑

Little A to G of Nickel Complexes

5.1. Hereunder some names of complexes are given. If you find some of the ones specified
above, fill in the corresponding letter. (Note: Whereas there will be no negative marks
for this part of the task in total, wrong answers will lead to deduction of points.)
hexaamminenickel(III) _____ hexaaquanickel(II) C
hexaethylendiaminonickel(II) _____ hexanitratonickel(II) _____
diamminetetraaquanickel(II) D tetraaquaethylendiaminonickel(II) E
tetracarbonylnickel(II) _______ tetracarbonylnickel(0) G
every correct assignment +0.5bp, wrong assignments – 0.5 bp, min 0 bp

5.2. Write down the complete electron configuration of the central atom in these complexes.
Ni2+: 1s2 2s2 2p6 3s2 3p6 3d8 1bp
5.3. Draw a diagram showing the splitting of the d-orbitals of Ni in the octahedral complex.
Decide which magnetic properties you expect.

2bp
X paramagnetic O diamagnetic 0.5bp

5.4. Fill in the missing values for ΔO . Into the first row write the letter (A, B, C) for the
corresponding complex.

complex C A B
ΔO/cm-1 8500 10800 13000
ΔO/eV 1.05 1.34 1.61
ΔO/kJ mol-1 101.68 129.20 155.51
assignment of complexes first row 1.5 bp, energy values 1bp each

5.5. Calculate the ligand field stabilization energy for the complex with ΔO=10800cm-1 in eV.
LFSE = 6 ⋅ 0.4 𝛥𝛥𝑂𝑂 − 2 ⋅ 0.6 𝛥𝛥𝑂𝑂 = 1.2 𝛥𝛥𝑂𝑂 = 1.2 ⋅ 1.34 = 1.61 eV 2bp
5.6. In this calculation you did not have to consider the pairing energy P because …
(tick right answer/s)
O ... it is only an approximation, P is negligible.
O ... you only have to consider P in orbitals that lie higher in energy as the others.
X ... the Ni central atom in the spherical ligand field has the same number of paired spins.
O Not true at all. One has to consider P and I did that.
0.5bp
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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

5.7. Tick the right answers a) which complex is thermodynamically more stable.
b) the name of the effect causing this stability.
a) O complex D [Ni(NH3)2(OH2)4]2+ X complex E [Ni(en)(OH2)4]2+ 0.5bp

b) O inert-pair-effect X chelate effect

O resonance O trans effect 0.5bp

5.8. Calculate the reaction entropies ΔRS° for (1) and (2).
for reaction (1)
𝛥𝛥𝑅𝑅 𝐺𝐺° = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑐𝑐 = −8.314 ⋅ 298 ⋅ 11.6 = −28740 J 0.5bp

𝛥𝛥𝑅𝑅 𝐻𝐻°−𝛥𝛥𝑅𝑅 𝐺𝐺° −33500+28740

𝛥𝛥𝑅𝑅 𝑆𝑆° = 𝑇𝑇
= = −15.97 J K −1 1.5bp
298

for reaction (2)

𝛥𝛥𝑅𝑅 𝐺𝐺° = −𝑅𝑅𝑅𝑅 ln 𝐾𝐾𝑐𝑐 = −8.314 ⋅ 298 ⋅ 17.78 = −44051 J 0.5bp

𝛥𝛥𝑅𝑅 𝐻𝐻°−𝛥𝛥𝑅𝑅 𝐺𝐺° −37200+44051

𝛥𝛥𝑅𝑅 𝑆𝑆° = = = 22.99 J K −1 1.5bp
𝑇𝑇 298

5.9. For reaction (3) calculate ΔRH°, ΔRS° and ΔRG° .

reactions: (3) = (2) – (1) 1.5bp

𝛥𝛥𝑅𝑅 𝐻𝐻°(3) = 𝛥𝛥𝑅𝑅 𝐻𝐻°(2) − 𝛥𝛥𝑅𝑅 𝐻𝐻°(1) = −37.2 + 33.5 = −3.7 kJ 1bp
𝛥𝛥𝑅𝑅 𝐺𝐺°(3) = 𝛥𝛥𝑅𝑅 𝐺𝐺°(2) − 𝛥𝛥𝑅𝑅 𝐺𝐺°(1) = −44.05 + 28.74 = −15.31 kJ 1bp
𝛥𝛥𝑅𝑅 𝑆𝑆°(3) = 𝛥𝛥𝑅𝑅 𝑆𝑆°(2) − 𝛥𝛥𝑅𝑅 𝑆𝑆°(1) = 22.99 + 15.97 = 38.96 JK −1 1bp

5.10. Complex D [Ni(NH3)2(OH2)4]2+ has two stereo isomers. Draw them using the
octahedral skeletons. Assign the appropriate stereodescriptors.

1.5bp each
trans cis 0.5bp each

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

5.11. Draw the Λ-isomer of complex F [Ni(en)3]2+ using the skeleton. Draw en in the way
shown below.

en =
Λ [Ni(en)3]2+ 3bp

5.12. In the VB-scheme for complex G ...

a) draw the electrons (electron pairs) of the Ni central atom with ↑ and ↑↓ respectively
1.5bp
b) mark the orbitals occupied by electron pairs from the ligands with an X. 0.5bp

3d 4s 4p 4d
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ X X X X

5.13. Denote the hybridization of the Ni central atom in complex G and choose the
geometrical shape resulting of this hybridization.
hybrid: ____ sp3 ______ shape: O octahedral X tetrahedral
O square planar O trigonal prismatic
1bp

5.14. One of the following MO-schemes shows the energies for the molecular orbitals of CO in
correct sequence. Choose the right scheme by correctly „occupying“ it with electrons
(arrows) and indicating the LUMO.

right scheme: 2.5 bp correct occupation 1 bp LUMO: 0.5bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Task 6 18 bp ≙ 5 rp; 𝒇𝒇 =
𝟓𝟓
𝟏𝟏𝟏𝟏
Bombastic Calorimetry

6.1. Give a balanced equation for the combustion including the symbols for the states of
matter.
C8H8(l) + 10 O2(g) → 8 CO2(g) + 4 H2O(l) 1bp
6.2. Calculate the molar standard enthalpies of combustion ΔcH° of A and B.
for compound A M(C8H8) = 104.16 g mol−1 0.7834g ≜ 0.007521 mol

𝛥𝛥𝛥𝛥 = 𝑄𝑄 − 𝑄𝑄𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = −34181 − (−30) = 34151 J 0.5bp

−34.151 kJ
𝛥𝛥𝛥𝛥° = = −4541 kJ mol−1 1bp
0.007521 mol

−2⋅8.314⋅298
Δc 𝐻𝐻° = 𝛥𝛥𝑐𝑐 𝑈𝑈° + 𝑝𝑝𝑝𝑝𝑝𝑝 = 𝛥𝛥𝑐𝑐 𝑈𝑈° + 𝛥𝛥𝛥𝛥𝛥𝛥𝛥𝛥 = −4541 + = −4546 kJ mol−1 2bp
1000

for compound B 0.6548g ≜ 0.006286 mol

𝛥𝛥𝛥𝛥 = 𝑄𝑄 − 𝑄𝑄𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 = −27623 + 30 = 27593 J 0.5bp

−27.593 kJ
𝛥𝛥𝛥𝛥° = = −4390 kJ mol−1 1bp
0.006286 mol

−2⋅8.314⋅298
Δc 𝐻𝐻° = 𝛥𝛥𝑐𝑐 𝑈𝑈° + 𝑝𝑝𝑝𝑝𝑝𝑝 = 𝛥𝛥𝑐𝑐 𝑈𝑈° + 𝛥𝛥𝛥𝛥𝛥𝛥𝛥𝛥 = −4390 + = −4395 kJ mol−1 2bp
1000

6.3. Calculate the molar standard enthalpies of formation ΔfH° of A and B.

In case you did not get a result in 6.2. use ΔcH°A = -4581 kJ mol-1 and
ΔcH°B= -4431 kJ mol-1.
für Verbindung A
𝛥𝛥c 𝐻𝐻°(A) = 8 ⋅ 𝛥𝛥f 𝐻𝐻°(CO2 ) + 4 ⋅ 𝛥𝛥f 𝐻𝐻°�H2 O(l) � − 𝛥𝛥f 𝐻𝐻°(A)
𝛥𝛥f 𝐻𝐻°(A) = 8 ⋅ 𝛥𝛥f 𝐻𝐻°(CO2 ) + 4 ⋅ 𝛥𝛥f 𝐻𝐻°�H2 O(l) � − 𝛥𝛥c 𝐻𝐻°(A) =
= 8 ⋅ (−393.5) − 4 ⋅ (285.8) + 4546 = 254.8 kJ mol−1 (289.8 kJ mol-1) 1.5bp

für Verbindung B
𝛥𝛥f 𝐻𝐻°(B) = 8 ⋅ 𝛥𝛥f 𝐻𝐻°(CO2 ) + 4 ⋅ 𝛥𝛥f 𝐻𝐻°�H2 O(l) � − 𝛥𝛥c 𝐻𝐻°(B) =
= 8 ⋅ (−393.5) − 4 ⋅ (285.8) + 4546 = 103.8 kJ mol−1 (139.8 kJ mol-1) 1.5bp

6.4. According to the standard enthalpies of formation, one of the substances should be
more stable with regard to dissociation in the elements than the other.
This is… (tick the right circle!).
O compound A X compound B 1bp
6.5. According to Hückel’s rule one compound is aromatic. Into the brackets write the
number of π-Elektrons of the ring systems and mark the aromatic compound.
O Cyclooctatetraene ( 8 ) X styrene (6) 1.5bp
6.6. Assign which compound was which sample by correctly filling in A or B respectively.

16
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

A was cyclooctatetraene B was styrene 0.5bp

6.7. For styrene calculate the standard enthalpy of combustion according to the incremental
system.

ΔcH° = 8·ΔcHI°(C-H) + 4·ΔcHI°(C-C) + 3·ΔcHI°(C=C2C) + ΔcHI°(C=C3C) + ΔcHI°(Ring) + ΔvapH° =

= 8·(-226.1) - 4·(206.4) - 3·(491.5) – 484.4 – 4.2 + 43.5 =
= -4554 kJ
3bp

6.8. For both hydrocarbons calculate the stabilization energy through a comparison
between the calculated and the measured enthalpies of combustion.
for cyclooctatetraene
𝛥𝛥𝛥𝛥 = 𝛥𝛥𝑐𝑐 𝐻𝐻°𝑡𝑡ℎ𝑒𝑒𝑒𝑒𝑒𝑒 − 𝛥𝛥𝑐𝑐 𝐻𝐻° = −4561.5 + 4546 = −15.5 kJ (19.5 kJ) 0.5bp
(opposite sign accepted likewise)
for styrene
𝛥𝛥𝛥𝛥 = 𝛥𝛥𝑐𝑐 𝐻𝐻°𝑡𝑡ℎ𝑒𝑒𝑒𝑒𝑒𝑒 − 𝛥𝛥𝑐𝑐 𝐻𝐻° = −4554 + 4395 = −159 𝑘𝑘𝑘𝑘 (-123kJ) 0.5bp
(opposite sign accepted likewise)

𝟕𝟕
Task 7 26 bp ≙ 7 rp; 𝒇𝒇 = 𝟐𝟐𝟐𝟐

A kinetic mixture
A. Nitrogen oxides

7.1. Put a cross into the box where the factor of the change in rate matches the concentration
change.
The rate changes with the factor
Change of concentration 1 1 1 1
1 2 4 8 16 2 4 8 16

[O2] quadrupled, [NO] unchanged ×

[O2] unchanged, [NO] quadrupled ×
[O2] unchanged, [NO] halved ×
[O2] halved, [NO] quadrupled ×
[O2] quadrupled, [NO] halved ×
Lines 1 -3: 0.5 bp each; Lines 4 and 5: 1 bp each

7.2. Calculate the activation energy of the reaction.

1
All initial concentrations ar halved ⇒ 8
of the former rate 1.5bp
⇒ k (T2):k (T1) = 8:1

17
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

𝑘𝑘(𝑇𝑇 ) 𝐸𝐸𝐴𝐴 1 1 1 1
𝑙𝑙𝑙𝑙 𝑘𝑘(𝑇𝑇2) = ∙ �𝑇𝑇 − 𝑇𝑇 � ⇒ 𝑅𝑅 ∙ 𝑙𝑙𝑙𝑙8 ∙ �733 − 873� = 𝐸𝐸𝐴𝐴 ⇒ 𝑬𝑬𝑨𝑨 = 𝟕𝟕𝟕𝟕. 𝟎𝟎 kJ 1bp
1 𝑅𝑅 1 2

B. The iodation of acetone

7.3. Calculate the amount of acetone in 1.00 L (= „concentration of Ac“).

𝑀𝑀(𝐴𝐴𝐴𝐴) = 58.09 g·mol-1; 1 L has 790 g ⇒ 𝒄𝒄(𝑨𝑨𝑨𝑨) = 𝟏𝟏𝟏𝟏. 𝟔𝟔 mol·L-1 1.5bp

7.4. Fill the missing values into the table, calculate the individual initial concentrations and
the reaction rates of the four experiments.
c (acetone)
Try c (H3O+) mol·L-1 c (I2) mol·L-1 v in mol·L-1.s-1
mol·L-1
1 0.784 1.515·10-3 1.36 3.86·10-5
2 0.392 1.515·10 -3 1.36 1.89·10-5
3 0.784 1.010·10-3 1.36 3.89·10-5
4 0.784 1.515·10 -3 1.02 2.86·10-5
For each (different concentration): 0.25bp; for each v : 0.5bp

7.5. Write down an equation for the differential reaction rate of the iodation of acetone
using the right integer reaction orders.

𝑣𝑣 = 𝒌𝒌 ∙ [𝑨𝑨𝑨𝑨] ∙ [𝑯𝑯𝟑𝟑 𝑶𝑶+ ] 2bp

7.6. Calculate a mean value of the rate constant with the right units.

𝑘𝑘 = 3.38 ∙ 10−5 L·mol-1·s-1

𝑘𝑘 = 3.55 ∙ 10−5 L·mol-1·s-1
𝑘𝑘 = 3.64 ∙ 10−5 L·mol-1·s-1 ⇒ 𝒌𝒌 = 𝟑𝟑. 𝟓𝟓𝟓𝟓 ∙ 𝟏𝟏𝟏𝟏−𝟓𝟓 L·mol-1·s-1 2bp
𝑘𝑘 = 3.57 ∙ 10−5 L·mol-1·s-1

7.7. Put a cross (crosses) left of the reaction equation which corresponds to a possible RDS
which matches the differential rate law. 2bp

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 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

C. The Rice-Herzfeld-Mechanism

7.8. Write down a balanced equation for the pyrolysis reaction.

CH3CHO → CH4+ CO 0.5bp

7.9. Write the formulae for the unstable particles of the propagation reactions into the two
boxes.
⦁CH3 1bp CH3CO⦁ 1bp

7.10. Give a proof for the differential rate law given above, assuming a steady state
mechanism for the unstable particles of the propagation reactions.

𝑑𝑑[𝐶𝐶𝐻𝐻4 ]
= 𝑘𝑘𝑏𝑏 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] ∙ [⦁𝐶𝐶𝐻𝐻3 ] 1bp
𝑑𝑑𝑑𝑑
𝑑𝑑[⦁𝐶𝐶𝐻𝐻3 ]
= 0 = 𝑘𝑘𝑎𝑎 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] − 𝑘𝑘𝑏𝑏 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] ∙ [⦁𝐶𝐶𝐻𝐻3 ] + 𝑘𝑘𝑐𝑐 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶⦁] − 𝑘𝑘𝑑𝑑 ∙ [⦁𝐶𝐶𝐻𝐻3 ]2 1bp
𝑑𝑑𝑑𝑑
𝑑𝑑[𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶⦁]
= 0 = 𝑘𝑘𝑏𝑏 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] ∙ [⦁𝐶𝐶𝐻𝐻3 ] − 𝑘𝑘𝑐𝑐 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶⦁] 1bp
𝑑𝑑𝑑𝑑

Adding the last two equations: 0 = 𝑘𝑘𝑎𝑎 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] − 𝑘𝑘𝑑𝑑 ∙ [⦁𝐶𝐶𝐻𝐻3 ]2 1.5bp
1
𝑘𝑘𝑎𝑎 2
[⦁𝐶𝐶𝐻𝐻3 ] = � ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶]� using the first equation leads to:
𝑘𝑘𝑑𝑑
1 1
3
𝑑𝑑[𝐶𝐶𝐻𝐻4 ] 𝑘𝑘𝑎𝑎 2 𝑘𝑘 2
= 𝑘𝑘𝑏𝑏 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶] ∙ �𝑘𝑘 ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶]� = 𝑘𝑘𝑏𝑏 ∙ �𝑘𝑘𝑎𝑎� ∙ [𝐶𝐶𝐻𝐻3 𝐶𝐶𝐶𝐶𝐶𝐶]2 q.e.d. 1bp
𝑑𝑑𝑑𝑑 𝑑𝑑 𝑑𝑑

7.11. Write down a relation between kEXP and the rate constants of the elemental steps.
1
𝑘𝑘 2
𝑘𝑘𝐸𝐸𝐸𝐸𝐸𝐸 = 𝑘𝑘𝑏𝑏 ∙ �𝑘𝑘𝑎𝑎 � 1bp
𝑑𝑑

19
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

Task 8 31 bp ≙ 8 rp; 𝒇𝒇 =
𝟖𝟖
𝟑𝟑𝟑𝟑

Another journey: electro chemistry and equilibrium

A. Another metal: Chromium

1.72

0.55 1.35 2.10 –0.42 -0.90

Cr(V) Cr(IV) Cr3+ Cr2+ Cr

0.95 –0.74

1.33

–0.11 –1.33
Cr(OH)3 Cr

–0,72 –1.33
Cr(OH)4–

8.1. Calculate the three missing 𝐸𝐸 𝑂𝑂 -values and write the respective results on the
corresponding lines.
2∙0.95−0.55
𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝑉𝑉)|𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼)} = 1
= 1.35 V
−3∙0.74−(−0.42)
𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼)|𝐶𝐶𝐶𝐶(0)} = = −0.90 V
2
2∙0.95+2.10
𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝑉𝑉𝑉𝑉)|𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼𝐼𝐼)} = 3
= 1.33 V 3bp

8.2. Are Cr(V) and Cr(IV) stable against disproportionation? Give reasoning for your
answers using inequalities.

Cr(V) not stable, because 𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝑉𝑉)|𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼)} > 𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝑉𝑉𝑉𝑉)|𝐶𝐶𝐶𝐶(𝑉𝑉)}

Cr(IV) not stable, because 𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼)|𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼𝐼𝐼)} > 𝐸𝐸 𝑂𝑂 ({𝐶𝐶𝐶𝐶(𝑉𝑉)|𝐶𝐶𝐶𝐶(𝐼𝐼𝐼𝐼)}

2bp

20
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

8.3. Calculate the equilibrium constant for the disproportionation of Cr(II) at 25°C.

3 Cr2+ ⇄ 2 Cr3+ + Cr0 1bp

∆𝐸𝐸 𝑂𝑂 = −0.90 − (−0.42) = −0.48 V 1bp
2∙96485∙0.48
∆𝐺𝐺 𝑂𝑂 = −𝑧𝑧 ∙ 𝐹𝐹 ∙ ∆𝐸𝐸 𝑂𝑂 = −𝑅𝑅 ∙ 𝑇𝑇 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙 ⇒ 𝑙𝑙𝑙𝑙𝑙𝑙 = − 8.314∙298 = −37.385
𝑲𝑲 = 𝟓𝟓. 𝟖𝟖 ∙ 𝟏𝟏𝟏𝟏−𝟏𝟏𝟏𝟏 2bp

8.4. Calculate the solubility product of Cr(OH)3 at 25°C.

Cr(OH)3 ⇄ Cr3+ + 3 OH- 𝐾𝐾𝐿𝐿 = [𝐶𝐶𝑟𝑟 3+ ] ∙ [𝑂𝑂𝐻𝐻 − ]3 1bp

−
bei pH = 14 ist [𝑂𝑂𝐻𝐻 ] = 1 ⇒ 𝐾𝐾𝐿𝐿 = [𝐶𝐶𝑟𝑟 3+ ] 1bp
0.059
𝐸𝐸 = 𝐸𝐸 𝑂𝑂 + 𝑧𝑧 ∙ 𝑙𝑙𝑙𝑙𝑙𝑙𝐾𝐾𝐿𝐿
0.059
−1.33 = −0.74 + 3
∙ 𝑙𝑙𝑙𝑙𝑙𝑙𝐾𝐾𝐿𝐿 ⇒ 𝑙𝑙𝑙𝑙𝑙𝑙𝐾𝐾𝐿𝐿 = -30 ⇒ 𝑲𝑲𝑳𝑳 = 𝟏𝟏. 𝟎𝟎 ∙ 𝟏𝟏𝟏𝟏−𝟑𝟑𝟑𝟑 2bp

8.5. Calculate the solubility of Cr(OH)3 at 25°C. If you didn’t get a result in 8.4. , you may use
1.0·10-28 (this is not the correct value!).

𝐾𝐾𝐿𝐿 = [𝐶𝐶𝑟𝑟 3+ ] ∙ [𝑂𝑂𝐻𝐻 − ]3 with x mol·L-1 Cr3+ we have 3x mol·L-1 OH-

4
𝟏𝟏.𝟎𝟎∙𝟏𝟏𝟏𝟏 𝟑𝟑𝟑𝟑
𝐾𝐾𝐿𝐿 = 27𝑥𝑥 4 ⇒ 𝑥𝑥 = � 27 = 1.4 ∙ 10−8
𝒔𝒔 = 𝟏𝟏. 𝟒𝟒 ∙ 𝟏𝟏𝟏𝟏−𝟖𝟖 mol·L-1 2bp

B. The „Voltameter“

8.6. Which products deposit at the platinum-cathode and at the platinum-anode? Give your
reasoning comparing all possible decomposition voltages.

H2 (at the cathode) and O2 (at the anode) will be produced, because this pair has the
smallest decomposition voltage possible
H2/O2: |𝑈𝑈𝑍𝑍 | = 1.77 − (−0.58) = 2.35V
H2/SO42-: |𝑈𝑈𝑍𝑍 | = 2.01 − (−0.58) = 2.59V
K/O2: |𝑈𝑈𝑍𝑍 | = 1.77 − (−2.92) = 4.69V
K/ SO4 :
2- |𝑈𝑈𝑍𝑍 | = 2.01 − (−2.92) = 4.93V 3bp

8.7 Write down a balanced equation for the overall electrolysis reaction.
2 H2O → 2 H2 + O2 0.5bp

21
 42nd Austrian Chemistry Olympiad
National Competition at the APP in Innsbruck
Theoretical Part - Solutions
June 2nd, 2016

8.8. Calculate the amount of the deposited products, and from there the total volume of the
gas in the left tube of the picture.
𝐼𝐼.𝑡𝑡.𝜂𝜂
𝑛𝑛(𝑋𝑋) = 𝑧𝑧∙𝐹𝐹
0.805∙7∙60
𝒏𝒏(𝑯𝑯𝟐𝟐 ) = 2∙96485 = 𝟏𝟏. 𝟕𝟕𝟕𝟕𝟕𝟕 ∙ 𝟏𝟏𝟏𝟏−𝟑𝟑 mol 1bp
𝒏𝒏(𝑶𝑶𝟐𝟐 ) = 0.5 ∙ (𝐻𝐻2 ) = 𝟖𝟖. 𝟕𝟕𝟕𝟕 ∙ 𝟏𝟏𝟏𝟏−𝟒𝟒 mol 0.5bp
𝑛𝑛∙𝑅𝑅∙𝑇𝑇 2.628∙10−3 ∙8.314∙293
𝑉𝑉 = 𝑝𝑝
= 99800
= 6.40 ∙ 10−5 m3 1bp
𝑽𝑽 = 𝟔𝟔𝟔𝟔. 𝟎𝟎 mL

C. An acid constant and its consequences

8.9. Calculate the molar concentration of the saturated solution of benzoic acid using the
unit mol·cm-3.

𝑀𝑀(𝐵𝐵𝐵𝐵) = 122.1 g·mol-1

2.90
𝑐𝑐 = 122.1 = 2.375 ∙ 10−2 mol·L-1 = 2.38·10-5 mol·cm-3 1bp

8.10. Calculate the protolysis degree of benzoic acid and the protolysis constant of the acid.

Λ 0 (𝐵𝐵𝐵𝐵) = 𝜆𝜆0 (𝐻𝐻 + ) + 𝜆𝜆0 (𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) = 350 + 32.4 = 382.4 S·cm2·mol-1 1bp
𝜅𝜅 0.453∙10−3
Λ 𝐶𝐶 (𝐵𝐵𝐵𝐵) = = = 19.11 S·cm2·mol-1 1bp
𝑐𝑐 2.38·10−5
Λ𝐶𝐶 (𝐵𝐵𝐵𝐵) 19.11
𝜶𝜶 = = 382.4 = 𝟓𝟓. 𝟎𝟎𝟎𝟎 ∙ 𝟏𝟏𝟏𝟏−𝟐𝟐 1bp
Λ0 (𝐵𝐵𝐵𝐵)
𝛼𝛼2 0.0025
𝑲𝑲𝑨𝑨 = �(1−𝛼𝛼)� ∙ 𝑐𝑐0 = 0.95
∙ 2.375 ∙ 10−2 = 𝟔𝟔. 𝟐𝟐𝟐𝟐 ∙ 𝟏𝟏𝟏𝟏−𝟓𝟓 1bp

8.11. Calculate the volume of NaOH, which was titrated by the student, if the result of 8.9.
is right.

𝑛𝑛(𝐵𝐵𝐵𝐵) = 𝑛𝑛(𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁)
10 ∙ 2.375 ∙ 10−2 = 𝑥𝑥 ∙ 0.01 ⇒ 𝒙𝒙 = 𝟐𝟐𝟐𝟐. 𝟕𝟕𝟕𝟕 mL 1bp

8.12. Calculate the pH of the solution at the end point of the titration.

10∙2.375∙10−2
There is only Na-benzoate present: 𝑐𝑐0 = = 7.04 ∙ 10−3 mol·L-1 1bp
10+23.75
1.0∙10−14
𝐾𝐾𝐵𝐵 (𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵𝐵) = 6.25∙10−5 = 1.6 ∙ 10−10 1bp
[𝑂𝑂𝐻𝐻 − ]2 [𝑂𝑂𝐻𝐻 − ]2
𝐾𝐾𝐵𝐵 = 𝑐𝑐 −] ≅ ⇒ 𝒑𝒑𝒑𝒑 = 14 − 0.5 ∙ (𝑝𝑝𝐾𝐾𝐵𝐵 − 𝑙𝑙𝑙𝑙𝑙𝑙𝑐𝑐0 ) = 14 − 0.5 ∙ (9.80 + 2.15) = 𝟖𝟖. 𝟎𝟎𝟎𝟎 2bp
0 −[𝑂𝑂𝐻𝐻 𝑐𝑐0

22