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 TiO 2:
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
Ti → 45 +¿+ν ¿
21 Sc +e
e
22

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 ln2
λ= = =0.2252 h−1
t 1 3.078 h A ( t )=65.91⋅ e−0.2252⋅3=33.54
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) A ( t )=5681.4 ⋅e−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:
ΔH =−N ion ¿ ¿
B=−N ion ¿¿
2
1 1 d¿ r 0 2
= − ⇒ =r 0−d ⇒ r 0−B r 0+ d B=0
¿ ¿
B r0 r0 B

B B2
r0 = +
2 4 √
−d ¿ B

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

r0 = 2.31Å = rTi + rN therefore rN = 1.64Å

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: ∠ ( Ti−Ti−C )= =30.8 °
2
x
and =( C−Ti ) ⋅cos 30.8 °=2.074 Å ⋅0.85896=1.781 Å ⇒ x=3.562 Å
2

y=2⋅ ( C−Ti ) ⋅ sin30.8 ° + ( C−C )=¿ 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
m 3.28
M(c) = M(d) = 266.47 g/mol n= = =0.123 mol ⇒ corresponds to 1.76 g AgCl
M 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

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

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

1.16. Calculate ΔO in kJ/mol.

ΔO = 156.7 kJ mo l -1
calculation:

c
E=h =h c ~ν=6.6262 ⋅10−34 ⋅2.9979⋅ 108 ⋅13100 ⋅ 100=2.6022⋅ 10−19 J
λ
E = 2.6022 ⋅10−16 ⋅ 6.0221⋅1023=156.7 kJ mo l -1

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

1.18. Calculate the magnetic moment in units of μB.

μ = 4.90 μ B
calculation:

μ= √ n ( n+ 2 ) μ B=√ 4 ( 6 ) μ B =4.90 μB

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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 Mn 2O3 → 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 Mn 2O3 → 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
0
Δ G10

K L=e −R·T
=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.
¿ 8.3·10-7 mol/L
calculation:
¿
[Ca2+]·[CO32-] = 8.7·10-9 ⟶ ¿

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

¿¿ ⟶
¿
[ H 2 C O 3 ]+ ¿ ⟶

[ H 2 C O3 ]=2.3 ·10−3−14826 · ¿
¿¿ ⟶ [H3O+] = 1.21·10-7

⟶ 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:
pH=0.5 · ( 4.76−log ( 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:

x·0.00263
=10−4.76 ⟶ x = 0.0003303 mol/L
0.05
[H3O+] = x + a + 2b ⟶ 0.00263 = 0.0003303 + a + 2b
b· 0.00263 10−1.92 · a
=10−1.92 ⟶ b= =4.571· a
a 0.00263
⟶ 0.00263 = 0.0003303 + a + 2·4.571·a
⟶ a = 0.000227 mol/L
⟶ b = 0.00104 mol/L
c total
H S O =a+b=0.001253 mol/ L
2 4

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

[ H 2 S O4 ]=¿ ¿
⟶ 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: v=k ∙ [ t−BuBr ]
calculation:
t−BuBr :V ∝m∝ n ∝c ; V ( AgN O3 )∝ v

t−BuBr ( exp 1−exp 2 ) :c (2 ) :c ( 1 )=1.5 :1∧V ( 2 ) :V ( 1 )=1,5 :1 ⇒ 1st order

H 2 O ( exp 3−exp 2 ) : c ( 3 ) :c ( 2 ) =1:0.75∧V ( 3 ) :V ( 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:

m=ρ ∙ V =1.20 ∙ 1.21=1.452 g

m 1.452
n= = =0.0106 mol
M 137
n 0.0106
c= = =0.212 mol /L
V 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:

n¿
nt ( t−BuBr )=n0 ( t−BuBr )−n ¿
nt 10.07
ct = = =0.2014 mol/ L
V 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:
c 0 ( t−BuBr ) −c t ( t−BuBr ) 0.212−0.2014
v= = =0.0106 mol/ L∙ h
∆t 1
v 0.0106
k= = =5.00 · 10−2 h−1
c 0 ( t−BuBr ) 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:
m 94.9
c ( C H 3 Br ) = = =1.00 mol / L
M ∙V 94.9 ∙1
c¿

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:

c t =V ( mixture ) −c ¿ ¿

c t =50−0.1∙ ¿ ¿
45+0.1 ∙33.9
c t ( 60 ) = =0.9678 mol / L
50

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 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
k= ∙ − (
t ct c0 )
1 1
k ( 60 ) = (
∙
60 0.9678 )
−1 =5.55∙ 10−4 L /mol ∙min

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

3.10.Give the formulae of A, B, C, and D. Show your calculations, if this is possible.

A: CF4 B: PF3

C: XeF4 D: SF4
Calculation:
m m ρ∙R∙T
A: ¿ pV =nRT ∧n= ∧ρ= we h ave : M =
M V p
3570∙ 8.314 ∙ 300
M ( A )= =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 PF 3, 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: M ( D )= =81.0 g/mol M ( element )=81.0−57=24.0 g/mol could be Mg, but MgF3
0.704

does not exist

4 ∙ 19 g
M ( D )= =108 g/mol . M ( element )=108−76=32 , sulphr, SF4 makes sense
0.704 mol

3.11.At 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.

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

P4 + 6 H2 ⇄ 4 PH3

3.13.Calculate the standard reaction enthalpy of process 3.12., and consequently the standard
formation enthalpy of phosphane at 298 K.
∆ B H O298 =¿ 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

3.14.Calculate the equilibrium constant of the phosphane synthesis at 300°C.

K = 4,9·10-9
Calculation:
∆ X=∑ X i ( end ) −∑ X i ( start )
i i
T2
∆ H ( T 2 )=∆ H ( T 1 ) +∆ C P ∙ ∆ T ∆ S ( T 2 )=∆ S ( T 1 ) +∆ C P ∙ ln
T1

∆ G=∆ H−T ∙ ∆ S
∆ C P =4 ∙37−6 ∙ 29−21=−47 J / K

∆ R H O298 =5−59=−54 kJ ∆ R H O573 =−54+ (573−298 ) ∙ (−0.047 )=−66.925 kJ

573
∆ R SO298 =4 ∙210−6 ∙131−280=−226 J ∆ R SO573 =−226+ (−47 ) ∙ ln =−256.73 J
298
∆ R G O298 =−66925−573∙ (−256.73 )=80181 J
O
−∆ G −80181
RT 8.314∙ 573
K=e =e =4.9 ∙10−9

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 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

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 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

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 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]+

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 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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