34th Austrian Chemistry Olympiad

National Competition
Theoretical part – solution
June 14th, 2008

Problem 1, 21 bp ≙ 8 rp; f = 0.38095

1.1. Coordination number in the hexagonal face centred cell: 12

Coordination number in the cubic body centred cell: 8 2 bp

1.2. Lattice constant: 334.4 pm 2 bp

Berechnung 4r  a 3
4  144.8
a  334.4 pm
3

1.3. Molar mass, element: 47.9 g/mol , titanum 4 bp

Calculation VZelle  ( 334.4  10 10 )3  3.74  10 23 cm 3
2M( X )   N A VZelle 4.506  0.944  6.022  10 23  3.74  10 23
 M( X )    47.9 g / mol
N A  VZelle 2 2

1.4.
Compound A: Compound B: Compound C: Compound D:
FeTiO3 2bp TiOSO4 2bp TiO2 1bp TiCl4 1bp
Compound E: Compound F: Compound G:
TiCl3 1bp [TiCl4(P(C2H5)3)2] 1bp Ti(O2)SO4 1bp

1.5. Geometry: octahedral 1 bp

1.6. Reaction equation: 2 Ti2+ + 2 H2O → 2 Ti3+ + H2 + 2 OH- 2 bp

1.7. Reasons for corrosion resistance: passivation by TiO 2 1 bp

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 2, 19 bp ≙ 7 rp; f = 0.36842

2.1. Reaction equation: Fe2O3 + 6 HCl → 2 FeCl3 + 3 H2O 1 bp

Reducing agents Reasoning

2.2.
Zn, Sn , SO32-
2+
1,5 bp E° (RM) < 0.77 V 1 bp

2.3. Reaction equation: 6 Fe2+ + Cr2O72- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O 1 bp

2.4. Mass fraction of Fe2O3: 3 bp

n( Fe 2  )  6  n( Cr2 O72  )  6  0.1  33.74  10 3 mol
m( Fe2O3 )  0.5  n( Fe 2  )  159.7  1.616 g
1,616
w  100  40.4%
4

2.5. Equilibrium constant K: E   1.33  0.77  0.56V 2 bp

6.F .E  6 964850.56
K e R .T
e 8.314298
 6.7  10 56

2.6. Potential at the equivalence point:

6  1.33  0.77
Eeq    1.25V
7
1.5 bp

Redox indicators Reasoning

2.7.
iron phenanthroline, ferroine 1bp E° (Ind) is in the region of Eeq 1 bp

2.8. no, because E°(Cl2/Cl-) > E°(Cr2O72-/Cr3+) 1 bp

2.9. minimum pH-value, at which Cl2 will be produced:

1.36  1.51 
0.059
5

lg H   8


lg H   
( 1.36  1.51 )  5
0.059  8
 
H   10 1.59
pH  1.59
3 bp

2.10. Change of standard potentials: they decrease 1 bp

2.11. Effect of the addition of phosphoric acid: complexation of Fe 3+ 1 bp

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 3, 19 bp ≙ 7 rp; f = 0.36842

3.1. Balanced reaction equations: 3 bp

C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O (l) (1)

C2H6O(l) + + 3 O2(g) → 2 CO2(g) + 3 H2O (l) (2)
C12H22O11(s) → C12H22O11(aq) (3)
C2H6O(l) → C2H6O(aq) (4)
C12H22O11(aq) + H2O (l) → 4 C2H6O(aq) + 2 CO2(g) (5)

3.2. ΔRH⊖ = -218 kJ 3 bp

Calculation
(5) = (1) – (3) – 4(B) + 4(D) = -5645 – 5 + 4‧1368 - 4‧10 = - 218

3.3. Balanced reaction equation: 2 NO2 → 2 NO + O2 1 bp

3.4. order of reaction: 2nd order k = 0.54 L/mol.s

Calculation:
v = k‧[NO2]x ⇒ log v = log k + x‧log [NO 2]
z.B.: log 5.4‧10-5 = log k + x‧log 0.010 und log 1.38‧10-4 = log k + x‧log 0.016 ⇒
0.4075 = x‧0.0204
x≈2
k = v/[NO2]2
k1 = 5.4‧10-5/0.012 = 5.40‧10-1
k2 = 7.78‧10-5/0.0122 = 5.35‧10-1
k3 = 1.57‧10-4/0.0142 = 5.41‧10-1
k4 = 2.05‧10-4/0.0162 = 5.39‧10-1
3 bp

3.5. ∆RH⊝ = 114.2 kJ 1 bp ∆RS⊝ = 145 J/K 1 bp ∆RG⊝ = 73,2 kJ 1 bp

Berechnung:
∆RH⊝ = 2‧90.3 - 2‧33.2 = 114.2 kJ
∆RS⊝ = 2‧211 + 205 - 2‧241 = 145 J/K
∆RG⊝ = 114.2 - 283‧0.145 = 73.2 kJ

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

3.6. T ≧ 788 K 1.5 bp

Calculation
∆RG⊝ = 0 implies that the equilibrium is located in the middle (on the right side before)
T = ∆RH⊝/∆RS⊝ = 787.6

3.7. a: to the right 0,5 bp b: to the left 0,5 bp c: to the left 0.5 bp

3.8. p(O2) ≦ 0.44 bar 3 bp

Calculation:
 RG   RG   RT  ln p( pNO( NO) p()O2 2 )  0
2

RT  ln 0.01 1p2 ( O2 )   114200  500  145  41700

2

41700
ln p( O2 )    ln( 0.01 )2  0.8209  p( O2 )  e 0.8209  0.44
8.314  500

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 4, 22 bp ≙ 8 rp; f = 0.36364

4.1. Equation:
O2NC6H4OCOCH3 + H2O → O2NC6H4OH + CH3COOH 1 bp

4.2. ε = 14560 L/mol.cm 2 bp

Calculation:
All of p-nitrophenyl acetate has been converted: ε =1.456/10-4

4.3. Proof:
At = A(PNP) + A(PNA) = ε(PNP)c(PNP) + ε(PNA)c(PNA) = [ε(PNP)(c 0- c(PNA)) + ε(PNA)c(PNA)]
At = A∞ + c(PNA)[ ε(PNA) - ε(PNP)] or
At = A∞ - c(PNA)[ -ε(PNA) + ε(PNP)]
A∞- At = [ε(PNP) - ε(PNA)]‧ c(PNA)
5 bp

4.4. Order  : 1st order k = 3.19‧10-4 s-1

Table :

t (s) 300 900 1500 3000 4500 6000

A∞ - A t 1.304 1.079 0.903 0.570 0.356 0.212
ln(A∞ - At) 0.265 0.076 -0.102 -0.562 -1.033 -1.551
1/(A∞ - At) 0.767 0.927 1.107 1.754 2.809 4.717
Strategy to find out graphically:

0 order: A∞ - At versus t should be a straight line, slope: -k

1st order: ln(A∞ - At) versus t should be a straight line, slope: -k
2nd order: 1/(A∞ - A) versus t should be a straight line, slope: k

with graphics quality required: 8 bp

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

⋆ (⋆)ln(E∞-Et)
(⋆)0.2 ↑

⋄
⋆

(⋆)0.0

(⋄)4.0 ⋆

∙
(∙)1.3
(∙)E∞-Et ↑
(⋄)3.0
⋄
(⋆)-0.5
∙
⋆
(∙)1.0
∙
(⋄)2.0 straight line

deviation of points

⋄
(⋆)-1.0
∙ ⋆
(∙)0.5
⋄
(⋄)1.0
⋄ ∙
⋄

deviation of points
∙

(⋆)-1,5
(⋄)1/(E∞-Et) t (s) → ⋆
↑
1000 2000 3000 4000 5000 6000

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

4.5. Correspondence: equation of hydrolysis – order of reaction: 1 bp

The reaction behaves according to 1st-order because water is present in a huge surplus and the
concentration remains constant.

4.6. k = 3.9‧10-4 s-1 3 bp

Calculation:
1 ( A  At )t 1
k ln 
t 2  t1 ( A  At )t 2
k1 = 3.89‧10-4
k1 = 3.94‧10-4 etc.

4.7. EA = 29.7 kJ 2 bp
Calculation:
1
k ( T2 ) E A  1 1 1 1 k ( T2 )
ln      E A  R      ln
k ( T1 ) R  T1 T2  T
 1 T2  k ( T1 )
1
 1 1  3.9
E A  8.314      ln  29.7
 298 303  3.2

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 5, 18 bp ≙ 7 rp; f = 0.38889

5.1. Tick the right box:

⊗ The concentration of iron is too low for an optimal determination, because the absorbance
expected will be too low.
1 bp

5.2. Concentration of the complex: 8.89•10-5 mol/L 2 bp

Calculation: Because of iron being present in surplus and bipyridyl is the limiting reagent, the
approximated concentration of the complex will be:
2.667  10 4
[[Fe(bipyr)3]2+] =  8.89  10  5
3

x
5.3. 4 4
 1017.58
( 10  x )  ( 2.667  10  3 x )3

3 bp

5.4. Concentration after the first iteration step: c = 8.798‧10 -5 mol/L

Concentration after the second iteration step: c = 8.800‧10-5 mol/L 10 bp

8.89  10 5
4 5 4
 1017.58
( 10  8.89  10 )  ( 2.667  10  3 x )3

8.89  10 5
 ( 2.667  10  4  3 x )3
( 10  4  8.89  10  5 )  1017.58

8.89  10 5
3  2.667  10  4  3 x
( 10  4 5
 8.89  10 )  10 17.58

x=8.798‧10-5 mol/L
8.798  10 5
 10 17.58
( 10  4 5 4
 8.798  10 )  ( 2.667  10  3 x )3

x= 8.801‧10-5 mol/L

5.5. A = 0.7372 2 bp
Calculation: A = ε‧c‧d = 8.377‧10 ‧8.800‧10 ‧1 = 0.7372
3 -5

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 6, 21 bp ≙ 7 rp; f = 0.33333

6.1. Reaction equation:

5 U4+ + 2 MnO4- + 2 H2O ⇌ 5 UO22+ + 2 Mn2+ + 4 H+
3 bp

6.2. Total concentration c = 0.0667 mol/L 3 bp

5  c KMnO4  VKMnO4  2  cU 4  VU 4
5‧0.02‧0.01334 = 2‧x‧0.01
x  cU 4  cPO 3  0.0667 mol / L = ctotal P
4

6.3. Calculation: 7 bp
[H3O+] = 10-6.5
[H3PO4] ≈ 0
[PO43-] ≈ 0
0.0667 = [H2PO4-] + [HPO42-]
[ HPO42  ]  [ H 3O  ]

 10 7.21
[ H 2 PO4 ]
[ HPO42  ]  10 6.5
2
 10 7.21
0.0667  [ HPO4 ]
[HPO42-] = 0.0109 mol/L
[H2PO4-] = 0.0558 mol/L
[ H 2 PO4 ]  [ H 3O  ] 0.0558  10 6.5
[ H 3 PO4 ]   2.23
  2.23
 3.00  10 6
10 10
12.32 2 12.32
10  [ HPO4 ] 10  0 ,0109
[ PO43  ]  
  1.65  10  8
[ H 3O ] 10 6.5
Neglect was correct!

6.4. Total concentration of calcium c = 3.32‧10-4 mol/L 2 bp

1.00-26 = x3‧(1.65‧10-8)2

1.00  10 26
x3  3.32  10  4 mol / L
( 1.65  10  8 )2

6.5. Calculation: 6 bp
2
n
cNaOH = cNaOH    0.05 mol / L
40
V 1
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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

assumption: reaction only with H2PO4- to give HPO42- →

[H2PO4-] = 0.05582 – 0.05 = 0.00582 mol/L

[HPO42-] = 0.0109 + 0.05 = 0.0609 mol/L

cS 0.00582
pH  pK A  lg  7.21  lg  8.23
cB 0.0609

[H3O+] = 10-8.23 = 5.89‧10-9 mol/L

[ H 2 PO4 ]  [ H 3O  ] 0 ,00582  5.89  10 9

[ H 3 PO4 ]   2.23
  2.23
 5.82  10  9
10 10
10 12.32  [ HPO42  ] 10 12.32  0.0609
[ PO43  ]    4.95  10 6
[ H 3O  ] 5.89  10  9

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 7, 25 bp ≙ 8 rp; f = 0.32000

7.1. Strucutres A to H

A: 1 bp B: 1.5 bp C: 2 bp D: 2 bp

O OH

OH
O
OH

E: 1 bp F: 1.5 bp G: 1bp H: 1bp

OH
Br

7.2. stereo descriptors geraniol: E- 1 bp nerol: Z- 1 bp

7.3. structur of K+ 1.5 bp

OH2+
7.3. structur of L +
1.5 bp

+
7.3. structur of M+ 2 bp

7.3. formulae + H2O -H+ 1 bp

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

7.4. centre 7.5. N 1 bp 7.5. O 1 bp

1 bp

OH

*
O
OH

7.6. mechanism 3 bp

+ H2O OH
+
- H+
+

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

Problem 8, 22 bp ≙ 8 rp; f = 0.36364

8.1. D-sorbit 1 bp 8.1. sorbose 2 bp

CH2OH CH2OH
H OH O
HO H HO H
H OH H OH
H OH HO H
CH2OH CH2OH

8.2. membership: 1 bp 8.3. stereochemical relationship 1 bp

L-series enantiomeric

8.4. Haworth-formulae of D-sorbose 4 bp

OH CH2OH CH2OH OH CH2OH CH2OH

O O O O
OH OH OH OH
CH2OH OH
OH CH2OH OH OH
OH OH OH OH

8.5. IUPAC-name: (3R,4S,5R)-1,3,4,5,6-Pentahydroxyhexan-2-on 2 bp

8.6. acetonide 3 bp 8.7. lactone X 2 bp

O
OH OO
O
O
HO O
CH2OH
O OO
H H
CH2OH

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 34th Austrian Chemistry Olympiad
National Competition
Theoretical part – solution
June 14th, 2008

8.8. relation X-vitamin C keto-enol-tautomerism 1 bp

8.9. centres of chirality HO O number of stereoisomeres 1 bp

1 bp
HO O 4 stereoisomeres
*
HO H
*
CH2OH

8.10. acidic groups HO 1 bp

O

HO O

HO H
CH2OH

8.11. conjugate base 1 bp 8.12. oxidized ascorbic acid 1 bp

O HO O O

O -O O O

HO HO H H
CH2OH
CH2OH

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