35th Austrian Chemistry Olympiad

National Competition
Theoretical part - Solution
June 15th, 2009

Task 1, 36 bp ≙ 11 rp; f = 0.30556

m.z.F 522600  2  96485

1.1. M   137.32g/mol →Ba 22 bp
I.t. 10000  (24  60  60)  0.85
A = Ba barium

B = BaCl2 barium chloride

C = BaO barium oxide

D = BaO2 barium peroxide

E = Ba(O2)2 barium hyperoxide

F = Ba3N2 barium nitride

G = Ba(OH)2 barium hydroxide

H = BaCO3 barium carbonate

I = BaS barium sulphide

J = BaSO4 barium sulphate

K = Ba(NO3)2 barium nitrate

1.2. binding order: 1.5 3 bp

Reasoning: O2—-ion, hyperoxide ion MO-scheme B.O.=(6-3)/2=1.5

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

1.3. Type of reaction: hydrolysis 1 bp

1.4. Reaction equation: 3 BaO + 2 Al → 3 Ba + Al2O3 1 bp

1.5. Calculation of KL : 3 bp

Ba2+ + 2e- ⇌ Ba(s) ∆E° = -2.92 V ∆G° = 563.47 kJ/mol

Ba(OH)2 (s) + 2e- ⇌ Ba(s) + 2 OH-(aq) ∆E° = -2.99 V ∆G° = 576.98 kJ/mol

Ba(OH)2 (s) ⇌ Ba2+(aq) + 2 OH-(aq) ∆G° = 576.98 – 563.47 = 13.51 kJ/mol

G

Ke RT
 4.3  103

1.6. Calculation of the composition of the mercury(I)-ion : 3 bp

RT c2
E  ln
zF c1
RT 0.5
0.029  ln
zF 0.05
RT 0.5
z ln 2  Hg22
0.029F 0.05

1.7. Calculation of the equilibrium constant: 3 bp

Cu2+ + e- ⇌ Cu+ ∆E° = 0.153 V ∆G° = -14.76 kJ/mol

I3- (aq) + e- ⇌ 3 I-(aq) ∆E° = 0.536 V ∆G° = -103.4 kJ/mol

∆GR° = 2.(-14.76) + 103.4 = 74 kJ/mol

G

Ke RT
 1.1 1013

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Task 2, 13 bp ≙ 4 rp; f = 0.30769

2.1. Element A: chromium 1 bp

2.2. Formula and name of K1: K3[Cr(CN)6] potassium hexacyanochromate(III) 2 bp

2.3. d-occupation:

eg

t2g
Verification: ber.  3  5  3.87 matches the experimental value well.
1 bp

2.4. Calculation of ∆:

h.c 6.62  1034  2.9979  108

E   NA   6.022  1023  319.1 kJ / mol
 3.745  10 7

2 bp

2.5. ∆ = 158 kJ/mol ∆ = 182 kJ/mol ∆ = 208 kJ/mol

Cl -
F -
H2O
1 bp

2.6. Formula and name of K2: K4[Cr(CN)6] potassium hexacyanochromate(II) 1 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

2.7. d-occupation/low-spin/high-spin: 3 bp

K2: K3:
eg
eg

t2g
t2g

low-spin high-spin

2.8. Jahn-Teller-effect 1 bp

2.9. Geometry of A(acac)2 : quadratic planar 1 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Task 3, 21 bp ≙ 7 rp; f = 0.33333

3.1. Asymmetric centres 1.5 bp 3.2. Number of stereoisomers:

of borneol:

* OH 4
*
* 1.5 bp

3.3. Equilibrium constant of isomerisation K = 0,106 2 bp

 9400
Calculation:  G 
Ke RT
e 5038.314

3.4. Free reaction enthalpy ∆RGT = 12.3 kJ System reacts towards left 2 bp
Calculation:
0.30
G  G  RT ln Q 9400  8.314  503  ln
0.15

3.5. neq(borneol) = 0.126 mol neq(iso-borneol) = 0.0134 mol

Calculation:
nc (i  B)
K C  KP  K x  Kn  M(borneol) = 154 g/mol
nc (B)
n0(B) = 7.5/154 = 4.87·10-2 mol n0(i-B) = 14/154 = 9.09·10-2 mol
9.09  102  x
0.106   x  0.07752
4.87  10 2  x
nC(B) = 0.0487 + 0.07752
nC(i-B) = 0.0909 - 0.07752 4 bp

3.6. Data not necessary: 800 mbar, 5.0 L 2 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

3.7. ∆RG⊝T = 9.37 kJ ∆RH⊝T = 2.85 kJ ∆RS⊝T = -16.3 J/K

Berechnung:
1088 1.51 105
ln K(400)  1.04    2.81625
400 4002
1088 1.51 105
ln K(410)  1.04    2.79538
410 4102
K(410) H  1 1 
ln    
K(400) R  400 410 
1
 1 1 
H  8.314      0.02087  2846
 400 410 
G  RT ln K  8.314  400  2.81625  9366


H  G 2846  9366

S     16.3
T 400
8 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Task 4, 20 bp ≙ 7 rp; f = 0.35000

k1k3[ HA]2 [ B]
4.1. Rate law: v 5 bp
k2 [ HB  ]  k3[ HA]

d [ A]
 0  k1[ HA][ B]  k2 [ HB  ][ A ]  k3[ A ][ HA]
dt
[ A ]   k2 [ HB  ]  k3[ HA]  k1[ HA][ B]
k1[ HA][ B ]
[ A ] 
k2 [ HB  ]  k3[ HA]
d [ P]  k1k3[ HA]2 [ B]
v  k3[ A ][ HA] 
dt k2 [ HB  ]  k3[ HA]

4.2. Initial rate: v(0.8) = 0.97 µmol/L.s v(3.0) = 1.7 µmol/L.s

Berechnung:
c 0.8  0.703 3  2.83
v v(0.8)  v(3.0)  2 bp
t 0.1 0.1

4.3. Michaelis-Menten-constant: 1.13 μmol/L Maximum rate: 2,34 µmol/L.s

vMAX [S] vMAX  0.8 v 3

v  0.97  und 1.7  MAX
KM  [S] KM  0.8 KM  3

0.97·KM + 0.776 = 0.8·vMAX ⇒ 2.91·KM + 2.328 = 2.4·vMAX

1.7·KM + 5.10 = 3·vMAX ⇒ 1.36·KM + 4.08 = 2.4·vMAX
1.55·KM = 1.652 ⇒ KM = 1.13
2.81·1.13+ 2.328 = 2.4·vMAX ⇒ vMAX = 2.34 5 bp

vMAX 2.34  106

4.4. Turnover number  : WZ    117 s1 1 bp
[E]0 20  109

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

4.5. c(0) = 0.0305 mol/L c(20) = 0.016 mol/L c(50) = 0.00935 mol/L

n(I2) = 12.2·0.005 = 0.061 mmol ⇒ n(S2O32-) = 0.122 mmol ⇒ c(S2O32-) = 0.061 mmol/mL
c(0)(S2O32-) = 0.0305 mol/L due to dilution!

n(I2) = 16·0.005 = 0.08 mmol ⇒ n(S2O32-) = 0.16 mmol ⇒ c(20)(S2O32-) = 0.0160 mol/L
n(I2) = 9.35·0.005 = 0.04675 mmol ⇒ n(S2O32-) = 0.0935 mmol ⇒
c(50)(S2O32-) = 0.00935 mol/L
4 bp

4.6. k = 1.48 L/mol.s 3 bp

Proof by calculation:

1 1 1 
k   
t  c c0 
1  1 1 
k     1.486
20  0.016 0.0305 
1  1 1 
k     1.483
50  0.00935 0.0305 
1  1 1 
k     1.482
30  0.00935 0.016 

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Task 5, 26 bp ≙ 8 rp; f = 0.30769

5.1. Reaction equation: N2 + 3 H2 ⇌ 2NH3 1 bp

5.2. p(N2) = 66.2 bar p(H2) = 199 bar p(NH3) = 85.2 bar
Calculation:

N2 H2 NH3
n (initial) 1 3 0
n (equilibrium) 1-x 3-3x 2x

nges = 4-2x

x = 0.3916 15 bp

5.3. [NH4+] = 1.046·10-3 mol

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Berechnung:

5.4. [NH3] * = 0.105 mg/L

Calculation:
[NH3] [NH4+] [OH-]
pH = 8.00 5.88·10-5 0.001046 10-6
pH = 7.00 5.88·10-5 - x 0.001046 + x 10-7

x = 5.264·10-5

[NH3] = 6.178·10-6 mol/L

Task 6, 24 bp ≙ 8 rp; f = 0.33333

6.1. 45: Fragment COOH 0.5 bp 18: Fragment H2O 0.5 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

6.2. Cn = m(cn) + (n-1)·18 2 bp

Xn = m(xn) - 27 + (n-1)·18 2 bp

6.3. Calculation of the hypothetical masses

molecule A An, Cn, Xn (g/mol) molecule B An, Cn, Xn (g/mol)

a1 = 88 133 a2 = 244.1 307.1

c2 = 289.1 307.1 a3 = 373.2 454.2

a3 = 315.1 396.1 x2 = 189 180

x1 = 132 105 c4 = 531.3 585.3

x5 = 594.2 639.2 a5 = 601.3 718.3

c6 = 659.2 749.2 a7 = 814.4 967.4

M+ = 1035.3 1035.3 M+ = 1072.4 1072.4

0.25 bp each ⇒ 3 bp

6.4. Sequence of amino acids

AS1 AS2 AS3 AS4 AS5 AS6 AS7 AS8

A Asp Arg Ala Ile Asp Ala Tyr Ser

B Asp Arg Glu Ile Asp Arg Gly Ser

1 bp each ⇒ 16 bp

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

Task 7, 46 bp ≙ 15 rp; f = 0.32609

7.1. Structures A to E

A: 2 bp B: 4 bp C: 3 bp

HO
HO OO
HO O
OH
OH
O

Br O
OO

D: 3 bp E: 2 bp
HHOO O

OH
OH

NN
OH
O

7.2. Mechanism: SN2 1 bp

7.3. Allocation 4.60 5 bp

4.40
6.8-7.3 OH 4.60
1.05
H2 H H CH3
C C C N
4.60 HO H C 2.5 CH3 1.05
4.40
H2
CH CH3 1.05
4.60 HO C 6.8-7.3
H
6.8-7.3

7.4. R-salbutamol: 2 bp
HO H H
N
HO

HO

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 35th Austrian Chemistry Olympiad
National Competition
Theoretical part - Solution
June 15th, 2009

7.5. Structures F to N

F: 2 bp G: 2 bp H: 2 bp J: 2 bp K: 2 bp
MgCl
Cl

NH Mg

Cl
ClCl

M: 4 bp N: 2 bp

N
NH+
Cl-
O MgCl+
OH
Cl
Cl

7.6. Name of the reaction: Mannich 1bp

7.7. Mechanism: SE 1bp

7.8. Mechanism: SR 1bp

7.9. chiral centres 2 bp

N
* *
OH
Cl

7.10. Stereoisomers: 4 1bp Relationship: enantiomers/diastereomers 2 bp

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