32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

28 bp 10 rp f =
0.35714

Task 1, 10 points
1.1. Element: silicon

1 bp

1.2. Name: silanes

Formel: SinH2n+2

1.3. formula and name:

1 bp

(CH3)2Si(OH)2

1 bp
dimethylsilandiol

1.4. reaction equation:

n HO-Si(CH3)2-OH H-O(-Si(CH3)2-O)n-H + (n-1) H2O
name of the product: silicones

1.5.

2 bp

general formula for n: n = 4x-2y

1 bp

1.6.

formula: Ag10[Si4O13]
1 bp

1.7.

formula of lapis lazuli: Na4[Al3Si3O12]S3

2 bp

1.8. accompanying rock: lime

2 bp
argumentation: CaCO3 + 2 HCl CaCl2 + H2O + CO2
CO2 + Ca(OH)2 CaCO3 + H2O
1.9. reaction equation:
2 S3- + 2 H+ 5 S + H2S

1.10. LEWIS-formula:

2 bp

1 bp

S
S

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

1.11. Element: selenium

2 bp
justification:
n(O) m(O).M(X)
28.84
=
=
.M(X)
n(X) M(O).m(X) 16 71.16
n(O)
= 1 M(X) = 39.48 g / mol no reasonable element
n(X)
n(O)
= 2 M(X) = 78,96 g / mol selenium
n(X)
78.96
verification : SeO3 ? w(Se) =
= 0.6219
126.96
1.12. formula of HaXOb: H2SeO3

formula of HcXOd: H2SeO4

1 bp

1.13. oxidant: MnO4redox equation:

2 MnO4- + 5 SeO32- + 6 H+ 5 SeO42- + 2 Mn2+ + 3 H2O

2 bp

1.14. argumentation for aromaticity:

24 valence electrons
8 -bond electrons
2 charge
- 8 lone-pair electrons
6 -electrons

Frost-Musulin-scheme:

order of -bonding: 2/8=

2 bp
1 bp

1.15. Element: xenon

1 bp

1.16. oxidation number: +2, +4, +6

1 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

1.17. geometry of the three compounds:

XeF2
XeF4
XeF6

linear
plane square
pentagonal pyramidal

3 bp

1.18. reaction equation:

XeF6 + 3 H2O XeO3 + 6 HF

1 bp

1.19. speciality:
exceedance of the octet rule

1 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

Task 2, 15 points

33 bp 15 rp f =
0,45455

2.1. reaction equation: 2 C (s) + O2 (g) 2 CO (g)

bp
2.2. BP:

BP =

p2 (CO)
p(O2 )

bp
2.3. Free standard enthalpie of the reaction:
bp

G1273
= R T ln K P = 8.314 1273 ln(1.5 1018 ) = 442950 J = 443 kJ

2.4. reaction quotien + direction of the reaction:

Q=

G1273 = -442950 + RTln(0.0169) = -486 kJ

G1273 < 0 left to right

0.132
= 0.0169
1
2 bp

2.5. entropy of the reaction:

H G 225000 + 486136
G = H T S S =
=
= 205 J / K
T
1273
2.6. reaction equation of the decomposition:

2 N2O 2 N2 + O2

2.7. molar initial concentration:

n
p
p V = nR T
=c=
V
RT
39200
c(694) =
= 4,876 mol/ m3 c0 = 0,00488 mol/ L
8,314 967
48000
c(757) =
= 5,605 mol/ m3 c0 = 0,00561mol/ L
8,314 1030
2.8. rate constants:
1

sec ond order
c0

2 bp

1 bp

3 bp

1
1 1
1

=k k =

0
c

c0A
A cA t

1
= 0.135 L / mol.s
1520 0.004876
1
k(695) =
= 0.842 L / mol.s
212 0.005605
k(695) =

3 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

2.9. activation energy:

k(T2 ) EA 1
k(T2 ) 1
1
1

ln
=
EA = R ln

k(T1)
R T1 T2
k(T1) T1 T2
bp
2.10. resonance formulae:

= 241kJ

N N O 2 bp
+

-N N O
+

2.11. VSEPR:

linear

2.13. structure and name:

CH3-CH2-OH, ethanol

1 bp

2.12. point group: C,v 1 bp

2.14. Newman-projection:

1 bp
bp

2.16. entropy of vaporisation:

2 bP
HV,m 39652
SV,m =
=
= 113 J / K
T
351.8
2.15. mean value of boiling point:

OH

H
H

HV,m = 86246 = 39652 J/mol

p(T2 ) HV 1
p(T2 )
1
1
1
R


=
=

ln
p(T1)
R T1 T2
T2 T1 HV
p(T1)
1
= 0.002840643 T2 = 352.033 K
calculation (60C):
T2
1
= 0.002844445 T2 = 351.562 K
calculation (70C):
T2
mean value: BP = 351.8 K = 78.7C
ln

bp

2.17. ebullioscopic constant:

TS2 R M
351.82 8.314 46
K EB =
=
= 1.19 Kkg / mol
1000 HV
1000 39652
bp
2.18. vapour pressure of the solution:
n (ethanol) = 100/46 = 2.1740 mol,
n (vanillic aldehyde) = 5/152 = 0.0329 mol,
ng = 2.2069 mol x (ethanol) = 0.9851
Aufgabe 2, 15
Name:
p (ethanol) = p0x = 46.0 kPa
Punkte
bp
Task 3, 10 points

2
25 bp 10 rp f =
0.40000

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

3.1. solubility of BaCrO4:

L(BaCrO4) =

K L (BaCrO4 = 9.2 10 6 M

1 bp

solubility of SrCrO4:
L(SrCrO4) =

K L (SrCrO4 = 6.0 10 3 M

1 bp

3.2. concentrationen of Cr2O72- and of CrO42-:

Cr2O72- + H2O 2 H+ + 2 CrO42-

K=

K=

1
= 6.6710-16
1.50 1015

Cr2O72-

H2O

H+

CrO4-

at the beginning

0.1

55.56

equilibrium

0.1-x

55.56

10-3

2x

[H+ ]2 [CrO24 ]2
10 6 4x 2
=
= 6.67 10 16
2
[Cr2O7 ] [H2O] (0.1 x ) 55.56
x1 = 3.0410-5 (x2 = -3.0410-5)
[Cr2O72-] = 1.010-1 M
[CrO42-] = 6.110-5 M

6 bp

Konzentrationen von Ba2+ und Sr2+:

[Ba2+][CrO42-] = 8.510-11

[Sr2+][CrO42-] = 3.610-5

8.5 10 11
= 1.410-6 M
5
6.1 10
3.6 10 5
[Sr2+] =
= 0.59 M
6.1 10 5
2 bp
[Ba2+] =

3.3. mass of sodium acetate:

pH = pK S lg

nS
nB

3.00 = -lg(1.7810-5) - lg

0.1
x

x = 1.7810-3 mol
m = nM = 1.7810-3 mol 82.03 g/mol = 0.146 g
6

2 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

3.4. standard potentials x and y:

3(-0.744) =-0.408 + 2y
Y = - 0.912 V
0.55+1.34+x-30.744 = 60.293
x = 2,1 V
2 bp

3.5. Is there any tendency of disproportionation of Cr(IV) to Cr(III) and

Cr(VI)?:
Yes!
Explaination: E=2,1-0,5(1,34+0,55) = 1,155 > 0 G < 0
1 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

3.6. half equation for Cr2O72-/Cr3+:

Cr2O72- + 6 e- + 14 H+ 2 Cr3+ + 7 H2O

1 bp

potential change per pH-step:

2

E = E +

RT [Cr2O7 ][H3O + ]14

ln
6F
[Cr 3+ ]2
2

RT [Cr2O7 ] RT
E = E +
ln

( ln[H3O + ]14 )
3+ 2
6F
6F
[Cr ]
2

RT [Cr2O7 ] RT 2.3026 14
E = E +
ln

( log[H3O + ])
3+ 2
6F
6F
[Cr ]
RT 2.3026 14
= 0.138V
6F
3 bp

3.7. coordination number: 6

1 bp

3.8. geometry: octahedral

1 bp

3.9. name of the ion: dichlorodioxalatochromat(III)

1 bp

3.10. stereoisomers:
one trans-isomer
two enantiomeric cis-isomers

3 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

40 bp 15 rp f =
0.37500

Task 4, 15 points
4.1.1. numbering

1 bp

4.1.2

3-tropanole

1 bp

N 1
5
6

2
4

4.2.1. empirical
formula of
hydrotropic acid

OH
4.2.2. constitutional
formula of
hydrotropic acid

4.2.3. constitutional
formula of tropic acid
OH

C9H10O2
2

O 3

bp

bp
OH 3 bp

4.2.4. configurational
formula of (S)-tropic acid
HO

4.2.5. constitutional formula of

hyoscyamine

OH 2

bp

OH

OH
2 bp

C6H5
O

4.3.1. reaction forming the Mannich base

OH
CHO

H+

CH=NHCH3+

+ CH3NH2
CHO

N
- H+

CHO

or
CH=NCH3
4.4.1. configurational formulae of A and B

CHO
4 bp

CHO

4 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

C6H5

+N

C6H5

+N

Br-

Br-

4.4.2. isomeric relation

enantiomeric 1
bp

4.4.3 type of reaction:

SN2
1
bp

4.5.1. constitutional formula of tropinic acid

N

COOH

4.6.1.

HOOC

COOH

COOH
3 bp

or

4.6.1.

O
N

4.6.1.

O
N

OMe

4.6.2. reagent ?
O

Cl
2 bp

4.7.2. stereoisomers
bp

OMe

2 bp
HO

OMe

2
bp

2
bp

OH

4.7.1. chiral centres

N *
*
2 bp

16

COOMe
* O
*

10

C6H5
O

4.7.3. configuration(s)
C-1: R;
C-2: R
C-3: S
C-5: S
2 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

Task 5, 5 Punkte

12 bp 5 rp f =
0.41667

5.1. Leu-Val-Ser:

OH
H
N

H3N +

O
N
H

O
3 bp

5.2. flight time: mv2

2E
2 3 10 15 J
E=
v=
=
= 76963 m/ s
0.610 kg/ mol
2
m
23
1
6.02210 mol
s
2.50
t= =
= 3.25 10 5 s
v 76963

3 bp

5.3.
masses of amino acids possible: 71,73,131,147,188
in the case of an AS within the chain the molar mass is reduced by 18 u.

within the chain (+18)

71

73

131

147

188

89 (Ala)

91

149 (Met)

165 (Phe)

206

Therefore: Ala, Met and Phe.

3 bp

5.4.
masses of amino acids possible: 73 and 188
At the C-terminal the mass of the AS is reduced by 2 u, at the N-terminal by
16 u.
73

188

C-terminal (+2)

75 (Gly)

190

N-terminal (+16)

89 (Ala)

204 (Trp)

AS at teh N-terminal: Trp

AS at the C-terminal: Gly
3 bp
6.3. Lebensdauer der Sonne:
mH ,Sonne = mSonne
0Sonne:
,7346 = 1,988 10 3 0,7346 = 1,461 10 30 g
6.4. Massendefekt
der
+

1,461 103326g
18
10
t
=
E
3,846 10
J = 2,429 10 9s = 7,697 10 a
14
m = 2 = 6,014 10 8 g/ s 2 = 4,279 10 kg
c
(2,9979 10 m/ s)
11

1 bp
1 bp

32nd Austrian Chemistry Olympiad

National Competition
Theoretical Part Solutions
June 19th, 2006

Task 6, 5 Punkte

11 bp 5 rp f =
0.45455

6.1. mass of the sun:

d
= 696000 km = 6.96 108 m
2
4r 3
VSonne =
= 1.412 1027 m3
3
Sonne = 1.408 g/cm3=1408 kg/m3
mSonne = VSonne Sonne = 1.9881030 kg = 1.9881033 g
rSonne =

2 bp
6.2. mass of hydrogen per second:

3 bp

E = 26.72 MeV/4 H+ = 6.68 MeV/H+ = 1.07010-12 J/H+ =

= 6.4451011 J/mol H+
3.846 1026 J / s
nH+ =
= 5.967 1014 mol/ s
11
6.445 10 J / mol
mH+ = nH+ MH+ = 5.967 1014 mol/ s 1.0078 g / mol = 6.014 1014 g / s

6.3. lifetime:
mH+ ,Sonne = mSonne 0.7346 = 1.988 1033 0 7346 = 1 461 1033 g
t=

1.461 1033 g
= 2 429 1018 s = 7 697 1010 a
14
6 014 10 g / s

2 bp
6.4. mass defect:
m=

E
3.846 1026 J
=
= 4.279 109 kg
2
8
c2
2.9979 10 m/ s

1 bp

6.5. solar constant:

Oorbit = 4 (1.4961011 m)2 = 2.8121023 m2
26
3.846 10der
J /Sonne:
s
6.3. Lebensdauer
E=
= 1368 J / s m2
23
2.812 10 m2
mH ,Sonne = mSonne
0Sonne:
,7346 = 1,988 10 3 0,7346 = 1,461 10 30 g
6.4. Massendefekt
der

3 bp

1,461 103326g
18
10
t
=
E
3,846 10
J = 2,429 10 9s = 7,697 10 a
14
m = 2 = 6,014 10 8 g/ s 2 = 4,279 10 kg
c
(2,9979 10 m/ s)
12

1 bp
1 bp