th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem A

6 Points

Environmental Chemistry
1. We are looking for a particle which plays an important role in the catalytic
degradation of ozone as well as in fotochemical consecutive reactions in the
troposphere. In the latter reactions it causes a backformation of hydroxyl radicals.
There are natural and anthropogenic sources for this particle.
a) Name the particle!
b) Name an anthropogenic and natural source each!
c) Write down a balanced equation for the backformation of the hydroxyl radicals
described above!
d) Write down all the single step reactions and also the overall reaction for the
catalytic degradation of ozone where this particle takes part in!
2. Mainly responsible for the degradation of ozone in the stratosphere are the CFCs.
Due to the difference stabilities different CFCs have not the same range of action in
the stratosphere. Combine the following compounds with the corresponding curves in
the diagram and give the right formulae and the IUPAC-names of: R11, R12, R13,
R14
R11:........................................
R12:........................................
R13:........................................
R14:........................................

3. At the surface of ice cristals of the PSCs heterogenic reactions of chloronitrate

which HCl and H2O molecules take place whereby reservoir gases are formed and
frozen consecutively. In the antarctic spring two particles emerge which catalize the
ozone degradation.
Write down the balanced equations for the formation of chloronitrate and also for the
formation of the two reservoir gases!

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem A - solutions

(17 b.p. correspond to 6 r.p.; f = 0.35294)

Environmental Chemistry
1.a) NO
b) anthropogenic: NO2
natural: N2O
c) NO + HO2 NO2 + HO
d) NO + O3 NO2 + O2
NO2 + O NO + O2
O + O3 2O2

1b.p.
1b.p.
1b.p.
1b.p.
1b.p.
1b.p.
1b.p.

2. R11: CFCl3
R12: CF2Cl2
R13: CF3Cl
R14: CF4

1b.p.
1b.p.
1b.p.
1b.p.

Trichlorofluoromethane
Dichlorodifluoromethane
Chlorotrifluoromethane
Tetrafluoromethane

3. ClO + NO2 ClONO2

ClONO2 + HCl Cl2 + HNO3
ClONO2 + H2O HOCl + HNO3

1b.p.
2b.p.
2b.p.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem B

7 Points

Noble gases
1. In order to gain noble gases liquified air is fractionated. In a first rectification step
one gets four fractions of which two contain nitrogen and two contain oxygen each as
main part. Assign the non radioactive noble gases to the corresponding fractions:

N2

O2

N2

O2

2. An ice-argon-clathrate has a cubic structure. Its unit cell consists of 46 water

molecules and 8 interstitial sites of which are filled with argon atoms. What is the
stoechiometrical formula of the clathrate?

3. In the formation of XePtF6 , discovered by Neil Bartlett in 1962 an intermediate

entdeckten dixenon-cation Xe2+ is generated. Sketch the MO-scheme of this cation.
(Only take into account the electrons with the main quantum number 5!) Which bond
order occurs in this ion and which magnetic properties does this particle have.
MO-scheme:

bond order:

magnetic property:

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

4. We know of four compounds of xenone which contain fluorine and oxygene or both
of them, where the noble gas has the oxidation number VI. What are the formulae of
these compounds? Which three dimensional structures do these noble gas
compounds have?
compound

three
dimensional
structure

5. Which noble gas compounds do not exist? Fill in the following table!
compound

yes/no

if no, reasons

XeF4
NeF2
KrF2
XeCl4
KrBr4
XeOF
XeF9

6. Which redox behaviour of XeF2 is to be expected? Write down a balanced

equation for the reaction of this compound with hydrochloric acid!

................................................................................................................................

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem B - solutions

( 31 b.p. correspond to 7 r.p.; f = 0.22581)

Noble gases
1.

N2

Ne

N2

Ar

He

1b.p.

O2

Kr

1b.p.

O2

Ar

Xe

1b.p.

1b.p.

2.

3E.23H2O

1b.p.

3.
MO-scheme:

x#

0,5

5p

bond order:

3 b.p.

5p

xb
s#

5s

5s

Xe

Xe2+

sb

1.b.p.

Xe+

magnetic property:
paramagenetic 1b.p.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

4.

compound

XeF6

1b.p.

three
dimensional distorted
structure
octahedral

XeO3

1b.p.

pyramidal

1b.p.

XeO2F2

1b.p.

distorted
tetrahedral

1b.p.

XeOF4

1b.p.

square
pyramidal
1b.p.

1b.p.

5.
compound

yes/no

if no, reasons

XeF4

yes

------------

1.bp.

NeF2

no

Ne has too high promotion energy

2b.p.

KrF2

yes

------------

1b.p.

KrBr4

no

Br2 has too high dissoziation energy

2 b.p.

XeOF

no

Xe-oxidation number 3 not possible

2b.p.

XeF9

no

Xe-oxidation number 9 not possible

2b.p.

6.
XeF2 strong oxidizing agent: XeF2 + 2 HCl Cl2 + Xe + HF
3b.p.
................................................................................................................................

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem C

7 Points

Thermochemistry
1st part
Nitrosylchloride (NOCl) is a very toxic gas, which by dissociation gives nitrogenoxide
and chlorine when heated.
The reaction is endothermic: H = 75.3 kJ per mol chlorine (this value remains
constant up to 600 K)
The standard entropy values of the substances involved at 25C are::
substance
S 298(J/mol.K)

NOCl
264

NO
211

Cl2
223

Solve the following problems:

a) Write down a balanced equation for the dissociation of nitrosylchloride, whereby
one mol of chlorine should be formed.
b) Calculate the KP of the reaction at 298 K.
c) Calculate the KP of the reaction at 475 K.
d) Verbally give reasons for the shift of the equilibrium.

2nd part
The equilibrium constant for the formation of hydrogeniodide has the value K = 160.
There is a mixture of the three gases with the partial pressures p(H2) = 1.5 atm, p(I2)
= 0.88 atm and p(HI) = 0.065 atm.
Do we find a possible reaction in this mixture at 500 K?
If yes, in which direction? Prove your statements by calculations.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem C - solutions

(15 b.p. correspond to 7 r.p.; f = 0.46667)

Thermochemistry
st

1 part
a) 1 b.p.

2 NOCl

2 NO + Cl2

b) 4 b.p.
Kth e G

/ RT

S298
117 J / K

c) 3 b.p.

G298
H298
T . S298

G298
40434 J

Kth K 817
. 10
. 10 8 atm
H if 1p 11atm KP 817
P (T2 )

ln

insertion of numerical values gives

KP (T1 )
R T1 T2

ln KP( 475) 5.00

KP 6.7410 3 atm

d) 2 b.p.

If an endothermic system is heated, the equilibrium will shift to the

right side (LeChatelier): KP(475)>>KP(298)

2nd part:
2 b.p.
3 b.p.

0,0652
Q
3.210 3
Q K yes, reaction!
15
. 0.88
Q
G RT ln
G 45 kJ
the reaction runs in the direction to HI.
K

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem D

8 Points

Blood as a buffer system

Blood is a very important buffer system. Its buffering effect is 2/3 due to the open
buffer system CO2/HCO3-. Throughout this problem only this buffer system is
regarded.
A possibility to get a right value of the proportion CO 2/HCO3- is the equibrilation
method by Astrup.
Principal of the method:
The pH-value of a blood sample is determined. Then the blood sample is exposesd
to high and CO2-pressures until equilibrium is reached and the pH-values are
measured in each case. The pressure of CO2 of the original sample can be
determined graphically:
measured values:
pH-value
7.4
7.2
7.3
7.5
7.6

P(CO2)
kPa

pCO2 (kPa)
x (blood sample)
10.0
7.60
3.30
1.00
pH

Problems:
1. Determine p(CO)2 at pH = 7.4 graphically using the diagram and the measured
values.
2. Calculate the concentration of the CO2 (=H2CO3) in solution at pH = 7.4;
KH
-4
= 2.25*10 mol/L.kPa
3. Calculate the concentration of hydrogencarbonae of the blood at pH = 7.4.
pKA1(CO2) = 6.35
4. The deviation of the the required pH of 7.4 must not be to large. pH-values below
7.0 are lethal already. Calculate the amount of H3O+-ions (in mol) which may be
generated in 5.0 L of blood so that the pH will not fall below 7.0. Pay attention to
the fact that blood is an open system, that means that CO 2-concentration remains
constant.
5. Calculate the theoretical pH-value which will come up if the above amount of H3O+
is generated in blood which is not an open system i.e. the concentration CO 2 in
solution increases.
In daily life one speaks about superacidulation by lactic acid. Show by calculation
that under the pH-conditions in blood all the lactic acid exists as lactate. pKA (HLac) =
3.86!

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem D - solutions

(14 b.p. correspond to 8 r.p.; f = 0.57143)

Blood as a puffer system

1.

10.0

p(CO2) = 5,30 kPa

p(CO2)

grafics: 1b.p.
Pressure: 1 b.p.

6.00

1.00
7.2
2.
3.

4.

5.

7.3

7.4 7.5 7.6

pH

c(CO2) = 5.30*2.25*10-4 = 1.1925*10-3

c(HCO3 )
pH pKS log
c(CO2 )
x
7.40 6.35 log
11925
.
*103
x
11925
.
*103
n( HCO3 ) n( H3O ) 8.07 *103

7.00 6.35 log

pH 6.35 log

5.33 *103
9.263 *103

c(CO2) = 1.19*10-3 mol/L 2 b.p.

c( HCO3 ) 0.0134 mol / L

2 b.p.

c *( HCO3 ) 0.00533 mol / L

n( H3O ) 0.0404 mol / 5 L 3 b.p.

pH = 6.11

3 b.p.

6.

7.40 386
. log

c( Lac )
c( HLac)

c(Lac- ) c(HLac) = 3467

pH = 6.11

2 b.p.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem E

8 points

Kinetics and Organic Chemistry

A compund with the general formula R-SO2-OR reacts in aqueous solution with OHgiving the two endproducts B and C. C is volatile.
After solving 1,000 g of A in 50,00 mL of CCl4 (KKR = 30.00 K.kg.mol-1; = 1.594
g/cm3), the melting point of tetrachloromethane is lowered 1,882C.
The 1H-NMR-spectrum of substance A is given:

Compund A is brought to reaction with OH- as described above. The initial

concentrations of A and OH- are the same. Observing the change of the OH
concentration by time we receive the following data:
t (min)
c(OH-) (mol/L)

0
0.0250

5.00
0.0155

10.0
0.0113

20.0
0.00727

60.0
0.00301

Solve the following problems:

a) Which family of compounds does A belong to??
b) Give a balanced equation for the reaction of A with OH- .
c) Calculate the molar mass of A.
d) What are A, B and C? Give structural formulae.
e) Prove by calculation that we have a second order reaction in b).
f) Calculate the velocity constant and the half life of the reaction.
g) What will the value of be if one starts with 1/10 of the initial concentration?
h) Calculate the neccessary time till only 1.00% of the initial concentration is present.
(c0 = 0.0250 mol/L)?

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem E - solutions

(20 b.p. correspond to 8 r.p.; f = 0,40000)

Kinetics und Organic Chemistry

a) sulfonic acid ester

1 b.p.

b) R-SO2-OR + OH- R-SO3- + R-OH

1 b.p.

c)
T KKR . m *

m*

n( A)
.V

T
0.0797 5.00.10 3 mol / L
KKR

n( A)

m
n

M 200 g / mol

3 b.p.

d)
O
A: CH3

S O CH2 CH3

4 b.p.

1 + 1 b.p.

O
B: CH3

C: CH3 CH2 OH

S O
O

e)

1 1 1
k
ct co t

t(min)
k(L/mol.min)

5
4.90

10
4.85

k remains constant, therefore second order reaction

f)

g)

k = 4.88 L/mol.min
1

= 8.21 min
k.co
= 10

1 b.p.
2 b.p.

= 82.1 min

1 1
1

h)
t
0.00025 0.025 k

t 811 min

1 b.p.
2 b.p.

20
4.88

60
4.87
3 b.p.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem F

7 Points

Organic Chemistry - Cyclic systems

There are given:
a) the structural formula of

pentalene,

b) the structural formula of

octalene

and the systematic names of

c) 1-(cyclopenta-2,4-diene-1-ylidene)-cyclohepta-2,4,6-triene,
d) tricyclo[3.2.1.01,5]octane,
e) 1,6:8,13-propano[14]annulene.
Give the empirical formula of (a)

the systematic name of (b)

and the structural formulae (resonating formulae) of c, d and e.
c

Give the answer to the following questions:

Which of the compounds a e are aromatic?
Which of the compounds a e show a significant dipole moment?
Which reaction mechanisms take if the compounds a e react with bromine?
arom.:
dip.mom.
reaction mechanism
J/N
J/N
SR
SN
SE
AR
AN
AE
(a)

(b)

(c)

(d)

(e)

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem F - solutions

(26 b.p. correspond to 7 r.p.; f =0,26923)

Organic chemistry Cyclic systems

Empirical formula of pentalene: C8H6
Systematic name of octalene: bicyclo[6.6.0]tetradeca-1,3,5,7,9,11,13-heptaene
Structural formulae of c, d and e:

Aromatic are c and e.

Only c gives a significant dipole moment.
Reaction mechanisms:
a
AE
b
AE
c
SE
d
SR
e
SR and SE

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem G

10 points

Synthesis of ()- Mamanuthachinone

O
HO
OCH3
H

The mamanuthachinone was discovered as an secondary metabolite of a sponge.

The name is derived from the island Mamanutha, where this organism was found. As
this substance has an anticancer effect in the case of intestine cancer, the synthesis
of this compound is of some interest.
The performance of 14 steps the synthesis of Danishefsky (1994) gives racemic
mamanuthachinone. The synthesis yields 13% mamanuthachinone taking 1,4benzochinone as starting material.
The main part of the synthesis is a Diels-Alder-reaction between the diene (I) and the
dienophile (E).

A) Preparation of the dienophile:

Methanol is added by 1,4-addition to 1,4-benzochinone. The 1,4-addition product
rearranges to a substituted hydrochinone (hydrochinone = 1,4-benzenediol). This is
followed by an oxidation step to compound B, a substituted benzochinone. A second
1,4-addition of methanol to B yields compound C, a double substituted hydrochinone.
Methylation of dimethylsulfate gives compound D, which is an aromatic compound
bearing 4 identical substituents at the positions 1,2,4 and 5.
Performance of a single Friedel-Crafts-acylation of D with E-2-methyl-2-butenoic acid
chloride yields the dienophile E.
Answer the following questions:
1) Draw the structural formulae of 1,4-benzochinone and the compounds A E.
2) Give the name of the compound D.
3) The substituents of compound D activates or deactivates the aromatic
compound.
4) Give the name of the reaction mechanism of the Friedel-Crafts-acylation.
5) Which type of catalyst is taken for Friedel-Crafts-acylations?

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem G (continued):

B) Preparation of the diene:

Deprotonation of 2-methylcyclohexanone with potassium hydride gives the
thermodynamic stable enol F. F reacts with methyl iodide giving compound G which
bears a quaternary carbon atom. G is attacked by the Grignard compound
ethenylmagnesiumbromide. The resulting alcohol H dehydrates giving compound I.
The driving force of this reaction is the formation of a conjugated system.
Answer the following questions:
1) Draw the structural formulae of 2-methylcyclohexanone and of the compounds F
I.
2) Give
the
balanced
equation
for
the
reaction
of
G
with
methyltriphenylphosphonium chloride (together with a strong base). Give the
name of this reaction.
C) Preparation of ()-mamanuthachinone
The Diels-Alder-reaction between E and I yields the basic structure of the molecule.
Several steps necessary to obtain the ()-mamanuthachinone. Some of them are
oxidations or reductions. The consecutive tasks describe parts of this synthesis:
Answer the following questions:
1. Draw the structure of the Diels-Alder-product.
2. The keto-function of the Diels-Alder-product is reduced to an alcoholic function.
Give the formula and the name of a possible reducing agent.
3. One of the steps of the synthesis is a Birch reaction. Which agents are used in this
reduction?
4. The figure below shows the product of a Birch reaction. Which property is typical
for the substituent S?

5. An oxidation of a substituted hydrochinone is one of the last steps forming a

substituted chinone. Give the formula and the name of a possible oxidation agent.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem G -solutions

(26 b.p. correspond to 10 r.p.; f = 0.38462)

Synthesis of ()- Mamanuthaquinone

I.

1.
O

OH

OCH3

OH
CH3O

CH3O

OCH3
O

OCH3

OH

OH

p-benzoquinone

OCH3
CH3O

OCH3

OCH3

OCH3
OCH3
D

2.
3.
4.
5.

D = tetramethoxybenzene
activating
SE
Lewis-acid

OCH3

.
II.

1.

2-methylcyclohexanone

OH
H

2.

CH2=P(C6H5)3

O=P(C6H5)3

Wittig-reaction
1.
CH3O
CH3O
O

OCH3
OCH3

2.
3.
4.
5.

e.g.: lithiumaluminiumhydride LiAlH4

Li/NH3
S electron acceptor
e.g. potassium dichromate K2Cr2O7

points : A) 1. 7 b.p. 2. 1 b.p. 3. 1 b.p. 4. 1 b.p. 5. 1 b.p.

B) 1. 5 b.p. 2. 3 b.p.
C) 1. 3 b.p. 2. 1 b.p. 3. 1b.p. 4. 1 b.p. 5. 1 b.p.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem H

7 Points

Biochemistry
The amanitines consist of 8 well defined compounds. They are beside the
phallotoxines the strongly toxic chemical agents of the green Knollenbltterpilz.
.
2.5g of the -amanitine are sufficient to kill a mouse. It is a bicyclic octapeptide with
the empirical formula C39H53N9O15S.
Ion exchange chromatography of -amanitine gives:
glycine (double amount of the other amino acids);
isoleucine;
,-dihydroxyisoleucine;
cysteine (IR shows a sulfoxide group);
tryptophane (NMR of the -amanitine gives a hydroxyl group at the
heterocyclic system in position 6 but no hydrogen atom in position 2)
aspartic acid;
hydroxyproline.
Chymotrypsine A (splits at the carboxylic side of aromatic amino acids) opens one of
the rings. This is followed by an Edman degradation which gives first glycine then
isoleucine and glycine once more again. The consecutive hydrolysate cannot be
determined because of its size.
Staphylococcus-protease (splits at the carboxylic side of asp und glu) opens a ring
too. Following Edman degradation gives hyroxyproline, ,-dihydroxyisoleucine and a
big hydrolysate (containing the remaining amino acids).
Determine the structure of the octapeptide and give the structure by amino acid code
and by structural formula as well (carboxylic group as COOH).
A table of amino acids is included.

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part

Problem H - solution

(12 b.p. correspond to 7 r.p.; f = 0.58333)

Biochemisty
The endopeptidases give the peptides: Trp-Gly-Ileu-Gly and Asp-Hypro-Ileu(OH)2.
Cystein-sulfoxide is missing. The bridge is built by Trp (as H misses in pos. 2) and
Cys-sulfoxide:
Ileu(OH)2 Trp Gly
Hypro

SO Ileu

AspCysGly
resp.

O
O

NH

NH
HO
OH

NH

NH
O

HO

O S
O O
NH

HOOC

OH

NH
O
NH

NH

th

24 Austrian Chemistry Olympiad 1998

National Competition - Frstenfeld
Theoretical Part