24

th
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 H
2
O 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!

24
th
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 1b.p.
b) anthropogenic: NO
2
1b.p.
natural: N
2
O 1b.p.
c) NO + HO
2
NO
2
+ HO 1b.p.
d) NO + O
3
NO
2
+ O
2
1b.p.
NO
2
+ O NO + O
2
1b.p.
O + O
3
2O
2
1b.p.

2. R11: CFCl
3
Trichlorofluoromethane 1b.p.
R12: CF
2
Cl
2
Dichlorodifluoromethane 1b.p.
R13: CF
3
Cl Chlorotrifluoromethane 1b.p.
R14: CF
4
Tetrafluoromethane 1b.p.



















3. ClO + NO
2
ClONO
2
1b.p.
ClONO
2
+ HCl Cl
2
+ HNO
3
2b.p.
ClONO
2
+ H
2
O HOCl + HNO
3
2b.p.

24
th
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:








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 XePtF
6
, discovered by Neil Bartlett in 1962 an intermediate
entdeckten dixenon-cation Xe
2
+
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.

















N
2


N
2


O
2


O
2



MO-scheme:
bond order:
magnetic property:
24
th
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
XeF
4

NeF
2

KrF
2

XeCl
4

KrBr
4

XeOF
XeF
9



6. Which redox behaviour of XeF
2
is to be expected? Write down a balanced
equation for the reaction of this compound with hydrochloric acid!



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







24
th
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.








2.




3.

















N
2
Ne He
N
2
Ar
O
2
Kr Xe
O
2
Ar
3E.23H
2
O
MO-scheme:
bond order:

0,5 1.b.p.
magnetic property:
paramagenetic 1b.p.
1b.p.
1b.p.
1b.p.
1b.p.
1b.p.
|+ |+
|+ |+ |+ |+ |+ |
|+
|+
|+
|+
|+
|+ |+
|
o
x
#

t
#

t
b

o
x
b

o
s
#

o
s
b

5s
5s
5p
5p
Xe
Xe
+

Xe
2
+

3 b.p.
24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part



4.


compound

XeF
6
1b.p.


XeO
3
1b.p.

XeO
2
F
2
1b.p.

XeOF
4
1b.p.

three
dimensional
structure


distorted
octahedral

1b.p.





pyramidal


1b.p.


distorted
tetrahedral


1b.p.


square
pyramidal

1b.p.


5.

compound yes/no if no, reasons
XeF
4
yes ------------
NeF
2
no Ne has too high promotion energy
KrF
2
yes ------------
KrBr
4
no Br
2
has too high dissoziation energy
XeOF no Xe-oxidation number 3 not possible
XeF
9
no Xe-oxidation number 9 not possible


6.

XeF
2
strong oxidizing agent: XeF
2
+ 2 HCl Cl
2
+ Xe + HF 3b.p.
................................................................................................................................



1.bp.

2b.p.

1b.p.

2 b.p.

2b.p.

2b.p.
24
th
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: AH
u
= 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 NOCl NO Cl
2

S
u
298
(J/mol.K) 264 211 223

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 K
P
of the reaction at 298 K.
c) Calculate the K
P
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(H
2
) = 1.5 atm, p(I
2
)
= 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.














24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part



Problem C - solutions (15 b.p. correspond to 7 r.p.; f = 0.46667)

Thermochemistry
1
st
part

a) 1 b.p.

b) 4 b.p.





c) 3 b.p.





d) 2 b.p. If an endothermic system is heated, the equilibrium will shift to the
right side (LeChatelier): K
P
(475)>>K
P
(298)


2
nd
part:

2 b.p.

3 b.p.


K e G H T S
S G
K K
th
G RT
th P
= =
= =
= - = = -

A O O O
O O
O
O
A A A
A A
/
.
. .

J / K J
if p atm atm
298 298 298
298 298
8 8
117 40434
817 10 1 817 10


ln
( )
( )
ln .
.
K T
K T
H
R T T
K ( )
K
P
P
P
P
2
1 1 2
3
1 1
475 500
674 10
=
|
\

|
.
|
=
= -

A
insertion of numerical values gives
atm

Q
G RT
Q
K
G
=
-
= - =
= ~

0065
15 088
32 10
45
2
3
,
. .
.
ln
Q K yes, reaction!
kJ the reaction runs in the direction to HI. A A

2 NOCl 2 NO + Cl
2
24
th
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 CO
2
/HCO
3
-
. Throughout this problem only this buffer system is
regarded.
A possibility to get a right value of the proportion CO
2
/HCO
3
-
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 CO
2
-pressures until equilibrium is reached and the pH-values are
measured in each case. The pressure of CO
2
of the original sample can be
determined graphically:

measured values:

pH-value pCO
2
(kPa)
7.4 x (blood sample)
7.2 10.0
7.3 7.60
7.5 3.30
7.6 1.00



Problems:

1. Determine p(CO)
2
at pH = 7.4 graphically using the diagram and the measured
values.
2. Calculate the concentration of the CO
2
(=H
2
CO
3
) in solution at pH = 7.4; K
H

= 2.25*10
-4
mol/L.kPa
3. Calculate the concentration of hydrogencarbonae of the blood at pH = 7.4.
pK
A1
(CO
2
) = 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 H
3
O
+
-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 H
3
O
+

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. pK
A
(HLac) =
3.86!

P(CO
2
)
kPa
pH
24
th
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(CO
2
) grafics: 1b.p.
Pressure: 1 b.p.
6.00




1.00

7.2 7.3 7.4 7.5 7.6 pH

2. c(CO
2
) = 5.30*2.25*10
-4
= 1.1925*10
-3
c(CO
2
) = 1.19*10
-3
mol/L 2 b.p.

3.





4.




5.


6.





pH pK
c(HCO )
c(CO )
x
c HCO
S
= +
= + =

log
. . log
. *
( ) .
3
2
3 3
7 40 635
11925 10
00134 mol / L 2 b.p.

7 00 635
11925 10
000533
807 10 00404
3 3
3 3
3
3
. . log
. *
*( ) .
( ) ( ) . * ( ) .
= + =
= = =

+ +
x
c HCO
n HCO n H O n H O
mol / L
mol / 5 L A 3 b.p.

pH p = +

635
533 10
9 263 10
3
3
. log
. *
. *
H = 6.11 3 b.p.
7 40 386 . . log
( )
( )
) = +

c Lac
c HLac
p c(Lac c(HLac) = 3467 H = 6.11
-
2 b.p.
24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part



Problem E 8 points

Kinetics and Organic Chemistry

A compund with the general formula R-SO
2
-OR reacts in aqueous solution with OH
-

giving the two endproducts B and C. C is volatile.
After solving 1,000 g of A in 50,00 mL of CCl
4
(K
KR
= 30.00 K.kg.mol
-1
; = 1.594
g/cm
3
), the melting point of tetrachloromethane is lowered 1,882C.
The
1
H-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) 0 5.00 10.0 20.0 60.0
c(OH
-
) (mol/L) 0.0250 0.0155 0.0113 0.00727 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 t

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.
(c
0
= 0.0250 mol/L)?


24
th
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-SO
2
-OR + OH
-
R-SO
3
-
+ R-OH 1 b.p.

c)



3 b.p.


d)


4 b.p.

1 +1 b.p.




e)

k remains constant, therefore second order reaction 3 b.p.

f) k = 4.88 L/mol.min 1 b.p.
t t =
1
k c
o
.
= 8.21 min 2 b.p.

g) t = 10 t t = 82.1 min 1 b.p.

h)
1
000025
1
0025
1
811
. .

|
\

|
.
| = =
k
t t min 2 b.p.

A
A
T K m m
n A
V
n A
T
K
M
m
n
M
KR
KR
= =
= - = - = =

. * *
( )
.
( ) . . .

mol / L g / mol

00797 500 10 200

3


1 1 1
c c t
k
t o

|
\

|
.
| =
t(min) 5 10 20 60
k(L/mol.min) 4.90 4.85 4.88 4.87
CH
3
S
O
O
O CH
2
CH
3
A:
CH
3
S
O
O
O CH
3
CH
2
OH B: C:
24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part




24
th
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[3.2.1.0
1,5
]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 d e





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 S
R
S
N
S
E
A
R
A
N
A
E
(a)
(b)
(c)
(d)
(e)



24
th
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: C
8
H
6

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 A
E

b A
E

c S
E

d S
R

e S
R
and S
E


24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part



Problem G 10 points

Synthesis of ()- Mamanuthachinone

H
O
O
OCH
3
HO


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 1,4-
benzochinone 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?







24
th
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.
S
24
th
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
O
OH
OH
OCH
3
O
O
OCH
3
OH
OH
OCH
3
CH
3
O
O
OCH
3
OCH
3
OCH
3
CH
3
O
OCH
3
OCH
3
OCH
3
CH
3
O


II. 1.



2.

Wittig-reaction

1.

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.
O
O
O
OH
O
CH
2
=P(C
6
H
5
)
O=P(C
6
H
5
)
3
3
+
+
O
CH
3
O
CH
3
O
OCH
3
OCH
3
p-benzoquinone A B C D
E
2-methylcyclohexanone F G H I
2. D = tetramethoxybenzene
3. activating
4. S
E
5. Lewis-acid

2. e.g.: lithiumaluminiumhydride LiAlH
4

3. Li/NH
3

4. S electron acceptor
5. e.g. potassium dichromate K
2
Cr
2
O
7


24
th
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.

.
2.5 g of the -amanitine are sufficient to kill a mouse. It is a bicyclic octapeptide with
the empirical formula C
39
H
53
N
9
O
15
S.
Ion exchange chromatography of -amanitine gives:
glycine (double amount of the other amino acids);
isoleucine;
,o-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, ,o-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.




24
th
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.























NH
O
NH
O
O
HO
NH
O
NH
N
HO
OH
NH
NH
O
O
NH
HOOC
O
NH
O
OH
S O
24
th
Austrian Chemistry Olympiad 1998
National Competition - Frstenfeld
Theoretical Part