XV Baltic Chemistry Olympiad april 2729, 2007, Tartu

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Problem 1. Polar winter in Antarcti c
Nitric acid hydrates have received much attention as possible catalysts for heterogeneous
reactions that bring about the Antarctic ozone hole. Worsnop et al. has measured
thermodynamic parameters for sublimation of nitric acid mono-, di- and trihydrates at 220 K:

r
G, kJ mol
1

r
H, kJ mol
1

HNO
3
H
2
O(s) HNO
3
(g) +H
2
O(g) 46.2 127
HNO
3
2H
2
O(s) HNO
3
(g) +2H
2
O(g) 69.4 188
HNO
3
3H
2
O(s) HNO
3
(g) +3H
2
O(g) 93.2 237
a) Calculate
r
G at 190 K (the conditions of the polar winter stratosphere). Assume that

r
H and
r
S do not depend on temperature.
a) Which hydrate is thermodynamically most stable at 190 K if p(H
2
O) =1.310
7
bar and
p(HNO
3
) =4.110
10
bar? Standard pressure is 1 bar.
Problem 2. Synthesis of bicyclic compound
The bicyclic skeleton of compound X appears in many naturally occurring alkaloids. The
simple approach to the synthesis of title compound is outlined in this problem. At the heart
of the synthesis is a nitro-aldol reaction between benzaldehyde and nitromethane.
a) Explain, why nitromethane is acidic enough for an aldol reaction to occur?
b) Under basic reaction conditions benzaldehyde and nitromethane in nitro-aldol reaction
give compound A (molecular formula C
8
H
7
NO
2
). Based on the knowledge of the
classical aldol reaction suggest structure of A.
CHO
+
CH
3
NO
2
C
8
H
7
NO
2
A
CH
3
ONa

c) A is fully reduced with hydrogen using palladium on charcoal as a catalyst to give B
(molecular formula C
8
H
11
N). B is fairly basic and readily forms salts with acids. Draw the
structure of compound B.
C
8
H
7
NO
2
A
H
2
, Pd(C)
B
C
8
H
11
N

d) B under acidic reaction conditions reacts with formaldehyde to give final compound X.
This transformation proceeds through formation of C (molecular formula C
9
H
11
N), which
under these reaction conditions undergoes cyclization to form bicyclic X (molecular
formula C
9
H
11
N). X is fairly basic and is usually isolated in a form of salt. Using your
knowledge of reactivity of carbonyl compounds suggest structures of C and X.

B
C
8
H
11
N
X
C
9
H
11
N C
9
H
11
N
C
HCHO, HCl

XV Baltic Chemistry Olympiad april 2729, 2007, Tartu
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Problem 3. Isoleucine dati ng
The rate of isomerization of isoleucine in fossilized bone can be used as an indication of the
average temperature of the sample storage.


At 20C this reaction has a half-life of 125000 years and its activation energy is
139.7 kJ /mol. After a very long time, the ratio allo/iso reaches an equilibrium value of 1.38.
You may assume that this equilibrium constant does not depend on temperature.
The time dependence of concentration for a reversible reaction is given by equation:
( )

| |
= +
|
|

\ .
eq
1 1
0 eq
[A] [A]
ln
[A] [A]
k k t
For a hippopotamus mandible which lived near a warm spring in South Africa, the present
allo/iso ratio in bones is 0.42. Radiocarbon dating, which is temperature independent,
determined the age of hippo tooth, which was 38600 years.
a) Assuming that no allo was present initially, determine constants for forward and reverse
reactions and overall isomerization constant (k
1
+k
1
).
b) Calculate an average conservation temperature of the hippopotamus remains in soil.

Problem 4. Gobl ins element
Metal X was discovered in 1735. Its name has derived from a German word meaning
goblin or evil spirit.
A sample of metal X immersed in H
2
O weights 13.031 g. Meanwhile the weight of the same
sample in CCl
4
is 12.046 g. The density of CCl
4
is 1.5940 g/cm
3
.
In order to identify the metal X, neutron diffraction is used. The diffraction pattern is specific
to the FCC structure and the angle of the reflection (2) from the (222) plane is 76.956.
The velocity of neutrons in the diffractometer is 3115.0 m/s.
The same sample is heated in O
2
atmosphere until metal X has reacted completely. The
product of the reaction is compound A containing 26.577% of oxygen (by mass). All the
amount of compound A reacts with diluted HCl releasing 1.0298 L of O
2
at 25.00C
temperature and 100.0 kPa pressure, giving salt B and water only.
Compound B is dissolved in an aqueous solution containing Cl

, Br

and I

ions. Complex
ion C forms as one of the products. The formula of ion C is [XCl
2
Br
2
I
2
]
n
and it is a
paramagnetic.
Complex carbonyl compound D is prepared by heating metal X under a high pressure of
carbon monoxide. The formula of compound D is [X
2
(CO)
8
] and it is a diamagnetic. The
both atoms of metal X are equivalent in the structure of compound D. A CO molecule
N H
2
OH
O
H H
CH
3
CH
3
H
OH
O
N H
2
H
CH
3
CH
3
L-isoleucine D-alloisoleucine
k
1
k
-1
XV Baltic Chemistry Olympiad april 2729, 2007, Tartu
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donates a pair of electrons to form a single bond only but not all the CO molecules are
equivalent in the structure of compound D.
a) Calculate the density of metal X in g/cm
3
.
b) Calculate the unit cell parameter (a) of metal X in pm.
c) Calculate the molar mass of metal X in g/mol. What element is metal X?
d) Write a chemical formula of compound A.
e) Write a balanced chemical equation of the reaction of compound A with diluted HCl.
f) Sketch the spatial structures of all possible isomers (including structural, geometrical
and optical) of ion C.
g) Count the number of unpaired electrons in ion C. Consider halogenides as weak field
ligands
h) Sketch the spatial structure of compound D.

Problem 5. Sigmatropic rearrangement
Pericyclic reactions are concerted processes that occur by way of a cyclic transition state in
which more than one bond is formed or broken within the cycle. The so called sigmatropic
rearrangements constitute a large group of pericyclic reactions. Of all the sigmatropic
rearrangements, the [3,3]-sigmatropic rearrangement has been used most in organic
synthesis. The reaction involves the transformation of 1,5-dienes and all-carbon system is
known as the Cope rearrangement, whereas with an allyl vinyl ether the reaction is termed
a Claisen rearrangement. The examples of these reactions are given bellow:
O O
Cope
Claisen

The sigmatropic rearrangement has been use in many syntheses of the complex molecules
and has industrial applications as well.
1. The key step in the synthesis of the alkaloid strychnine was made by use of this
chemistry:
XV Baltic Chemistry Olympiad april 2729, 2007, Tartu
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HN
HO
Ar
BuO
N
OBu
Ar
O
CH
2
O/H
+
MeCN, Na
2
SO
4
, 80
o
C

2. The chemical company BASF manufactures citral (intermediate in the synthesis of
vitamin A) by the remarkable synthesis shown bellow:
CHO
OH
-H
2
O
CHO

Write the reaction mechanism (except for the loss of water in the example 2) and possible
intermediates for both reactions.
HINT: by treating acetaldehyde with ethanol under the same reaction conditions as in
example 2, vinylethyl ether could be obtained.

Problem 6. Dolomite
One of the most widespread minerals is dolomite, which in huge amounts is also in bowels
of the earth of Baltic States. Dolomite contains two metallic elements A and B. Metal A
crystallizes in hexagonal close packed atomic structure (unit cell parameters: a =3.2094 ,
b =3.2094 , c =5.2108 and =120
o
), while metal B crystallizes in cubic close packed
atomic structure (unit cell parameter: a =5.5884 ).
a) What are metals A and B? Calculate atomic radii for these elements!
b) Calculate by how many percent (of initial atomic radii) reduce radii for both metallic
elements, when ions are produced from atoms. It is known that oxides of both elements
have sodium chloride structure and radii of oxide anion is 1.28 . Unit cell parameters
for both oxides are 4.213 un 4.811 , respectively.
Industrially metal A can be produced from sea water. To purify chloride of metal A from
other salts hydroxide of metal B is added to sea water. The obtained white precipitate is
dissolved in hydrochloric acid and evaporated, till metal A salt hydrate forms. Then the
hydrate is heated and salt melted and electrolyzed.
c) Write down equations of all chemical reactions described above and calculate time for
electrolysis which has to be performed to isolate 1.0 ton of metal A. Current intensity
9.0 kA.
XV Baltic Chemistry Olympiad april 2729, 2007, Tartu
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One of the most favorite reactions for students is burning of metal A in the air. Reaction
produces huge amount of UV light and two binary compounds, one of them is oxide of
metal A.
d) What is the second compound that is produced in this reaction? Write equations of both
reactions and propose chemical reactions which could be useful for experimental
identification of this compound.
Metal A also is used in army of USA, for preparing food in field conditions. To heat food
wrapped in aluminum foil a special heater (in English Flameless Ration Heater), which
contains 30 mL water, is used. Heating material is a composite, where powder of metal A
and iron are associated in matrix of high density polyethylene. In presence of chloride ions
metal A reacts with water, forming hydroxide and hydrogen, which is available for burning
to obtain extra heat.
e) Using thermodynamical constants shown below calculate minimal mass of element A,
which is needed for heating 1.0 L of water from temperature 20C to 100C. Assume
that all chemical reactions proceed under standard conditions.
Compound AH
f,298
(kJ /mol) C
p
(J /(molK))
H
2
, g 0 28,83
H
2
O, g 241,81 33,61
H
2
O, l 285,83 75,30
Metal A, s 0 24,89
Hydroxide of metal A, s 924,66 76,99
f) Metal A hydroxide, which forms in reaction, is slightly soluble. Calculate solubility (mg/L;
milligrams per liter) of mentioned hydroxide in distilled water. pK
s
=11,25.