27th Austrian Chemistry Olympiad – 2001

National Competition – Salzburg

Theoretical Part

Information, constants, formulae

Information

 You have five hours to complete the theoretical competition.

 Solve the tasks using paper, a non programmable calculator, a blue or black pen or
biro, and a triangle no other devices.
 Use one sheet of paper for each task.
 Do not write answers to different tasks on one sheet of paper.

Constants

R = 8.314 J/mol.K F = 96485 A.s/mol NL = 6.0231023 mol-1

C = 2.998108 m/s h = 6.6210-34 J.s p = 1 bar

Formeln
dp S
H  U  pV  U  nRT G  G  RT ln Q  RT ln K  RT ln Q 
dT V
p 2 HV  1 1 k(T2 ) E A  1 1  K P (T2 ) HR  1 1
ln     ln     ln    
p1 R  T1 T2  k(T1 ) R  T1 T2  K P ( T1 ) R  T1 T2 
2 1 1
K P  K C (RT )n  K Xp n KS  c0   0  k.t
1  cA cA c A  c 0A .e k.t

v max . S 
EA
c A  c 0A  k.t v0  k  A.e G   z.F.E
K M   S
RT

RTG2M1 RTS2M1
p i  p i0 .x i p i  p g .x i TG   m *2 TG   m *2
H S H V

T2 T2
C  1 1
H( T2 )  H( T1 )   C P dT S(T2 )  S(T1 )  T T P dT   RH  2  2 
T1  n1 n2 
1

l   eq
  eq    eq   0  k. c  mag   B . n n  2
A.R c.n e 0

Spectrochemical series:

I-<Br-<Cl-SCN-<F-<OH-<C2O42-H2O<NH3<CO32-<en<NO2-<CN-CO
27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part

1st task (4 points)

Physical Chemistry – Phases

A. A simple phase diagram

a) Which states of aggregation are possible for CO2 at normal pressure?

b) What is the minimum pressure for CO2 to become a liquid?
c) To which temperature must CO2 be cooled down at least in order to condense?
d) What is the temperature of dry ice (CO 2(s)) if it is in equilibrium with CO 2(g) at normal
pressure?
e) A fire extinguisher contains liquid CO2. Which pressure must the extinguisher resist at
least?

B. Boiling point of ethanol

The vapour pressure of ethanol is 60.0°C at 46.7 kPa. The vaporization heat of ethanol is
HV = 862 J/g between 60°C and ist melting point.

a) Calculate the boiling point of ethanol at 1013 mbar.

b) Calculate the vaporization entropy SV at the boiling point.
27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part

Phase diagram of CO2:

p (bar)

50

10

5,0

1,0

0,5

T (K)

200 250 300

2nd task (7 points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Physical Chemistry
Thermodynamics and Equilibrium

C. Heat of formation

Calculate the heat of formation of nitrous acid (HNO 2) in aquous solution at constant
pressure and constant volume using the following data, valid at 25.00°C.

a. NH4NO2(s)  N2(g) + 2H2O(l) H(kJ) = -300.4

b. 2H2(g) + O2(g)  2H2O(l) H(kJ) = -569.2
c. N2(g) + 3H2(g) + aq  2NH3(aq) H(kJ) = -170.8
d. NH3(aq) + HNO2(aq)  NH4NO2(aq) H(kJ) = -38.08
e. NH4NO2(s) + aq  NH4NO2(aq) H(kJ) = +19.88

D. Equilibrium

Halogens form a series of interhalogen compounds being more or less stable. One of
these compounds is bromine chloride (BrCl) which decomposes to the elements at 500°C.
The equilibrium constant at this temperature is K C = 32, if one looks at the decomposition
of 2 mol of BrCl.
Let us assume a system which contains 0.25 mol/L of each of the participating
substances.

a) Write down a balanced reaction equation for the decomposition.

b) Proove by calculation that the above described mixture is not in an equilibrium state.
c) In which direction will the mixture react?
d) Which work (energy) is liberated if the mixture moves to the equlibrium?
e) Give the values of KP and KX of the reaction.
f) Calculate the equilibrium concentratioins of all substances if you start from the above
given mixture.

3rd task (7 points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Physical Chemistry - Kinetics

Dinitrogen pentoxide decomposes according to the following equation giving nitrogen

dioxide and oxygen:
2 N2O5  4 NO2 + O2

a) Draw two possible resonance structures of dinitrogen pentoxide including formal

charges.
b) Write down the rate law for the decomposition which may be deduced from the above
reaction equation.

The decomposition follows the given mechanism:

k1
(1) N2O5 NO2 + NO3
k -1
k2
(2) NO2 + NO3 NO2 + O2 + NO

k3
(3) NO + N2O5 3 NO2

c) Try to find the real rate law and the order of the reaction applying the steady state
theory for NO and NO3.

The activivation energy of the decomposition at 300 K is E A = 103 kJ.

d) To which temperature must the system be brought to in order to double the reaction
rate. Start your calculation using the assumptions that you have the same initial
concentrations, that EA remains constant, and that the frequency factor A does not
change.

4th task (8 points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Elektrochemistry

A) Conductivity

Measuring the conductivity of a solution of methanoic acid (formic acid) gave a value for
the specific conductivity of  = 7.52 mScm-1. The solution contained 9,55% by mass of
formic acid and had a density of =1.02 gcm-3. Additionally the following data are given for
calculation:
0(HCOO-Na+) = 90.5 Scm2mol-1 0(HCl) = 380.5 Scm2mol-1 0(NaCl) = 109 Scm2mol-1

a) Calculate the limiting conductivity 0 for the methanoic acid!

b) Give a balanced equation for the protolysis of methanoic acid!
c) Calculate the degree of protolysis  of the investigated solution!
d) Calculate the pKS-value of methanoic acid!

B) Elektrosynthesis of a complex compound

The instruction for the preparation of Triphenylphosphoniumtetrachlorocobaltate(II) says:

In an electrolysis cell 1g of triphenylphosphine is dissolved in 40 mL of acetonitrile and 2.5
mL of conc. hydrochloric acid are added. A platinum electrode is used as a catode. The
cobalt electrode must be weighed and inserted into the cell as an anode. The two
electrodes are connected to a direct current source and an amperemeter must be
integrated into the system. The current must remain constant during the electrolysis which
should last 90 minutes. The outcoming blue solution is evaporated. The remaining blue-
green substance is dissolved in a minimum amount of acetonitrile, again evaporated to 5
mL and subsequently brought to cristallization in the refrigerator. The bright blue crystals
are filtered off, washed with ether and weighed after drying. The cobalt electrode has to be
dryed and weighed again.

A student gets the following values doing this synthesis:

Co-elektrode before electrolysis: mbefore = 10.542 g
Co-elektrode after electrolysis: mafter = 10.440 g
mass of product:: mkomplex = 1.015 g
electrolysis time: t = 90 min
current (constant): I = 100 mA

a) Write down balanced equations (ionic form) for the process taking place at the anode
and catode respectively!
b) What is the formula of the complex compound?
c) Calculate the yield of the product (percentage of mass) related to the mass of cobalt
which was used up!
d) Calculate the current yield !

5th task (8 points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Complexes of cobalt

A. Pauling Theory

Adding aquous potassium hydroxide to an aquous solution of Co 2+, a blue precipitate

develops. In a very concentrated solution of potassium hydroxide a high spin complex with
six fold coordination is formed.
a) Write down balanced ionic equations for the formation of the precipitate and the
complex!
b) What is the systematic name of the complex!
c) Write down the Pauling scheme for the complex! Name the type of hybridization!

B. Ligand field theory

The bis(terpyridyl)cobalt(II)-ion exists at room temperature partly in a high-spin, partly in a

low-spin state depending on the counter-ions ClO 4-/Cl-/NCS-/Br-.

a) Give the three dimensional geometry of the complex!

b) Draw the occupation of the orbitals for a high-spin and a low-spin complex according
to the ligand field theory!
c) Give the range of magnetic moments (in terms of B.M.) of the actual magnetic
moments of the different complexes?

The following complexes are considered: [Co(CN) 6]3-, [Co(CO3)2(NH3)2]-, [Co(CO3)3]3- and
[Co(NO2)6]3-. The colours of these complex ions are: green, pale yellow, orange and blue
(not neccessarily in the same order as the above complexes).

d) Name the complexes and label the colour to the corresponding complex using the
following table for your answers:

formula name colour

6th task (14 points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Organic Chemistry
Synthesis of Linalool

Linalool (C10H18O) is a terpene which occurs in cinnamon, sassafrasoil or in oil of orange

blossoms. It is often used in perfume essences.
This compound may be synthesized from three components A, B and C.

2-methylbut-3-en-2-ol (D) serves as starting material for A. D is converted into the bromo-
compound A using HBr (48 %):
HBr (48%)
D A
allylic rearrangement
A has a molar mass of M (A) = 149 g/mol and shows three signals in the proton–NMR:
1 = 5,49 ppm (J = 8 Hz, 1 H), 2 = 3,95 ppm (J = 8 Hz, 2 H) and 3 = 1,75 ppm (6 H).

To synthesize B, acetoacetic ester ( ethyl-3-oxobutanoat ) reacts with A in the presence of

a strong base giving E. In a first step E reacts with NaOH, in a subsequent step the
resulting product is heated with HCl yielding B:

1.) NaOH/H2O
O O
C2H5O-Na+/C2H5OH 2.) HCl/H2O,
+ A E B
O

The last step is a chain propagation. A C 2-piece (M = 26 g/mol) is used which reacts at first
with HBr(aq) yielding F which then is transformed using Mg in absolute ether giving G. G
reacts with B to the product H, which leads to linalool after work up in an acidic aqueous
solution.
HBr Mg +B H+/H2O
C F G H Linalool
Ether

a) Draw the constitutional formulae of A, B, C, D, E, F, G, H and linalool.

b) Which multiplets would you assign to the NMR-signals 1, 2 und 3?
c) Give the IUPAC names of B and linalool.
d) To which group of compounds belongs G?
e) Give the name of the mechanism of the reaction from G with B.
f) How do you call the two steps from E to B in terms of usual names of organic
synthesis?
g) Draw the structure of the nonstable ionic intermediate in the step from acetoacetic
ester to E.

7th task (12 Points)

27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part
Biochemistry
Bovine Pancreatic Trypsin Inhibitor (BPTI)

BPTI is a polypeptide containing 58 amino acids (AA).

The picture shows parts with -helix- und -sheetstructure, but also parts
with a non-regular backbone structure. Important for the structure of BPTI
are also three disulfide bridges.

A. Tasks:

a) Threonin is an AA with two asymetrical substituted C-Atoms. Draw all possible

configuration formulae of Threonin and name one of them systematically.

b) Put numbers to the structures above and indicate for every possible pair the kind of
stereoisomerism.

c) Calculate for glutamate the isoelectric point and draw the corresponding constitutional
formula at this pH.
pK (-COOH) = 2.2 pK (-NH3+) = 9.7 pK (sidechain) = 4.3

B. Primary Strucure:

The AA-sequence from 1-37 is given in the table on the next page.

Try to find the sequence from AA 38 to AA 58 using the following information:

After breaking the disulfide bridges, BPTI in one experiment was split enzymatically
(splitting at the carboxy site of lysin and arginin). In another experiment BPTI was split by
2-Nitro-5-thiocyanobenzoat (splitting at the amino site of cystein). The AA-sequence of the
fragments was investigated.

Thereby arginin and the following peptides were found:

(Hint: The AA 38 and 39 are the only ones which are found just in one of the peptides.
They are part of a longer fragment, which was identified earlier.)
 27th Austrian Chemistry Olympiad – 2001
National Competition – Salzburg
Theoretical Part

(1) Thr – Cys – Gly – Gly – Ala

(2) Cys – Arg – Ala – Lys – Arg – Asn – Asn – Phe – Lys – Ser – Ala – Glu – Asp
(3) Cys – Met – Arg – Thr
(4) Ser – Ala – Glu – Asp – Cys – Met – Arg
(5) Ala – Lys
(6) Asn – Asn – Phe – Lys
(7) Cys – Gly – Gly -Ala

Arg-1 Pro-2 Asp-3 Phe–4 Cys-5 Leu-6 Glu-7 Pro-8 Pro-9 Tyr-10
Thr-11 Gly-12 Pro-13 Cys-14 Lys-15 Ala-16 Arg-17 Ile-18 Ile-19 Arg-20
Tyr-21 Phe-22 Tyr-23 Asn-24 Ala-25 Lys-26 Ala-27 Gly-28 Leu-29 Cys-30
Gln-31 Thr-32 Phe-33 Val-34 Tyr-35 Gly-36 Gly-37 -38 -39 -40
-41 -42 -43 -44 -45 -46 -47 -48 -49 -50
-51 -52 -53 -54 -55 -56 -57 -58

Tasks:

a) Name the fragments of the enzymatical splitting (only for AA 38 – 58).

b) Put the missing AA in the table above.
c) Draw the constitutional formula of the dipeptide Ala-Lys.
d) How many fragments would a splitting with cyanobromide cause?

C. Secondary Structure:

The Ramachandranplot and the

following data are given:

Phi  Psi 
Tyr - 21 - 96,66 149,81
Arg - 53 - 67,79 - 36,00

Tasks:

a) Give a definition of the torsion angle  using the Newman projection.

b) What kind of secundary structure do you expect in the region of

1. Tyr – 21?
2. Arg – 53?