INChO 2010 Chemistry Question Paper from India Indian National Chemistry Olympiad

39 Pages·2010·0.266 MB·English

by  HBCSE Chemistry Team

Indian National Chemistry Olympiad Theory 2010

Instructions for students

• Write your name and roll no. at the top of the first pages of all problems.
• This examination paper consists of 39 pages of problems including answer
boxes.
• You have 3 hours to complete all the problems.
• Request the supervisor to provide you with rough sheets for rough work.
• Use only a pen to write the answers in the answer boxes. Anything
written by a pencil will not be considered for assessment.
• All answers must be written in the appropriate boxes. Anything written
elsewhere will not be considered for assessment.
• For calculations, you must show the main steps.
• Use only a non-programmable scientific calculator.
• For objective type questions: Mark X in the correct box. Some of the objective
questions may have more than one correct choice.
• Values of fundamental constants required for calculations are provided on
page 2.
• A copy of the Periodic Table of the Elements is provided at the end of the
paper.
• Do not leave the examination room until you are directed to do so.
• The question paper will be uploaded on the HBCSE website by 31st January
2010.
© Homi Bhabha Centre For Science Education
Tata Institute of Fundamental Research
V.N. Purav Marg, Mankhurd, Mumbai 400 088.
HBCSE, 30th January 2010 1
Indian National Chemistry Olympiad Theory 2010

Fundamental Constants

Avogadro constant N = 6.022 x 1023 mol–1
A
Electronic charge e = 1.602 x 10–19 C
Molar gas constant R = 8.314 J K–1mol–1
= 8.314 K Pa.dm3 K–1mol–1
= 0.082 L.atm K–1mol–1
1 atomic mass unit (1u) = 931.5 MeV/c2
1 eV = 1.602 x 10–19 J
Rydberg constant R = 2.179 x 10–18 J
H
Mass of electron m = 9.109 x 10–31 kg
e
Planck’s constant h = 6.625 x 10–34 Js
Speed of light c = 2.998 x 108 ms- 1
Acceleration due to gravity g = 9.8 ms- 2
Density of mercury = 13.6 x 103 kg m- 3
HBCSE, 30th January 2010 2
Indian National Chemistry Olympiad Theory 2010

N ame of Student Roll No.
Problem 1 17 marks
Thermal and photolytic decomposition of Acetaldehyde
The stoichiometric equation for the pyrolysis of acetaldehyde to methane and carbon
monoxide is as follows: CH CHOfi CH +CO
3 4
1.1 (a) The order of this reaction determined experimentally was 1.5. Write the rate
equation for the reaction.

(0.5 mark)

(b) If v is the rate corresponding to P = P , what is the (i) order and (ii) rate
CH3CHO 1
of reaction, when P = 4P ?
CH3CHO 1

(1 mark)
1.2 The pyrolysis of acetaldehyde under certain conditions, can be an intramolecular
process. What products are formed in the pyrolysis of a mixture of CH CHO and
3
CD CDO?
3

(1 mark)
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Indian National Chemistry Olympiad Theory 2010

1.3 The major steps in the gas phase thermal pyrolysis of acetaldehyde, as identified by
Rice and Herzfeld are as follows
k
CH CHO (g) (cid:190) (cid:190)fi(cid:190) 1 •CH (g)+•CHO(g)..............................(i)
3 3

k
•CH (g)+CH CHO(g)(cid:190) (cid:190)fi(cid:190)2 CH (g)+•CH CO(g)....................(ii)
3 3 4 3
k
•CH CO (g) (cid:190) (cid:190)fi(cid:190)3 •CH (g)+CO(g)..............................(iii)
3 3
k
2 •CH (g) (cid:190) (cid:190)fi(cid:190)4 C H ...............................................(iv)
3 2 6

(a) Identify the propagation and termination steps from the above reactions.

(1 mark)
(b) Assuming •CH and •CH CO to be under steady state (i.e. the rate of
3 3
formation and rate of consumption of an intermediate species are equal),
derive expressions for (i) [•CH ] and (ii) [•CH CO] in terms of [CH CHO].
3 3 3

(2 marks)
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Indian National Chemistry Olympiad Theory 2010

(c) Deduce d [CO]/dt in terms of [CH CHO].
3

(1 mark)
1.4 (a) In the photochemical decomposition of acetaldehyde, one photon of absorbed
light decomposes one molecule of CH CHO into •CH and •CHO. If ‘I ’ is
3 3 abs
the intensity of light absorbed in the reaction,
(i) Write the rate equation for this photochemical decomposition. (Note: the
first step in the photochemical reaction is temperature independent)
(ii) Calculate [•CH ] and d[CO]/dt assuming steps (ii) to (iv) given in 1.3 are
3
same and [•CH ], [•CH CO] are under steady state.
3 3

(1.5 marks)
(b) If C-C, C-H, and C=O bond energies in acetaldehyde are 377, 421 and
720 kJ mol- 1 respectively, calculate the wavelength of radiation (in nm)
required to bring about the photochemical decomposition of acetaldehyde.

(1 mark)

HBCSE, 30th January 2010 5
Indian National Chemistry Olympiad Theory 2010

1.5 The Arrhenius (pre exponential) factors and activation energy values for steps (i) to
(iv) in 1.3 are A , A , A , A and E , E , E and E respectively.
1 2 3 4 1 2 3 4
(a) Calculate the overall activation energy E for the thermal decomposition
thermal
of acetaldehyde.

(1.5 marks)
(b) Write the expression for overall activation energy, E of
photochemical
photochemical decomposition of acetaldehyde.

(1 mark)
1.6 The recombination of methyl radicals has no activation barrier. The activation
energy values for the first step in the thermal decomposition of acetaldehyde in (1.3)
and E are 309.32 kJ mol-1and 41.8 kJ mol-1 respectively.
photochemical
(a) Calculate the overall activation energy for the thermal decomposition of
acetaldehyde

(1 mark)

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Indian National Chemistry Olympiad Theory 2010

(b) Calculate the rate constant and rate of overall reaction for the thermal
decomposition of acetaldehyde at 101 kPa and 800 K, if overall Arrhenius factor is
2.3 · 1012 dm3/2 mol - 1/2 sec - 1.

(2 marks)
1.7 CH CHO can be formed from CH CH OH and further get oxidised to CH COOH as
3 3 2 3
k k
CH CH OH(cid:190) (cid:190)fi(cid:190)5 CH CHO(cid:190) (cid:190)fi(cid:190)6 CH COOH
3 2 3 3

(a) Qualitatively sketch the concentration vs time plots of CH CHO, CH CH OH
3 3 2
and CH COOH, till the reaction goes to completion.
3

(1.5 marks)
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Indian National Chemistry Olympiad Theory 2010

(b) If both the reactions in 1.7 are of 1st order, [CH CHO] is related to initial
3
concentration of alcohol [CH CH OH] by the equation,
3 2 0
[CH CHO] k - k t - k t
3 = 5 (e 5 - e 6 )
[CH CH OH] k - k
3 2 0 6 5
Derive the expression for [CH CHO] in terms of [CH CH OH]
3 3 2
if k << k .
5 6

(1 mark)
HBCSE, 30th January 2010 8
Indian National Chemistry Olympiad Theory 2010

Name of Student Roll No.
Problem 2 19 marks
Chemistry of coordination compounds
Developments in the field of coordination chemistry have led to new concepts in
chemical bonding and molecular structure, revolutionized the chemical industry and
provided insight into functions and structures of vital components of biological
systems. Coordination compounds find extensive applications in metallurgical
processes, analytical and medicinal chemistry.
2.1 Anhydrous copper sulphate, a white solid, when dissolved in water, gives a blue
coloured solution. On addition of dilute ammonia, a blue precipitate is obtained,
which dissolves in excess of concentrated ammonia giving a deep blue solution. Write
the chemical reactions involved in the formation of these coloured species.

(1.5 marks)
2.2 Most copper(I) compounds are found to be colourless. This is due to
a] presence of low oxidation state of copper.
b] completely filled d-level in Cu(I).
c] diamagnetic nature of the compound.
d] high polarizability of Cu(I) ion.
(0.5 mark)

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Indian National Chemistry Olympiad Theory 2010

2.3 The expected spin-only magnetic moments of complexes of a transition metal like
nickel or cobalt depend on
a] oxidation state of the metal.
b] nature of the ligand.
c] geometry of the complex.
d ] number of unpaired electrons in free transition metal ion.
(1 mark)

2.4 Ni2+ forms a variety of complexes with different ligands. Thus, it gives [Ni(H O) ]2+
2 6
with H O and [NiCl ]2- with Cl-. Both the complexes show paramagnetism
2 4
corresponding to two unpaired electrons. Draw the crystal field splitting diagrams for
the two complexes showing the d-electron distribution to explain the observed
magnetic properties. State the geometries of the two complexes.

(2 marks)

HBCSE, 30th January 2010 10