Indian National Chemistry Olympiad Equivalent solutions may exist Problem 1 Thermal and photolytic decomposition of Acetaldehyde

1.1
a)

Theory 2010

17 marks

d[CH 3CHO] = k[CH 3 CHO]3 / 2 dt d[CH 4 ] d[CO] = = k[CH 3 CHO]3 / 2 dt dt

(b)

Order = 3/2 Rate = 8 v

1.2

CH4, CD4 and CO

1.3

(a)

Propogation steps : (ii) and (iii) Termination step: (iv)

(b) k [CH3 ] = 1 2k 4

1/2 [CH3CHO]1/2 1/2 [CH3CHO]3/2

k k [CH3CO] = 2 1 k 3 2k 4

(c)
k d[CO] = k2 1 2k dt 4
1/2

[CH 3 CHO] 3/2

HBCSE, 30th January 2010

Indian National Chemistry Olympiad

1.4 (a) CH3CHO + h CH3 + CHO Rate = Iabs [CH3] = (Iabs/2k4)1/2 [CH3CHO]3/2 d[CO]/dt = k2 (Iabs / 2k4)1/2 [CH3CHO]3/2 (b)

Theory 2010

= 317.5 nm

1.5

(a)
E thermal = E 2 + 1 (E 1 E 4 ) 2

(b)

Ephotochemical = E2 E4

1.6

(a)

Ethermal =196.46 kJ mol1

(b)

5.879 104 mol dm3 sec 1

1.7

(a)
CH3CH2OH CH3CHO CH3COOH

Conc

Time

(b)

[CH3CHO] = k5/k6 [CH3CH2OH]

HBCSE, 30th January 2010

Indian National Chemistry Olympiad Problem 2 Chemistry of coordination compounds

2.1 CuSO4 + 6H2O [Cu(H2O)6]2+ + SO42
White Blue solution

Theory 2010 19 marks

or balanced equation with [Cu(H2O)4]2+ entity [Cu(H2O)6]2+ Cu(OH)2 + 2OH

From dil NH3

Cu(OH)2
Blue ppt.

6H2O 2OH

+ 4NH3

[Cu(NH3)4]2+ +
Deep blue soln

2.2

b] completely filled d-level in Cu(I)

2.3

a] oxidation state of the metal. b] nature of the ligand. c] geometry of the complex.

2.4

[Ni(H2O)6]2+ [Ni(H2O)6]2+ is octahedral.

[NiCl4]2[NiCl4]2- is tetrahedral

HBCSE, 30th January 2010

Indian National Chemistry Olympiad

a] . IUPAC Name : 2.5

Theory 2010

Dichlorobis(ethylenediamine)cobalt(III) ion. Dichlorobis(ethane-1,2-diamine)cobalt(III) ion Dichloridobis(ethylenediamine)cobalt(III) ion. Dichloridobis(ethane-1,2-diamine)cobalt(III) ion

b]. Geometrical isomers:

+ +

en Cl Co Cl en en

Cl Co Cl en

c] cis-[CoCl2(en)2]+ is optically active. d] Two optical isomers of cis-[CoCl2(en)2]+ :

+ +

en Cl Co Cl en Cl en en Cl Co

Ni2+ [Ar] 3d8 2.6 [NiCl4]2-

LP

LPLP LP sp3

sp3 hybridization Tetrahedral Paramagnetic (2 unpaired electrons) Pt2+ [Xe] 5d8

[PtCl4]22

LP

LP dsp2

LPLP

dsp hybridization Square planar Diamagnetic (no unpaired electrons)

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Indian National Chemistry Olympiad

Theory 2010

2.7

A i) [CrF6]3ii) [Cr(H2O)6]3+ iii) [CrF6]2iv) [Cr(CN)6]3-

B o (cm-1) d) 15,000 c) 17,400 b) 22,000 a) 26,600 a) [Fe(CN)6]3 Fe(III) of Fe(III) : 6 35 b) Ni(CO)4 Ni(0) of Ni(II) : 4 36

2.8

Answer: Oxidation state Coordination No. EAN of central metal ion

2.9

dz2 dx2 y2 dz2

dx2 y2

dx2 y2 dyz, dxz

dz2

dxy dxy dyz, dxz

dxy

dyz, dxz

Tetragonally distorted octahedron contraction along z-axis

octahedron

Tetragonally distorted octahedron elongation along z-axis

a) b)

(i) by elongation along z-axis. (ii) dx2-y2 orbital.

NH3

NH3

NH3
NO2

NH3
NO2

2.10

Cl

Pt Cl

NO2

O2N

Pt Cl

Cl

Pt NH3

O2N

Pt NH3

NO2

HBCSE, 30th January 2010

Indian National Chemistry Olympiad Problem 3 Chemistry of isomeric benzenes

3.1 Z,Z,E -1,3,5-cyclohexatriene
2 1 5 3

Theory 2010 14 marks

(D)

3.2

H+ C

+
H

H+ E H

3.3

H COOH COOH H F

3.4

3.5
Br Br Br Br Br

Br

Br Br

3.6

(b) Three

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Indian National Chemistry Olympiad

3.7
_ J + Li

Theory 2010

.. CHCl K

3.8
CH2Br

BrH2C

CH2Br N

3.9
R R R R R R

R=COOEt

3.10

HBCSE, 30th January 2010

Indian National Chemistry Olympiad Problem 4 s-Block Elements

4.1 a) only one valence electron b) large atomic size X X

Theory 2010 10 marks

4.2

Inhalation Exhalation or or

2 KO2 + 2 H2O 2 KOH + H2O2 + O2 KOH + CO2 KHCO3 4 KO2 + 2 CO2 2K2 CO3 + 3O2 2KOH + CO2 K2 CO3 + H2O

4.3

4 Li + O2 2 Li2O Cs + O2 CsO2

II

4.4

i)

Bond order = 1 X

ii)

diamagnetic

4.5

Na + (x + y) NH3 [Na(NH3)x]+ + [e(NH3)y] OR Na + NH3 Na+ + e solvated / (am)

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Indian National Chemistry Olympiad

4.6 b) It is paramagnetic in nature c) On standing this solution slowly liberates hydrogen resulting in the formation of sodium amide

Theory 2010
X X

4.7

c) half the number of tetrahedral

4.8

b) cyclohexane c) diisopropyl ether

X X X X X

4.9

a) ionization energy of alkali metal b) electron gain enthalpy of halogen d) sizes of cations and anions

4.10

LiF

HBCSE, 30th January 2010

Indian National Chemistry Olympiad Problem 5 Carboxylic acid derivatives

5.1

Theory 2010 17 marks

R + NH2

.. _ :O: ..

.. _ :O:
+
R NH2

.. _ :O: .. R + .. OR'

.. _ :O:
+
R OR'

..

5.2

(c) Amide > Ester > Acid Chloride X

5.3

Amide

5.4

1650 cm-1 1750 cm-1 1800 cm-1

A C B X Poorest B

5.5 5.6

CH3CH2COCl Best C

5.7

.
NO2 COOH COOCH3 5 major

Cl

NO2

COOCH3 Monochloro derivative (major)

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Indian National Chemistry Olympiad

5.8
OLi EtO I or Cl OMe OMe O

Theory 2010

or Br or OTs or N2+
8

5.9
O O OMe O

O OH CO2Et OMe OMe OMe MeO 10 11 OMe 12

5.10
Me Me H HO H H O

14

5.11

(i)

(ii)

Both are S

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Indian National Chemistry Olympiad

5.12
Me Me H O 15 H H O

Theory 2010

5.13
O S O Me Me O a N S O O H H b H 16 N O

5.14
Me Me O N H 17 H H H

O NH Me HN O 18 H H H Me

O NH

HBCSE, 30th January 2010

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Indian National Chemistry Olympiad Problem 6 Chemical Thermodynamics

6.1 2930 J

Theory 2010 17 marks

Kp = 0.7030

6.2

Kp = Kc

6.3

XCO = 0.342, XH2 = 0.458, XH2O = 0.092, XCO2 = 0.108 XCO = 34.95%, XH2 = 45.41%, XH2O = 9.59%, XCO2 = 10.06%

6.4

H1400 = 31258 J

6.5

a) Kp will increase with increase in temperature

6.6

Air intake (engine;m3s1) = VA = 4 9.902 103 m3s1 = 0.0396 m3s1

6.7

T1 = 2060K T2 = 708 K

Compound 6.8
N2 (g) O2 (g) CO (g) CO2 (g) H2O (g)

Molar composition of gases after leaving the bed (Mol 10 4)

407.64 38.55 0.78 44.14 49.44

HBCSE, 30th January 2010

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Indian National Chemistry Olympiad Problem 7

7.1 V= 87.5 mL

Theory 2010 10 marks

7.2

CH3COOH + H2O H3O+ + CH3COO

Ka = [H3O+][ CH3COO]/[ CH3COOH]

7.3

[H 3O + ] =

Ka Ka 2 + 4KaC T 2

7.4

pH = 2.88

7.5

a)
CH 3 COOH + H 2 O CH 3 COO + H 3 O + CH 3 COO + H 2 O OH + CH 3 COOH

b) [CH 3 COOH]eq = C T [H 3 O + ] + [OH ] [CH 3 COO ]eq = [CH 3 COONa ] + [H 3 O + ] [OH ]

c)

[H 3 O + ] = Ka

CT [CH 3 COONa ]

d)

pH = 3.80

7.6

pH = 8.73

HBCSE, 30th January 2010

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