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Indian National Chemistry Olympiad Equivalent solutions may exist Problem 1 Thermal and photolytic decomposition of Acetaldehyde
1.1
a)
Theory 2010
17 marks
(b)
1.2
1.3
(a)
(b)
k [CH3 ] = 1 2k 4
.1
1/2 [CH3CHO]1/2 1/2 [CH3CHO]3/2 k k [CH3CO] = 2 1 k 3 2k 4
k d[CO] = k2 1 2k dt 4
1/2
(c)
[CH 3 CHO] 3/2
00
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ks
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1
Theory 2010
= 317.5 nm
1.5
(a)
E thermal = E 2 + 1 (E 1 E 4 ) 2
(b)
Ephotochemical = E2 E4
(b)
1.7
(a)
.1 w w
CH3CH2OH CH3CHO CH3COOH
Conc
(b)
00
Time
ar
1.6
(a)
ks
.in
2
Cu(OH)2
Blue ppt.
6H2O 2OH
+ 4NH3
[Cu(NH3)4]2+ +
Deep blue soln
2.2
2.3
a] oxidation state of the metal. b] nature of the ligand. c] geometry of the complex.
2.4
.1
00
m
[NiCl4]2[NiCl4]2- is tetrahedral
[Ni(H2O)6]2+
[Ni(H2O)6]2+ is octahedral.
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3
Theory 2010
en Cl Co Cl en en
Cl Co Cl en
en Cl Co Cl en
ks
Cl
Cl
2.6 [NiCl4]2-
.1
00
m w w
LP LPLP LP sp3
sp3 hybridization Tetrahedral Paramagnetic (2 unpaired electrons) Pt2+ [Xe] 5d8 [PtCl4]22
ar
LP LP dsp2
.in
en Co en
LPLP
Theory 2010
2.7
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
2.9
m
dxy dyz, dxz octahedron
ar
NH3 Pt NH3 NO2
dx2 y2
dz2
.1
00
dxy
ks
dxy C
dz2
a) b)
.in
dx2 y2 dz2 dyz, dxz
NH3 O2N Pt NH3 NO2
NH3
NH3
2.10
Cl
Pt Cl
NO2
O2N
Pt Cl
NO2
Cl
(D)
3.2
H+ C
+
H
H+ E H
3.3
H COOH COOH H F
3.4
3.5
Br
Br
.1
Br Br Br Br Br Br
3.6
(b) Three
00
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6
Theory 2010
.. CHCl K
3.8
CH2Br
BrH2C
CH2Br
R R R
3.10
.1
00
O
R R R
R=COOEt
ar
3.9
ks
.in
N
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 Li + O2 2 Li2O Cs + O2 CsO2
II
4.4
i)
Bond order = 1
4.5
ii)
diamagnetic
.1
X
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4.3
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8
Theory 2010
X X
4.7
4.8
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
.1
00
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9
R + NH2
.. _ :O: ..
.. _ :O:
+
R NH2
.. _ :O: .. R + .. OR'
.. _ :O:
+
R OR'
..
5.2
5.4
A C B
5.5 5.6
CH3CH2COCl Best C
.1
Poorest B
Cl NO2 COOCH3 Monochloro derivative (major)
5.7
.
NO2 COOH COOCH3 5 major
00
5.3
Amide
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Theory 2010
or Br or OTs or N2+
8
5.9
O O OMe OMe MeO 10 O
O OH CO2Et OMe
.in ar ks
OMe
O
OMe
HO
5.11
(i)
(ii)
Both are S
Me
14
.1
Me
00
5.10
11
12
11
Theory 2010
5.13
O S O Me Me O a N S O O H H b H 16 N O
5.14
00
m
O Me Me HN O 17 18 H H H
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O NH
w
N H
w
O H
Me
.1
H H
Me
NH
12
Kp = 0.7030
6.2
Kp = Kc
6.3
H1400 = 31258 J
6.6
6.7
T1 = 2060K T2 = 708 K
Compound 6.8
N2 (g) O2 (g) CO (g) CO2 (g) H2O (g)
.1
00
6.5
ar
X
ks
6.4
.in
13
7.2
7.3
[H 3O + ] =
Ka Ka 2 + 4KaC T
7.4
pH = 2.88
CH 3 COO + H 2 O OH + CH 3 COOH
b)
c)
[H 3 O + ] = Ka
d)
pH = 3.80
7.6
pH = 8.73
CT [CH 3 COONa ]
.1
00
CH 3 COOH + H 2 O CH 3 COO + H 3 O +
7.5
a)
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