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DINITROGEN
Ph.D. Seminar I
G. Magesh
9-5-06
Contents
Importance of fixation of dinitrogen
Properties of dinitrogen
Various methods for fixation of dinitrogen
Shortcomings in available methods
Merits of photo catalytic fixation of dinitrogen
Fundamentals of photo catalysis
Challenges in photo catalytic route
Ways of overcoming them
Nitrogen cycle
Haber process
Fixed nitrogen by bacteria and algae
Chile salt petre (Sodium nitrate)
Destructive distillation of decayed vegetable and animal matter
Reduction of nitrous acid and nitrites with nascent hydrogen
Decomposition of ammonium salts by alkaline hydroxides or quicklime
Mg3N2
6 H2O
3 Mg(OH)2 + 2 NH3
1934
World
843.5
1972.0
Chile
476.7 (56.5%)
141.8 (7.2%)
Germany
131.6
462.5
Great Britain
99.5
175.0
United States
39.5
256.7
Norway
22.0
65.5
France
18.9
187.6
Canada
12.7
41.1
Belgium
11.0
109.8
Italy
6.3
98.6
Japan
3.9
208.0
Russia
3.2
45.0
Non-polar
N 2 H2
H = 213.5 kJ mol-1
2 C + H2
C2H2
H = -175.8 kJ mol-1
Nitrogen
Carbon
Oxygen
Argon
14.3
11.256
13.614
15.755
0.073
1.595
1.461
0.083
Insoluble
0.153
0.140
Property
High ionization potential and low electron affinity - difficult to reduce and
oxidize
Solubility very less - reactions in solution phase - difficult
Activation of dinitrogen
LUMO
22.9 eV
HOMO
N2 + 3H2
2NH3
H= -36 kJ mol-1
Change in entropy, S = - ve
II law of thermodynamics - Natural processes tend to increase the entropy
Formation of ammonia by this route cannot be a natural process
Spontaneous reaction G = ve
G negative at very low temperatures
11
Fe based catalyst
N2 + 3H2
2NH3
12
Conversion of 15%
Hydrogen
Obtained from fossil fuels a limited resource
Production requires major part of plant and cost
Releases green house gases like CO2 and CO
13
Enzyme nitrogenase
14
N-N bond
length(
)
Structure of
N2 gas
1.0975
[(TMS2N)2Ti]2-(N2)2-
H2NNH2
1.460
complex
[(TMS2N)2Ti]2-(N2)2-
1.379
Limitation:
N2 evolution during reduction
Fryzeuk M D, Johnson S A, Coord. Chem. Rev., 200 (2000) 379
15
Alternatives
Haber process
Binding N2 Perturb e-
e- donation LUMO of N2
Limited success
Look for
Perturb orbital (wave function) of e- donor and acceptor
e- donation to LUMO N2 activation
16
17
Photo catalysis
Photo catalysis - reaction assisted by photons in the presence of a catalyst
In photo catalysis - simultaneous oxidation and reduction
Light excites electrons from valence to conduction band - electrons and
holes
18
CB
Metal
CB
No band gap
Only reduction or oxidation band
position
Semiconductor
UV or Visible light
Insulator
CB
VB
Metal
E
n
e
r
g
y
VB
Semiconductor
VB
Insulator
Band gap of available
materials
19
Types of semiconductors
For reduction
Conduction band potential - more negative than potential of reduction reaction
For oxidation
Valence band potential - more positive than potential of oxidation reaction
-ve
P
Reduction
O Type
Oxidation
X type
- None
t
e
n
t
i
a
l
Reduction (A / A-)
Oxidation (D/D+)
+ve
Band positions of various types of semiconductors
20
E
n
e
r
g
y
N2/NH3
eV
21
Photocorrosion
CdS, ZnS, ZnO undergo
photocorrosion
Activity decrease as the time increases
Catalyst gets oxidised
Oxidation potential of catalyst More
-ve than desired oxidation reaction
potential
S deposition on catalyst - reduce
light absorption
h+ = hole
22
M-X
Percentage
ionic
character
TiO2
Ti-O
Ti-O-Sr
Fe-O
Zn-O
W-O
Zn-S
Cd-S
Cd-Se
59.5
68.5
47.3
55.5
57.5
18.0
17.6
16.5
SrTiO3
Fe2O3
ZnO
WO3
ZnS
CdS
CdSe
X- electronegativity
23
2 NH3
3H2O + 6h+
3/2 O2 + 6H+
(requires 6 electrons)
Photo-splitting of water
2H+ + 2e-
H2
H2O + 2h+
24
25
eV
Has a bandgap of 2 eV
Fe2Ti2O7 Conduction band at 0.4 eV
compared to TiO2 (0.2 eV) high reduction
potential
VB (Fe2Ti2O7)
Band positions of Fe2Ti2O7
1.6
26
Mechanism
SC (h+,
SC + h
SC (h+,
e-) + H2O
SC (h+) + CH3CH2OH
SC + CH3HCOH
SC (e-) + H2O
N2 +
Had
e-)
SC + CH3HCOH + H+
SC (e-) + CH3CHO + H+
Photocurrent
doubling
27
2Had
Metal
Electron
affinity
(eV)
Ru
1.050
Rh
1.136
Pd
0.557
Pt
2.127
Fe
0.163
Ti
0.079
2NH3
28
29
30
eV
Polyfuran and polycarbazole - active
Reactivity order:
Carbazole > Furan > Thiophene
Band position change at TiO2-polymer
interface
Tomohisa O et al, J. Photopolym. Sci. Technol., 17 (1) (2004) 143
31
32
reducing radicals
HCOO- + h+
COO- + H+
RCH2OH + h+
RCHOH + H+
RCHOH + SC
RCHO + SC (e-) + H+
N2/NH3
33
34
High polarity:
Property
Viscosity Refractive
(g cm-1 s-1)
index
Polarity
Solvent
Methanol
0.544
1.326
0.60
Ethanol
1.074
1.359
0.54
1-Propanol
1.945
1.383
0.52
2-Propanol
2.038
1.375
0.48
1-Butanol
2.544
1.397
0.47
iso-Butanol
4.312
1.394
0.40
35
36
Mechanism
37
6 Ti3+-OH
6 Ti3+ + 3 H2O + 3/2 O2
6 Ti4+-OH + 2 NH3
38
Yields of ammonia
Not sufficient
Reasons
CB of photo catalyst
N2 adsorption
39
40
41
Ammonia reactants
Steam reforming
CH4(g) + H2O(g) CO(g) + 3 H2(g)
15-40% NiO/low SiO2/Al2O3 catalyst (760-816C)
products often called synthesis gas or syngas
Water gas shift
CO(g) + H2O(g) CO2(g) + H2(g)
Cr2O3 and Fe2O3 as catalyst
carbon dioxide removed by passing through sodium hydroxide.
CO2(g) + 2 OH-(aq) CO32-(aq) + H2O(l)
42
Biological N-Fixation
Most nitrogen is
fixed by microorganisms in the soil
which include
bacteria and
cyanobacteria.
44
N2
45
- viscosity of solvent
46
N2
N2H5+
E = - 0.23 V
N 2H 5 +
NH4+
E = + 1.275 V
N2
NH4+
E = + 0.275 V
47
Structures of polymers
48
49
50
51
Li
Be
Na Mg
K
Ca (Sc) Ti (V) Cr Mn Fe
Rb
Sr
Cs
Ba La (Hf) Ta W Re (Os) Ir
C
Co Ni Cu Zn
Zr Nb Mo (Tc) (Ru) Rh Pd Ag Cd
Pt Au Hg
Al
C
Si
Ga Ge
In Sn
Tl Pb
52
53
54
Free-living (asymbiotic)
Cyanobacteria
Azotobacter
Associative
RhizosphereAzospirillum
Lichenscyanobacteria
Leaf nodules
Symbiotic
Legume-rhizobia
Actinorhizal-Frankia
55
56
57
N2*
Physisorption
2 N 2* + *
2N*
3 N* + H*
NH* + *
4 NH* + H*
NH2* + *
NH2* +
H*
NH3* + *
6 NH3*
NH3(g) + *
Exothermic
58
59
60