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Elementary Reactions
IIT Kanpur
Hydrocarbon Combustion
Reaction type
Concentration
Rate
Reactant A Reactant B Reactant A Reactant B coefficient
Reaction
rate
molecule
molecule
large
large
very small
small
molecule
radical
large
small
Intermediate
large
radical
radical
small
small
large
small
A + B products
reaction rate = k[A][B]
k = ATbexp[-EA/(RuT)]
molecule + radical fast reaction
important
Chain Reactions
reactant
product
chain 1
reactant
product
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stable species radical radical radical first radical stable species
termination
initiation propagation branching
second radical stable species
Chain Initiation: H2 + M H + H + M
stable
species
chain 2
reactant product
formation of
radical(s)
produce 2
radicals
produce 1
radical
stable
species
Thermal Explosion
IIT Kanpur
IIT Kanpur
H2 Br2 System
Global reaction
H2 + Br2 2HBr
,
298 = 0
298 = 30,910
,
,
298 =
36,300
&
Reaction mechanism
Br2 + M Br + Br + M
= 103,510 (
H2 + Br2
exothermic
(initiation)
chain carriers:
H and Br
Br + H2 H + HBr
H + HBr H2 + Br
H + Br2 HBr + Br
(propagation)
(propagation, inhibition)
(propagation)
Br + Br + M Br2 + M
(termination)
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H2 Br2 System
Br2 + M Br + Br + M
reactant
product
Br + H2 H + HBr
reactant
product
1
H + Br2 HBr + Br
reactant
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Global reaction
298
H2 + 0.5O2 H2O ,
H2 O2 System
= ,)
298 = 0
,)
298 = 241,845
&
= 241,845 (
exothermic
Reaction mechanism
H2 + O2 HO2 + H
(initiation)
H + O2 O + OH
O + H2 H + OH
H2 + OH H2O + H
H2O2 + M OH + OH + M
HO2 + H2 H2O2 + H
H2O2 + M OH + OH
relatively
H wall
unreactive
H + O2 + M HO2 + M
(branching)
(branching)
(propagation)
(branching)
(termination)
(termination)
chain carriers:
H, O and OH
H2 O2 System
H2 + O2 H + HO2
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reactants
1
H2 + OH H2O + H
H + O2 O + OH
reactant
product
2
O + H2 H + OH
reactant
product
3
H2 + OH H2O + H
reactant
In one cycle: 1 radical (H) is consumed and 3 radicals (H) are produced
along with consumption of 2 molecules of H2 and 1 molecule of O2 and
production of 2 molecules of H2O
If branching is not suppressed by termination reactions, the radical
concentration will build up geometrically
isothermal system we have purely chain branching explosion
H2 O2 Explosion Behavior
Branching dominates termination
reaction
HO2 + H2 H2O2 + H
becomes
OH + OH
active
Equivalence ratio (
= 1)
IIT Kanpur
Third limit
Pressure (mm-Hg)
1 atm
no-explosion
competing
reactions
high P
relatively stable
(terminates at wall)
HO2, unstable T > 600 C
Second limit
explosion
Branching dominates
wall termination
H2 + O2
First limit
Temperature (C)
10
Flames
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Flame:
o Self-sustaining propagation
o Localized combustion zone (occupies only a small portion
of the combustible mixture at any point of time)
o Subsonic velocity
Premixed Flame: Reactants are perfectly mixed at molecular
level before chemical reaction (e.g. bunsen burner)
Diffusion Flame: Reactants diffuse into each other during
chemical reaction (e.g. candle)
11
explosion
fast chemistry
slow chemistry
burned
hot
cold
heat diffusion
unburned
flame