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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)

Chain Branching: O + H2O  OH + OH


consume 1
radical

produce 2
radicals

Chain Propagation: OH + H2  H2O + H


consume 1
radical

produce 1
radical

Chain Termination: H + OH + M  H2O + M


consumption
of radicals

stable
species

Thermal Explosion

IIT Kanpur

Explosion: Very rapid (accelerating) reaction  positive feedback


Thermal explosion: Fast increase in overall reaction rate due
to temperature rise which in turn is caused by overall
exothermic chemical reactions
Exothermic reaction  leads to temperature rise 
increases reaction rates  rapid temperature rise  very
rapid reaction  explosion
Rate of heat released is greater than the rate of heat loss
Hydrogen-bromine reaction: no chain branching steps
(purely thermal explosion)

IIT Kanpur

H2 Br2 System

Global reaction
H2 + Br2  2HBr

,
298 = 0

298 = 30,910
,

,
298 =

closed system adiabatic


initially - Treac




36,300


 (298 ) = #$%& 



&

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

In one cycle: 1 radical (Br) is consumed and 1 radical (Br) is produced,


along with consumption of 1 molecule of H2 and 1 molecule of O2 and
production of 2 molecules of HBr
With increase in temperature (due to exothermic reaction) 
both propagation and initiation reactions become faster
no chain branching  we have purely thermal explosion

Chain Branching Explosion


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Chain branching explosion: Concentration of radicals can


increase significantly due to chain branching  causing rapid
consumption of reactants and formation of products
Chain branching  increase in number of radicals  increases
reaction rates  rapid increase in radical count  very rapid
reaction  explosion
Overall reaction rate increases tremendously if chain branching
dominates chain termination
Responsible for hydrocarbon flames being self propagating

IIT Kanpur

Global reaction

298
H2 + 0.5O2  H2O ,

H2 O2 System

= ,)
298 = 0


,)
298 = 241,845

 (298 ) = #$%& 






&

= 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)

closed system constant T and P


H2 + O2

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)

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Third limit

Pressure (mm-Hg)

1 atm

Gas termination dominates branching


H + O2  O + OH
H + O2 + M  HO2 + M

no-explosion

competing
reactions

high P

relatively stable
(terminates at wall)
HO2, unstable T > 600 C

Second limit

explosion

closed system constant T & P

Branching dominates
wall termination

H2 + O2
First limit

Temperature (C)

Wall termination dominates branching


~ T/P (very large)
H  wall

10

Flames
IIT Kanpur

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 in Premixed Flames


IIT Kanpur
Stoichiometric Methane+Air

explosion
fast chemistry

slow chemistry

Ignition source locally raises temperature


substantially  mixture state moves to
explosion regime  region of explosive
reactions can propagate  flame

burned

hot

cold

heat diffusion

unburned

Premixed fuel/oxidizer, say: methane/air, is


unreactive at room temperature and
ambient pressure

flame

radical (mass) diffusion

Heating of the unburned mixture  heat


diffusion from burned gas
Transport of the radicals to the unburned
mixture  mass diffusion from burned gases

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