3 - Chemical Kinetics V2020-02-18

Chap.
3
Chemical kinetics
1
Chap. 3 Chemical kinetics
Ø Introduction to chemical kinetics

Ø Global and elementary reactions
Ø Elementary reaction rates
ØBimolecular reactions and collision theory
ØUnimolecular and termolecular reactions
Ø Multistep reactions
ØNet production rates
ØCompact notation
ØRate coefficients and equilibrium constants
ØSteady state approximation
ØMechanism for unimolecular reactions
ØChain and chain branching reactions
ØChemical time scale 2
Introduction to chemical kinetics(1)
What problems does chemical thermodynamics solve ?
gas oven，
Fuel combustion
IC engine，
oxidizer product
alcohol
burner… Outlet
Inlet condition： condition:
temperature,
equilibrium
specie, heat
release…
What problems does chemical kinetics solve ?
3
ØThermodynamics:
ØThermodynamics laws relate the initial states of the
chemical reactive system to its final equilibrium state;
ØIt does not distinguish the path and time in the
process;
ØIf one assumes the reactions are fast compared to the
other processes, like diffusion, heat conduction, and
flow,
Øthen, thermodynamics describes the system locally.
ØHowever
4
ØChemical kinetics:
ØIn most combustion cases, however, chemical reactions
are not significantly faster (chemical time scale) than
the flow and transport process(physical time scale).
ØChemical kinetics then describes the paths and rates of
individual reactions and reactants;
ØThe reactive system can be extremely complex with
more than 103 intermediates and 104 elementary
reactions.
ØChemical reaction rates control pollutant formation,
ignition and flame extinction in most combustion
processes. 5
6
ØBasic concepts in chemical kinetics:

ØReaction rate and law of mass action:
ØThe speed of a particular reaction.
ØIt quantifies how fast or slow a reaction takes place.
ØPhysically, it measures the rate of change in the reactant
concentration per unit volume.
(3.1)
(3.2)
The unit: mole.cm-3s-1

Reaction rate proportional to product
concentrations 7

ØReaction rate:
ØRate of change of a particular species mole concentration
ØPositive value in a general cognition
ØChange in [M] DOES not necessarily mean there is a
reaction
(3.1)
Reaction rate =
8

ØReaction rate:
9

ØReaction rate:
10

ØLaw of mass action:
ci =[Mi]
11

ci =[Mi]
12

ci =[Mi]
Question: What is the

expression for the
reverse reaction?
13

ØReaction rate constant:
Øk (T) in Eq.(3.2) is the proportionality constant, which is
only temperature dependent (later we will show that for
some particular reaction it is also pressure dependent), we
call it reaction rate constant.
ØThe unit of depends on the reaction order.
Reaction rate =
14

ØReaction rate constant: Typical rate constant expressions:
15
ØReaction rate constant: The activation energy
16

ØReaction order:
ØThe unit of reaction rate depends on the reaction order.
ØThe reaction order is not necessarily the stoichiometric
coefficient of the reaction, but it is with respect to the
given substance and defined as the exponent to which its
concentration term in the rate equation is raised.
(3.2)
17

ØReaction order:
ØReaction order of Eq.(3.1) with respect to reactant F is n,
with respect to reactant Ox is m; and the overall reaction
order is m+n .
ØIf the reaction is elementary reaction, then m=a, n=1
18

ØChemical kinetics:
ØPart of physical chemistry
ØIt studies reaction rates
19

ØCompact notation
Global and elementary reactions(1/6)
ØGlobal reaction:
ØE.g. CH4+2O2=CO2+2H2O
ØThis is an example of global or overall reaction.
ØGenerally, the kinetic mechanism of an overall reaction
involves a mole of oxidizer with 1 mole of fuel to form
b mole of products. (3.1)
ØThe rate of this reaction is:

Reaction rate =
21
ØWhere[M] represents the concentrations of species M,

with a typical unit of kmol/cm3.
Ø kG(T) is the global rate coefficient.
Ø n and m relate to the reaction order.
ØAccording to Eq. (3.2), the reaction is
Ønth order with respect to fuel
Ømth order with respect to fuel
Ø(m+n)th overall order
Ø m and n are determined experimentally, thus they are
not necessarily integers.
22
ØThe one step overall reaction provides some physical basis
for understanding the combustion process, like one can
experimentally correlate the overall reaction rate with the
combustion parameters in an Arrhenius manner.
wG ~ f 2  (l / C p ) Le  exp( Ea / R0Tad )
Øf ,the mass burning flux; Cp, specific heat;
Øl , the thermal conductivity; Le, Lewis number;
ØEa, global activation energy; Tad, adiabatic flame temperature.
ØHowever, to express the chemistry, the one step overall
reaction is usually a black box approach because it does
not actually express what is happening.
23
ØConsidering the global reaction:
(3.3)
ØIt implies that two moles of hydrogen molecules react

with one mole of oxygen to form 2 mole of water, which is
too ideal and not strictly true, and seldom or never
happens in real combustors
ØIn reality, many sequential processes occur that involve
several intermediate species:
(3.4)
(3.5)
(3.6)
(3.7)
24
ØThe above elementary reactions, among others, are important

in conversion of H2 and O2 to water.
ØRadicals, or free radicals, are reactive molecules, atoms that
have unpaired electrons.
ØTo have a complete scheme of the combustion of H2 and O2, a
lot of more elementary reactions need to be considered.
ØA reaction mechanism is the collection of elementary reactions
to describe the overall reaction.
ØReaction mechanism may involve a few or hundreds or
thousands of elementary reactions and it is the state of the art
technique for combustion study.
25
ØElementary reaction:
Ø An elementary reaction is a
chemical reaction in which one or
more of the chemical species react
directly to form products in a
single reaction step and with a
single transition state
Ø The advantages of using the elementary reaction:
Ø Reaction order is constant and can be
experimentally determined.
Ø Number of species that form the reaction is clear
Ø Unimolecular
Ø Bimolecular
Ø Trimolecular/termolecular 26

ØCompact notation
ØChain and chain reactions
Bimolecular reactions and
collision theory(1/12)
ØBimolecular reactions and collision theory:
ØMost combustion related reactions are bimolecular
(3.8)
ØThe reaction rate of this elementary reaction:
(3.9)
ØAll bimolecular reactions have the order of 2;

ØThe reaction rate of bimolecular reaction is proportional to
the concentration of either reactant and the rate constant,
which is temperature dependent.
ØThe concepts of wall collision frequency, the mean molecular
speed, and the mean free path are needed to understand the
rate constant, based on the collision theory. 28
ØConsidering a single molecule of diameter s, travelling at a
velocity n, and experiencing collisions with identical, but
stationary molecules.
ØThe moving molecule sweeps out a cylindrical volume of
πns2Δt.
ØFor random distribution of stationary molecules with
number density n/V , number of collisions
(3.10)
ØMaxwellian velocity distribution for all molecules
(3.11)
29
ØEq. (3.11) applies for identical molecules, for different
molecules, sAB=(sA+sB)/2
(3.12)
which expresses the frequency of collisions of a single A molecule

with all B molecules
ØFor all A molecules
(3.13)
ØIf we express the molecular speed in terms of temperature,

we have
30
(3.14)
where kB is the Boltzman constant = 1.381E-23 J/K;

m here is the reduced mass = mAmB/(mA+mB);
T is the absolute temperature.
31
ØWe can relate the collision frequency to the reaction rate
or (3.15)
The first, second and the third factor in Eq.(3.15) is respectively the
collision frequency, ZAB/V, the probability that a collision leads to reaction
and the inverse Avogadro constant (6.022E26 molecules/mole) 32
ØThe probability that a collision leads to reaction has two
factors:
① An energy factor,
which expresses the fraction of
collisions that occur with an energy
a
above the activation energy
② A geometric or steric factor p, that takes into account the geometry
of collisions between A and B
33
34
Possible collisions
35
The collision energy is higher than Ea
Effective collisions
The geometry of the collision
36
ØNote nA/V=[A]NAV, nB/V=[B]NAV, substituting Eq.(3.15)
(3.16)
Ea
ØComparing Eq.(3.16) with Eq.(3.9)
Eaa
(3.17)
37
ØCollision theory does not provide any means to determine
the activation energy or the probability factor.
ØMore advanced theories do allow calculation of k(T) to a
limited extent.
ØIf the temperature range is not too large, kbimolec can be
expressed by the semi-empirical Arrhenius form
Eaa
(3.18)
where A is a constant called pre-exponential factor or

frequency factor
38
ØCollision theory does not provide any means to determine
the activation energy or the probability factor.
ØMore advanced theories do allow calculation of k(T) to a
limited extent.
ØIf the temperature range is not too large, kbimolec can be
expressed by the semi-empirical Arrhenius form
Eaa
(3.18)
where A is a constant called pre-exponential factor or

frequency factor
39
ØUnder most circumstances, the experimental values for
rate constants in the Arrhenius form are expressed as,
Eaa
ØWhere A, b and Ea are three empirical parameters

ØThe standard method for obtaining Ea is to graph
experimental rate constant data versus the inverse
temperature, i. e., log k~1/T, the slope being Ea/Ru
40
Unimolecular reactions(1/10)
ØInvolves single species

(3.20)
(3.21)
ØExamples:
ØFirst order only at high pressure limit
ØHowever,
Why???, and what is [M] ?
41
ØHowever, the unimolecular reaction is 2nd order in nature

ØThe reason is that,
ØA unimolecular reaction describes a chemical process in which a
reactant undergoes an isomerization or decomposition process.
ØSufficient energy required to activate the reaction, the only way is
intermolecular energy transfer through collision with another
molecule.
ØAn arbitrary species M is added to the reaction, as in
A+M*→A* + M
ØUnimolecular reactions are of critical importance to

combustion. e.g., during methane ignition, CH4+M →CH3+H+M
is often the initiation reaction of radical chain processes. 42
ØFurthermore, the reverse of a unimolecular decomposition
reaction is precisely a radical-radical or radical-molecule
recombination reaction, with M being the third body. These
recombination reactions tend to slow down the reaction by
removing the radicals.
ØHigh and low pressure limit
ØAt fixed temperature, the rate constant varies with pressure.
d [A]
 =  k[A] (L1)
dt
 k  k  = constant as p  
 First  order reaction
Pressure fall-off
 k  k 0 p ~ k 0 [M]as p  0
 Second  order reaction 43
ØLindemann-Hinshelwood theory:
ØPhenomenologically captures the fall-off behavior of a
unimolecular rate constant.
ØIt states that stable molecules cannot spontaneously
break up into products in the manner of Eq.(3.20), the
reactant A must attain sufficient energy to undergo
reaction.
① The process of forming an energized molecule, A*, involved
collisions between A and another molecule M.
② A* may undergo a unimolecular reaction to form products,
③ or it may undergo de-energization by collision with other
molecules.
44
ØLindemann-Hinshelwood theory:
45
ØLindemann-Hinshelwood theory :
ØThe above three processes ban be depicted as,
k1, f k2
* *
A+M A +M (L2) *
A B (L3)
k1,b
Ø The reaction rate based on A and A*, are respectively

given by,
d[A]
=  k1,f [A][M]+k1,b [A * ][M] (L4)
dt
d[A* ]
=k1,f [A][M]  k1,b [A * ][M]  k2 [A * ] (L5)
dt
46
ØTypically, the energized molecule is formed steadily,
invoking the steady state assumption for [A*], that is
setting d[A*]/dt=0, we have
k1,f [A][M]
(L6)
*
[A ]=
k1,b [M]+k2
Ø Putting Eq.(L6) in to Eq.(L4) and rearranging,

d[A] k2 k1,f
= [A] (L7)
dt k1,b + k 2 /[M]
such that the rate constant in Eq.(L1) is,
k2 k1,f
k= (L8)
k1,b + k2 /[M] 47
ØSince any molecule can participate in the de-energizing
process, and if it assumed that only a single collision is
needed to de-energize A*, and [M]~ gas density ~
pressure, thus,
 k = k 2 (k1,f / k1,b ); high pressure limit[M]  ;1 storder 
k2 k1,f  
k= = k 0 = k1,f [M]; low pressure limit[M]  0; 2 nd order 
k1,b + k2 /[M]  
 k k0 /(k0 + k ); 1/ k = 1/ k + 1/ k0 
48
k = k2 (k1,f / k1,b );high pressure limit[M] ;1st order 
 
k = k0 = k1,f [M]; low pressure limit[M]  0; 2nd order 
p1/2~[A]1/2=k∞/k1,f k k /(k + k ); 1/ k = 1/ k +1/ k 
  0 0   0 
Ø Lindemann theory qualitatively explains the variation of unimolecular reaction

rate constant as a function of pressure.
Ø However,
① quantitatively, the theory is not able to capture the transition pressure, p1/2; experimental value is
several orders smaller than the calculated one(obtained from experimentally measured k∞ and k1,f);
② 1/k~1/k0~1/[M] such that, however, the experimental results actually is not linear;
③ higher order theory needed to address these weaknesses. Such as RRK theory, RRKM theory, etc.
49
ØTroe fall-off formula:

k (T )k0 (T , p)
k (T , p)= F (T , p)
k0 (T , p) + k (T )
ØExtension of Lindemann’s treatment on the rate

constant dependence on pressure;
ØThe Troe’s fall-off formular is the most widely used
representation of the unimolecula reaction rate
constant;
ØIt corrects the Lindemann fall-off by a pressure
dependent factor called broadening factor F(T, p);
ØThough there is not much theoretical development for
the broadening factor, it is usually empirically
expressed as , 50
ØTroe fall-off formula(cont’d):

log10 Fc (T )
log10 F (T , p)= 2
 log10[k0 (T , p) / k (T )] + c 
1+  
 N  d log [k
10 0 (T , p) / k (T )] + c 
Fc(T) is the central broadening factor, empirically fitted as,
51
Termolecular reactions
ØTermolecular reactions
(3.24)
Typically, there reactions are three body termination

reactions. They involve the elimination of free radicals to
form stable species and the de-energization was realized by
collision with M, thus this kind of reactions are inhibition
reactions.
52
Description of Pressure dependence in
CHEMKIN (1)
ØPressure dependence rate expressions in

Chemkin:
53
CHEMKIN (2)

Chemkin:
54
CHEMKIN (3)

Chemkin:
55
CHEMKIN (4)

Chemkin:
56
CHEMKIN (5)

Chemkin:
ØTroe fall-off formula(cont’d):
k (T )k0 (T , p)
k (T , p)= F (T , p) (10)
k0 (T , p) + k (T )
57
CHEMKIN (6)

Chemkin:
(10)
58
CHEMKIN (7)
ØTroe fall-off formula :


ØCompact notation
ØChemical time scale
60
Multistep reactions(1/25)
ØNet production rate:

ØConsider some of the reactions in H2-O2 system
61
ØNet production rate(cont’d):

ØThe net production rate of the species Mi is the sum of
all the individual reaction rates producing Mi minus all
the rates destroying Mi.
Øe.g. The production rate of O2 is
(3.26)
62
ØNet production rate(cont’d):

Øe.g. The production rate of H is
(3.27)
63
ØCompact notation:
ØA mechanism may involve many elementary reactions
(totally L) and many species (totally N), a generalized
compact notation has been developed for the
mechanism and then the individual reaction rate.
ØFor the mechanism,
(3.29)
ØThus the reaction mechanism can be compactly noted

as the following matrix:
64
=8 =4
Mj Ri
65
ØThe stoichiometric coefficient matrices
66
ØNet production rate of Mj in a multistep reaction is

then,
(3.31)
Where
(3.32)
(3.33)
67
ØNet production rate of Mj in a multistep reaction is

then,
(3.31)
Where
(3.32)
(3.33)
is the rate of change of the jth species concentration

68
ØFor example, for the ith (i=1)reaction, qi=q1
(3.34)
69
ØSimilarly, write down qi for all the other

reactions, say, i=2, 3, …, L.
(3.33)
ØThe reaction rate with respect to the jth

species is then correspondingly summed up
as in Eq.(3.31)
70
ØRate coefficient and equilibrium constant

ØWhat is the relation between this two ?
ØAt equilibrium, forward and reverse reaction rates
must be equal, such that,
(3.35)
ØProduction(or consumption) rate of species A is,
(3.36)
ØAt equilibrium, rate of change of [Mi] must be zero. So,

71
(3.37)
ØRearranging Eq.(3.37)
(3.38)
ØPreviously we have defined the equilibrium constant

as,
N
pi ( vivi )
 （ 0）
i =1 P
= K p (T ), (3.39)
72
ØThe mole concentrations are related to the mole fractions
and partial pressure, as
(3.40)
ØWe can define an equilibrium constant based on the mole

concentrations, Kc to Kp
N
pi ( vivi ) N
[M i ]RuT ( vivi ) N ( vi vi ) Ru T (  vi  vi ) (3.41)
 （ 0）
i =1 P
= （
i =1 P 0
） =  [M i ]
i =1
( 0 )
P
ØWhere Kc is defined as
N
K c =  [M i ]( vivi ) (3.42)
i =1
73
ØComparing with Eq. (3.38)
k f (T )
Kc = (3.43)
kr (T )
ØIf the forward reaction rate is NUI Curran group
given, the reverse reaction rate is

to be calculated.
Ø That is the reason why some
investigated can just specify the forward
reaction rate constant in the , while
some mechanism developer prefer to
give the rate constant of the reverse GRI 3.0
reaction.
74
ØSteady-State Approximation
ØIn order to simplify the reactive system analysis, steady
state approximation to the reactive species or radicals
can be applied.
ØSteady-state approximation is justified when the
reaction forming the intermediate species is slow,
while the reaction destroying the intermediate species
is fast.
ØAs a result the concentration of the radical is small,
compared with the reactant and products.
75
ØExample: (Zeldovich mechanism for NO formation)
The first reaction is slow (rate limiting); the second one is fast.
ØNet production rate of NO:
ØAssume SS for N, d[N]/dt=0
76
ØChain and chain reactions

ØIn most reaction mechanisms there are present small
concentrations of highly reactive intermediate species
(radicals), which participate and are regenerated in a
sequence of reactions.
ØIt is through the participation of these species, called
the chain carriers, that the reactants are converted to
the products.
ØChain reactions can be further classified into straight-
chain and branched chain reactions.
77
Ø Straight chain reactions: the hydrogen-halogen system
Ø Hydrogen-halogen system has a direct reaction path of
(X0)
Ø Production rate of HX given by
where X2 =F2, Cl2,
Br2, or I2 (3.44)
Ø It is found that reaction between H2 and X2 to produce HX actually

follows a more complex scheme consisting of the following five
major steps:
78
Ø In the hydrogen-halogen system, reaction (X1f) is called chain
initiation reaction because the chain reaction is initiated through
the production of X atoms.
Ø Once [X] reaches a certain level, the production of HX is effected
by reactions (X2f) and (X3f) through the reaction intermediates,
also called chain carriers, H and X.
Ø These reactions are called chain carrying steps because in each of
them the destruction of one chain carrier lead to the creation of a
new chain carrier such that the number of chain carriers in each
step remains unchanged, and a closed sequence if formed.
79
Ø Reaction (X1b) and (X2b) are simply the backward reaction of (X1f)
and (X2f) . Reaction (X1b) is a chain termination step in which the
chain carriers are recombined through collision with the third body
M. Reaction (X2b) is a chain carrying step though it is inhibitive to
the net production rate of HX.
Ø The reaction rate with respect to the five components are give :
(3.45)
(3.46)
(3.47)
(3.48)
(3.49)
80
Ø Invoking the steady-state assumption by setting d[H]/dt=0,
d[X]/dt=0 and in Eqs.(3.47) and (3.48), solving for [H] and [X].
(3.50)
(3.44)
① The rate dependence on [H2] is still first power, the dependence on [X2] is
more involved for the chain mechanism.
② The chain mechanism also correctly predicts the inhibitive effect of
increasing product concentration on its own production rate.
81
Ø Branched chain reactions: H2-O2 system
Ø In straight chain reactions there is no net production of chain
carries for each cycle of reactions.
Ø There are, however, reactions in which there is a net generation
of chain carriers →extremely rapid rate of the overall reaction,
which may eventually culminate into an explosion.
Ø A well know example is the chain cycle in H2-O2 system.
Chain initiation
Chain branching
Chain carrying/ propagating
Chain termination
82
ØChemical time scale

ØThe chemical time scale (tchem) is important in combustion
because its comparison with flow time scale (tflow)
determines whether the problems can be simplified with
equilibrium assumption, especially in non-premixed flame
problems.
ØThe Damköhler number is a dimensionless number which
measures the ratio of the characteristic fluid time to the
chemical time.
t flow
Da =
t chem
83
Ø Damköhler number very large, →the fluid composition is very
close to chemical equilibrium (because reaction is so fast
compared to the time taken to mix with neighboring fluid.) →
models based on equilibrium assumption may be used with
confidence.
Ø However, in most turbulent flames, a range of turbulent time
scales → a corresponding range of Damköhler numbers.
Ø As Damköhler number decreases at any given physical
location(as a result of an increase in the local scalar dissipation
rate) → departures from equilibrium become significant and
may result in local extinction.
Ø If Damköhler number too small to sustain stable combustion in
a sufficiently large fraction of the fluid volume, → global
extinction occurs.
84
Ø tchem is defined as time required for concentration of A to fall
from its initial value to a value equal to 1/e times the initial value.
ØFor unimolecular reaction
ØBimolecular reaction
if
ØTermolecular reaction
if
85
Problems: chemical reaction time
(1/6)
chemical reaction time
Ø Prove the chemical time scale of unimolecular reaction,
bimolecular reaction and termolecular reaction is respectively
if
if
86
(2/6)
Ø For unimolecular reaction
use the definition of tchem
87
(3/6)
88
(4/6)
Ø For bimolecular reaction
(P_Bimo_tchem_0)
89
(5/6)
(P_Bimo_tchem_1)
(P_Bimo_tchem_2)
90
(6/6)
Substituting Eq. (P_Bimo_tchem_1) into Eq. (P_Bimo_tchem_0), and integrating,
(P_Bimo_tchem_3)
Substituting Eq. (P_Bimo_tchem_2) into Eq. (P_Bimo_tchem_3), and set:
gives,
(P_Bimo_tchem_4)
91
Problems: Steady state assumption
application
Problem 1:
93
Problems: Steady state assumption
application
Problem 2:
Invoking suitable S.S. A, show the concentration of the product HCl as a

function of Cl2 and H2w
94

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Chap.

Ø Introduction to chemical kinetics

What problems does chemical thermodynamics solve ?

What problems does chemical kinetics solve ?

ØBasic concepts in chemical kinetics:

The unit: mole.cm-3s-1

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

Question: What is the

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

ØBasic concepts in chemical kinetics:

Ø Introduction to chemical kinetics

ØThe rate of this reaction is:

ØWhere[M] represents the concentrations of species M,

ØIt implies that two moles of hydrogen molecules react

ØThe above elementary reactions, among others, are important

Ø Introduction to chemical kinetics

ØAll bimolecular reactions have the order of 2;

ØMaxwellian velocity distribution for all molecules

which expresses the frequency of collisions of a single A molecule

ØIf we express the molecular speed in terms of temperature,

where kB is the Boltzman constant = 1.381E-23 J/K;

The collision energy is higher than Ea

where A is a constant called pre-exponential factor or

where A is a constant called pre-exponential factor or

ØWhere A, b and Ea are three empirical parameters

ØInvolves single species

ØFirst order only at high pressure limit

ØHowever, the unimolecular reaction is 2nd order in nature

ØUnimolecular reactions are of critical importance to

Ø The reaction rate based on A and A*, are respectively

Ø Putting Eq.(L6) in to Eq.(L4) and rearranging,

Ø Lindemann theory qualitatively explains the variation of unimolecular reaction

ØTroe fall-off formula:

ØExtension of Lindemann’s treatment on the rate

ØTroe fall-off formula(cont’d):

Fc(T) is the central broadening factor, empirically fitted as,

Typically, there reactions are three body termination

ØPressure dependence rate expressions in

ØPressure dependence rate expressions in

ØPressure dependence rate expressions in

ØPressure dependence rate expressions in

ØPressure dependence rate expressions in

ØPressure dependence rate expressions in

ØTroe fall-off formula :

Ø Introduction to chemical kinetics

ØNet production rate:

ØNet production rate(cont’d):

ØNet production rate(cont’d):

ØThus the reaction mechanism can be compactly noted

ØThe stoichiometric coefficient matrices

ØNet production rate of Mj in a multistep reaction is