MECH 6120: Combustion
Notes on Chemical Kinetics and
Chain Reactions
1 Chemical Kinetics
Thermodynamics is all one needs to predict the equi-
librium state that a system reaches following a pro-
cess and the heat/work transfers that occur during
the process. Thermodynamics, however, cannot pre-
dict the rate at which a process will occur, i.e., the
speed at which a system reaches a new equilibrium
state. For example, we could have a coffee cup ini-
tially at 50◦ C, surrounded by an ambient at 22◦ C.
Thermodynamics will tell us that heat will flow from
the cup to the environment and that the final state
has the cup in equilibrium with the environment (2nd
law). It can also tell us how much heat was trans-
ferred (1st law). It cannot tell us how long it took
the coffee to cool down. To predict this, we would
need to know how the rate of heat transfer depended
on the temperature difference between the cup and
the environment (i.e., Newton’s law of cooling).
Likewise, Thermodynamics can predict the chemi-
cal equilibrium state when all reactions (forward and
backwards) are in balance. For example, say we have
a system of O and O2 in equilibrium. The equilib-
rium condition implies that the rate of O formation
by the forward reaction;
O2 → 2O
is balanced by the rate of destruction of O by the
reverse reaction;
2O → O
Thermodynamics cannot predict how fast either of
these reactions will occur – it can only predict the
state when they are in balance.
The topic of chemical kinetics deals with reaction
rates. Obviously, we would need to know something
about reaction rates to predict many types of com-
bustion phenomena, i.e., the rate at which gasoline
vapor is consumed in a cylinder, the speed of flame
spread over a combustible surface, etc.
1
By reaction rate, we mean
change in moles of species
Rate =
unit time × unit volume
Since the number of moles per unit volume is equiv-
alently a concentration C of the species, the reaction
rate of species i, denoted Ri , corresponds to
dCi
Ri = , moles/cm3 · s
dt
From the reaction, we can gather how the reaction
rates for the various species are related. For example,
consider
CH4 + 2O2 −→ CO2 + 2H2 O
The reaction rates for the products would be positive,
and they would be negative for the reactants. And
by the stoichiometry of the reaction;
1 1
RCH4 = RO2 = −RCO2 = − RH2 O
2 2
which follows because for every mole of methane, we
consume 2 moles of O2 and create 1 mole of CO2 and
2 moles of H2 O.
1.1 Elementary vs. Overall Reactions
Overall (or, equivalently, global ) reactions describe
the overall conversion of a set of reactants to a set
of products. These are the type of reactions we have
been dealing with so far, i.e.,
CH4 + 2O2 −→ CO2 + 2H2 O
describes the stoichiometric, complete–combustion
oxidation of methane. This reaction does not rep-
resent the actual molecular event that takes place in
the process. That is, a molecule of methane does not
run into a molecule of oxygen to form one CO2 and
two H2 O molecules (perhaps this could occur, but it
would be very, very unlikely). In reality, the oxida-
tion process involves a chain of elementary reactions,
in which an elementary reaction is the actual molec-
ular reaction event.
 Most elementary reaction can be classified as uni- where A, B, C, and D correspond to arbitrary
molecular, bimolecular, or trimolecular. The molec- species. The overall reaction rate, which is given by
ularity of a reaction is defined as the number of
dCA dCB dCC dCD
molecules taking part in each act leading to a chem- R=− =− = = (6)
ical reaction. For example, at high temperatures dt dt dt dt
propane can decompose via is by the law of mass action equal to

C3 H8 −→ C2 H5 + CH3 (1) R = kCA CB (7)

The molecularity of the above reaction is one (uni- In the above, Ci is the molar concentration of species
molecular) because only one molecule is required for i (kmol/m3 or mol/cm3 ). Note that Turns uses the
the reaction to occur. Examples of bimolecular reac- notation [A], [B], etc. to denote concentration. Since
tions are the attack of H2 by the hydroxyl radical; we are assuming ideal gases, the concentration is re-
lated to the partial pressure of the species by
H2 + OH −→ H2 O + H (2) Pi
Ci = (8)
Ru T
and the attack of methane by the hydrogen radical;
The quantity k in Eq. (7) is referred to as the rate
CH4 + H −→ CH3 + H2 (3)
‘constant’ of the reaction, and it has whatever units
are neccessary for the reaction of interest to allow the
Finally, an example of a termolecular (molecular- rate to be in units of mole/cm3 ·s. In the above reac-
ity=3) reaction is tion, for example, k would have units of cm3 /mole·s.
In general, k will be a strong function of the temper-
H + OH + M −→ H2 O + M (4) ature, but is independent of the concentrations.
In general, for the reaction
In the above, M refers to an arbitrary third–body
molecule, and serves the purpose of either carrying XN XN
away or providing energy in the reaction. In the νi0 Mi −→ νi00 Mi (9)
above reaction, the reaction of H with OH is highly i=1 i=1
exothermic. If a third body was not present to take we write, by the law of mass action, the reaction rate
away the energy released during the reaction, the by,
H2 O molecule that was formed would simply fly apart N
Y
back into H and OH. ν0
R=k Ci i (10)
i=1

1.2 Law of Mass Action
A fundamental principle in predicting the reaction
rate is the law of mass action, which states:
The rate of an elementary chemical reac-
tion is proportional to the active masses of
the reacting substances. The active masses
are the species concentrations raised to their
stochiometric coefficients.
To illustrate, consider the simple elementary reac-
tion
A + B −→ C + D (5)
The changes in concentration of the species due to
the reaction are
dCi
≡ Ri = (νi00 − νi0 )R (11)
dt
Molecularity precisely applies only elementary (or
single-step) reactions. Often, however, the formation
of a product species from reactants occurs not from
a single, elementary reaction but from a sequence of
reactions. For example, in the conversion of hydrogen
and bromine to hydrogen bromide, the reaction
H2 + Br2 −→ 2HBr (12)

2
refers to the overall process. The actual process which can also be solved analytically.
actually consists of a series of intermediate reac- Most chemical reactions are bimolecular and pro-
tions – which ultimately result in the formation of 2 ceed as the result of reactions following binary col-
molecules of HBr and the destruction of one molecule lisions. It is therefore not surprising that chemical
of Br2 and one molecule of H2 . It is therefore not en- reactions frequently follow second-order kinetics. For
tirely meaningful to assign a molecularity of 2 to the the general second-order bimolecular reaction,
above reaction.
It is more convenient and meaningful to classify k AB
A + B −→ (20)
overall reactions by order rather than molecularity.
The order of a reaction is the number of atoms or the rate law will be
molecules whose concentration determines the rate of
dCA dCB dCAB
conversion to products. From the law of mass action, = =− = −kCA CB (21)
one would predict the order to be equal to the molec- dt dt dt
ularity assigned to the reaction. This will be true for The initial conditions would have CA = CA,0 , CB =
elementary reactions, but is not always the case for CB,0 , and (most likely) CAB = 0 at time t = 0. So-
overall reactions. Most often, the order of a reaction lution of this set of equations is fairly simple. If we
is determined from experimental observations. integrate over time the left hand side of the above
All unimolecular elementary reactions involving DE, we get
decomposition (or dissociation) will have first-order
rate kinetics. For example, the reaction CA (t) − CA,0 = CB (t) − CB,0 (22)

k1 or
A2 −→ 2A (13)
CB (t) = CA (t) + CB,0 − CA,0 (23)
will have a rate law of Put this back into the DE for A, and
dCA dCA2
= −2 = 2k1 CA2 (14) dCA
dt dt = −kCA (CA + CB,0 − CA,0 )
dt
with typical initial condition of = −kCA2
− k(CB,0 − CA,0 )CA (24)
CA2 (0) = CA2 ,0 , CA (0) = 0 (15) There are two special cases in which the solution to
the above is easy. First, if we start off with equal
Integrating the first two terms in Eq. (14) gives
concentrations of A and B, then the second term in
2(CA2 ,0 − CA2 (t)) = CA (t) (16) the left hand side disappears. Integrating leads to
· ¸−1
and integrating the last two terms (assuming that k 1
CA = + kt (25)
is constant) gives a solution for the concentration of CA,0
A2 ;
CA2 = CA2 ,0 e−k1 t (17) The second case is when CB,0 À CA,0 , i.e., A is a
trace compound in B. The second term in Eq. (24)
Likewise, the reaction now dominates, and the reaction becomes effectively
k2 first–order, i.e.,
AB −→ A+B (18)
dCA
≈ −k(CB,0 − CA,0 )CA , CB,0 À CA,0
will have dt
dCA dCB dCAB under which CA will undergo an exponential decay.
= =− = k2 CAB (19)
dt dt dt When CB,0 and CA,0 are similar yet not equal, we

3
need to integrate the full form of Eq. (24). This can
be done analytically, although there is no need to do
it here. Suffice to say that it can be done.
Third order elementary reactions are less common
than bimolecular reactions – simply because they re-
quire the simultaneous collision of three molecules.
Although there are plenty of reactions to which we
could assign a molecularity of three, e.g.,

2NO + O2 −→ 2NO2 (26)

3H −→ H2 + H (27)
2CO + O2 −→ 2CO2 (28)

the rate laws will usually be described by orders

around 2. Again, this is because the above reactions
refer to overall processes consisting of a number of
elementary, usually bimolecular reactions. The most
relevant trimolecular (i.e, third order) elementary re-
actions for combustion phenomena are the radical
recombination reactions, such as H + OH + M −→
H2 O + M. The importance of these will be discussed
in a subsequent section.
Sometimes a reaction does not have a rate law to
which an order can be assigned. For example, it is
known that the H2 – Br2 reaction mentioned previ-
ously has a rate law of the form,
1/2
dCHBr kCH2 CBr2
= (29)
dt CHBr
1+ 0
k CBr2
where k and k 0 are constants. If CHBr ¿ k 0 CBr2 ,
the order is 3/2 – whereas mass action would predict
an order of 2. If this inequality does not hold, the
reaction has no order – in that the order cannot be
defined.
1.3 Temperature Dependence of the
Rate Constant
The most widely used formulation for the temper-
ature dependency of the rate constant k resulted
from the experimental and theoretical investigations
of Svante Arrhenius (1859-1927). His experiments
consisted of measurements of species concentration
Figure 1: Arrhenius’ plot of ln(k) vs 1/T showing
the straight–line behavior
vs. time for reactions occurring at constant temper-
atures, from which the rate constant kn for an nth -
order reaction could be obtained. When he plotted
ln kn vs. 1/T , where T is the temperature at which
the reaction took place, he obtained the straight-line
behavior illustrated in Fig. 1.
From such plots, Arrhenius deduced that the rate
constant could be expressed in the form
k = A e−E/Ru T (30)
where the constants A and E are referred to as the
preexponential factor and the activation energy.
The theoretical foundation behind Eq. (30) is
fairly straightforward. It is known that the energies
of molecules (kinetic, rotational, vibrational, elec-
tronic) form a distribution – in that some molecules
have more energy than others. Arrhenius reasoned
that only molecules possessing an energy equal to
or exceeding a certain activation energy E would,
upon collision with other molecules, react to form
a new molecule. From the kinetic theory of gases,
the fraction of molecules having this energy is
exp(−E/Ru T ). Note that as T → ∞, the fraction
goes to unity – because as temperature increases,
so do the energies of the molecules, and more and
more molecules would have an energy in excess of E.

4
The second factor that comes into the theory is the In the above, A is a constant, and the exponent n
collision rate between the different molecules. For a accounts for the temperature dependence in the pre-
second-order reaction involving species A and B, the exponential factor. Turns has a listing of the param-
collision rate between molecules of A and B will be eters A, n, and E many elementary reactions involv-
related to the species concentrations by ing hydrocarbon species (see, e.g., Table 4.1, Tables
5.1—5.3). The data listed in the book was obtained
collision rate = A0 CA CB (31) from many sources – experimental and theoretical.
In these tables, some of the listed reactions have E
The factor A0 is a weak (≈ T 1/2 ) function of tem- (and perhaps n) equal to zero – indicating that the
perature. The reaction rate would be expected to reaction rate constant is nearly independent of tem-
be simply the fraction of molecules having adequate perature. In reactions of this type, basically there
energy to react times the collision rate. However, is no energy ‘barrier’ to overcome to form a prod-
not all collisions fulfilling the energy requirement will uct. That is, the reactants molecules are so reactive
result in a reaction. For many types of molecules, (i.e., unstable), that if they collide at all a reaction
the orientation of the colliding molecules with respect is assured. An example is the radical recombination
to each other is an important factor in determining reaction of H to form H , in which
2
whether or not a reaction will occur. The orientation
dependency is included in the reaction rate formula- H + H + M −→ H2 + M ∗ (34)
tion through a so-called steric factor P, which can be
The radical species H are very reactive – we will see
viewed as a sort of collision efficiency. Putting it all
in the next set of notes that the formation of these
together, the reaction rate can be written
species is a key element in combustion reactions. The
0
R = A CA CB e −E/Ru T
P = k C A CB (32) reaction between H and H is also very exothermic
– and a ‘third body’ – such as a wall or another
in which k is given by Eq. (30), with A = A P 0 molecule – is needed to carry away the energy that
Generally, the more exothermic a reaction is, the is released during the reaction. This third body is
∗
smaller the activation energy E. And for small E, the represented in the above by M , and M denotes that
reaction is more sensitive to temperature. It is also the third body has been energized by the reaction. If
important to note that while the Arrhenius formula- the third body is not present, the H2 molecule would
tion accurately predicts the rates of simple reactions receive the energy of reaction, and likely dissociate
over a moderate temperature range, it generally can- again into H + H.
not describe overall combustion processes over a wide
temperature range – because at different tempera- 1.4 Chemical Kinetics and Chemical
tures, different reactions involved in the combustion Equilibrium
process will become more or less dominant in deter-
mining the overall rate. For example, a rate constant Up to now we have examined the rate of a single re-
of a reaction could be obtained from a set of mea- action as it proceeds in a single direction (reactants
surements at relatively low temperatures. At higher to products). For most combustion situation, there
temperatures, however, measurements could result in will be more than one reaction occurring simultane-
a completely different rate constant. Therefore, one ously. The topic of chain reactions, which is a key
must exercise caution when extrapolating a specific element in initiating and sustaining combustion, will
reaction rate to broad temperature ranges. be covered in a subsequent section. What we want to
In reporting data on reaction rate constants for el- examine now is a reaction that can go ‘both ways’,
ementary reactions, often a modified Arhennius form i.e., forward and backwards, and relate this to what
is used, in which we know about chemical equilibrium.
Consider the simple situation in which A decom-
k = AT n e−E/Ru T (33) poses to B and C, and simultaneously B and C

5
recombine back to A. This sequence is known as When the reactions are in balance – leading to the
reversible reactions. The equations governing the equilibrium concentration relation in Eq. (41) – we
concentrations would be get essentially the same relation that we would pre-
kf dict from chemical equilibrium. Since the reactions
A −→ B + C (35) are balanced, we could view the pair of reactions af-
fecting A, B and C as an equilibrium reaction,
kr
B + C −→ A (36)
A*
)B+C (42)
Since A is destroyed in the first reaction and created
for which
in the second, the net rate change of A is PB,e PC,e
= KP (T ) (43)
dCA PA,e P∅
= −kf CA + kr CB CC (37)
dt where the extra e subscript denotes that the partial
By writing a rate law for B or C, we’ll get the same pressures are at their equilibrium values (which is
thing – except negative, something we always assumed solely in the context of
thermodynamics) and P∅ is the standard state pres-
dCB dCC dCA sure of 1 atm. This equation looks similar to Eq. (41).
= =− (38)
dt dt dt In fact, if we use the ideal gas law (our species are all
assumed to be ideal gases), then
which should make sense because the net rate of B
and C formation has to balance the net rate of A PA
destruction. CA = (44)
Ru T
Suppose that the initial concentrations of B and C
are zero. The above then gives That is, concentration (kmols/m3 ) is a molar den-
sity. Replace the above into Eq. (41) and compare to
CB (t) = CC (t) = CA,0 − CA (t) (39) Eq. (43), and we find that for this particular reaction
where CA,0 is the initial concentration of A. The rate Ru T kf
law for A then becomes KP (T ) = (45)
P∅ kr
dCA
= −kf CA + kr (CA,0 − CA )2 (40) This provides a nice physical interpretation of the
dt
equilibrium constant KP , i.e., it is proportional to
which we could (in principle) integrate to obtain the the ratio of the characteristic rates (i.e., the rate con-
solution for CA at all times. For now, however, we stants) of the forward and reverse reactions in an
want to simply get the value of CA for t −→ ∞, i.e., equilibrium reaction. If we have a situation where
the steady–state, or equilibrium, value of the concen- the forward reaction is a lot ‘faster’ than the reverse,
tration. Equilibrium occurs when the reactions are we would then have kf À kr and KP À 1. From
in balance: the net rate of formation of A (by the re- Eq. (43), we would then expect PB,e and PC,e À PA,e
verse reaction) is balanced by the net rate of destruc- because the forward reaction, being so much faster
tion (by the forward reaction) so that dCA /dt = 0. than the reverse, would result in little of A being
Applying this to Eq. (37) gives, for the equilibrium around – it would react to form B and C.
concentrations, For a general equilibrium reaction involving a pair
CB,e CC,e kf (forward and reverse) of elementary reactions, the
= (41) equilibrium constant is related to the rate constants
CA,e kr
by
µ ¶∆ν
in which the subscript e denotes the equilibrium Ru T kf
value. KP (T ) = (46)
P∅ kr

6
in which ∆ν is the change in the number of molecules
in the forward direction. For our example we had
∆ν = 1 (i.e., started with 1 (A), ended with 2 (B
and C). This relationship is very useful: if we can
use experiments and/or kinetic theory to determine
a forward rate constant, then this information, along
with thermodynamics, will provide the rate constant
for the reverse reaction.
2 Chain Reactions
As mentioned in the notes on kinetics, few combus-
tion processes consist of a single elementary reaction,
and the overall reaction equation seldom represents
the detailed mechanism of the actual chemical reac-
tion. In reality several reactions may proceed simul-
taneously or in sequence. The intermediate species
(i.e., the species not appearing in the overall reac-
tion) produced and consumed in such reactions are
important in determining the overall order of the re-
action.
A chain reaction occurs, as the name implies, in
a chain or sequence of steps. Often the most seem- 2.1 Chain Reaction Mechanisms
ingly simple overall reactions can in reality be due We begin our analysis of chain reactions by examining
to a complex chain reaction. A good example is the the simplest of chain mechanisms, i.e.,:
stoichiometric oxidation of methane:
CH4 + 2O2 −→ CO2 + 2H2 O (47)
From experimental and theoretical investigations, it
is known that the following reactions are involved in
the oxidation process:
CH4 + O2 −→ CH3 + OH + O
CH4 + OH −→ CH3 + O + H2
CH4 + O −→ CH3 + OH
CH3 + O2 −→ H2 CO + OH
H2 CO + OH −→ HCO + H2 O
HCO + OH −→ CO + H2 O
CO + OH −→ CO2 + H
H + O2 −→ OH + O
H + H2 O −→ OH + H2
O + O + M −→ O2 + M∗
2OH + M −→ H2 O + O + M∗
7
In the above, M denotes any third body – which
can be any other atom or molecule in the system,
or even the walls of the system. The asterisk on M
indicates that M is an energized atom or molecule
– in that M has received the energy of the reaction.
Note that there are several intermediate species in
the above mechanism: CH3 , H2 , OH, HCO, H2 CO,
CO, H, and O. The important intermediate species,
as we will see, are the radicals CH3 , OH, O, H, and
HCO. These species are very unstable and tend to
react with almost anything they collide with. Thus,
the formation of these species tends to promote addi-
tional reactions, which results in the propagation of
the chain.
Although the above chain mechanism may seem
complicated, it is actually a greatly–simplified ap-
proximation to reality. The current understanding
of the methane oxidation mechanism includes 279
elementary reaction steps, which can operate either
in the forward or reverse direction (see table 5.3 of
Turns).
k1
A −→ B (R1)
k2
B −→ C (R2)
In the above, B is the intermediate species, and the
overall process is the conversion of A to C.
The law of mass action can be applied to each in-
dividual step in the mechanism. Since species B is
formed in reaction 1 and destroyed in reaction 2, and
both reactions are first-order, we have
dCB
= k1 CA − k2 CB (48)
dt
Similarly, for A and C we get
dCA
= −k1 CA (49)
dt
dCC
= k 2 CB (50)
dt
and initial conditions would typically be CA (0) = 1. initiation reaction: mechanistic step that pro-
CA,0 , CB (0) = CC (0) = 0. The rate laws for the duces the free radicals.
problem, in Eqs. (48–50) are a coupled set of first–
order differential equations. This particular set can 2. propagation reaction: a reaction that allows the
be solved analytically, giving chain to continue by producing at least as many
radicals as it consumes.
CA = CA,0 e−k1 t (51)
k1 CA,0 ¡ −k1 t ¢ 3. inhibition reaction: a reaction in which the final
CB = e − e−k2 t (52)
k2 − k1 products are consumed rather than formed.
CA,0 © ¡ ¢ ¡ ¢ª
CC = k2 1 − e−k1 t − k1 1 − e−k2 t 4. termination reaction: a reaction that results in
k2 − k1
(53) a net destruction of free radicals.

All of the details of the derivation (and there are Using the simple methane oxidation chain given
plenty) were omitted. The point of this example above, the reactions can be divided into:
was simply to demonstrate that a seemingly simple
chain can lead to a complicated mathematical solu- Initiation:
tion. Most of the chain mechanisms involved in com-
bustion reactions will have no analytical solution – CH4 + O2 −→ CH3 + OH + O
and numerical methods must be used to predict the
evolution of the concentrations from the chain. Propagation:
An additional point of the example was to demon-
strate how we apply the law of mass action to obtain CH4 + OH −→ CH3 + O + H2
rate laws for the species that participate in the chain. CH4 + O −→ CH3 + OH
In more complicated chains (such as the methane CH3 + O2 −→ H2 CO + OH
oxidation mechanism given above) we can get more
CO + OH −→ CO2 + H
than one intermediate. On a chemical basis, these
intermediates are usually free radicals. In a precise H + O2 −→ OH + O
sense, a free radical is a species that has a spin- H2 CO + OH −→ HCO + H2 O
unpaired electron. It may be thought of as a molec-
ular fragment of a stable molecule. For example, the Inhibition:
H atom is a free radical, as is illustrated below, where
the dots symbolize electrons H + H2 O −→ OH + H2
H : H −→ H· +H· (54) Termination:
Similarly, if one H atom is taken away from methane
(CH4 ), two free radicals are formed: HCO + OH −→ CO + H2 O
H H O + O + M −→ O2 + M∗
H: C̈ : H −→ H : C̈· +· H (55) 2OH + M −→ H2 O + O + M∗
Ḧ Ḧ
Free radicals are of utmost importance in chain
mechanisms because they are very unstable compared
to the reactant and product species in the overall re- We can write a general chain reaction mechanism
action, and thus tend to promote chemical reactions. involving the four types of chain mechanisms. In
The reactions that make up a chain have certain what follows, M denotes a (stable) chemical species,
general characteristics that are classified as follows: R is a radical, P is a product, and α is simply a

8
number. this approximation is that the radicals are so reac-
k1 tive that once they build up to a small level they
M −→ R initiation react quickly, and thus stay at the low and constant
k2 level. Therefore, we can simply set Eq. (60) equal to
R+M −→ αR + M 0 propagation zero and algebraically solve for CR to obtain,
k3
R+M −→ P termination k1 CM
k4 CR = (61)
R −→ destroyed termination (1 − α)k2 CM + k3 CM + k4 + k5
wall
R k5 destroyed termination
−→
gas Using the above in Eq. (59), we get

Note that radicals can be removed in reactions 4 and 2

dCP k1 k3 CM
5 through interactions with the container walls or = (62)
dt (1 − α)k2 CM + k3 CM + k4 + k5
simply with the gas molecules. In reaction 2, if α = 1
the reaction is termed chain carrying – in that the Of utmost interest in combustion reactions is
net production of radicals by the reaction is zero. If whether or not the above rate can go to infinity. In
α > 1, the reaction is called chain branching – a other words, under what conditions will the rate of
net amount (i.e., (α − 1)) of radicals are created by product formation essentially ‘blow up’. By examin-
the reaction. In the methane oxidation chain prop- ing the denominator, we see that a critical value of α
agation reactions listed above, the first, second, and can be defined,
fifth propagation reactions would be chain branch-
ing, since they produce two radicals in consuming k3 CM + k4 + k5
αcritical = 1 + (63)
one. The third, fourth, and sixth propagation reac- k 2 CM
tions are chain carrying – one radical is produced by
For α < αcritical , the denominator in Eq. (62) will
the consumption of one radical.
stay positive and finite, and thus so will the rate of
We would like to obtain an expression for the rate
P production. But for α = αcritical , the denominator
change of CP in terms of CM . Using the law of mass
goes to zero and the rate becomes infinite. We will see
action, we set
in the following section that an infinite reaction rate
dCM is referred to as explosive. A necessary criteria for
= −k1 CM − k2 CR CM − k3 CR CM (58) the chain mechanism to exhibit explosive behavior is
dt
dCP the existence of a chain branching step. On the other
= k3 CR CM (59) hand, if all the propagation reactions are chain car-
dt
dCR rying (i.e., α = 1), then the reaction does not exhibit
= k1 CM + (α − 1)k2 CR CM − k3 CR CM explosive behavior. However, it is important to note
dt
− k4 CR − k5 CR (60) that for some actual explosion processes, the steady
state approximation may not be valid because the
We have three differential equations for the three concentration of R does not remain small and con-
unknowns CM , CR , and CP . Assuming that we have stant. Other reaction steps may also be important,
values for the rate constants, we could in principle and the postulated reaction mechanism given above
integrate these equations to get the concentrations may not be applicable during an explosion.
as a function of time – although this would probably
have to be done numerically (as in the case above).
2.2 Chain Explosions
A commonly used approach to quickly estimate
the rate law from the above equations is the steady What we later will call a flame is a reaction that
state approximation, for which the rate change of CR propagates through a fuel-oxidizer mixture that is
(Eq. (60)) is set equal to zero. The rationale behind explosive. By explosive, we mean that the rate of

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reaction is fast – so fast that the rate at which prod- What will be the minimum time required for all the
ucts are formed becomes nearly infinite. Note that in molecules to react to form products? Since it takes
a strict combustion sense, ‘explosive’ does not have one radical to make one product molecule, then we
the common meaning of ‘blowing up’ (as in an explo- have to produce 1019 radicals for the reaction to com-
sive device, i.e., a bomb), the latter will be referred plete. Since the most efficient process would be if ev-
to as a detonation. ery collision resulted in a reaction, then the reaction
There are two general ways by which a mixture can time for this case would simply be on the order of the
explode. One, as mentioned above, is called a chain time required for the 1019 molecules to collide:
explosion. Here the cause of the explosion results
from the existance of chain branching reactions in the 1019 collisions
t≈ = 1011 s ≈ 30 years (66)
chain mechanism. Because of the branching, more 108 collisions/s
and more radicals are formed which continuously ac-
Such a slow process cannot be called combustion.
celerate the reaction. The other is referred to as a
However, let’s now assume that the chain propaga-
thermal explosion. Here the explosion results from
tion reaction in the container is a chain branching
the nature of the Arrhenius rate law. The rate, which
reaction, and two free radicals are produced for ev-
is proportional to exp(−E/Ru T ), increases rapidly
ery one consumed during a chain, i.e.,
with T . Thus a snowball effect can occur – the reac-
tion heats up the reactants, which increases the rate, M + R −→ M 0 + 2R0 (67)
which increases the heating of the products, and so
on. Eventually, the rate ‘runs away thermally’, and Again, we have to produce 1019 radicals to completely
an explosion occurs. convert the reactant molecules to product molecules.
Actually, explosions are the result of both effects, After the first chain branching reaction, there will be
and any general theory of explosions must incorpo- 2 radicals; after the second, 4; and so on. We then
rate both. However, it is instructive to look at both get the series:
effects separately, from which the general physical
and chemical characteristics of explosions can be ex- 1 + 2 + 4 + 8 + · · · + 2N = 1019 (68)
tracted.
The profound effect chain branching has on reac- where N is the ‘number of generations’ of the chain
tion rate can be dramatically illustrated by the fol- branching reaction – equivalently the number of cy-
lowing simple example. Consider a 1 cm3 container cles or loops the chain has to go through. We can
which initially contains 1 free radical among other- sum this well-known series to get
wise gas reactant molecules. Assume the container is
at S.T.P., for which the number of molecules in the 2N +1 − 1 = 1019 , or N = 64 generations (69)
container will be around 1019 and the average molecu-
So we need 64 loops of the chain to complete the
lar collision rate will be around 108 collisions/s. (i.e.,
reaction. The time required to complete each loop
a molecule will experience, on the average, 108 col-
will still be on the order of the collision rate – thus
lisions with other molecules each second). Say the
chain propagation reaction in the container is chain t ≈ 64 × 10−8 s ≈ 1 µs (70)
carrying, in that
This would certainly be considered an explosive pro-
M + R −→ M 0 + R0 (64)
cess. In actual combustion processes, not all reactions
are chain branching. Using the example given in the
So one free radical is produced for every one con- previous section, we could have a chain branching re-
sumed. Also, the chain termination reaction is of the action of the form,
form,
R0 + M −→ P (65) M + R −→ M 0 + αR0 (71)

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where α > 1. After the first reaction, we would have Turns gives a good overview of such global formulas
α radicals; after the second, α2 , and so on. We then on p. 157. Note that the global laws have the look of
get the series the law of mass action – yet they apply to the overall
reaction and not the elementary steps in the chain.
1 + α + α2 + α3 + · · · + αN = 1019 (72) The formulas are of the form,

or dCCx Hy
αN +1 − 1 = A exp (−Ea /Ru T ) CCmx Hy CO
n
(74)
= 1019 (73) dt 2

α−1
Say α = 1.01 – which appears to be a small number.
Solving the above for the number of generations N ,
we get N = 3934. The reaction time would now be
on the order of 40 µs – which is still a very fast (and
explosive) reaction. Consequently, even a relatively
small degree of chain branching can have a profound
effect on the reaction rate.
The explosive behavior of a fuel/air mixture can be
highly dependent on the temperature and pressure at
which the mixture exists. A good example of this is
discussed at the beginning of Ch. 5 in Turns, in which
he describes the explosion limit characteristics of the
H2 /O2 system.
where A, Ea , m, and n depend on the specific hy-
drocarbon fuel type (i.e.,x and y). Values of these
constants are listed in Table 5.1 of Turns.
The overall order of the rate law in Eq. (74) is sim-
ply m + n, i.e., the rate is proportional to concentra-
tion raised to the m + n power. Since concentration
is proportional to pressure (ideal gas law), the rate
is proportional to P m+n . In addition, Eq. (74) also
shows that the rate is m–order with respect to fuel
and n–order with respect to oxygen.

2.3 Global Rate Laws

From the previous discussion, an explosive system
was defined as that in which the reaction rate could,
essentially, go to infinity. Of course, the reaction rate
will not be infinite in combustion systems – it will be
very fast (compared to most other processes) yet still
finite.
We need to predict the reaction rate of reactants
in order to predict, say, flame speeds or flammabil-
ity limits. One route is simply to employ a com-
prehensive numerical solution of the detailed chain
mechanism for the reaction. This approach may be
useful for detailed, scientific–oriented computations
(i.e., comparison of theory with experiment), yet it is
not practical for many engineering–type calculations.
In this respect, there has been much effort to con-
struct approximate, yet accurate, correlations for the
reaction rates of hydrocarbon/air mixtures. Such
correlations are often referred to as global rate laws,
and are obtained via a combination of experimental
measurements (curve fitting) and theoretical analy-
sis.

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