270 Effect of dissociation on combustion parameters

05

06

dissociation

07

09

08

I t

12

13

Equivalence ratio, 4
Fig. 13.6 Variation of temperature with equivalence ratio for combustion of octane. Initial pressure:
1 bar; initial temperature: 300 K, compression ratio: 12; compression index: 1.4

The carbon/hydrogen ratio varies from 0.25 to 0.44 for methane and octane
respectively, and this affects the composition of the products, both with and without
dissociation. The mole fractions of the products for the combustion of methane (taking
account of dissociation) are shown in Fig 13.7. It can be seen that the largest mole
fraction is that of water, which is more than twice that of carbon dioxide: this reflects
the greater proportion of hydrogen atoms in the fuel. (Note: the mole fraction of
0.20

0.

II

0.70

0.80

0.90

9
I

H>O

0.15

0I
.
*,

u
a

0.10

0.05

0.00
0.50

0.60

1.00

1.10

1.20

Equivalence ratio, 4
Fig. 13.7 Variation of composition of products with equivalence ratio for combustion of methane.
Initial pressure: 1 bar; initial temperature: 300 K; compression ratio: 12; compression index: 1.4

nitrogen, N,, has been omitted from Figs 13.7, 13.8, 13.9 and 13.10 because it
dominates the composition of the products. Its mole fraction remains around 0.79 in all
cases.)
The mixture is weak at equivalence ratios of less than unity, and there is excess oxygen
for complete combustion up to an equivalence ratio of unity. This can be seen in Figs 13.8

The effect offuel on composition of the products

27 1

0.10

&

0.08

c
0

0.06

ba
k

0.04

0.02

0
Q

0.00
0.50

0.60

0.70

0.80

0.90

1.00

1.10

1.20

Equivalence ratio, $
Fig. 13.8 Variation of carbon reactions, with and without dissociation, for combustion of methane
0.20

0.15

dissociation

0.10

0.05

0.00
0.50

0.60

0.70

0.80

0.90

1.00

1.10

1.20

Equivalence ratio, 4
Fig. 13.9 Variation of hydrogen reactions, with and without dissociation, for combustion of
methane

and 13.9, where the composition of the products, both with and without dissociation, has
been plotted. It can be seen from Fig 13.9, which includes the mole fraction of oxygen,
that there is no oxygen in the products at equivalence ratios of greater than unity if there is
no dissociation. However, when there is dissociation the quantity of oxygen in the
products is increased, simply due to the reverse reaction. This reverse reaction also
produces some unreacted hydrogen, and dissociation causes this to be produced even with
weak mixtures. It should be noted that it was assumed that the hydrogen would be oxidised
in preference to the carbon in the reactions without dissociation, and this explains the
absence of hydrogen in those cases.
The carbon-related reactions are shown in Fig 13.8. When dissociation is neglected, the
carbon is completely oxidised to carbon dioxide in the weak and stoichiometric mixtures,
with no carbon monoxide being formed. After the mixture becomes rich, the level of
carbon monoxide increases linearly with equivalence ratio. When dissociation is

272 Eflect of dissociation on combustion parameters

0. I F
K
c

.*
0

0.10

c,

bk
2

0.05

0.0
0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

Equivalence ratio, 4
Fig. 13.10 Variation of composition of products with equivalence ratio for combustion of octane.
Initial pressure: 1 bar; initial temperature:300 K; compression ratio: 12; compression index: 1.4

considered, carbon monoxide is formed even in the weak mixture region, but surprisingly
there is a lower level of carbon monoxide in the rich region than when there is no
dissociation. The explanation of this is that the dissociation of the water releases some
oxygen that is then taken up by the carbon. The production of carbon monoxide in lean
mixtures is the reason for carbon monoxide in the untreated exhaust gas from internal
combustion engines even when they are operating stoichiometrically or lean.
Considering the carbon dioxide, it can be seen that this peaks at an equivalence ratio of
unity (@ = 1) without dissociation. However, it peaks at an equivalence ratio of around
$I = 0.9 to 1.0 (i.e. weak) when there is dissociation, when the peak level of carbon
dioxide is only about 75% of that without dissociation.
The mole fractions of products for the combustion of octane are shown in Fig 13.10.
The trends are similar to those for the combustion of methane. The carbon dioxide fraction
maximises on the lean side of stoichiometric, at @ of about 0.9. It is also noticeable that
the mole fractions of water and carbon dioxide are much closer with octane than methane,
which simply reflects the higher carbon/hydrogen ratio of octane.

13.6 The effect of fuel on composition of the products

Two different fuels were used in the previous analysis of the effect of dissociation on
combustion products. Both are paraffinic hydrocarbons, with a generic structure of
CnH2n+2:
for methane the value of n = 1, while for octane n = 8. This means that the
carbon/hydrogen ratio varies from 0.25 to 0.44. This has an effect on the amount of CO,
produced for each unit of energy released (i.e. kg CO,/kJ, or more likely kg CO,/kWh).
The effect of this ratio can be seen in Figs 13.7 and 13.10. The maximum mole fraction of
CO, released with octane is almost lo%, whilst it peaks at around 7.5% with methane: the
energy released per unit mass of mixture is almost the same for both fuels, as shown by
the similarity of temperatures achieved (see Figs 13.5 and 13.6). Hence, if it is required to
reduce the amount of carbon dioxide released into the atmosphere, it is better to bum fuels
with a low carbon/hydrogen ratio. This explains, in part, why natural gas is a popular fuel
at this time.

Theformation of oxides of nitrogen

273

13.7 The formation of oxides of nitrogen

It was shown in Chapter 12 that when air is taken up to high temperatures, the nitrogen and
oxygen will combine to form oxides of nitrogen, and in particular nitric oxide, NO. It was
also stated that it is not enough simply to add the equation

N,

+ 0, w 2 N O

(13.7)

but a chain of reactions including 11 species has to be introduced. This is necessary

because the formation of atomic oxygen and nitrogen, and the radical OH play a
significant part in the amount of NO produced in the equilibrium mixture.
These equations representing equilibrium of the 11 have been used to analyse the
equilibrium constituents of the products of combustion for the cases considered above, i.e.
the combustion of methane and octane in an engine operating on an Otto cycle. The
results are shown in Figs 13.11 and 13.12. It should be noted that the ordinate axis is in
logarithmic form to enable all the important constituents to be shown on a single graph.
The numerical results for carbon monoxide, carbon dioxide and water are similar to those
in Figs 13.9 and 13.10; it is simply the change in scales which has changed the apparent
shapes. These results will now be analysed.

0.1

0
.I
4-

&
0)

I
I

0.01

0.001
0.6

0.8

1 .0

Equivalence ratio,

1.2

Fig. 13.11 Products of combustion at tdc for the combustion of methane in an Otto cycle

274 Effect of dissociation on combustion parameters

0.1

EI^
0

+
u

.H

co

Q)

s
I

0.01

0.001

0.6

0.8

1.0

1.2

Equivalence ratio, 4
Fig. 13.12 Products of combustion at tdc for the combustion of octane in an Otto cycle

Considering Fig 13.11 first: this shows the equilibrium constituents of the mixture at tdc
after adiabatic combustion of methane. The temperatures and pressures achieved by this
combustion process are similar to those shown in Figs 13.3 and 13.5, although there will
have been a slight reduction in both parameters because the dissociation processes all
absorb energy. It can be seen that the maximum values of the mole fraction of both water
( ~ 0 . 1 9 )and carbon dioxide (~0.07)have not been significantly changed by the extra
dissociation processes, and the CO, still peaks in the vicinity of q5 = 0.8 to 0.9. However,
detailed examination shows that the levels of CO, and CO have been changed in the rich
region, and in this case the mole fraction of CO exceeds that of CO, at q5 = 1.2. This is
because more reactions are competing for the available oxygen, and the carbon is the loser.
Now considering the formation of nitric oxide: it was shown in Chapter 12 that nitrogen
and oxygen will tend to combine at high temperatures to produce nitric oxide because the
enthalpy of formation of nitric oxide is positive. This combination process will be referred
to under the general heading of dissociation, although strictly speaking it is the opposite.
This example is different from that shown in Chapter 12, when the variation in the amount
of NO with equivalence ratio at constant pressure and temperature was depicted. In this
case the peak pressure and temperature achieved in the combustion process are functions
of the equivalence ratio, and the variations are shown in Figs 13.3 and 13.5. In fact, the

Effect of dissociation on combustionparameters 275

peak temperature increases from about 2200 K at Q, = 0.5, to 3000 K at Q, = 1.1; the peak
pressure goes from about 87 bar to 122 bar over the same range of equivalence ratio. The
increase in temperature will tend to increase dissociation effects in all cases, whereas an
increase in pressure will tend to decrease the dissociation effects in cases where
dissociation increases the total amount of substance (e.g. the CO, reaction); this was
discussed in Chapter 12. Hence, the changes occurring in the conditions in the cycle tend
to run counter to each other to some extent, although the effect of temperature dominates.
The value of mole fraction of NO peaks at around Q, = 0.7 to 0.8, and obviously does not
occur at the highest temperature. This is because the reaction which creates NO is
dependent on the amounts of nitrogen (N,) and oxygen (0,)present in the mixture, as
well as the temperature of the products. At low equivalence ratios there is an abundance of
components to react but the temperature is low, whilst at high temperatures the driving
force to react is high but there is a deficiency of oxygen. In fact, the nitrogen has to
compete with the carbon monoxide and hydrogen for any oxygen that becomes available,
and it gains most of the oxygen from the carbon reactions. The maximum level of NO
attained is a mole fraction of about 0.13, and this is equivalent to about 13 000 ppm (parts
per million [by mass]); this level is typical of that which would be achieved at equilibrium
conditions in an engine.
Before considering the effect of the rate of reactions on the actual levels of NO
achieved, it is worthwhile seeing the effect of fuel on the level of exhaust constituents. The
additional reactions do not have a major effect on the exhaust composition with octane as a
fuel, and the CO, level is still significantly higher than with methane, as would be
expected. However, the general level of NO is higher with octane than methane because of
the slightly higher temperatures achieved with this fuel, and the larger proportion of CO,
which can be robbed for oxygen. The maximum levels of NO again occur around Q, = 0.7
to 0.8, and result in about 14 000 ppm.
The levels of NO in the exhaust gas of an engine are significantly lower than those
calculated above for a number of reasons. First, the reactions occurring in the cylinder are
not instantaneous, but are restricted by the rate at which reacting molecules meet; this is
known as chemical kinetics or rate kinetics, and is the subject of Chapter 14. The effect of
these kinetics is that the instantaneous level of NO in the cylinder does not achieve the
equilibrium level, and lags it when it is increasing as shown in Fig 13.2. When the
equilibrium concentration is decreasing, the actual level of NO still cannot maintain pace
with it, and again lags the level while it decreases down the expansion stroke of the
engine, as shown qualitatively in Fig 13.2; in fact these reactions tend to freeze at around
2000K, and this level then dominates the exhaust value. Secondly, the combustion
process does not take place instantaneously at tdc as shown here, but is spread over a
significant period of the cycle and the pressures and temperatures are lower than those
attained in the Otto cycle: this will reduce the peak equilibrium level of NO.
It is shown in Figs 13.11 and 13.12 that the peak level of NO at equilibrium occurs at
around Q, = 0.7 to 0.8, but experience shows that the maximum values of NO in engine
exhaust systems (around 2000 to 5000 ppm) occur at about @ = 0.9. This can be explained
by considering the effect of rate kinetics. It will be shown in Chapter 14 that the rate at
which a reaction occurs is exponentially related to temperature. Hence, while the
equilibrium level of NO is a maximum at g5 = 0.7 to 0.8, the lower temperature at this
equivalence ratio limits the amount of NO produced by the reaction. The peak value of NO
occurs at Q, = 0.9 because the driving force (the equilibrium concentration) and the rate of
reaction combine at this equivalence ratio to maximise production of this pollutant.

14
Chemical Kinetics

14.1 Introduction
Up until now it has been assumed that chemical reactions take place very rapidly, and that
the equilibrium conditions are reached instantaneously. While most combustion processes
are extremely fast, often their speed is not such that combustion can be considered to be
instantaneous, compared with the physical processes surrounding them. For example, the
combustion in a reciprocating engine running at 6000 rev/min has to be completed in
about 5 ms if the engine is to be efficient. Likewise, combustion in the combustion
chamber of a gas turbine has to be rapid enough to be completed before the gas leaves the
chamber. Such short times mean that it is not possible for all the gases in the combustion
chamber to achieve equilibrium - they will be governed by the chemical kinetics of the
reactions.
Chemical kinetics plays a major role in the formation of pollutants from combustion
processes. For example, oxygen and nitrogen will coexist in a stable state at atmospheric
conditions, and the level of oxides of nitrogen (NO,) will be negligible. However, if the
oxygen and nitrogen are involved in a combustion process then they will join together at
the high temperature to form NO, which might well be frozen into the products as the
temperature drops. This NO, is a pollutant which is limited by legislation because of its
initant effects. NO, is formed in all combustion processes, including boilers, gas turbines,
diesel and petrol engines; it can be removed in some cases by the use of catalytic
converters.
It was shown in Chapters 12 and 13 that significant dissociation of the normal products
of combustion, carbon dioxide and water can occur at high temperature. The values
shown were based on the equilibrium amounts of the substances, and would only be
achieved after infinite time; however, the rates at which chemical reactions occur are
usually fast and hence some reactions get close to equilibrium even in the short time the
gases are in the combustion zone. An analysis of the kinetics of reactions will now be
presented.

14.2

Reaction rates

Reaction rates are governed by the movement and breakdown of the atoms or molecules in
the gas mixture: reactions will occur if the participating particles collide. The number of

Reaction rates 277

collisions occurring in a mixture will be closely related to the number densities (number
per unit volume) of the 'particles'. The number density can be defined by the molar
concentration, c , which is the amount of substance per unit volume. This is obviously a
measure of the number of particles per unit volume since each amount of substance is
proportional to the number of molecules; this is illustrated in Fig 14.1. The molar
concentration will be denoted by enclosing the reactant or product symbol in [ 1.

. . .
.
.
. .
0

. O

1:

..

'd.1

Fig. 14.1 Diagrammatic representation of molar concentration. Molar concentration in (a) is

approximately half that in (b)

Reactions occur when two, or more, reactants are capable of reacting. Many simple
chemical reactions are second order, e.g.

kf

A+B-C+D
kb

(14.1)

kf

C02 + H2-H20

+ CO

kb

where the first reaction is a general one and the second is an example based on the water
gas reaction (chosen because the same number of reactants and products exist on both
sides).
These reactions can be written as
(14.2)

where A , , A,, .. . etc are the elements or compounds involved in the reaction, and
Y , , v 2 ,... etc are the respective stoichiometric coefficients. Equation (14.2) can be further
generalised to
(14.3)
where q = total number of species being considered, v' represents the stoichiometric
coefficients of the reactants, and Y" that of the products.
In this case q has been taken as the same on both sides of the equation because it is
assumed that the same species can exist on both sides. If a species does not exist on one of
the sides it is represented by a stoichiometric coefficient of zero ( Y = 0). For example,
CO,

+ H, wH,O + CO

(14.4)

278

Chemical kinetics

can be represented by
4

b 4
v:,~i-.C

V;A,

kb

i= 1

(14.5)

i=l

where q = 4
vij = stoichiometric coefficient of i in reaction j
A,=C02
v\=l
v~=O
v;=o
A, = H2
v;=1
A,=H,O
v;=O
~l;=l
vk=O
v:=1
A,= CO
The law of mass action, which is derived from the kinetic theory of gases, states that the
rate of formation, or depletion, of a species is proportional to the product of molar
concentrations of the reactants, each raised to the power of its stoichiometric coefficient.
Hence the rate of formation of species j , for an elementary reaction, is

Rja [Al]J[A2]*J [A,]

or

(14.6)
n

Rj=n[Ai]

f o r ( j = 1, ...s)

i= 1

and s = total number of simultaneous reactions.

Equation (14.6) may be written as
n

R j = k , n [ A J y J f o r ( j = 1, ... s)

(14.7)

i= 1

where kj is the rate constantfor the reaction. In eqns (14.1) to (14.5) the reaction was
described as having a forward and backward direction, with rates k, and kb.The reaction
shown in eqn (14.7) can be described in this way as
n

R, = bj

[A,]

for ( j = 1, ...s)

(14.8)

for ( j = 1 , . ..S)

(14.9)

i= 1

and

n
n

Rbj= kbj

[A,]

i= 1

The rate of change with time of species i is proportional to the change of the
stoichiometric coefficients of Ai in the reaction equation (the system is effectively a first
order one attempting to achieve the equilibrium state). Thus, for the forward direction
(14.10)

Chemical kinetics of NO

279

and, for the backward direction

(14.11)

Hence the net rate of formation of Ai is

d [Ailj

[A,]'' - kbj

(14.12)

[Ai]"

i= 1

Consider the following rate controlled reaction equation:

kf
vaA + vbB-vcC

+ vdD

(14.13)

kb

The net rate of generation of species C is given by

-d[C1
- - [kf[A]'"[B]"

- kb[c]''[DP]

(14.14)

dt
Using the notation [A]/[Al, = a , [Bl/[B], = /3, [Cl/[Cl,
the suffix e represents equilibrium concentrations, gives
d [C ]/d t = k, a "0/3"b[A]2[B 12- kbyVc
6 vd [C 1,'. [D ]2

=y

and [Dl/[Dl,

= 6,

where
(14.15)

At equilibrium
k,[A]:[B]?

= k,[C],'.[D],'d=

Rj

(14.16)

Therefore the net rate is

d[C]/dt

= R j [ a v ~ / 3-vy"C6vd1
b

(14.17)

14.3 Rate constant for reaction, k

The rate constant for the reaction, k, is related to the ability of atoms or ions to combine.
In combustion engineering this will usually occur when two or more particles collide.
Obviously the collision rate is a function of the number of particles per unit volume, and
their velocity of movement, i.e. their concentration and temperature. Most chemical
reactions take place between two or three constituents because the probability of more than
three particles colliding simultaneously is too small. It has been found experimentally that
most reactions obey a law like that shown in Fig 14.2.
This means that the rate constant for the reaction can be defined by an equation of the
form

k = Ae - E / R T

(14.18)

This equation is called the Arrhenius equation. The factor A is called the preexponential factor, or the frequency factor, and is dependent on the rate at which
collisions with the required molecular orientation occur. A sometimes contains a
temperature term, indicating that the number of collisions is related to the temperature in
those cases. The term E in the exponent is referred to as the activation energy. The values
of A and E are dependent on the reactions being considered, and some values are