POLLUTANT FORMATION AND CONTROL

Lean flme-out
region: HC

Initial rapid
combustion:
noise

573

Rate constants for NO formation mechanism1

Fuel jet
mixing with air:
rich mixture

(1) 0 N, + NO + N
(-~)N+No+N,+o

+ 0,+ N O + o
(-2) 0 + NO + 0, + N
(3) N + OH +NO + H
(-3) H + NO + OH + N
(2) N

Premixed

Rate constant,
cm3/mol.s

Temperature
nnge, K

Uncertainty,
factor of or %

7.6 x loi3 exp [-38,000/TJ

1.6x10i3

2000-5000
300-5000

6.4 x lo9 T exp [ - ~ I S O / T ~

300-3000

1.5 x 10' T exp [-19,50O/Tj

1000-3000

4.1 x lo1=
2.0 x loi4 exp [-23,65O/T]

300-2500
22004500

20% at 300 K
2 at 2000-5000 K
*30% 3m-1500 K
2 at 3000 K
f 30% at 1000 K
2at3000K
*80%
2

Flame
on wal

FIGURE 113
Summary of pollutant fo
mechanisms in a direct-i
controlled" combustion

W i g controlled

11.2 NITROGEN OXIDES

11.21 Kinetics of NO Formation
While nitric oxide (NO) and nitrogen dioxide (NO,) a
as NO, emissions, nitric oxide is the predominant
inside the engine cylinder. The principal source of NO is the oxidation
spheric (molecular) nitrogen. However, if the fuel
the oxidation of the fuel nitrogen-~ontainingCOmpO
of NO. Gasolines contain negligible amounts of nitrogen; although d
contain more nitrogen, current levels are not significant.
The mechanism of N O formation from atmospheric nitrogen has
studied extensively.' It is generally accepted that in combustion of
stoichiometrjc fuel-& mixtures the principal reactions governing the
of NO from molecular nitrogen (and its destruction) are?

The forward and reverse rate constants (k: and k;, respectively) for these reactions have been measured in numerous experimental studies. Recommended
values for these rate constants taken from a critical review of this published data
are given in Table 11.1. Note that the equilibrium constant for each reaction, Kc,i
(see Sec. 3.7.2), is related to the forward and reverse rate constants by Kc,i =
k:/k;.
The rate of formation of NO via reactions (11.1) to (11.3) is given by [see
Eqs. (3.55) and (3.58)]
2]

N+OH=NO+H

called the extended Zeldovich mechanism. Zeldovichl was the first to suggest
importance of reactions (11.1) and (11.2). Lavoie et al.' added reaction (11.3) to the mechanism;
d m contribute significantly.

MCOH]

k, mO][O] - k;mO][H]
(11.4)
where [ 1 denote species concentrations in moles per cubic centimeter when ki
have the values given in Table 11.1. The forward rate constant for reaction (11.1)
and the reverse rate Constants for reactions (11.2) and (1 1.3) have large activation
energies which results in a strong temperature dependence of NO formation

- k;mOIml-

A similiar relation to (1 1.4) can be written for d[N]/dt:

21

- k:PJl[02]

- k$m][OH]

-k;mOIM

O+N,=NO+N
N+02=NO+0

+ k:

+ k ; w m O ] + k;pJO][H]

(11.5)

Since N is much less than the concentrations of other species of interest

(-lo-' mole fraction), the steady-state approximation is appropriate: d[a/dt is
set equal to zero and Eq. (1 1.5) used to eliminate N. The NO formation rate
1 - mo12/(KCo21CN21)
1 + k; CNOl/(k: [O2]+ k: [OH])

+ hi^ is

here K = (k:/k;)(k:/k;).

(11.6)

574

INTERNAL C O M B O N E

POLLUTANT FORMATION AND CONTROL

N FUNDAMENTALS

TABLE 11.2

Typical values of R,, R1/R2, and RlI(R2

575

+ R3)t

Equivalence
ratio

Rd

RJRz

RiI(Rz

0.8
1O
.
1.2

5.8 x
2.8 x lo-'
7.6 x

1.2
2.5
9.1

0.33
0.26
0.14

+Rd

t At 10 atm pressure and 2600 K.

$ Units gmol/cm3~s.

NO forms in both the flame front and the postflame gases. In engines
however, combustion occurs at high pressure so the flame reaction zo
extremely thin (-0.1 mm) and residence time within this zone is short. Als
cylinder pressure rises during most of the combustion process, so burned
produced early in the combustion process are compressed to a higher
perature than they reached immediately after combustion. Thus, NO fo
in the postflame gases almost always dominates any flame-front-produce
is, therefore, appropriate to assume that the combustion and NO formation p
cesses are decoupled and to approximate the concentrations of 0, O,, OH,
and N, by their equilibrium values at the local pressure and equilibrium temperature.
TO introduce this equilibrium assumption it is convenient to use the notation R, = k:[O],CN,],
= k;CNO],N,,
where [ 1, denotes equilibrium concentration, for the one-way equilibrium rate for reaction (11.1), with similiar
definitions for R, = k:CNIe[O21. = k~CNOI,COI, and R3 = k:Ne[Ofle
= k;CNO],[H],
. Substituting [Ole, [O,],, [OH],,
and CNzI, for [Ol,
[O,], [OH], [HI, and CN,] in Eq. (11.6) yields

[a,,

dm01-dt

2R1{1 - (CN01/CN01e)2)
1 + (CNOIICNOle)RII(R~+ R3)

Typical values of R,, RJR, and Rl/(R2 + R3) are given in able 11.2. The difierence between R,/R, and R,/(R, + R3) indicates the relative importance of
adding reaction (11.3) to the mechanism.
The strong temperature dependence of the NO formation rate can be
4],
demonstrated by considering the initial value of dCNO]/dt when ~ 0 ] / ~ 0
1. Then, from Eq. (11.7),

-dCNol
dt

- 2Rl = 2k:[o].CN

J.

The equilibrium oxygen atom concentration is given by

Cole =

0 COzlt'z
;Rnl/2

FIGURE 11-4
Initial NO formation rate, mass fraction per
second (for mOl/CNOl, 4 I), as a function of
temperature for different equivalence ratios (4)and
15 atm pressure. Dashed line shows adiabatic
flame tmperature for kerosene combustion with
700 K, 15 atm air.=

where K,(,,

is the equilibrium constant for the reaction

30, = 0

(-'f")

KHo, = 3.6 x lo3 exp --

atmli2

(11.10)

The initial NO formation rate may then be written [combining Eqs. (11.8), (11.9),
and (11.10) with k: from Table 11.11 as
dB01

6 x 1016

- 69,090
exp ( ~ ) ~ o ~ I ~ ~ c N
mol/cm3.
, I . s (11.11)
The strong dependence of dPJO]/dt on temperature in the exponential term is
evident. High temperatures and high oxygen concentrations result in high NO
formation rates. Figure 11-4 shows the NO formation rate as a function of gas
temperature and fuellair equivalence ratio in postflame gases. Also shown is the
adiabatic flame temperature attained by a fuel-air mixture initially at 700 K at a
constant pressure of 15 atm. For adiabatic constant-pressure combustion (an
appropriate model for each element of fuel that burns in an engine), this initial
NO formation rate peaks at the stoichiometric composition, and decreases
rapidly as the mixture becomes leaner or richer.
A characteristic time for the NO formation process,
, ,T
can be defined by
-=-

z&

1 dl301

;
,
l

CNoIe

dt

(11.12)