POLLUTANT FORMATION AND CONTROL 573

Lean flme-out Initial rapid

region: HC combustion: Rate constants for NO formation mechanism1
\
/ noise
Rate constant, Temperature Uncertainty,
Fuel jet cm3/mol.s nnge, K factor of or %
mixing with air:
rich mixture +
(1) 0 N, + NO + N 7.6 x loi3 exp [-38,000/TJ 2000-5000 2
(-~)N+No+N,+o 1.6x10i3 300-5000 20% at 300 K
2 at 2000-5000 K
(2) N + 0,+ N O + o 6.4 x lo9 T exp [ - ~ I S O / T ~ 300-3000 *30% 3m-1500 K
Premixed 2 at 3000 K
(-2) 0 + NO + 0, + N 1.5 x 10' T exp [-19,50O/Tj 1000-3000 f 30% at 1000 K
2at3000K
(3) N + OH +NO + H 4.1 x lo1= 300-2500 *80%
(-3) H + NO + OH + N 2.0 x loi4 exp [-23,65O/T] 22004500 2
Flame
on wal
FIGURE 113
Summary of pollutant fo The forward and reverse rate constants (k: and k;, respectively) for these reac-
mechanisms in a direct-i tions 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
W i g controlled controlled" combustion (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
11.2 NITROGEN OXIDES Eqs. (3.55) and (3.58)]

11.21 Kinetics of NO Formation 2] + k: MCOH]

While nitric oxide (NO) and nitrogen dioxide (NO,) a
as NO, emissions, nitric oxide is the predominant - k;mOIml- k, mO][O] - k;mO][H] (11.4)
inside the engine cylinder. The principal source of NO is the oxidation
spheric (molecular) nitrogen. However, if the fuel where [ 1 denote species concentrations in moles per cubic centimeter when ki
the oxidation of the fuel nitrogen-~ontainingCOmpO have the values given in Table 11.1. The forward rate constant for reaction (11.1)
of NO. Gasolines contain negligible amounts of nitrogen; although d 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
contain more nitrogen, current levels are not significant.
The mechanism of N O formation from atmospheric nitrogen has
A similiar relation to (1 1.4) can be written for d[N]/dt:
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? 21 - k:PJl[02] - k$m][OH]
O+N,=NO+N -k;mOIM + k ; w m O ] + k;pJO][H] (11.5)
N+02=NO+0 Since N is much less than the concentrations of other species of interest
N+OH=NO+H (-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)
+ hi^ is called the extended Zeldovich mechanism. Zeldovichl was the first to suggest
1 + k; CNOl/(k: [O2]+ k: [OH]) (11.6)
importance of reactions (11.1) and (11.2). Lavoie et al.' added reaction (11.3) to the mechanism;
d m contribute significantly. here K = (k:/k;)(k:/k;).
574 INTERNAL C O M B O N E N FUNDAMENTALS
POLLUTANT FORMATION AND CONTROL 575

TABLE 11.2
Typical values of R,, R1/R2, and RlI(R2 + R3)t
Equivalence
ratio Rd RJRz RiI(Rz +Rd
0.8 5.8 x 1.2 0.33
1O
. 2.8 x lo-' 2.5 0.26
1.2 7.6 x 9.1 0.14

t At 10 atm pressure and 2600 K.

$ Units gmol/cm3~s.

FIGURE 11-4
NO forms in both the flame front and the postflame gases. In engines Initial NO formation rate, mass fraction per
second (for mOl/CNOl, 4 I), as a function of
however, combustion occurs at high pressure so the flame reaction zo temperature for different equivalence ratios (4)and
extremely thin (-0.1 mm) and residence time within this zone is short. Als 15 atm pressure. Dashed line shows adiabatic
cylinder pressure rises during most of the combustion process, so burned flame tmperature for kerosene combustion with
produced early in the combustion process are compressed to a higher 700 K, 15 atm air.=
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 where K,(,, is the equilibrium constant for the reaction
cesses are decoupled and to approximate the concentrations of 0, O,, OH,
and N, by their equilibrium values at the local pressure and equilibrium tem- 30, = 0
perature.
TO introduce this equilibrium assumption it is convenient to use the nota-
tion R, = k:[O],CN,], = k;CNO],N,, where [ 1, denotes equilibrium con-
centration, for the one-way equilibrium rate for reaction (11.1), with similiar KHo, = 3.6 x lo3 exp -- (-'f") atmli2 (11.10)
definitions for R, = k:CNIe[O21. = k~CNOI,COI, and R3 = k:Ne[Ofle
= k;CNO],[H], . Substituting [Ole, [O,],, [OH],, [a,,
and CNzI, for [Ol, 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
[O,], [OH], [HI, and CN,] in Eq. (11.6) yields
dm01- 2R1{1 - (CN01/CN01e)2) dB01 6 x 1016 - 69,090
-- -=-
dt 1 + (CNOIICNOle)RII(R~+ R3) exp ( ~ ) ~ o ~ I ~ ~ c N , I . s (11.11)
mol/cm3.
Typical values of R,, RJR, and Rl/(R2 + R3) are given in able 11.2. The difier- The strong dependence of dPJO]/dt on temperature in the exponential term is
ence between R,/R, and R,/(R, + R3) indicates the relative importance of evident. High temperatures and high oxygen concentrations result in high NO
adding reaction (11.3) to the mechanism. formation rates. Figure 11-4 shows the NO formation rate as a function of gas
The strong temperature dependence of the NO formation rate can be temperature and fuellair equivalence ratio in postflame gases. Also shown is the
demonstrated by considering the initial value of dCNO]/dt when ~ 0 ] / ~ 0 4], adiabatic flame temperature attained by a fuel-air mixture initially at 700 K at a
1. Then, from Eq. (11.7), 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
dCNol
--
dt
- 2Rl = 2k:[o].CN J. NO formation rate peaks at the stoichiometric composition, and decreases
rapidly as the mixture becomes leaner or richer.
The equilibrium oxygen atom concentration is given by A characteristic time for the NO formation process,
, ,T can be defined by
K 0 COzlt'z z& ;
,l-
1 -
dl301
Cole = ;Rnl/2 CNoIe dt (11.12)