Preprint

UCRL-JC-138169

Chemical Kinetics of Hydrocarbon

Ignition in Practical CombustionSystems

C.K. Westbrook

This article wassubmittedto

28 th International Symposium
on Combustion,Edinburgh, Scotland,
July 30 - August 4, 2000

July 7, 2000

U.S. Department
of Energy

Lawrence
Livermore
National
Laboratory
/

Approvedfor public release; further dissemination unlimited

 Chemical Kinetics of HydrocarbonIgnition
in Practical Combustion Systems

Charles K. Westbrook
Lawrence Livermore National Laboratory, Livermore, CA 94550 USA

Abstract

Chemical kinetic factors of hydrocarbon oxidation are examined in a

variety of ignition problems. Ignition is related to the presence of a dominant
chain branching reaction mechanismthat can drive a chemical system to
completion in a very short period of time. Ignitio n in laboratory environments is
studied for problems including shock tubes and rapid compression machines.
Modeling of the laboratory systems are used to develop kinetic models that can
be Used to analyze ignition in practical systems. Twomajor chain branching
regimes are identified, one consisting of high temperature ignition with a chain
branching reaction mechanism based on the reaction between atomic hydrogen
with molecular oxygen, and the second based on an intermediate temperature
thermal decomposition of hydrogen peroxide. Kinetic models are then used to
describe ignition in practical cOmbustionenvironments, including detonations
and pulse combustors for high temperature ignition, and engine knock and
diesel ignition for intermediate temperature ignition. The final example of
ignition in a practical environment is homogeneouscharge, compression ignition
(HCCI) which is shown to be a problem dominated by the kinetics
intermediate temperature hydrocarbon ignition. Model results show why high
hydrocarbon and CO emissions are inevitable in HCCIcombustion. The
conclusion of this study is that the kinetics of hydrocarbonignition are actually
quite simple, since only one or two elementary reactions are dominant.
However, there are many combustion factors that can influence these two major
reactions, and these are the features that vary from one practical system to
another.

........................... z__ " .... 2_ 2_

Introduction

In manypractical steady combustion systems, ignition is simply a means

of starting the system on its way to steady state: Performance and emissions are

essentially independent of ignition in such systems as boilers, furnaces and

burners. However, in other practical problems, ignition has a great influence on

performance, emissions and other characteristics, and ignition can explain the

performance of the entire system.

Ignition can depend on physical, chemical, and mixing and transport

features of a problem, and in some cases on heterogeneous phenomena.

Excellent reviews of ignition can be found in current sources [1-4], describing

thermal feedback, chemical kinetic chain branching reactions, and other

elements. However, ignitionin general is an enormous subject, and the present

work cannot provide a thorough treatment.

This paper focuses on chemical kinetic factors in practical systems, with

special attention on ignition in automotive engines. Recent advances in

experimental and kinetic modeling capabilities have provided new insights into

ignition, offering newpossibilities for control strategies and newclasses of

combustors.

General Features of Ignition

Manyinteresting systems involve chain reactions, such as nuclear

reactors, with neutrons as chain Carriers. Chain termination is provided by

neutron absorbers, and chain branching is associated with the term

"supercritical’, normally a condition to be avoided. Populations of living

organisms obey the same reactivity laws. Organisms can grow exponentially via

2
chain branching until limited availability of nutrients first stabilizes the

population and eventually quenches the system via chain termination.

Reacting systems follow the general equation

dn(t) = k n(t) (1)

dt

where n(t) is the numberof chain carriers. This indicates that the change

number of neutrons in a reactor depends on the number of neutrons available to

produce further neutrons, or the change in the number of bacteria depends on

the number of bacteria which can reproduce, a reflection that the current

population of chain carriers produces the next generation of chain carriers.

Solution of equation (1) leads to the expression

n(t) = n(0) exp(k (2)

Whenk < 0, the result is exponential decay; whenk > 0 the radical population

experiences exponential growthl Thus k --- 0 is equivalent to criticality or steady

combustion (or population stability). In a chemically reactive system, the

coefficient k is an average Over all reactions taking place, including initiation,

termination, propagation and branching reactions. Wecan define ignition by

requiring that the reacting system must experience exponential growth both in

temperature and number of chain carriers, and the exponential chain reaction

must proceed for a significant degree of fuel consumption.

Chain reactions

Early analyses [5,6] established the chain character of reaction of the

H2-O2 system, and the same principles apply to hydrocarbon oxidation. Chain

carriers are radical species such as H and O atoms, and OH, CH3, HO
2 , and it is

Usually straightforward to identify reactions as initiation, propagation,

branching, and termination.

Initiation reactions generate radicals from stable species, such as the

decomposition of propane:

C3H8 ---~ CH3 +

5 C2H (3)

Chain propagation reactions maintain the numberof radical species, as in:

C2H 6 + OH ~ C2H 5 + H20 (4)

consuming OHand producing ethyl radicals. Chain termination reduces the

number of radicals, as in recombination producing stable butane:

C2H5 + C2H5 ~ C4Hi0 (5)

The key to understanding ignition kinetics is to identify the chain

branching steps under conditions being studied. In chain branching reactions,

the numberof radicals increases, as in:

CH4 + O --+ CH3 + OH (6)

consuming one O atom and producing two radicals. The most important high

temperature chain branching reaction consumes one H atom and produces two

radicals, O and OH:

4
 H + 0 2 -+ O + OH (7)

These illustrations are encapsulated into single reactions. However,it is

commonto find situations where chain propertie s are best attributed¯t.o a

sequence of reactions. ¯ For example, an important reaction sequence is

C3H8 + HO2.~ C3H7 + H202 (8)

H202 --~ OH + OH (9)

consuming one hydroperoxy radical and producing three radicals, a propyl

radicaland two hydroxyl radicals. In some situations, the sequence of reactions

can be muchlonger before its chain properties become evident.

¯ Finally, not all radical species have the sameinfluence on the overall

reaction rate, dueto subsequent reactions with different branching

characteristics. For example, at high temperatures, where reaction (7)is the

major chain branching step, production of ethyl radicals accelerates the overall

rate of igniti6n because C2H5 produces H atoms Which then provide

C2H5 --~ C2H4 + H (10).¯

chain branching via reaction (7), while production of methyl radicals actually

decreases or inhibits the overall rate of ignit!on at high temperatures because

methyl radicals recombine, resulting in chain termination:

CH3 + CH3 ~
6 C2H (11)

The specific reaction sequences that provide chain branching change as the

temperature, ¯ pressure and reactant composition change. In discussions below,

chemical kinetic factors for ignition under a variety of conditions will be

5
examined, and for each environment, the essential task will be to identify the

chemical kinetic reaction sequences that lead to chain branching,

High temperature ignition, shocl~ tubes, detonations and pulse combustors

At temperatures above about 1200K, the dominant chain branching stepin

hydrocarbonignition is reaction (7) [7-12], with H atoms that are produced

thermal decomposition of radicals such as ethyl, vinyl, formyl, isopropyl and

others. Activation energies of these reactions are quite large (e.g., 30 kcal/mol)

and the activation energy of reaction (7) is also quite ¯large (16.8 kcal/mol),

these reactions need high temperatures to proceed.

Shock Tubes

High temperature (T > ~1200K)shock tube ignition is controlled by reaction

(7). At shock tube temperatures, there is an initiation period for radical

generation, followed by a period of explosive, exponential growth in radicals,

dominated by reaction (7), consuming fuel and increasing the temperature. An

interesting series Of experiments was reported by Burcat et al. [i3] for ignition of

stoichiometric mixtures of n-alkanes in oxygen/argon. Fuels included methane,

ethane, propane, n-butane and n-pentane. Measured ignition delay times are

¯ summarized as symbols in Figure 1, together with computed values using kinetic

reaction mechanisms, with the exception of ethane; the heavy dashed line is a fit

to the experimental results forethane ignition, and no computed results for

ethane are presented in Fig. 1. Calculated results for iso-butane are indicated as

a dotted line and are virtually indistinguishable from n-butane and n-pentane.

Of these five n-alkane fuels, methane ignites slowest, ethane most rapidly, and

6
the three higher n-alkanes have intermediate reactivity and are very similar ~to

each other. Kinetic modeling shows that methaneignites slowest because methyl

radicals, resulting¯’from H atomabstraction from methane,lead to chain

termination through reaction (11). Ethane is most reactive because every ethyl

radical, resulting from H atom abstraction from ethane, produces an H atomvia

’reaction (10). For higher n-alkanes, two or morealkyl radicals are produced,

some of which produce H atoms and chain branching through reaction (7), and

some produce methyl radicals and chain termination through reaction (11). For

example, butyl radicals from n-butane decompose:

1-C4H9 ---~ C2H4 + C2H5 (12)

2-C4H 9 ~ C3H6 +
3 CH (13)

Since reaction (10) produces H atoms from C2H

5, these two steps show that

n-butane produces a mixture of H atoms and CH

3 radicals, and the same is true

with propane and n,pentane. Thus methane and ethane represent extremes of

reactivity, while larger alkane hydrocarbonshave intermediate ignition

properties due to their mixed production of H and CH3.

¯ Sensitivity of the high temperaturemechanismto reaction (7)

responsible for manypractical phenomena:Flame and detonation inhibitors

catalyze removalof¯H atoms[14-19], as illustrated here in the case of HBr:

H q- HBr---~ H2 +,Br (14)

H+ Br 2 --+ HBr + Br (15)

2Br+ Br + M ~ Br +M (16)

7
for a net reaction of:

H+H
2 --~ H

This net removal of H atoms reduces the number of H atoms available for chain

branching via reaction (7) and slowing the overall rate of ignition.

This discussion addresses the most commonshock tube experiments.

However, some shock tube experiments are carried out at lower temperatures

(e.g., [20]) or at significantly elevated pressures (e.g., [21]), wherethe chain

branching reaction sequences are different from the conventional high

temperature conditions outlined here; these reaction environments will be

discussed below.

Detonations

High temperature ignition kinetics and reaction (7) play essential roles

propagation of gaseous detonations, where post compression detonation

temperatures and pressures are comparable with those in shock tubes. Although

it is often convenient to consider a detonation as a planar phenomenon,

detonations have a complex, three dimensional structure caused by interactions

between transverse waves in the reac rive medium[22,23]. The reactive shock

wave decays during propagation and would fail if new ignition spots were not

created by intersecting shock waves, or Machstems. For this reason, detonation

propagation depends very strongly on ignition kinetics. The result of these

interactions is a cellular structure that can be measured using smokedfoils in

laboratory experiments. The widths of these detonation cells are fundamental

8
features relating to the initiation, propagation and stability of gaseous

detonations.

Because detonation structure is inherently three dimensional, and the

reaction zone is spatially thin relative to cell sizes, computermodels for

detonations [24] have been unable to include full chemical submodels, although

recent models [25], have used tabular look-up techniques to include finite-rate

kinetics. Advancesin massively parallel computer capabilities are likely to

permit inclusion of detailed kinetics in future three dimensional CFDmodels of

detonations.

Given computer costs of a 3D detonation model, the pseudo-one-

dimensional ZNDmodel [26-28] has been used to relate computed ignition delay

times to characteristic spatial and energy scales in a detonation. This approach

calculates ignition delay times behind a CJ Shock wave to define a characteristic

length scale in thereacting gas mixture [29-37], which is then proportional to the

cell width, ~critical tube diameter, minimuminitiation energy and other

detonation characteristics.

An exciting current development is extension of kinetic modeling to study

detonations of condensed phase explosives [38-41], such as ammonium

perchlorate, RDXor HMX:These models require treatment of three-dimensional

fluid mechanics, multiphase phenomena and detailed chemical kinetics, and

massively parallel computing is essential computational tool. Ignition kinetics in

such an environment are complex, and a great deal of new research is needed.

9
Pulse combustion

Pulse combustion has been knownfor centuries, but only recently have its

physical and chemical principles become understood. Ignition and heating in the

pulse combustor force exhaust gases out through an exhaust pipe; the resulting

lower pressure in the combustion chamber then draws in fresh fuel and air. This

fresh mixture combines with hot residual products of the previous burn, and the

resulting fresh reactants and residual gases ignite, starting a new cycle. Because

the average temperature is relatively low, production of NO

x is also low.

Keller et al. [42-45] examinedmixing, kinetics of ignition, and resonant

acoustic wave propagation in the pulse combustor, showing that ignition must

be timed to occur in phase with resonant pressure waves in the combustion

chamber..

The kinetic submodelfor this system mixes fresh fuel and air, initially at

room temperature, with hot residualgases from the preceding cycle, steadily

increasing the temperature of the fresh mixture as well as diluting it with the

residual products. The overall reaction rate remains negligible until the mixture

reaches temperatures about 1200K, where ignition is controlled by reaction (7).

The kinetic model for this system predicts the influence of additives and

variability in natural gas composition [46] to manipulate the kinetics of ignition

in a pulse combustor. This is a very rich system in terms of the parameters that

can be adjusted to optimize the phasing between kinetic ignition ¯ and the

resonant pressure wave in the combustion chamber. In addition to the kinetic

parameters; the combustion chamber acoustic time scales can be modified, and

the mixing rate can be varied by adjusting intake ports for fuel and air.

10
Interinediate temperature ignition/rapid compression machines, engine

knock, diesel ignition and homogeneous charge compression ignition (HCCI)

At temperatures above about 850K but below 1200K, reaction (7)is too

slow to provide sufficient branching rates for ignition, and a different reaction

path dominates. Key reactions include:

H + 02 + M --+ HO2 + M (17)

RH + HO2 --+ R + H202 (18)

H202 + M -+ OH + OH + M (19)

where RHis an alkane, R is an alkyl radical and Mis a third body. Collectively,

reactions (17-19) consume one H atom radical and produce two OHradicals,

providing chain branching.

Kinetic studies in flow reactors and stirred reactors [47-49] at

temperatures about 1000Kshow that reactions (17-19) control combustion rates.

In this range, reaction. (19) is rapid, so H202decomposesas rapidly.as it

formed and H202 concentrations do not build up to appreciable levels.

However, in manypractical systems, the dominant feature of ignition is the

accumulation of H202 until a temperature is reached where it decomposes to

cause ignition. This is true in the laboratory rapid compression machine, and it

is also the central kinetic feature in engine knock in spark ignition engines,

ignition in liquid fueled diesel engines, and in the operation of homogeneous

11
charge
2 compression ignition (HCCI) engines. In each of these systems, H20

forms at lower temperatures and remains relatively inert, until increasing

temperature from compression and exothermic reactions reaches a level where it

decomposesrapidly via reaction (19). Each of these examples will be discussed

below.

Rapid compression machine

Rapid compression machines (RCM)have been used for many years [50-

52] and provide a fertile environment for study of hydrocarbon oxidation. The

apparatus providesa combustion chamber with a single piston stroke, leaving

the compressed gases at temperatures from 550K to 950K, depending on the

compression ratio of the RCMand specific heats of reactant gases. Compressed

gases can undergo~a single-stage or two-stage ignition, or the reactants maynot

ignite at all while heat transfer cools the mixture to room temperature.

Typical results in Figure 2 are taken from numerical simulation of ignition

of a stoichiometric mixture of neopentane and oxygen in N2 and Ar in

proportions of C5H12/O2/N2/Ar= 0.0256/0.2048/0.38/0.39 at a post-

compression temperature of 757K[53]. In this example, the temperature history

shows a well defined two-stage ignition, the first stage occurring after a delay of

5 msec, reaching a new temperature of about 880K. Temperature then remains

relatively constant, rising slowly for the next 6-8 msec, then rising more rapidly

until a total elapsed time of 14 msec, whenthe second stage ignition is observed

and the temperature rises rapidly, consumingall of the fuel. In other cases, the

12
first stage can occur during the compression :stroke [54,55] and is completed

before the end of the compression, while in other cases there is no discernible-

first stage ignition.

The first stage ignition is a result of rather complexkinetic features of low

temperature hydrocarbon oxidation [56]. This regime has considerable

importance in theoretical and practical systems, and we will return to describe it

in more detail below.

Figure 2 plots the concentrations of fuel, H202 and OH. During the time

preceding the second stage ignition, H202concentration increases steadily.

Until the temperature approaches 1000K, decomposition of H202 is much slower

than its production, and the small amounts of OHthat are produced are

consumedby reactions with the fuel [57]. Whena temperature close to 1000Kis

reached, reaction (19) accelerates, H202disappears and OHconcentration

increases rapidly. The increased OHconcentrations rapidly consume any

remaining fuel, followed by a rapid increase in temperature. Thus,

decomposition of H202 and consumption of fuel result in ignition.

There is a critical temperature for ignition through H202 decomposition

that is a ftmction of the pressure of the reactive system. This is seen by

examining the rate of H202 decomposition

d [H202]_ = - [H202] [MI k (20)

dt
where Mis the total molar concentration. This equation can be rearranged into

the form [H202]/(d[H202] /dt), a characteristic decomposition time is

z = [H202] /(d[H202l/dt) = 1/(k[M]) (21)

With the rate constant for reaction (19), k19 = 1.2 x 10!7 * exp(-45500/RT),

becomes

-1 18
~ 8.3
= x 10 * exp(+22750/T) * [M] (22)

As temperature increases, ~. becomes smaller, and when it is "short" compared to

the residence timG, ignition occurs. Characteristic decomposition time also

decreases with increasing total concentration [M], or with increasing pressure at

constant temperature. Therefore as pressure increases, the Critical temperature

for ignition decreases gradually.

Total post-compression concentrations in a representative RCM

experiment are I x 10-4 mol/cm3, so ¯ is approximately 7.8 ms at

T = 900K, 640 bts at T = 1000Kand 80 ~ts at T = 1100K.With total reaction times of

tens of milliseconds, rapid decomposition is observed at about 950 - 1000K, with

characteristic times for ignition tess than a millisecond. In studies of ignition at

the higher pressures of internal combustion engines, including spark ignition,

diesel and HCCIengines, the same calculation of equations 20-22 shows that this

simple mechanism predicts ignition at temperatures between 900K and 950K

[58]. Analysis of reaction (19) by Griffiths and Barnard [1] at its high pressure

limit shows similar rates of decomposition at somewhatlower temperatures,

consistent with the above trends as pressure increases.

14
 The key is that H202 decomposes rapidly at.temperatures of 900 - 1000K,

so this temperature can be considered as a critical value in systems Wherethe

temperature approaches this value from lower temperatures. ¯H202 is produced

at lower temperatures by low and intermediate temperature kinetic pathways,

until the decomposition temperature is reached, when the system suddenly

produces large numbers of OHradicals and rapidly ignites. ~The most important

variable is the time at which they reach this critical¯temperature. ’Anything that

will accelerate reaching this critical temperature advances its ignition, while
\

delaying it inhibits ignition. The importance of the first stage, low temperature

oxidation period, is that it provides heat release early in the reaction history, so

the reactive mixture arrives at the decomposition temperature earlier than would

have occurred without that ¯early heat release.

Lowtemperature chemical kinetics

Low temperature hydrocarbon oxidation has been studied extensively

[56]. Following abstraction’of H atoms from the fuel, at high temperatures the

alkyl radical R decomposes, producing olefin and smaller alkyl radicals, and

reaction (7) is the dominant chain branching reaction as discussed above.

lower temperatures, 02 adds to the alkyh

R + 0 2 ÷ M --~ RO2 + M (23)

The equilibrium constant for reaction (23) is strongly temperature dependent and

is strongly in favor of RO2 at low temperature, shifting toward R +02 as

15
temperature increases. RO2 radicals isomerize to produce a QOOH
radical

species

RO2 --> QOOH (24)

Isomerization depends sensitively on the size and structure of the original fuel

molecule and the site in that fuel where the 02 2group is located [56,58]. The RO

will be produced with excess energy, so it is important to understand the rate of

collisional stabilization, and whether subsequent reactions occur from the

activated or ground state of RO2. The simplest example of such a system is the

ethyl radical, with RO2 being the ethylperoxy radical C2H502 and QOOH
being

the hydroperoxyethyl radical C2H4OOH.This system has been studied

extensively [59~63], andeven this small system is not fully understood. Bozzelli

et al. [64,65] examinedthe propyl + 02 system, but little experimental or

theoretical work has been done for larger systems.

Several factors influence the rate of internal H atom transfer or radical

isomerization. The species forms a ring-like transition state where the terminal O

atom approaches an extractable H atom within the RO2 species. The number of

atoms in this transition state ring influences the rate of reaction, with 6- and 7-

memberedrings having the most rapidrate. The type of C - H bond broken has

a strong influence,.with primary C - H bonds being strongest, secondary C - H

bonds next, and tertiary C - H bonds being weakest. The rate and number of

16
possible RO
2 isomerization reactions increase with the fuel molecule size and are

fastest in long, linear alkane fuel molecules, with a large numberof 6- and 7-

memberedtransition state rings and a high percentage of easily abstracted

secondary C - H bonds, and are slowest in highly branched fuel molecules, with

fewer low energy transition state rings and large percentages of difficult-to-

abstract primary C - H bonds [58].

QOOH
species react via several alternative paths which are formally Chain

propagation steps, beginning with one alkyl radical and produce one

QOOH Q
2 ~_ HO (25)

QOOH QO + OH (26)

HO
2 or OHradical, in addition to a stable olefin or cyclic ether. However,it is

also possible for a second 02 molecule to add to QOOH,creating a radical

QOOH + 0 2 --~ O2QOOH (27)

O2QOOH
, which can then isomerize further, again with rates dependent on the

structure
2 and size of the original fuel molecule, as observed for RO

isomerization. The isomerized product decomposes into a relatively stable

ketohydroperoxide species and one OHradical. The ketohydroperoxide species

then has its own temperature for decomposition at about 800K, somewhat lower

than that of H202. Upon reaching this temperature, the ketohydroperoxide

decomposesinto several pieces, at least two of which are radicals. Thus, it is not

until this final ketohydroperoxide decomposition step that chain branching is

17
finally achieved in the low temperature Oxidation regime. Since at least three of

the ultimate products of this reaction sequence are radicals, chain branching is

quite strong once the ketohydroperoxide decomposes. Production of metastable

intermediates, ketohydroperoxide in this case and H202 earlier, followed later

by the higher temperature decomposition of the metastable intermediate to

finally provide chain branching, are examples of degenerate chain branching.

Detailed low temperature reaction mechanisms have been developed [53-

55,58,66,67] for a variety of hydrocarbonfuels.

This highly branched, low temperature oxidation phase continues until

the temperature has increased enough that the equilibria in the molecular oxygen

addition reactions (23) and (27) begin to shift towards dissociation. Because

acti~cation energies for dissociation are large (i.e., ~35 kcat/mol), the reactions

shift rapidly towards dissociation as temperature increases. This shift with

hydrocarbon fuels occurs at temperatures near 850K. The temperature above

which these equilibria favor dissociation has been termed the "ceiling

temperature" by Benson [68,69].

The effect of fuel molecular structure on both the first and second stage

ignition is illustrated in Figure 3, from Ribaucour et al. [53]. The three isomers of

pentane are compared at the same post-compression temperature of 757K. All

three mixtures ignite at about 950K. N-pentaneignites first since its first stage

occurs first and provides the largesttemperature increase, neopentane (2,2-

dimethyl propane) ignites next and iso-pentane (2-methyl butane) is last,

because the time of occurrence and temperature increase of the first stage

ignition Vary in that order. All ignite when¯theyreach the same critical

¯ 18
temperature for H202 decomposition, and the differences between the isomers

are the times whenthe fuel mixtures reach the critical temperature.

Total heat release in this low temperature regime is .quite modest. In

Figure 3, this varies from 50Kfor 2-methyl butane to 150Kfor n-pentane. In

engine studies, at TDCthis difference makes a significant impact on ignition

properties of the combustion system.

An interesting variation of this analysis simulates an RCMexperiment in

which anadditive has been included in the neo-pentane fuel. This additive,

ozone, has an initial concentration of 10 ppm and decomposesearly in the

experimental cycle, since .the activation energy for ozone decomposition is 24

kcal/mol, much less than the 45.5 kcal/tool forH202 decomposition. Repeating

the analysis of equations 20 -22, the critical decomposition temperature for

ozone at present conditions is about 600K. Computedresults of this example are

shown in Figure 4.

Decomposition of ozone at 5 ms before TDC(at ~600K) produces O atoms.

Each O atom consumes two fuel molecules

03 + M ~ 02 + O + M (28)

C5H12 + O --~ C5Hil + OH (29)

C5H12 + OH --~ C5Hll + H20 (30)

Pentyl radicals then proceed via reactions (23-27) and produce the metastable 5

ketohydroperoxide species, the production of which is shown in Fig. 4,

immediately following the decomposition of ozone.

19
 Ketohydroperoxide decomposition has an activation energy of about 42

kcal/mol, so it decomposesat about 800K, as seen in Fig. 4. Production of OH

from decomposition produces further water and heat release. Decomposition of

H202 and the ketohydroperoxide and the resulting heat release brings the

reactive mixture to the first ignition stage before the conclusion of the

compression stroke. Fig. 4 shows a slight inflection point at TDC,indicating that

the low temperature ignition is well underway as the compression stroke ends.

This phase stops at about 850K, the same temperature at which the first stage

ended in the original mixture, without ozone (Figs. 2 and 3). Kinetics of the first

stage have not been altered by the additive, but the time at which if begins was

advanced by adding ozone, which stimulated early heat release.

The major intermediate being produced is still H202, and it still

decomposes at 950 1000K, producing the real ignition. The ozone additive

advances the time of ignition from about 14 msec after TDCto about 9 msec after

TDC.The second stage ignition is the same in both cases, but the addition of

ozone makes that mixture reach the ignition temperature at an earlier time.

Finally, note the peak in O atom concentration that occurs at each of the three

stages of ignition, at times of -6, +1 and +9 msecafter ¯ TDC.

Engine Knock

In spark ignition engines, thermodynamic combustion efficiency increases

with engin e compression ratio. However, increased compression ratio

eventually results in engine knock, limiting engine efficiency in practical engines.

Numerical studies have used reduced [70-74] and detailed [66,74-78] kinetic

models to understand chemical factors responsible for knock.

20
 In a spark ignition engine, a flame propagates through a combustion

chamber, starting at the point of spark ignition. Somereactant gases in the

combustion chamber will naturally be the last to be consumedby the flame,

termed the "end gases’q End gas conditions are determined by piston motion

and combustion in the engin e chamber. As piston motion and flame propagation

proceed, end gases see increasing levels of pressure and temperature and react

accordingly. If end gasesreach the point of ignition before being consumedby

t~he flame, knocking behavior will be observed. Mixtures that react more rapidly

are more susceptible to knock, while mixtures that ignite more slowly resist

knock. Increasing the engine compression ratio increases the rate of autoignition

while having little effect on flame propagation, so this increases the potential for

knocking behavior. Thus engine knock is essentially an ignition problem.

Computational modeling of autoignition at engine conditions shows the

same features as described for the rapid compression machine. This can be

illustrated by examining the way that fuel composition, molecular size and

structure influence autoignition behavior and tendency to knock by simulating

the critical compression ratio. Experiments are carried out in a CFRengine at a

low engine speed of 600 rpm and intake manifold temperature of 403K. These

are essentially the same conditions as those in standardized tests for research

octane number (RON)For stoichiometric fuel/air mixtures, the engine

compression ratio is steadily increased until autoignition is observed. A series of

such experiments were carried out by Leppard [79] for a range of alkane and

primary reference fuel mixtures, and a kinetic model was used to simulate those

experiments [66,72]. Computedand experimental critical compression ratio

results are plotted in Figure 5, together with measured research octane numbers

21
of each fuel. A rather smooth curve results, although it is clearly not a straight

line, indicating that octane rating is a rather nonlinear scale.

A numerical experiment can be carried out to use this information to

construct a fuel mixture with an arbitrary octane rating. For example, to create a

fuel with a research octane number (RON)of 90.8, a motor octane number

(MON)of 83.9, and an overall octane rating (RON+MON)/2

of 89, to compare

with ordinary gasoline, a mixture of two isomers of hexane and two isomers of

pentane was defined in terms of their individual RONand MONvalues. These

four fuel components are indicated by the arrows in Fig. 5. Whentested

numerically, this mixture had a critical compression ratio corresponding to a

RONof 90A, very close to the blending value, as shown in Fig 5.

A critical feature of these’computed histories is that they reach peak

compression temperatures that are all very nearly the same. Considerable

differences in octane numberresult in only a few degrees of temperature at top

dead center (TDC), resulting in considerable difference in time of ignition and

demonstrating that the octane number scale is highly nonlinear.

Just as observed in the RCMresults, these computed results indicate that

ignition in each of these cases occurs when H202 decomposes. Differences in

octane numberare reflected in small differences in cool flame heat release, with

greater
2 amounts of low temperature heat release and higher quantities of H20

correlating with earlier ignition and lower octane values. Similar conclusions

2were obtained by Blin-Simiand et al. concerning the central role of H20

decomposition and its role in autoignition [103].

22
 The effects of various antiknock compoundscan be understood in this

same framework. Additives including tetraethyl lead, now no longer used,

provide kinetic sinks for HO

2 [58,80,81],
2 greatly reduce the production of H20

and interfere with the intermediate temperature ignition process. Other

additives including methyl tert-butyl ether (MTBE)act by interfering with low

temperature oxidation [18,58], reducing the amount of low temperature heat

release,
2 and retarding the time at which the end gas reaches the H20

decomposition temperature.

Diesel ignition

Diesel engines have existed for manyyears, but until recently manyof the

basic physical and chemical principles of diesel combustion had not been well

understood. Recently, in a series of insightful laser diagnostic studies, Dec

provided a coherent, self-consistent picture of diesel combustion [82]. His

results, summarizedin Figure 6, show that the fuel jet vaporizes rapidly and

mixes with hot, compressed air. The air steadily reduces the fuel/air equivalence

ratio at the same time that it is increasing the mixture temperature, and the

mixture begins to react. In Dec’s observations, this mixture eventually ignites

while the equivalence ratio is still quite high (~ ~ 4). Soot production was

observed to proceed immediately from the products of this rich, premixed

ignition, and soot is consumedin a diffusion flame at the periphery of the

downstream cloud.

This large scale ignition problem has been analyzed using detailed

chemical kinetics [83]. The premixed region begins to react when the local

23
equivalence ratio reaches ~ ~ 10, although the rate of reaction is initially quite

slow. As air mixes and the mixture temperature increases, the rate of reaction

increases. Rapid reaction begins when the mixture temperature reaches about

700K. As noted above for other Classes of applications, this low temperature

reaction produces ~ H202 and produces a modest amount of heat release and

temperature increase. Eventually the mixture reaches the temperature where

H202 decomposes and ignition is observed. Thus the kinetic mechanism of

diesel ignition is identical with that of the RCMand that of engine knock in

spark-ignition engines. The major differences occur because diesel ignition takes

place under very fuel-rich conditions.

Diesel ignition improvers [84] are species like ethyl-hexyl nitrate that

decompose at temperatures much lower than the ignition temperature provided

by H202 decomposition. Radicals produced by decomposition of the additive

consume some fuel and release some heat, raising the temperature of the

premixed gases and getting them closer to th e H202 decomposition temperature.

Other additives that decompose at lower temperatures and provide radicals

would also be effective diesel ignition improvers or cetane improvers. The

example of ozone discussed earlier for the RCMwould enhance diesel ignition in

this same manner.

Anespecially interesting additional feature of this premixed ignition is the

observation by Dec that the products of the rich premixed ignition immediately

begin the process of soot precursor and soot production. In computed models of

this rich premixed ignition [83], the products of the ignition are the same species

4
that have been shown [85-88] to preferentially produce small aromatic ring

species such as benzene, toluene and naphthalene. Small aromatic species then

react to produce larger polycyclic aromatic species and eventually soot. It has

been shown experimentally [89] that addition of oxygenated species to the fuel

can reduce soot emissions in diesel combustion, and this trend has been

reproduced by kinetic modeling [83] by correlating the total product

concentrations of aromatic formation precursors with the amounts of these

simple species that survive the premixed rich ignition stage. Thus soot

production is directly related to ignition kinetics in the diesel engine.

Figure 7 shows concentrations of soot produced in diesel engines with the

relative amounts of oxygenates in the fuel from the experimental work of

Miyamotoet al. [89]. Also shownis the total concentration of ethene, acetylene,

and propargyl radical, summedtogeiher, to roughly produce a curve similar to

that derived experimentally by Miyamotoet al. These modeling calculations [83]

were carried out for a variety of oxygenated species (i.e., methanol, ethanol,

dimethyl ether, dimethoxy methane, methyl butanoate) added to n-heptane; n-

heptane is a realistic surrogate diesel fuel with a cetane numberof 56. This work

suggests strongly that rich premixed ignition does indeed produce the seeds of

soot formation, and that lowering the post-ignition concentrations of these

elementary species effectively reduces soot production. The sequence of fuel/air

mixing, rich premixed ignition and production of soot precursors, followed

eventually by soot burnout, provides a framework for diesel combustion in

which each of the detailed steps leads very naturally and continuously to the

next step.

25
Homogeneous Charger Compression Ignition (HCCI)

Combustion in reciprocating engines under homogeneous charge,

compression ignition (HCCI) conditions is an intriguing technology that may

offer the opportunity to eliminate NO

x emissions from engine combustion.

Particulate emissions are also observed to be very low. Disadvantages are high

unburned hydrocarbon and COemissions, along with high peak pressures and

high rates of heat release.

In an HCCIengine, a premixed, very lean mixture of fuel and air is drawn

into the engine chamber and compressed by a piston. Near TDCthe majority of

the charge in .the engine ignites homogeneously. The time of ignition can be

varied by changing compression ratio, fuel/air equivalence ratio, the time of

intake valve opening, and intake manifold temperature.

HCCIwas identified as a distinct combustion phenomenonabout 20 years

ago. Initial studies [90-92] recognized the basic characteristics of HCCI;ignition

occurs at manypoints simultaneously, with no flame propagation. It is

controlled primarily by chemical ignition kinetics, with little influence from

effects such as turbulence or mixing that play such a large role in other engine

combustion problems. Simplified kine tics models have been used to analyze

HCCIcombustion, coupled usually to multidimensional CFDmodels [93-97],

with limited success.

Recently, detailed kinetic modeling has been used to examine HCCI

combustion [97-99]. For a numberof practical fuels, including natural gas,

propane and others, model calculations have reproduced the onset of ignition in

good agreement with experimental results carried out at the Lund Institute of

26
Technology [100,101], using a spatially homogeneous model. The product

temperature is kept low by operating at very lean conditions, so temperatures are

too low to produce significant NO

x emissions. However, a one-zone,

homogeneous treatment produces much too rapid a combustion duration, as

shown in Figure 8, and cannot predict COand hydrocarbon emissions.

HCCIengine wall temperatures are low, so there is an extensive engine

chamber thermal boundary layer, and not all the boundary layer fuel bums

together with the initial bulk ignition. In addition, there is unburned fuel in

piston ring and other crevice volumes that does not burn immediately. Since the

peak bulk temperatures are low and decrease further after TDC,most fuel in the

boundary layer and crevices cannot diffuse out into the bulk gas and bum; this

material is ultimately exhausted without further reaction. However, some

fraction of these gases can be partially burned, resulting in products of

incomplete combustion and especially CO.

A full kinetic, spatially varying model [98] can account for the

temperature distribution in the boundary layer and crevices, in addition to the

main bulk Charge, to predict unburned hydrocarbon and COemissions from this

engine. As a result of this varying temperature distribution in the fuel/air

mixture, the overall heat release is spread out in time relative to the one-zone

homogeneous treatment, in much better agreementwith experimental results, as

shown in Fig. 8 for cases in which the bulk region and boundary layer were

defined by 10 spatial zones. This more refined model describes many

experimental features of HCCIvery well except for the predicted COemissions,

as shown in Figure 9.

27
 The kinetic details of these model computations indicate that HCCI

ignition is controlled by H202decomposition. Computedvariations in selected

species concentrations are summarizedin Figure 10, in which it is clear that

H202 decomposition occurs at the time of autoignition, observed experimentally

[99] to occur at about 1° after TDC.The fuel/air mixture follows a temperature

and pressure history Very similar to those encountered by end gases in spark-

ignition engines and in a rapid compression machine. Modest heat release

occurs at lower temperatures, depending on the cool flame reactivity of the

specific fuel or fuel mixture, resulting in variable amountsof early temperature

increase. Variation in any engine parameter that gets the reactive fuel/air

mixture to the H202 decomposition temperature of about 1000Kearlier will

¯ advance ignition, and anything that delays reaching that temperature will retard

ignition. Increasing the intake manifold temperature and use of pro-ignition

additives suchas ozone (see Fig. 4) or ethyl-hexyl nitrate advance igntion, while

exhaust gas recirculation (EGR) and addition of knock suppressants retard

ignition.

In many ways, HCCIcombustion is very simple. Low and intermediate

temperature reaction sequences process the fuel/air mixture during its

compression; the amount of low temperature, cool flame heat release varies,

depending on the composition of the fuel. Ignition occurs at the temperature

where the core fuel/air charge reaches the H202 decomposition temperature, so

models developed for engine knock and rapid compression machines are directly

28
applicable to HCCIsystems. LowNO
x production is a result of the very low

overall fuel/air equivalence ratio; the low equivalence ratio is possible because

flame propagation is not required in the HCCIengine [102]. Combustion is

spread out in time because the extended boundary layer reacts later than the core

gases. High hydrocarbon and COemissions are an inevitable result of the low

bulk gas temperatures and wall boundary layers, and it is very likely that post-

combustion, exhaust gas treatments will be necessary to make HCCIcombustion

viable; If low temperature hydrocarbon catalysts were to become available,

HCCIwould represent an important competitor to conventional spark-ignition

and diesel engines.

Summary

The role of chain branching in determining the onset of ignition has

identified two distinct chain branching mechanisms affecting hydrocarbon

ignition in practical systems. The high temperatures (above ~1200K), mechanism

is important in shock tube ignition and practical systems including detonations

and pulse combustors. These are primarily thermal ignitions, where heat release

increases the temperature, further increasing:the rate of ignition until reactant

depletion ends the ignition.

The Second chain branching regime depends on H202 decomposition at

about 900 - 1000K. Experiments in rapid compression machines and flow

reactors
2 and corresponding modelcalculations confirm the importance of H20

decomposition kinetics and provide insight into the mechanisms of ignition,

29
Whenthese models are then applied to practical systems, especially in engine

environments, it is clear that the samekinetic features control ignition in all of

these systems. Modifications of the combustion environment that enable a

system to reach the decomposition temperature at earlier times advance ignition,

while modifications that delay reaching that temperature retard ignition.

This analysis shows that autoignition in engines is dominated by only one

elementary reaction, H202 decomposition. Low temperature reactions or cool

flames, including the highly chain branched alkylperoxy radical isomerization

kinetic system, simply advance the time at which H202 decomposition is

observed. This simplifies the analysis of combustion ignition phenomenaand

focuses kinetic attention on a very limited family of reactions that control

autoignition phenomenain a very wide range of practical systems.

ACKNOWLEDGMENTS

The manycontributions of colleagues are gratefully noted, including Bill

Pitz, Henry Curran, Fred Dryer, Bill Leppard, Nick Marinov, Nick Cernansky,

John Griffiths, J~irgen Warnatz, Jim Miller, Pat Flynn, Bengt Johansson, Magnus

Christensen and many others who have provided experimental data, theoretical

insight, hard work, and encouragement: Kinetic modeling is a collaboration in

many ways, and the insights provided by the present work are the collective

product of all of these individuals. This work has been carried out under the

auspices of the U. S. Department of Energy by University of California Lawrence

Livermore National Laboratory under Contract W-7405-Eng-48.

3O
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36
FIGURE CAPTIONS

° Ignition delay times for C1 - C5 alkanes. Experimental data are from

Burcat et al. [13], computed lines are Westbrookand Pitz [10]. The dark
dashed line is a fit to the experimental results for ethane ignition from
[13], and no computed results for ethane ignition were carried out.
Experimental points: open triangles - methane; filled circles - propane;
filled squares - n-pentane; open squares - n-butane.

° Computed temperature and concentrations of neo-pentane, H202 and OH

from Ribaucour et al. [53].

° Computedtemperatures in ignition of the three isomers of pentane, from

Ribaucouret al. [53].

° Computedtemperature and selected species concentrations from rapid

compression machine ignition of neo-pentane. Same initial conditions as
Figure 2, but with 10 ppmozone included.

Correlation of computed critical compression ratio with research octane

.
numbers. Solid circles are primary reference fuel mixtures, other symbols
are isomers of hexane and pentane, stars are experimentally measured
values [66].

Schematic model of diesel spray combustion, based on work of Dec [82].

.
The ignition region is identified, and the temperatures of the different
regions in the combusting spray are noted.

° Experimentally observed variation in Bosch smoke number with fuel

oxygenate content, from Miyamotoet al. [89], and Variation in computed
soot precursor concentrations with fuel oxygenate content, from Flynn et
al. [83].

° Comparison between experimental pressure traces [100] and calculated

values, using both a single-zone and a 10 zone modeling treatment [97],
for three natural gas experiments at different boost pressures.

° Ratios of experimental [100] to numerical results [97] for the main

combustion parameters of HCCI, for natural gas at different boost
pressures, using the 10 zone spatial model.

10, Computedconcentrations of basic species in parts per million in the bulk

gases in HCCIignition, with natural gas fuel [97]~

37
Ignition-delay time (s)
 0.03 neo-pentane I 1200

1100
/ -,.
EI ~
0.02 1000

,,,- . ..
~~ 900 ~.
OH
Temperature " -, .." "~ &
:~. 0.01 800
""

L "" ~ ~lP
1--
700

0.00 i i I 60O
-5 0 5 10 15
Time .after TDC[ms]
 1.400
n-pentane

1200
neopentane

= 1000

E 800

6OO iso-pentane

400 I" J

-20.0 -10.0 o.o ~o.o 20.0 30.0

time after TDC(ms)
o03 neo-pentane
il r

-15 -10 -5 0 5 10 15

Time after TDC[ms]

 600 rpm, T--403 K, MAP--81.6 kPa
120 I

110 iC5H12
neoC5H12
100
m- 90 .. [ o 2-3C6H14
~- 8o 3i361
.~
~"
surrogate
7O (RON = 90.4)
6o .’/..~/
~ 5o
4O
~ 3o
2O
10
-6 .z
0 8 10
I

12 14 16 18 20
Critical Compression Ratio
Temperatu res
950 K ~1600 K ~2700 K
350 K 825 K Ignitionzone]

Cold Rich Fuel/Air

Fuel NOx
Mix~-~ = 4 CO2 &
Warm Productsof Rich H20
Air Combustion
CO, U HC& Particulates
Chemistry
0 0 0 0 0 0 0 O 0 0 0 0 0
(%) e~lomSqosoB ¯ sJosJnoeJd swJO=lqo!qM-
uoqJeolan-I jo aBe~ueoJed
3OO

experimental -""-
....... 10¯ zonemodel ~
’E" %. ^2 ’oar ’boost
...... ~--single zonemodel ,

,!.~ ~"

-~,, . ,~
,,’rr 1 bar boost ".,,, ’-:.
100

~ i ’
0 I I I
-30 -20 -10 0 10 20 30
crankangle, degrees
1.,2

0 bar boost
1 bar boost
2 bar boost

Max.Pressure Indicated
Efficiency HC
BurnDuration CombustionEfficiency CO
 2
2
10
H202 ..- ....... ........ OH

H 2
.-°"/i. " ............
=’~ HO
2
,,

,°|
’ H202
,: :’,
.i.,

OH °°. ...°.,. ........

H o...°"
2
.2
10 ,." ..’°;’"

..°,
2 .,,., ...’’"

10-3
-15 -13 -11 -9 -7 -5 -3 -1 1 3 5
crankangle, degrees