Fundamental Concepts in Combustion

Kinetics

CEFRC Princeton University

Charles Westbrook
Lawrence Livermore National Laboratory
Livermore, California

June, 2010
Combustion chemistry
• Combustion is the sequential disassembly of a
(hydrocarbon) fuel molecule, atom by atom, eventually
producing stable products (CO2 and H2O)

• All possible chemical species are included with coupled

differential equations

• Elementary reactions take place between these

species, with assigned reaction rates

• Chain carriers are free radicals H, OH, O, HO2,

CH3, others

2
Chain reactions exist in many forms

 Populations of bacteria
 Populations of people
 Nuclear reactors
 Chemical reactions
dn/dt = α n
n(t ) = no exp α t
α > 0 growth
α < 0 decay
α = 0 stable
Reaction mechanisms

 A reaction mechanism is a collection of the

reactions that are “important” and their
rate expressions as functions of
temperature and pressure

4
 Goals for modeling of large hydrocarbon fuels

• Provide validated chemistry models for combustion in:

Diesel engines
Homogeneous Charge Compression Ignition (HCCI) engines
Spark Ignition (SI) engines
Turbine engines

• Assist in mechanism reduction for simulations with computational

fluid dynamics (CFD)

• Provide combustion insights from kinetic simulations of engine

processes

5
Computational Combustion Chemistry

Fuel + (n1) O2 (n2) CO2 + (n3) H2O

Rate = A Tn exp[- E / R T ] [ Fuel ] a [ O2 ] b

Single reaction step: Useful simplification in 2D or 3D simulations

However, it misrepresents actual reaction paths

An example: propane oxidation
H H H H H •
H C C C H + OH → H C C C H + H2O
H H H H H H

H H H
H C• + C = C
H H H

↓ ↓

H H H
C = O C = C → H C = C H
H H •
Reaction mechanism construction

Reactions N2 + O = NO + N
N + O2 = NO + O

d[NO] = k1+ [N2][O]+k2+[N][O2]-k1-[NO][N]-k2-[NO][O]

dt
d[N] = k1+ [N2][O]+ k2-[NO][O]- k1-[NO][N]- k2+[N][O2]
dt
d[O2] = k2-[NO][O] - k2+[N][O2]
dt
 Chemical Kinetic Model
Contains a large database of:
Thermodynamic properties of species
Reaction rate parameters

Size of mechanism grows with molecular size:

Fuel: H2 CH4 C3H8 C6H14 C16H34

(Propane) (Hexane) (Cetane)

Number of species: 7 30 100 450 1200

Number of reactions: 25 200 400 1500 7000

 LLNL uses chemical kinetic modeling
for a wide range of fuels and problems

Hydrocarbons
Methane, ethane, paraffins through decane
Natural gas
Alcohols (e.g., methanol, ethanol, propanol
Other oxygenates ( e.g., dimethyl ether, MTBE, aldehydes )
Automotive primary reference fuels for octane and cetane ratings
Aromatics (e.g., benzene, toluene, xylenes, naphthalene )
Biodiesel fuels (e.g., alkyl monomethyl esters)
Others
Oxides of nitrogen and sulfur (NOx, SOx)
Metals (Aluminum, Sodium, Potassium, Lead)
Chlorinated, brominated, fluorinated species
Silane
Air toxic species
Chemical warfare nerve agents
Kinetic modeling covers a wide range of systems

Types of systems studied

Flames Waste incineration

Shock tubes Kerogen evolution
Detonations Oxidative coupling
Pulse combustion Heat transfer to surfaces
Flow reactors Static reactors
Stirred reactors Ignition
Supercritical water oxidation Soot formation
Engine knock and octane sensitivity Pollutant emissions
Flame extinction Cetane number
Diesel engine combustion Liquid fuel sprays
Combustion of metals HE & propellant combustion
CW agent chemistry Gasoline, diesel, aviation fuels
Catalytic combustion CVD and coatings
Material synthesis Chemical process control
many others . . . . Rapid compression machine

These studies provide extensive model validation

Hydrogen oxidation mechanism
Overall H 2 + ½ O 2 → H 2O

Actual H2 + OH → H2O + H
H + O2 → H + OH
H + O2 → HO2
H2 + O2 → HO2 + H
………
Rates of elementary reactions

 Reaction A + B → C + D

Rate = k+ = A Tn exp[- E / R T ] [ A ] [ B ]

Usually also a reverse reaction C + D = A + B

k- = k+ / Keq with equilibrium constant from thermochemistry

Of k+ k- and Keq, only two are independent

Some authors use k+ and k-, but most use k+ and Keq

13
14
We focus on three distinct chain branching
pathways

1) H + O2 → O + OH High T

2) H + O2 + M → HO2 + M Medium T

RH + HO2 → R + H2O2
H2O2 + M → OH + OH + M

3) R + O2 → RO2 Low T
RO2 → QOOH → O2QOOH → 3+ radicals
Chain branching at high temperatures

H + O2 → O + OH
“The most important reaction in combustion”

• Activation energy is relatively high (16.8 kcal/mol)

• H atoms produced by thermal decomposition of radicals

e.g. C2H5 , C2H3 , HCO, iC3H7 , etc.
Activation energies relatively high ( ~ 30 kcal/mol)

• Therefore this sequence requires high temperatures

• Illustrated best by shock tube experiments

Chain branching at high temperatures

H + O2 → O + OH

• Chain branching for oxidation, not for pyrolysis

• Lean mixtures ignite earlier than rich mixtures

• Different fuels produce H atoms at different rates,

and their ignition rates vary correspondingly

• Additives that produce H atoms will accelerate ignition,

and additives that remove H atoms slow ignition
Chain branching often occurs over a series
of reactions

Chain branching at intermediate temperatures

H + O2 + M → HO2 + M

RH + HO2 → R + H2O2

H2O2 + M → OH + OH + M

• At temperatures below about 900K, H2O2 decomposition is

inhibited, leading to degenerate chain branching (see below)

• At higher temperatures, H2O2 decomposes as quickly as it is

formed, leading to conventional chain branching

• Other low temperature chain branching paths can be much longer

than this sequence (see below)

H2O2 decomposes at a fairly distinct temperature

• Reaction consuming H2O2 is:

H2O2 + M → OH + OH + M

k+ = 1.2 x 1017 x exp(-45500/RT)

• Resulting differential equation is:

d [ H2O2 ] = -[ H2O2 ] [ M ] k+
dt
Characteristic time for H2O2 decomposition

d [ H2O2 ] = -[ H2O2 ] [ M ] k+
dt

define τ = [ H2O2 ] / (d [ H2O2 ]/dt)

τ = 1 / ( k+ [M])
τ = 8.3 x 10-18 x exp(22750/T) x [M]-1

At RCM conditions, with [M] ≈ 1 x 10-4 mol/cc, values of τ are

approximately:

7.8 ms at 900K 640 µs at 1000K 80 µs at

1100K

At higher compressions (pressures), values of τ are smaller at

comparable temperatures
Rapid compression machine and some turbulent flow reactor
experiments are controlled by H2O2 decomposition

• Rapid compression machine (RCM) usually operates in a

degenerate branching mode

- H2O2 produced at temperatures lower than 900K

- When system reaches H2O2 decomposition temperature,

ignition is observed

• Many turbulent flow reactor experiments operate at temperatures

between 900 - 1100K where H2O2 decomposes as quickly as it

is produced
The central role of the high temperature
chain branching reaction

H + O2 = O + OH

Ignition
Flame propagation
Flame inhibition
Sensitization of methane for natural gas
Effects of pressure on oxidation rates from
competing H + O2 + M reaction
Laminar flames in quenching problems

 Mid-volume quenching in direct injection

stratified charge (DISC) engine
 Bulk quenching due to volume expansion in lean-
burn engine mixtures
 Flame quenching at lean and rich flammability
limits
 Flame quenching on cold walls and unburned
hydrocarbon emissions from internal combustion
engines
Causes and implication of flammability limits

H + O2 = O + OH
H + O2 + M = HO2 + M

 Law and Egolfopoulos for atmospheric pressure

flames
 Flynn et al. extensions to engine pressures

Lean limit moves to richer compositions as pressure

increases, and at engine pressures, lean-limit
mixtures still produce significant amounts of NOx
Flame quenching on engine walls

 Previous concept of UHC emissions

 Idea of making wall layers thinner

 Simple flame model results at Ford weren’t

believed

 Detailed modeling results

 Evidence had been there, Wentworth

 Pictures of wall quenching

Fuel diffuses away from wall

Flame approaching wall
and is rapidly consumed
Flame inhibition

 Halogens
 HBr Dixon-Lewis, Lovachev 1970’s
 CF3Br Biordi et al., Westbrook 1980’s

 Organophosphorous compounds (OPC’s)

 Twarowski early studies
 NIST studies, Linteris, Babushok, Gann, etc.
 Korobeinichev, Melius, Jayaweera et al.

 Net removal of H atoms from radical pool reduces

chain branching from reaction of H + O2 = O + OH
Flame inhibition by halogens

H + HBr = H2 + Br
H + Br2 = HBr + Br
Br + Br = Br2
H + H = H2

CH3Br + H = HBr + CH3

CH3 + Br2 = CH3Br + Br
H + HBr = H2 + Br
Br + Br = Br2
H + H = H2
Other inhibitors

 Organophosphorus compounds
 Iron and other metal compounds

H + H = H2
H + OH = H2O
others
 All remove radicals and reduce the overall
chain branching rates

31
Hierarchical mechanisms
 H2/O2 is the foundation

 CO/CO2 is the next level

 CH4/CH2O/CH3OH is the next level

 C2H6/C2H4/C2H2 is next

 This pattern continues to C10 and C20

 There are many side branches to this tree

32
33
One of the most significant reaction flux
diagrams in all of combustion chemistry

34
Delay of final oxidation by fuel
36
Calculations of H2/Air
Laminar Flame Speeds
 elements
c h n o ar he
end

species
h h2 o o2 oh
h2o n2 ho2 h2o2 ar
co co2 ch4 c2h6 he
!
end
h+o2<=>o+oh 3.547e+15 -0.406 1.660e+04
!rev/ 1.027e+13 -0.015 -1.330e+02 /
o+h2<=>h+oh 5.080e+04 2.670 6.292e+03
!rev/ 2.637e+04 2.651 4.880e+03 /
oh+h2<=>h+h2o 2.160e+08 1.510 3.430e+03
!rev/ 2.290e+09 1.404 1.832e+04 /
o+h2o<=>oh+oh 2.970e+06 2.020 1.340e+04
!rev/ 1.454e+05 2.107 -2.904e+03 /
h2+m<=>h+h+m 4.577e+19 -1.400 1.044e+05
!rev/ 1.145e+20 -1.676 8.200e+02 /
h2/2.5/ h2o/12/ co/1.9/ co2/3.8/

o2+m<=>o+o+m 4.420e+17 -0.634 1.189e+05

!rev/ 6.165e+15 -0.500 0.000e+00 /
h2/2.5/ h2o/12/ ar/.83/ co/1.9/ co2/3.8/
ch4/2/ c2h6/3/ he/.83/

oh+m<=>o+h+m 9.780e+17 -0.743 1.021e+05

!rev/ 4.714e+18 -1.000 0.000e+00 /
h2/2.5/ h2o/12/ ar/.75/ co/1.5/ co2/2/ ch4/2/
c2h6/3/ he/.75/

h2o+m<=>h+oh+m 1.907e+23 -1.830

1.185e+05
!rev/ 4.500e+22 -2.000 0.000e+00 /
h2/.73/ h2o/12/ ar/.38/ ch4/2/ c2h6/3/ he/.38/
h+o2(+m)<=>ho2(+m) 1.475e+12 0.600 0.000e+00
!!rev/ 3.091e+12 0.528 4.887e+04 /
low / 3.4820e+16 -4.1100e-01 -1.1150e+03 /
troe / 5.0000e-01 1.0000e-30 1.0000e+30 1.0000e+10 / !troe fall-off reaction
h2/1.3/ h2o/14/ ar/.67/ co/1.9/ co2/3.8/ ch4/2/ c2h6/3/ he/.67/

ho2+h<=>h2+o2 1.660e+13 0.000 8.230e+02

!rev/ 3.166e+12 0.348 5.551e+04 /

ho2+h<=>oh+oh 7.079e+13 0.000 2.950e+02

!rev/ 2.028e+10 0.720 3.684e+04 /

ho2+o<=>oh+o2 3.250e+13 0.000 0.000e+00

!rev/ 3.217e+12 0.329 5.328e+04 /

ho2+oh<=>h2o+o2 1.973e+10 0.962 -3.284e+02

!rev/ 3.989e+10 1.204 6.925e+04 /
h2o2+o2<=>ho2+ho2 1.136e+16 -0.347 4.973e+04
!rev/ 1.030e+14 0.000 1.104e+04 /
dup
h2o2+o2<=>ho2+ho2 2.141e+13 -0.347 3.728e+04
!rev/ 1.940e+11 0.000 -1.409e+03 /
dup
h2o2(+m)<=>oh+oh(+m) 2.951e+14 0.000 4.843e+04
!!rev/ 3.656e+08 1.140 -2.584e+03 /
low / 1.2020e+17 0.0000e+00 4.5500e+04 /
troe / 5.0000e-01 1.0000e-30 1.0000e+30 1.0000e+10 / !troe fall-off reaction
h2/2.5/ h2o/12/ ar/.64/ co/1.9/ co2/3.8/ ch4/2/ c2h6/3/ he/.64/
h2o2+h<=>h2o+oh 2.410e+13 0.000 3.970e+03
!rev/ 1.265e+08 1.310 7.141e+04 /
h2o2+h<=>h2+ho2 2.150e+10 1.000 6.000e+03
!rev/ 3.716e+07 1.695 2.200e+04 /
h2o2+o<=>oh+ho2 9.550e+06 2.000 3.970e+03
!rev/ 8.568e+03 2.676 1.856e+04 /
h2o2+oh<=>h2o+ho2 2.000e+12 0.000 4.272e+02
!rev/ 3.665e+10 0.589 3.132e+04 /
dup
h2o2+oh<=>h2o+ho2 1.700e+18 0.000 2.941e+04
!rev/ 3.115e+16 0.589 6.030e+04 /
dup
!
 Transport coefficients for species in flames

!
ar 0 136.500 3.330 0.000 0.000 0.000
c2h6 2 247.500 4.350 0.000 0.000 1.500 ! nmm
ch4 2 141.400 3.746 0.000 2.600 13.000
co 1 98.100 3.650 0.000 1.950 1.800
co2 1 244.000 3.763 0.000 2.650 2.100
h2o 2 572.400 2.605 1.844 0.000 4.000
h2o2 2 107.400 3.458 0.000 0.000 3.800
he 0 10.200 2.576 0.000 0.000 0.000 ! *
n2 1 97.530 3.621 0.000 1.760 4.000
o 0 80.000 2.750 0.000 0.000 0.000
o2 1 107.400 3.458 0.000 1.600 3.800
oh 1 80.000 2.750 0.000 0.000 0.000
h2 1 38.000 2.920 0.000 0.790 280.000
h 0 145.000 2.050 0.000 0.000 0.000
ho2 2 107.400 3.458 0.000 0.000 1.000 ! *
 H2/Air
350
Burning velocity cm/sec
300

250

200

150
H2/Air
100

50

0
0 1 2 3 4 5

Equivalence ratio
 Kinetic Modeling of Autoignition:
Engine Knock, HCCI and fuel economy

Charles K. Westbrook
Lawrence Livermore National Laboratory

CEFRC

June 2010
The fuel situation in 1922 looks pretty familiar

• Thomas Midgley, Chief of Fuels Section for General Motors, 1922

– US Geological Survey -- 20 years left of petroleum reserves
– Production of 5 billion gallons of fuel in 1921

• Potential new sources of petroleum

– Oil shale
– Oils from coal
– Alcohol fuels from biomass

• Higher efficiency a high priority for conservation reasons

– People will not buy a car “lacking in acceleration and hill climbing”
– Solution is higher compression ratio, then at about 4.25 : 1
– Obstacle is engine knock, whose origin is unknown
– Result was development of TEL as antiknock
– Phenomenological picture with no fundamental understanding
Explanation of engine knock, ON, antiknocks, diesel ignition, and HCCI
ignition came in the 1990’s from DOE/BES theoretical chemistry and
supercomputing and EERE knock working group

Reactant Transition
state
O O
H O
R O R C
H O O OH
R C O
H + O2
R H

R H
R H
O
OH + OH

R R O
O

R O
O O OH O
O O

H H O

+ OH
H H O

Alkylperoxy radical isomerization rates are different

in paraffin and cyclic paraffin hydrocarbons Low temperature chain branching paths

Most work has been done for alkane fuels, and many questions remain for
aromatics, cyclic paraffins, large olefins
Chemistry of alkylperoxy radical isomerization has
reached street-level awareness
• Heat release rates in HCCI combustion of two fuels,
iso-octane with no low T heat release, and
PRF-80 with two stage heat release
• We are seeing researchers debating which makes the
better HCCI fuel. Both debaters have completely accepted
the existence and source of the low T reactivity.
250

200
Low temperature
heat release This is serious,
150
PRF80
black-belt
100 fuel chemistry
iso-
and computational
50 Octane chemistry

0
330 340 350 360 370 380 390
Crank Angle
Results from experiments of Sjöberg and Dec, SNL 2006
New conceptual picture developed 1990 - 1997

• Extended role of multiple advanced laser diagnostic techniques

• Team led by John Dec, SNL

• Explains
– 2 stages in diesel burning
– ignition and cetane
– sooting logic
• This is serious, black-belt
optical physics science
Lots still unknown,
soot chemistry, spray dynamics
fuel effects, etc.
 Homogeneous Charge Compression Ignition
(HCCI) engine delivers high efficiency, and low
particulate and NOx emissions:

Advantages: Technical challenges:

 low NOx  engine control

 low particulate matter  multi-cylinder balancing
 high efficiency  startability
 low power output
 high HC and CO emissions
Have we have come a long way since 1922?

• We still are looking to oil shale, oil sands and biomass for the
future
• However, our understanding of knocking, antiknocks and low T
chemistry has grown enormously
e.g., Current engine designers debate how much low T heat release is
best, and take its sources for granted
• Conceptual model for diesel combustion has led to breakthroughs
e.g., Understanding of anti-sooting action of oxygenates
• Entirely new concept engine (HCCI) is being developed
Great majority of this progress is due to basic science
understanding, e.g., optical diagnostics, quantum chemistry and
electronic structure theory, high performance computing, etc.
We have used basic science advances to make big jumps in
understanding, but we are back to trial and error in many cases
Octane numbers of
heptanes are due
exclusively to their
different molecular
structures

This was recognized

in 1920’s but no
explanation in
fundamental terms
had been provided
prior to our work
Engine knock is an undesirable thermal ignition
We focus on three distinct chain branching
pathways

1) H + O2 → O + OH High T

2) H + O2 + M → HO2 + M Medium T

RH + HO2 → R + H2O2
H2O2 + M → OH + OH + M

3) R + O2 → RO2 Low T
RO2 → QOOH → O2QOOH → 3+ radicals
 n-hexane ignition
1,600

1,400

1,200
Temperature

1,000

800
Heat release rate
600
Temperature
400

200

0
0.00E+00 2.00E-01 4.00E-01 6.00E-01 8.00E-01 1.00E+00 1.20E+00
Time
Chain branching at high temperatures

H + O2 → O + OH

• Activation energy is relatively high (16.8 kcal/mol)

• H atoms produced by thermal decomposition of radicals

e.g. C2H5 , C2H3 , HCO, iC3H7 , etc.
Activation energies relatively high ( ~ 30 kcal/mol)

• Therefore this sequence requires high temperatures

• Illustrated best by shock tube experiments

Chain branching often occurs over a series of
reactions

H + O2 + M → HO2 + M

RH + HO2 → R + H2O2

H2O2 + M → OH + OH + M

• At temperatures below about 900K, H2O2 decomposition is

inhibited, leading to degenerate chain branching

• At higher temperatures, H2O2 decomposes as quickly as it is

formed, leading to conventional chain branching

• Other low temperature chain branching paths can be much longer

than this sequence (see below)

H2O2 decomposes at a fairly distinct temperature

• Reaction consuming H2O2 is:

H2O2 + M → OH + OH + M

k+ = 1.2 x 1017 x exp(-45500/RT)

• Resulting differential equation is:

d [ H2O2 ] = -[ H2O2 ] [ M ] k+
dt
Characteristic time for H2O2 decomposition

d [ H2O2 ] = -[ H2O2 ] [ M ] k+
dt

define τ = [ H2O2 ] / (d [ H2O2 ]/dt)

τ = 1 / ( k+ [M])
τ = 8.3 x 10-18 x exp(22750/T) x [M]-1

At RCM conditions, with [M] ~ 1 x 10 -4 mol-cm-3, values of τ are

approximately:

7.8 ms at 900K 640 µs at 1000K 80 µs at 1100K

At higher compressions (pressures), values of τ are smaller at

comparable temperatures
Rapid compression machine and some turbulent flow
reactor experiments are controlled by H2O2
decomposition

• Rapid compression machine (RCM) usually operates in a

degenerate branching mode

- H2O2 produced at temperatures lower than 900K

- When system reaches H2O2 decomposition temperature,

ignition is observed

• Many turbulent flow reactor experiments operate at temperatures

between 900 - 1100K where H2O2 decomposes as quickly as it

is produced
 Pentane isomers ignite in order of their octane numbers

1400

1200 neopentane
temperature (K)

n-pentane (RON 85)

1000 (RON 62)

800

600 iso-pentane
Ribaucour et al., 2000 (RON 92)
400
40.0 50.0 60.0 70.0 80.0 90.0
tim e (m s)
n-Pentane (RON 62) and PRF 60 show different
behavior in rapid compression machine
(Cox et al., 26th Comb. Symp., 1996)

PRF 60

n-Pentane (RON 62)

Role of H2O2 decomposition is very general

• RCM ignition

• Engine knock

• HCCI ignition

• Diesel ignition

• Each system follows a unique pathway in the relevant phase

space to arrive at this ignition temperature where H2O2
decomposes
Kinetic features of engine knock

• History of octane numbers and empirical observations

• End gas self-ignition prior to flame arrival

• Actual ignition driven by H2O2 decomposition at ~ 900K

• Kinetic influence of molecular size and structure

• Effects of additives, both promoters and inhibitors

• Reduced models must retain H2O2 decomposition reaction to

describe ignition

• Issue of real SI engine fuel being complex mixture of components

• Lots of kinetics research still needed (aromatics, cyclics, etc.)

 Detailed Chemical
Includes high and low Kinetics for
temperature ignition chemistry: Components

Important for predicting low temperature combustion regimes

RH

R olefin + R

O2

RO2

olefin + HO2
QOOH
cyclic ether + OH
O2 olefin + ketene + OH

O2QOOH keto-hydroperoxide + OH

(low T branching)
21
 High Temperature Mechanism

Reaction Class 1: Unimolecular fuel decomposition

Reaction Class 2: H-atom abstractions

Reaction Class 3: Alkyl radical decomposition

Reaction Class 4: Alkyl radical + O2 = olefin + HO2

Reaction Class 5: Alkyl radical isomerization

Reaction Class 6: H atom abstraction from olefins

Reaction Class 7: Addition of radical species to olefins

Reaction Class 8: Alkenyl radical decomposition

Reaction Class 9: Olefin decomposition

22
 Class 1 – Unimolecular fuel decomposition

H H H H H H
HC–C–C–C–C–CH →
H H H H H H

H H H H H H
HC–C–C–C• •C–CH
H H H H H H

Products are two alkyl radicals pC4H9 and C2H5

 Class 2 – H atom abstractions

H H H H H H
HC–C–C–C–C–CH + O→
H H H H H H

H H • H H H
HC–C–C–C-C–CH + OH
H H H H H H

Rate depends on the abstracting radical and on the site

where the H is located (more later)
Two major keys to low temperature reactions

BE (primary) > BE (secondary) > BE (tertiary) 25

25
 Class 3 – radical decomposition

H H • H H H
HC–C–C–C-C–CH →
H H H H H H

Decomposition reaction based on beta-scission or

“one bond away”
 Class 3 – radical decomposition

H H • H H H
HC–C–C–C-C–CH →
H H H H H H

Decomposition reaction based on beta-scission or

“one bond away”
 Class 3 – radical decomposition

H H • H H H
HC–C–C–C-C–CH →
H H H H H H

H H H H H
HC–C–C=C + • C–CH
H H H H H H

1C4H8 + C2H5 one stable olefin and one radical

Class 5: Alkyl radical isomerization

H H • H H H
HC–C–C–C-C–CH
H H H H H H
Class 5: Alkyl radical isomerization

H H • H H H
HC–C–C–C-C–CH
H H H H H H
Class 5: Alkyl radical isomerization

H H • H H H
HC–C–C–C-C–CH
H H H H H H

H H H H • H
HC–C–C–C-C–CH
H H H H H H
Class 5: Alkyl radical isomerization

H H • H H H
HC–C–C–C-C–CH
H H H H H H

H H H H • H
HC–C–C–C-C–CH → nC3H7 + C3H6
H H H H H H
Low Temperature (High Pressure) Mechanism

Reaction Class 10: Alkyl radical addition to O2

Reaction Class 11: R + R’O2 = RO + R’O
Reaction Class 12: Alkylperoxy radical isomerization
Reaction Class 13: RO2 + HO2 = ROOH + O2
Reaction Class 14: RO2 + H2O2 = ROOH + HO2
Reaction Class 15: RO2 + CH3O2 = RO + CH3O + O2
Reaction Class 16: RO2 + R’O2 = RO + R’O + O2
Reaction Class 17: RO2H = RO + OH
Reaction Class 18: Alkoxy radical decomposition
Reaction Class 19: QOOH decomposition and production of cyclic ethers
Reaction Class 20: QOOH beta decomposition to produce olefin + HO2
Reaction Class 21: QOOH decomposition to small olefin, aldehyde and OH
Reaction Class 22: Addition of QOOH to molecular oxygen O2
Reaction Class 23: O2QOOH isomerization to carbonylhydroperoxide + OH
Reaction Class 24: Carbonylhydroperoxide decomposition
Reaction Class 25: Reactions of cyclic ethers with OH and HO2
33
 Class 10 – addition of O2 to alkyl radical

H H • H H H
HC–C–C–C-C–CH →
H H H H H H

•
O
H H O H H H
HC–C–C–C-C–CH
H H H H H H

Rate depends on the type of site where the O2 attaches

 Class 10 – addition of O2 to alkyl radical

H H H H H H
HC–C–C–C-C–C• →
H H H H H H

H H H H H H
HC–C–C–C-C–C–O–O•
H H H H H H

Rate depends on the type of site where the O2 attaches

 Class 12 – RO2 isomerization

•
O
H H O H H H
HC–C–C–C-C–CH
H H H H H H

Transfer H atom within the molecule

 Class 12 – RO2 isomerization

•
O
H H O H H H
HC–C–C–C-C–CH
H H H H H H
 Class 12 – RO2 isomerization

•
O
H H O H H H
HC–C–C–C-C–CH →
H H H H H H

H
O
H H O H • H
HC–C–C–C-C–CH
H H H H H H
 Class 12 – RO2 isomerization

•
O 6-membered transition
H H O H H H state ring, secondary
HC–C–C–C-C–CH → C – H bonds
H H H H H H 2 H atoms available

H
O
H H O H • H
HC–C–C–C-C–CH
H H H H H H
 Class 12 – RO2 isomerization

•
O 7-membered transition
H H O H H H state ring, tertiary
HC–C–C–C-C–CH → C – H bonds
H H H H H H 3 H atoms available

H
O
H H O H H •
HC–C–C–C-C–CH
H H H H H H
 Class 12 – RO2 isomerization

•
O 5-membered transition
H H O H H H state ring, secondary
HC–C–C–C-C–CH → C – H bonds
H H H H H H 2 atoms available

H
O
H H O • H H
HC–C–C–C-C–CH
H H H H H H
Rates of Class 12 reactions

• Size of the transition state ring, “transition state ring

strain energy barrier”
– 5 membered ring has highest energy barrier
– 7 membered ring has lowest energy barrier

• Type of C – H bond that is broken to remove the H

atom
– Primary bond strongest, tertiary bond is weakest

• Number of equivalent H atoms

We have rules for each class of reactions:
Reaction rates for RO2 isomerization rate
constants

k = A Tn exp(-Ea/RT)

43
Class 19 – QOOH decomposition into cyclic ether

H
O
H H O H • H
HC–C–C–C-C–CH
H H H H H H
Class 19 – QOOH decomposition into cyclic ether

H
O
H H O H • H
HC–C–C–C-C–CH
H H H H H H

Reaction begins by breaking O – O bond,

which produces OH radical
Class 19 – QOOH decomposition into cyclic ether

H
O
H H O H • H
HC–C–C–C-C–CH
H H H H H H

O
H H H H
HC–C–C–C-C–CH 4-membered ring
H H H H H H cyclic ether
 Low temperature kinetics involve intra-molecular
H atom transfers

These reactions lead to OH radical production at

low temperatures, which then produce water and heat
This heating reduces the time delay for the fuel to reach
the H2O2 decomposition temperature
Two major keys to low temperature reactions

BE (primary) > BE (secondary) > BE (tertiary) 48

48
RSE (5-ring) >

RSE (6-ring) >

RSE (7-ring) <

RSE (8-ring)

49
49
Class 22 – addition of O2 to QOOH

H
O
H H O H • H
HC–C–C–C-C–CH + O2 →
H H H H H H
Class 22 – addition of O2 to QOOH

H
O
H H O H • H
HC–C–C–C-C–CH + O2
H H H H H H

H •
O O
H H O H O H
HC–C–C–C-C–CH
H H H H H H
Class 23 – isomerization of O2QOOH

H •
O O
H H O H O H
HC–C–C–C-C–CH
H H H H H H
Class 23 – isomerization of O2QOOH

H •
O O
H H O H O H
HC–C–C–C-C–CH
H H H H H H •
O
H H H H O H
HC–C–C–C-C–CH
H H O H H H
O
H
Class 23 – isomerization of O2QOOH

•
O
H H H H O H
HC–C–C–C-C–CH
H H O H H H
O
H
Class 23 – isomerization of O2QOOH

•
O
H H H H O H
HC–C–C–C-C–CH
H H O H H H
O
H
Class 23 – isomerization of O2QOOH

H
O
H H • H O H
HC–C–C–C-C–CH
H H O H H H
O
H
Class 23 – isomerization of O2QOOH

H
O
H H • H O H
HC–C–C–C-C–CH
H H O H H H
O
H
Class 23 – isomerization of O2QOOH

H
O
H H H O H
HC–C–C–C-C–CH
H H O H H H

to produce a ketohydroperoxide species

+ OH (#1)
Class 24 – decomposition of ketohydroperoxide

H
O
H H H O H
HC–C–C–C-C–CH
H H O H H H

Because this is a stable species, it requires a

temperature increase to break the O – O bond
Class 24 – decomposition of ketohydroperoxide

H
O
H H H O H
HC–C–C–C-C–CH
H H O H H H
Class 24 – decomposition of ketohydroperoxide

•
H H H O H
HC–C–C–C-C–CH
H H O H H H

+ OH (#2)
Class 24 – decomposition of ketohydroperoxide

•
H H H O H
HC–C–C–C-C–CH
H H O H H H
Class 24 – decomposition of ketohydroperoxide

H H H O H
HC–C–C–C• H C– CH
H H O H H
Class 24 – decomposition of ketohydroperoxide

H H H O H
HC–C• C=C H C– CH
H H O H H
Class 24 – decomposition of ketohydroperoxide

H H H O H
H C=C C=C H C– CH
H H O H H
Class 24 – decomposition of ketohydroperoxide

H H H O H
H C=C C=C H C– CH
H H O H H

H (radical) + ethene + ketene + acetaldehyde

Class 24 – decomposition of ketohydroperoxide

H H H O H
H C=C C=C H C– CH
H H O H H

H (radical) + ethene + ketene + acetaldehyde

and don’t forget OH (#1) and OH (#2)

Alkylperoxy radical isomerization, followed by
the dihydroperoxide pathway

• At least 3 small radical species

– OH + OH + H (or another OH or HO2)

• Several small stable species, many of them highly

reactive aldehydes and olefins

• These reaction pathways provide intense chain

branching

• This pathway quits when increasing temperature

shuts down the R + O2 and O2 + QOOH equilibria
Key to understanding the low temperature chemistry of MCH
was getting the isomerizations of RO2 correct:
RH (fuel)
β-scission
at high T:
R olefin + R'
Low
temperature O2
chemistry
RO2

olefin + HO2
QOOH cyclic ether + OH
O2 β-scission products
O2QOOH Only 6-membered
rings lead to significant
HO2Q'=O + OH
Low chain branching
temperature 2 OH’s produced
branching
OQ'=O + OHUniversity of Iowa 69
Alkyl radical isomerization possible for most fuels

• Remember the key kinetic factors

• Primary, secondary and tertiary C – H bonds

• Ring strain energy variations with ring size, especially

for nearest-neighbor abstractions

• Other molecular structure effects

Octane numbers of
heptanes are due
exclusively to their
different molecular
structures

Low octane fuels have

lots of secondary C-H
bonds and high octane
fuels have lots of primary
C-H bonds and lots of
tight, 5-membered TS
rings
N-alkanes all have straight C chains with lots of
secondary C – H bonds and low ring strain
energy barriers

 n-octane (n-C8H18)
 n-nonane (n-C9H20)
 n-decane (n-C10H22)
 n-undecane (n-C11H24)
 n-dodecane (n-C12H26)
 n-tridecane (n-C13H28)
 n-tetradecane (n-C14H30)
 n-pentadecane (n-C15H32)
 n-hexadecane (n-C16H34)
72
72
 Experimental
Validation
Good agreement with ignition delay times at Data
“engine-like” conditions over the low to high
temperature regime in the shock tube

13.5 bar
stoichiometric fuel/air
fuels:
n-heptane
n-decane

Shock tube experiments:

Ciezki, Pfahl, Adomeit
1993,1996

[K] 73
 Experimental
Comparison to rapid compression Validation
machine data which is at “engine-like” Data

conditions (14.3 bar, n-decane)

RCM experiments scaled from

φ=0.8 to φ=1.0

Experiments:
Shock tube: Ciezki, Pfahl,
Adomeit
1993,1996
RCM: Kumar, Mittal, and
Sung 2007 [K]
74
 Family of ignition simulations – a valuable analysis tool

n-decane, φ = 1.0, 13 bar pressure

Same approach used by Petersen et al. for propane ignition analyses

75
All large n-alkanes have very similar ignition properties

76
New experiments agree with our computer predictions

77
 Ignition of n-dodecane at 800K, 13 bar pressure is a
familiar 2-stage ignition

Note that 80% of the fuel is consumed in the first stage ignit
Examples of use of Chemkin Reaction Path Analysis78Tools
First stage produces H2O but very
little CO2

79
A lot of the “action” occurs at the time of the first ignition stage

80
During the low temperature ignition, alkyl radicals add to mo

oxygen and also decompose directly to smaller alkyl radical

81
QOOH species can react
by 3 pathways

QOOH + O2 → O2QOOH

QOOH → β-scission

QOOH → cyclic ether

82
Each QOOH species
has multiple possible
reaction pathways
available

The rates of those possible

reaction pathways depends
on the exact structure of the
QOOH species

83
 nc7h16 - 13.5bar - phi=1.0
100.00

Ignition delay - ms
10.00

nc7h16
5% EHN
1.00 0.1% EHN
5% DTBP

0.10
0.8 1 1.2 1.4 1.6
1000/T
85
 Composition of Biodiesels
methyl palmitate O

O
70
60
methyl stearate O

Soybean
50
O

Rapeseed
40 methyl oleate O
%

30 O

20
methyl linoleate
10
0 O

C16:0 C18:0 C18:1 C18:2 C18:3 O

methyl linolenate O

87
Biodiesel fuels can be made from vegetable oils
such as soy, palm, flaxseed, canola, and olive oil
and animal fats

QuickTime™ and a
TIFF (LZW) decompressor
are needed to see this picture.
Methyl stearate (n-C18 methyl ester) has the
same ignition properties as large alkanes

1.E-01
Fuel/air, phi=1
Methyl decanoate, 13 bar

Methyl stearate, 13 bar

1.E-02 Methyl stearate, 50 bar

n-Decane, 13 bar
Ignition delay (s)

n-Heptane, 13 bar

n-Decane, 50 bar
1.E-03 n-Heptane, 13 bar

n-Decane, 50 bar

ms13

ms13 50
1.E-04

1.E-05
0.7 0.9 1.1 1.3 1.5
1000/T (1/K)

89
 Comparison with n-Decane Ignition
1.E+02
Delay Times Ignition delay times
P = 12 atm
Equivalence ratio: very close
P = 50 atm 1, in air
1.E+01
n-Alkanes:
Ignition Delay Time (ms)

1.E+00
cannot reproduce
the early formation
of CO2
1.E-01
but
Symbols: n-decane experiments (Pfahl et al.)
Line: methyl decanoate mechanism reproduce the
1.E-02 reactivity of methyl
0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
-1
esters very well
1000/T (K )

90
Interesting note
O
Experience with biodiesel
O
and methyl esters

suggests strategies for

kinetic modeling of n-alkyl

benzenes and n-alkyl

cyclohexanes

91
Branched hydrocarbons are different
 Both octane and cetane rating systems have a straight-
chain reference fuel that is easy to ignite and a branched
reference fuel that is hard to ignite
 iso-octane and 2,2,4,4,6,8,8-heptamethyl nonane
 n-heptane and n-hexadecane
 Are all branched hydrocarbons as similar to each other
as the straight-chain hydrocarbons?
 Very few laboratory experiments available for
mechanism validation of HMN
 Base a reaction mechanism on previous sets of reaction
classes
92
• Iso-octane

• 2,2,4,4,6,8,8 heptamethylnonane (iso

HMN and iso-octane ignition is slower than
n-alkanes only in the Low Temperature regime
13.5 bar pressure

94
 n-hexadecane
PFR Ignition results at 13 bar:
2,2,4,4,6,8,8, heptamethylnonane

2.0

1.5
fuel/air Iso-octane
stoichiometric HMN
nc7h16 expt
1.0 13 bar
nc7h16 calc
τ [ms]

0.5 nc10h22 calc

nc10h22 expt
0.0
log

n-alkanes iso-c8h18 calc

CN 50
ic8h18 expt
-0.5
hmn calc
-1.0

-1.5
0.7 0.9 1.1 1.3 1.5
1000/T [K]
PFR Ignition results at 40 bar: n-hexadecane

2,2,4,4,6,8,8, heptamethylnonane

fuel/air mixtures
stoichiometric HMN
Iso-octane
40 bar

n-alkanes

CN 50
Octane numbers of
heptanes are due
exclusively to their
different molecular
structures

Low octane fuels have

lots of secondary C-H
bonds and high octane
fuels have lots of primary
C-H bonds and lots of
tight, 5-membered TS
rings
Heptane isomers provide an interesting family of fuels
RON varies from 0 to 112

98
 Effect of the position of the
16
double bond
1-Hexene
Exp.
100
14

Ignition delay time [ms]

2-Hexene
12 80
3-Hexene
10 60
Pressure [bar]

3-Hexene

16 40 2-Hexene
1-Hexene Calc.
14 2-Hexene 20
1-Hexene
12 0
3-Hexene
650 700 750 800 850 900
10 T [K]
0.94 MPa
8
0 10 20 30 40 50 60 70 80 The length of the free saturated
Time [ms]
carbon chain determines the
reactivity
C = C - C - C - C - C 1-hexene

C - C = C - C - C - C 2 – hexene

C - C - C = C - C - C 3 – hexene

100
Ignition delay time [ms]

80
3-Hexene
60

40 2-Hexene

20
1-Hexene
0
650 700 750 800 850 900
T [K]

RCM Ignition delay times of hexene

isomers (0.86-1.09 MPa, Φ=1):
 Composition of Biodiesels
O

R triglyceride R

O O

+ 3 CH 3 OH Methyl Palmitate (C16:0)

O

O methanol
O

R
O
OH Methyl Stearate (C18:0)
3
CH3 + OH
R O HO

methyl ester glycerol

Methyl Oleate (C18:1)

70
60
Soybean
50 Methyl Linoleate (C18:2)
Rapeseed
40
%

30
20
10 Methyl Linoleanate (C18:3)
0
C16:0 C18:0 C18:1 C18:2 C18:3
 Cycloalkanes: methyl cyclohexane

• Cycloalkanes are interesting due to oil sands

• Cycloalkanes are present in most practical fuels

and surrogate fuels

methylcyclohexane
 Oil-sand derived fuels have focused attention on cyclo-alkanes

Slide courtesy Phil Smith, University of Utah

Asphaltene molecule
typical of oil sands
 Experiments: Rapid compression
machine (RCM) at NUI Galway

• Opposed piston RCM originally used by Shell

– => fast compression times of about 16 ms
• Large crevice on perimeter of piston to contain
wall boundary layer
– =>uniform temperatures across combustion chamber
• Use N2 and Ar as diluents to attain range of
compressed gas temperatures
• Stoichiometric mixtures of MCH/O2/Ar/N2
• 10,15 and 20 atm pressure at the end of
compression.

University of Iowa 105

Experimental data at 10 atm shows distinct NTC region:
Ignition delay time [s] 1.000

0.100

0.010
Experimental data NUI Galway

0.001
650 750 850 950 1050 1150
Temperature at the end of compression [K]
University of Iowa 106
N-alkane based RO2 isomerization rates gave too slow ignition delay
times in rapid compression machine at low temperatures:
1.000
MCH mechanism
result
Predictions show complete
Ignition delay time [s]

absence of a negative
0.100 temperature coefficient
region

0.010
Experimental data NUI Galway

0.001
650 750 850 950 1050 1150
Temperature at the end of compression [K]
University of Iowa 107
Rates of important isomerization reactions were estimated by
comparison with known reactions for alkanes
 Comparisons with rapid compression
machine results shows predicted low
temperature chemistry for MCH is too slow
0.05

0.04
Ignition delay time [s]

0.03
Model
0.02
Runs 5-23
mechanism: mch_v1a.mech
thermo: surrogate_ver8b.therm

0.01
Experimental data
NUI Galway
0.00
700 800 900 1000 1100
Temperature at the end of compression [K]
Examine RO2 isomerization rate constants based on n-alkane rates:

Small fraction going to six membered ring that leads to chain

branching

University of Iowa 110

Walker et al. has carried out low temperature
kinetic experiments on simple cycloalkanes.

• Small amounts of cyclohexane added

to H2/O2
• Derived cyclohexylperoxy (RO2)
isomerization rates from initial
products observed

University of Iowa 111

Experimentally-based RO2 isomerization rate constants give lots of 6
membered rings and chain branching:

Rate constants emphasize 6-membered rings

University of Iowa 112

New MCH isomerization rates give good behavior for low temperature
chemistry in rapid compression machine:
1.000
Original rate based on n-
Alkylperoxy corrected estimate
alkanes
Hanford-Styring and
Walker based
estimate
Ignition delay time [s]

0.100 Gulati and Walker

based estimate

10 atm pressure
0.010
Experimental
data NUI Galway

0.001
650 750 850 950 1050 1150
Temperature at the end of compression [K]
University of Iowa 113
 0.10 Behavior at other pressures also follows trends in
rapid compression machine:

0.08 10 atm
Ignition delay time [s]

0.06
15 atm

Gulati and Walker based

0.04 RO2 isomerization rate
constants

0.02 20 atm

0.00
650 750 850 950 1050
Temperature at the end of compression [K]
University of Iowa 114
 6-member ring RO2 isomerization:

O O H
O O
H
H 5-membered
H
7-membered H
H H
6-membered

University of Iowa 115

Low temperature RO2 isomerizations are a key

H
H
Trans (chair) ring form
of cyclohexylperoxy
does not readily H
isomerize O

O..

Cis (boat) ring form O.. H

O
of cyclohexylperoxy H
does isomerize
H
 Compare Handford-Styring rates to n/iso-
alkane rates and see diff in A-factor and Ea

Ring size in A n Ea Rate at 750K Branching

transition state [cal] fraction
Hanford-Styring and Walker based estimate:
5 6.20e10 0 27495 6.0e2 11%
6 4.63e10 0 24076 4.5e3 81%
7 5.50e9 0 24355 4.3e2 8%
Non-cyclic alkylperoxy rates [7]
5 1.00e11 0 26850 1.5e3 9%
6 1.25e10 0 20850 1.0e4 64%
7 1.50e9 0 19050 4.4e3 27%

University of Iowa 117

Explanation of engine knock, ON, antiknocks, diesel ignition, and HCCI
ignition came in the 1990’s from DOE/BES theoretical chemistry and
supercomputing and EERE knock working group

Reactant Transition
state
O O
H O
R O R C
H O O OH
R C O
H + O2
R H

R H
R H
O
OH + OH

R R O
O

R O
O O OH O
O O

H H O

+ OH
H H O

Alkylperoxy radical isomerization rates are different

in paraffin and cyclic paraffin hydrocarbons Low temperature chain branching paths

Most work has been done for alkane fuels, and many questions remain for
aromatics, cyclic paraffins, large olefins
There are many poorly understood phenomena
• All of our intuition, experience and theory of flame properties is
based on flames at atmospheric and lower pressures
• In engines, at high pressures due to compression, unburned gas
temperatures are also quite high
• Characteristic times to autoignition can be much shorter than
characteristic times for flame propagation
• Assumptions built into our picture of flame propagation break
down at high pressures, and it is not clear how to define limiting
conditions
• Extrapolation of flame data to 100 bar not appropriate; great
need for high pressure “flame” data of all kinds
• We don’t know very much about combustion at high pressures
• We simply extrapolate phenomena from atmospheric pressure
to high pressure, but they probably are no longer valid
• We don’t even know if “flames” still exist
 Reference Fuels
and Surrogate Fuels

C.K. Westbrook, W.J. Pitz, H.J. Curran and M. Mehl

Lawrence Livermore National Laboratory

June 2010
Practical hydrocarbon fuels present new
challenges for kinetic modeling
• For many years, methane and propane were “large” fuel
molecules, and they still can be challenging
• Most common transportation fuels produced from
petroleum or other common sources contain molecules
much larger than C1 to C4
• Hydrogen and C1 – C4 species will continue to be an
essential part of fuel models and still need lots of work
• Large fuel species modeling requires significant
computing resources
• Mechanism reduction will be necessary for applications
with realistic geometry

2
All petroleum-derived fuels contain a complex
mixture of HC molecules

 Refining produces a still-complex mixture that is

“targeted” towards its application type
 Gasoline 6 < C < 10
 Jet fuel 9 < C < 13
 Diesel 13 < C < 22

 HCCI 1 < C < 22

3
Variability of real transportation fuels

• Composition of gasolines at different gas stations on a single

day is often quite different

• Composition of same gas station will vary every day

• Same is true of diesel and other fuels

• Quantity used to test fuels is often not very demanding or

specific (e.g., ON, CN)
There are two important pathways for
practical fuel mixture mechanisms
 Reference fuels
• Gasoline - n-heptane and iso-octane
• Diesel - heptamethyl nonane and n-hexadecane
• Jet fuel – n-dodecane (?) and iso-dodecane (?)

 For the first time, we now have detailed

kinetic mechanisms for both diesel and
gasoline primary reference fuels

 Surrogate fuels
5
Use of surrogate fuels is an important
current theme in combustion chemistry

 First surrogate for diesel fuel was n-heptane

 Early surrogates included one representative

from each fuel molecule class

6
Classes of compounds in practical fuels

7
 Gasoline
composition

Many branched paraffins

8
 Gasoline has
many
branched
alkanes

Jet fuel has the

highest
n-alkane

Gasoline is lower in
cycloalkanes

9
 Fuel components that have higher Surrogate Fuel
Component
molecular weights are needed Selection

 Diesel fuel has mostly C14 to C24 components centered

around C16

Real Diesel
Amount

(SAE 2007-01-0201
Presentation)

Molecular Weight

C10 C16 C24

10/16/2007 WSS meeting 10/2007 10
Recommended components by the surrogate fuel
working group, gasoline team
 n-heptane

 iso-octane

 pentene
CH 3

 cyclohexane, methylcyclohexane
CH 3

 toluene

 ethanol OH

11
 Fuel Surrogate Palette for Diesel

n-dodecane
tetralin n-tridecane
n-tetradecane
n-pentadecane
n-hexadecane

n-alkane
n-decyl-benzene branched alkane
alpha-methyl-naphthalene
cycloalkanes
hepta-methyl-nonane aromatics
others

butylcyclohexane
decalin

12
Use of surrogate fuels is an important
current theme in combustion chemistry

 Advantages of having multiple samples from

each class of molecules

 Our research has been focused on developing

kinetic models for many examples in each class

 Mechanism reduction can then be applied to

those fuel components to be used
13
In some classes, we have many examples of
fuels with reaction mechanisms

• n-paraffins
– CH4 (methane) through nC16H34 (n-hexadecane)

• iso-paraffins
– all isomers through octanes, selected larger iso-paraffins

• Large variety of olefins through C8 and selected larger species

Alkylperoxy radical isomerization and low temperature
are important in all types of engines
• Heat release rates in HCCI combustion of two fuels,
iso-octane with no low T heat release, and
PRF-90 with two stage heat release
250
Low
200 temperature
heat release
150
PRF80
100
iso-
50 Octane

0
330 340 350 360 370 380 390
Crank Angle
Results from experiments of Sjöberg and Dec, SNL 2006
15
Includes high and low temperature ignition chemistry:
Important for predicting low temperature combustion regimes

RH

R olefin + R

O2

RO2

olefin + HO2
QOOH
cyclic ether + OH
O2 olefin + ketene + OH

O2QOOH keto-hydroperoxide + OH

(low T branching)
16
n-Hexadecane and heptamethyl nonane are primary reference
fuels for diesel and recommended diesel surrogate components
 The two primary reference fuels for diesel
ignition properties (cetane number) Recommended surrogate for diesel
fuel (Farrell et al., 2007):

n-hexadecane
 n-hexadecane

heptamethylnonane

 2,2,4,4,6,8,8 heptamethylnonane

n-decylbenzene

1-methylnapthalene

17
We have greatly extended the components in
the palette that can be modeled into the high
molecular weight range:

 n-octane (n-C8H18)
 n-nonane (n-C9H20)
 n-decane (n-C10H22)
 n-undecane (n-C11H24)
 n-dodecane (n-C12H26)
 n-tridecane (n-C13H28)
 n-tetradecane (n-C14H30)
 n-pentadecane (n-C15H32)
 n-hexadecane (n-C16H34)
18
 We have mechanisms for many
oxygenated components
OH
• Methanol, ethanol OH
O O O
• dimethyl ether,
dimethoxymethane O

• Methyl butanoate
(surrogate for biodiesel) O

• TPGME (tripropylene O O
O OH
glycol monomethyl ether)
O
• DBM (di-butyl maleate) H
CH 3 O C
• DGE (diethylene glycol C
H
O CH3

diethyl ether) O

O O
O

19
We have developed a detailed kinetic reaction mechanism
for the other diesel PRF, heptamethyl nonane

2,2,4,4,6,8,8-heptamethyl nonane is 2 iso-octyl radicals

C C C C

C - C - C - C - C - C - C - C - C

C C C

C C C C
C - C - C - C - C C - C - C - C - C•

C • C

We should expect HMN kinetics to be quite similar to iso-octane

20
We have been modeling the effect of the position of the double bond

on ignition of olefins
Amount of low T
reactivity

C = C - C - C - C - C 1-hexene high

C - C = C - C - C - C 2 – hexene medium

C - C - C = C - C - C 3 – hexene low
 Composition of Biodiesels
methyl palmitate O

O
70
60
methyl stearate O

Soybean
50
O

Rapeseed
40 methyl oleate O
%

30 O

20
methyl linoleate
10
0 O

C16:0 C18:0 C18:1 C18:2 C18:3 O

methyl linolenate O

O
see paper Tuesday afternoon by Naik for more
complete description of biodiesel fuel kinetics
22
 Choice of Surrogates

Methyl butanoate : O

Molecular size too small O

methyl butanoate
compared to biodiesel

More realistic: O

O
→ methyl decanoate methyl decanoate O

→ methyl decenoate O
methyl decenoate

23
Includes high and low temperature ignition chemistry:
Important for predicting low temperature combustion regimes

RH

R olefin + R

O2

RO2

olefin + HO2
QOOH
cyclic ether + OH
O2 olefin + ketene + OH

O2QOOH keto-hydroperoxide + OH

(low T branching)
24
 Experimental
Good agreement with ignition delay times at Validation
Data
“engine-like” conditions over the low to high
temperature regime in the shock tube

13.5 bar
stoichiometric fuel/air
fuels:
n-heptane
n-decane

Shock tube experiments:

Ciezki, Pfahl, Adomeit
1993,1996

[K]
25
All large n-alkanes have very similar ignition properties

26
27
Methyl stearate (n-C18 methyl ester) has the
same ignition properties as large alkanes

1.E-01
Fuel/air, phi=1
Methyl decanoate, 13 bar

Methyl stearate, 13 bar

1.E-02 Methyl stearate, 50 bar

n-Decane, 13 bar
Ignition delay (s)

n-Heptane, 13 bar

n-Decane, 50 bar
1.E-03 n-Heptane, 13 bar

n-Decane, 50 bar

ms13

ms13 50
1.E-04

1.E-05
0.7 0.9 1.1 1.3 1.5
1000/T (1/K)

28
 Comparison with n-Decane Ignition
Delay Times
1.E+02
Ignition delay times
Equivalence ratio: 1, in air very close
P = 12 atm
P = 50 atm

1.E+01
n-Alkanes:
Ignition Delay Time (ms)

1.E+00
cannot reproduce
the early formation
of CO2
1.E-01
but
Symbols: n-decane experiments (Pfahl et al.)
Line: methyl decanoate mechanism reproduce the
1.E-02 reactivity of methyl
0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
-1
esters very well
1000/T (K )

29
Branched hydrocarbons are different
 Both octane and cetane rating systems have a straight-
chain reference fuel that is easy to ignite and a branched
reference fuel that is hard to ignite
 iso-octane and 2,2,4,4,6,8,8-heptamethyl nonane
 n-heptane and n-hexadecane
 Are all branched hydrocarbons as similar to each other
as the straight-chain hydrocarbons?
 Very few laboratory experiments available for
mechanism validation of HMN
 Base a reaction mechanism on previous sets of reaction
classes
30
Recent experimental results show
excellent agreement with modeling

Oehlschlager data phi=0.5 13.5 bar Oehlschlager data phi=0.5 40 bar

0.1 0.1

Ignition dela
0.01
Ignition dela

0.01
Oehlschl data Oehlschl data
0.001 0.001
model calc model calc

0.0001 0.0001

0.00001 0.00001
0.6 0.8 1 1.2 1.4 1.6 0.6 0.8 1 1.2 1.4 1.6
1000/T
1000/T

31
HMN and iso-octane ignition is slower than n-alkanes
only in the Low Temperature regime

13.5 bar pressure

32
Interesting note
O
Experience with straight
O
chain, biodiesel

and methyl esters

suggests strategies for

kinetic modeling of n-alkyl

benzenes and n-alkyl

cyclohexanes

33
Assembled chemical kinetic model for a whole series of iso-alkanes
to represent this chemical class in gasoline and diesel fuels

Includes all 2-methyl

alkanes up to C20 which
covers the entire distillation
range for gasoline and
diesel fuels

Built with the same

reaction rate rules as our
successful iso-octane and
iso-cetane mechanisms.

7,900 species
27,000 reactions
 DieselFuel
Fuel Surrogate
Surrogate Palette palette:
for Diesel

New n-dodecane
component tetralin n-tridecane
n-tetradecane New
this year n-pentadecane component
n-hexadecane
last year

hepta-methyl-nonane n-alkane
n-decyl-benzene branched alkane
alpha-methyl-naphthalene
cycloalkanes
aromatics
others

butylcyclohexane
decalin

New diesel
components this year
Have assembled primary reference fuel mechanism
for diesel fuel

 Diesel PRF: (n-hexadecane)

 n-cetane

 iso-cetane (2,2,4,4,6,8,8-heptamethylnonane

 PRF for Diesel mechanism:

 2,837species
 10,719 reactions
 n-hexadecane
PFR Ignition results at 13 bar:
2,2,4,4,6,8,8, heptamethylnon

2.0
fuel/air
1.5 Iso-octane
stoichiometric
13 bar HMN
nc7h16 expt
1.0
nc7h16 calc
τ [ms]

0.5 nc10h22 calc

nc10h22 expt
0.0
log

n-alkanes iso-c8h18 calc

ic8h18 expt
-0.5
hmn calc
CN 50
-1.0

-1.5
0.7 0.9 1.1 1.3 1.5
1000/T [K]

LLNL-PRES-427539
PFR Ignition results at 40 bar:
n-hexadecane

2,2,4,4,6,8,8, heptamethylnon
fuel/air mixtures
stoichiometric
40 bar HMN
Iso-octane

n-alkanes

CN 50
Diesel PRFs: Cetane number has a big
effect at low temperatures

High cetane PRFs lead to

more H2O2 which
decomposes to reactive
OH radicals

(n-cetane)

Perfectly stirred reactor

stoichiometric mixtures
10 atm
(iso-cetane)

LLNL-PRES-427539
Improved toluene model well predicts ignition at
high pressure

Shock tube ignition delay times at high pressure

10000
toluene/air mixtures Φ=1.0
Ignition delay [μs]

50 atm

1000 Φ=2.0
Φ=0.5

100

10
0.6 0.7 0.8 0.9 1 1.1
1000/T[K]
Experimental data: Shen, Vanderover and Oehlschlaeger (2009)

LLNL-PRES-427539
 Improving building blocks for toluene:
benzene
Benzene ignition delay times in a shock tube
10000
Φ=1.0
Φ=2.0
Ignition delay [μs]

1000 Φ=2.0

100 Φ=0.5

10
2 atm Experimental data: Burcat et al. 1986

1
0.55 0.6 0.65 0.7 0.75 0.8 0.85
1000/T[K]

LLNL-PRES-427539
Improved the predictive behavior of hexenes and pentenes
mechanisms over the entire temperature range

2-hexene
3-hexene
Shock tube
1-hexene Mehl, Pitz, Westbrook,
Yasunaga and Curran, The
Rapid compression machine 33rd International Symposium
on Combustion, 2010.

RCM experiments: Vanhove et al. 2007

Shock tube experiments: Yasunaga and Curran,
2010

LLNL-PRES-427539
 Recent improvements to fuel surrogate models:
Gasoline
n-butane
ethanol n-pentane Improved component models
n-hexane
toluene n-heptane
xylene

CH3 n-alkane
branched alkane
iso-pentanes
olefins
iso-hexanes cycloalkanes
iso-octane aromatics
methylcyclohexane
cyclohexane oxygenates

pentenes
hexenes

LLNL-PRES-427539
 Successful simulation of intermediate heat release
in HCCI engine using gasoline surrogate blends

Dec and Yang, 2010: Intermediate heat release allows highly retarded
combustion phasing and high load operation with gasoline

Gasoline: Sandia Experiments Gasoline Surrogate: Calculations

Heat-Release Rate / Total HR [1/°CA]

0.01 0.001
Pin = 325 kPa HRR 324kPa Norm
Pin = 240 kPa HRR 240kPa Norm
Normalized HRR

0.008

Normalized HRR
0.0008
Pin = 200 kPa HRR 200kPa Norm
Pin = 180 kPa HRR 180kPa Norm

0.006 Pin = 160 kPa 0.0006 HRR 160kPa Norm

Pin = 130 kPa HRR 130kPa Norm

Pin = 100 kPa HRR 100kPa Norm

0.004 0.0004

b.
0.002 0.0002

Dec and Yang SAE 2010-01-1086

0
0
-35 -25 -15 -5 5
-35 -25 -15 -5 5
Crank Angle relative to Peak HRR [°CA]
Crank Angle [ºCA] Crank Angle [ºCA]

(Curves are aligned by time of peak heat release and normalized by tota
4-component gasoline surrogate:
Matched gasoline composition targets and reactivity
Gasoline surrogate:
n-heptane (n-alkanes) Surrogate (%Vol) Gasoline (%Vol)
n-alkanes 0.16
0.731
iso- alkanes 0.57
iso-octane (iso-alkanes)
olefins 0.04 0.04
aromatics 0.23 0.23
A/F Ratio 14.60 14.79
H/C 1.92 1.95
2-hexene (olefins)

Matched the reactivity of a mixture having the same

RON and MON as the gasoline
toluene (aromatics)
Reaction contributions to intermediate heat
release rate
3.00E+09
HRR 200kPa 377K

HRR [Erg/CAD]
HRR [Erg/CAD] 2.50E+09

2.00E+09 formaldehyde oxidation to CO

1.50E+09
H+O2 => HO2
1.00E+09
methyl radical oxidation
5.00E+08 to formaldehyde

0.00E+00
-15 -10 -5 0 5 10
-5.00E+08
HO2+HO2 => H2O2
-1.00E+09

CAD ATDC
Cyclic paraffins are a fuel type that is poorly represented

CH 3
Next steps
 We are continuing to add new species to
each fuel class in the surrogate palette
 We have added 2-methyl and are adding
3-methyl alkanes to simulate F-T fuels
 We are adding component models for
biodiesel species with double bonds

48
 Next Activities
 Develop detailed chemical kinetic
models for another series iso-alkanes:
3-methyl alkanes

 Validation of 2-methyl alkanes mechanism with new data from

shock tubes, jet-stirred reactors, and counterflow flames
 Develop detailed chemical kinetic models for alkyl aromatics:

 More accurate surrogates for gasoline and diesel

 Further develop mechanism reduction using functional group
method
n-decylbenzene - Diesel Fuels

49
 Surrogate fuels
 past use of n-heptane surrogate for diesel
 many similarities between all large n-alkanes
 n-decane surrogate for kerosene (Dagaut)
 n-hexadecane surrogate for biodiesel
 n-decane and methyl decanoate similarities
 role of methyl ester group
 potential of n-cetane + methyl decanoate or
smaller methyl ester for biodiesel surrogate

10/16/2007 WSS meeting 10/2007 50 50

 Lawrence Livermore National Laboratory

Detailed kinetic modeling of transportation fuels

EFRC
June 2010

Charles K. Westbrook, Marco Mehl

Lawrence Livermore National Laboratory

Lawrence Livermore National Laboratory, P. O. Box 808, Livermore, CA 94551

This work performed under the auspices of the U.S. Department of Energy by
Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344
 Combustion in human history: from the early steps…
• 500,000 – 100,000 BP
First use of controlled fire

• 100,000 – 50,000 BP
Routine use of fire

• 500 BC
Heraclitus - Fire as fundamental substance

• 500 – 430 BC
Empedocles – Fire as one of the four elements
Prometheus Brings Fire to Mankind, 1817
Heinrich Friedrich Füger
Lawrence Livermore National Laboratory
2
…to today
“Stripped to its bare bones, the industrial revolution consisted of the application of
new sources of power to the production process, achieved with transmission
equipment necessary to apply this power to manufacturing.
[…]
The industrial revolution progressively replaced humans and animals as the power
sources of production with motors powered by fossil fuels […].”
The industrial revolution in world history
By Peter N. Stearns
Share of total primary energy supply in 2006 (World)

IEA Energy Statistics - www.iea.org/statist/index.htm

Lawrence Livermore National Laboratory

3
 Combustion and Emissions
There are drawbacks to large scale use of
combustion:
• GHG emissions  Global warming
• Micropollutant emissions (NOx, soot,
SOx, water pollution, …)
• Fossil fuels are a limited resource

Source: EPA

Transportation accounts for

the 30% of the emissions of
GHG, the trend is growing.
Source: EPA

Lawrence Livermore National Laboratory

4
 Engine typologies and Combustion Processes

Hi T burnt gases  NOx Hi T Flame Front NOx

CR limited by Knock (Lower Eff) Rich Combustion  Soot 2008 annual report
Higher CR (Higher Eff) ADVANCED COMBUSTION ENGINE TECHNOLOGIES,
VehicleTechnologiesProgram
The heat release timing is The heat release timing is Paul Miles - Low-Temperature Automotive Diesel
determined by the spark controlled through the injection Combustion
(premixed flame) strategy

Lawrence Livermore National Laboratory

5
The HCCI Concept

Very lean conditions (no Soot)

Low T (no NOx, some UHC) The heat release timing is
High CR (Hi Eff)
determined by autoignition
(Chemical Kinetics)
Lawrence Livermore National Laboratory
6
 Fuels and energy carriers

Traditional Fossil fuels: Fuels from gasification:

NG: CH4 FT fuels

LPG: C3-C4 Hydrogen
Gasoline: C6-C10, reforming
Kerosene: C9-C13 Biofuels:
Diesel: C13-C22
…. Ethanol
Biodiesel

Lawrence Livermore National Laboratory

7
 Real Fuels and Surrogates
Real fuels are complex mixtures of
hundreds of components
Qualitative composition is known
Their composition is intrinsically
variable (seasonally, depending on
the feedstock, ….)
The introduction of alternative fuels
is making things even more
complicated
Simpler surrogates have to be
defined for modeling and more
reproducible experiments

Gasoline 6 < C < 10 Jet fuel 9 < C < 13 Diesel 13 < C < 22
Lawrence Livermore National Laboratory
8
 The development of Surrogate Fuels

• First surrogate for diesel fuel was n-heptane (iso-octane and

then Primary Reference Fuels for gasoline fuel)

• Early surrogates included one representative from each fuel

molecule class

• Advantages of having multiple samples from each class of

molecules

• Our research has been focused on developing kinetic models for

many examples in each class

• Mechanism reduction can then be applied to those fuel

components to be used

Lawrence Livermore National Laboratory

9
 Kinetic Mechanisms
n
Modified Arrhenius Law: A ·T ·exp(-Ea/RT)
Reaction A n Ea
Initiation
H2+M<=>H+H+M 4.577E+19 -1.40 1.044E+05
(Stable molecules decompose to
O2+M<=>O+O+M 4.420E+17 -0.63 1.189E+05
H2O2(+M)<=>OH+OH(+M) 2.951E+14 0.00 4.843E+04 unstable radicals)

H+O2+H2H+2OH
H+O2<=>O+OH 3.547E+15 -0.40 1.660E+04 Chain Branching
O+H2<=>H+OH 5.080E+04 2.67 6.292E+03 (The number of radical is
increased through a chain
reaction)
OH+H2<=>H+H2O 2.160E+08 1.51 3.430E+03
HO2+H<=>OH+OH 7.079E+13 0.00 2.950E+02 Propagation
H2O2+H<=>H2+HO2 2.150E+10 1.00 6.000E+03
(the number of radicals is
H+O2(+M)<=>HO2(+M) 1.475E+12 0.60 0.000E+00 conserved)

HO2+OH<=>H2O+O2 1.973E+10 0.96 -3.284E+02 Termination

H2O+M<=>H+OH+M 1.907E+23 -1.83 1.185E+05
(radicals recombine to stable
H2O2+O2<=>HO2+HO2 1.136E+16 -0.34 4.973E+04
products)
Lawrence Livermore National Laboratory
10
 From “the Simple”… to the Complex!
Hydrogen Methane Propane
7 Species - 20 Reactions 30 Species - 200 Reactions 100 Species - 400 Reactions

CH4

CH3 O2
O2 H2 H2O
H C2H6 CH3OO
O
C2H5 CH3OOH

C2H4 CH3O CH3OH

OH
HO2 C2H3 CH2O CH2OH
O2
HO2
C2H2 HCO

H2O2 Aromatics CO
OH
Soot CO2

Lawrence Livermore National Laboratory

11
 The LLNL Kinetic Mechanism
General Aspects and
Structure C7
C6
C5
hexenes

•All the blocks are constantly

updated on the basis of the available
fundamental information and
validated on a wide range of
operating conditions when new
experimental data are published.
• New sub-mechanisms have been
recently added (low temperature
reactivity of some large alkenes.
•The oxidation of the reference components is interconnected by the
mechanism core and by the direct cross reactions among the different fuels
Lawrence Livermore National Laboratory
12
 Diesel fuel composition
Detailed hydrocarbon analysis of
commercial diesel fuels
• Compositional variability

• Broad range of molecular

weight

• The straight chain structures

are dominant

• Aromatics are important as

well

• n-heptane is traditionally
used to approximate their
autoignition behavior

J.T. Farrell, N.P. Cernansky, F.L. Dryer, D.G. Friend, C.A. Hergart, C. K. Law, R.M. McDavid,
C.J. Mueller, A.K. Patel, and H. Pitsch, SAE 2007-01-0201
Lawrence Livermore National Laboratory
13
 Fischer-Tropsch fuel composition
Syntroleum S-8 synthetic jet fuel
0.20
cycloalkanes
 FT analysis (NIST*)
other isoalkanes
single methyl branch • 57% single
n-alkanes methyl branch
0.16
alkanes
• 25% n-alkanes
• 16% multiple
0.12
branched
Mole fraction

alkanes
• 2% cycloalkanes
0.08
* Smith, B. L.; Bruno, T. J. J.
Propulsion 2008, 24, 618.

0.04

0.00
C8 C9 C10 C11 C12 C13 C14 C15 C16

Lawrence Livermore National Laboratory

14
 Cool flames
R• H
Fast High
Long Chain Alkanes
- RH Temperature Combustion
•
•

+ O2

Reactivity
OO• Low T
Mechanism Hi T
+ HO2• NTC Mechanism

•
OOH O
+ + •OH
+ O2
O Reactor Temperature
OOH + •OH

•OO
Degenerate
- •OH Branching Path
O O
•OH
+ O +
HOO
•
Lawrence Livermore National Laboratory
15
 Alkanes oxidation in different reacting systems
Long Chain Alkanes T Conv. Closed Adiabatic
Reactivity

Low T
Mechanism Hi T
NTC Mechanism
Closed
T Conv. Non-Adiabatic

Reactor Temperature
U∆T

Open
T Conv. Non-Adiabatic

U∆T
time time
Lawrence Livermore National Laboratory
16
 HCCI combustion kinetics: two Stage Fuels
R• H
Fast High Typical HCCI Combustion
- RH Temperature Combustion
Temperature and Heat Release Rate
•
profiles
•

+ O2
OO•

T, P
+ HO2•

•
OOH O
+ + •OH
+ O2
O
OOH + •OH

•OO
HRR
Degenerate
- •OH Branching Path
O O
•OH
+ O + TDC CAD
HOO
•
Lawrence Livermore National Laboratory
17
Predicted ignition behavior similar for C7-C16 n-alkanes

13.5 bar
Stoichiometric fuel/air

High T
Low T chemistry
chemistry

Lawrence Livermore National Laboratory

18
Experimental ignition behavior similar for C7-C14 n-alkanes

Recent experiments by
Oehlschlaeger et al. , RPI
Recent shock tube
experiments show all
large n-alkanes ignite
within a factor of 3
Lawrence Livermore National Laboratory
19
Gasoline and gasoline surrogates

EtOH, MTBE, ETBE • Compositional variability

Oxigenates n-paraffins
• The branched chain
structures are dominant
CH3

aromatics
• Aromatics, oxygenates and
olefins are desirable octane
enhancer

Iso-paraffins • iso-octane is traditionally

used to approximate their
naphtenes autoignition behavior
CH 3

olefins

Lawrence Livermore National Laboratory

20
 PRFs: Validation
100 Shock tube and rapid compression machine
3-4.5 atm validation of n-heptane & iso-octane
Ignition Delay Times [ms]

mechanisms:
10
6.5 atm
10 atm n-heptane:
20 atm
13 atm P = 3 - 50 atm T = 650K - 1200K
30 atm
1 Fi = 1
41 atm
100
50 atm n-heptane

Ignition Delay Times [ms]

0.1
0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 15 atm
34 atm
1000K/T 10

iso-octane: 41 atm
P = 15 - 45 atm T = 650K - 1150K
1
Fi = 1

Iso-octane
0.1
0.8 0.9 1 1.1 1.2 1.3 1.4 1.5
1000K/T
Minetti R., M. Carlier, M. Ribaucour, E. Therssen, L. R. Sochet (1995); H.K.Ciezki, G. Adomeit (1993); Gauthier B.M., D.F. Davidson, R.K.
Hanson (2004); Mittal G. and C. J. Sung,(2007); Minetti R., M. Carlier, M. Ribaucour, E. Therssen, L.R. Sochet (1996); K. Fieweger, R.
Blumenthal, G. Adomeit (1997).
Lawrence Livermore National Laboratory
21
 Alkenes reactivity & Mechanism Validation
R• H H •
•

- RH OH OH
• + O2
•
H OO• O
+ O2 HTHR + + •OH
O
OO• OH
Non- Branching Low Temperature Pathways
+ HO2•
1000
OOH 1-pentene
• O
+ + •OH

Ignition Delay Times [ms]

6.8-8.4 atm
100
+ O2 O 6.8-8.4 atm

OOH + •OH

10
•OO
8.6-10.9 atm
Degenerate
- •OH Branching Path 1-hexene
O 1
O O 1 1.1 1.2 1.3 1.4 1.5 1.6
HOO + + •OH 1000K/T
•
Lawrence Livermore National Laboratory
22
 Effect of the position of the double bond
16

1-Hexene
Exp.
100
14

Ignition delay time [ms]

2-Hexene
12 80
3-Hexene
10 60
Pressure [bar]

3-Hexene

16 40 2-Hexene
1-Hexene Calc.
14 2-Hexene 20
1-Hexene
12 0
3-Hexene
650 700 750 800 850 900
10 T [K]
0.94 MPa
8
0 10 20 30 40 50 60 70 80 The length of the free saturated
Time [ms]
carbon chain determines the
reactivity

Lawrence Livermore National Laboratory

23
 Toluene: a Single Stage Fuel
Φ=1.0

Ignition delay times [μs]

H•
12
atm

O2 O 50
O
HO2• atm

OH• O

Ring Opening Reactions 1000K/T

O2 Branching

Ignition delay times [μs]

HO2• O Φ=0.5
Hi T (O and H
Φ=0.2
radical formation) 5
Φ=1.0

Low T (HO2 radicals,

resonantly stabilized
radicals and termination
reactions
1000K/T
Lawrence Livermore National Laboratory
24
 Iso-octane/Toluene Mixtures
Extremely long delays between cool flame
65% 35% and thermal ignition:
1000

Toluene 15 atm Mixture 12-14.6 atm R• RH •

Ignition Delay Times [ms]

100

10
Active radicals abstract the benzylic hydrogen

Iso-octane 12.6-16.1 atm • •

Vanhove, G., Minetti, R., Petit, G. (2006)
1
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6
1000K/T
1500
Iso-Octane

1300 Mixture
Termination of the benzyl radicals
1100
T [K]

• HO2• •OH
900

700

500
0 50 Time [ms] 100 150 Activation of peroxy radicals
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25
 Iso-octane/1-hexene Mixtures

R• RH
82% 18% •
Active radicals abstract the allylic hydrogen
1000
Ignition Delay Times [ms]

KETOHYDROPEROXIDES
Iso-octane 12.6-16.1 atm •
100
Some LT reactivity from 1-hexene
Mixture 11.4-14 atm
•OH
10 HO •

1-hexene 8.5-10.9 atm

Radical Scavenging from the double bond
Vanhove, G., Minetti, R., Petit, G. (2006)
1
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6
HO2• •OH
1000K/T
Limited effect on the Ignition from
•
the mixing (LT reactivity too close) O•
but complex chemistry behind it Activation of peroxy radicals

Lawrence Livermore National Laboratory

26
 Gasoline Surrogates

45% 35% 20% OH 40% 12%

1000

RCM
38% 10%
Ignition Delay Times [ms]

100

10

Surrogate 11.8-14.8 atm

1
0.9 1 1.1 1.2 1.3 1.4 1.5 1.6
1000K/T
1E-3
CH2O C4H6 C6H6
CH2O C4H6 C6H6

1E-4
Mole fractions

1E-5

1E-6

Vanhove, G., Minetti, R., Petit, G. (2006), M. Yahyaoui, N. Djebaïli-Chaumeix, P. Dagaut, C.-E.

1E-7
JSR Paillard, S. Gail (2007) , Cancino L.R., Fikri M., Oliveira A.A.M., Schulz C. (2009)

700 800 900 1000 1100 1200

T [K]
Lawrence Livermore National Laboratory
27
 Composition of Biodiesels
O

R triglyceride R

O O

+ 3 CH 3 OH Methyl Palmitate (C16:0)

O

O methanol
O

R
O
OH Methyl Stearate (C18:0)
3
CH3 + OH
R O HO

methyl ester glycerol

Methyl Oleate (C18:1)

70
60
Soybean
50 Methyl Linoleate (C18:2)
Rapeseed
40
%

30
20
10 Methyl Linoleanate (C18:3)
0
C16:0 C18:0 C18:1 C18:2 C18:3

Lawrence Livermore National Laboratory

28
 CO2 Formation Routes Involving the Ester Group

Methyl Stearate (C18:0)

Decomposition of 3-alkyl-ester radicals

O O

CO2 + CH3
 + 
O O

CH3OCO

….but we still have a long residual chain

Lawrence Livermore National Laboratory

29
 Long Chain Methyl Esters
1.E-01
methyl decanoate
Early CO2 formation due to the
1.E-02
ester function…
Mole Fraction

1.E-03
(Experiments refer to
Rapeseed oil)
1.E-04

O2 CO2 CO CH4 C2H4

1.E-05
790 840 890 940 990 1040
Temperature (K)

… but the autoignition

behavior is similar to the one
of n-alkanes (long alkyl chain)
(Experiments refer to n-
decane)

Lawrence Livermore National Laboratory

30
 Kinetic Mechanisms for New Fuels
n-heptane Methyl Oleate (C18:1)

3-hexene

Iso-cetane (2,2,4,4,6,8,8-heptamethylnonane)

Methyl Butanoate

iso-octane
n-decylbenzene

Toluene

Ethanol Butanol

Lawrence Livermore National Laboratory

31
Alkene effect in gasoline surrogate

Surrogate 1 Surrogate 2
Density (15°C) Kg/m3 .7572 .7504
Reid Vapour Pressure kPa 21.0 19.5
RON - 97.3 97.3
MON - 89.2 86.6

IBP °C 66 76
10% °C 89 89
50% °C 99 99
90% °C 102 102
FBP °C 108 109

n-heptane vol % 13 19
iso-octane vol % 42 24
Toluene vol % 32 26
MTBE vol % 13 13
di-isobutylene vol % - 18
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32
Applications: Engine simulations

FIAT-Lancia Engine
schematization:
Intake/exhaust: 1D Model
Cylinder: 0D – 2 zone
model

Full Chemistry,
Simplified fluid
dynamics

Lawrence Livermore National Laboratory

33
Octane performances

Experimental and Calculated

Octane Performances of different
fuels in on-road conditions…

92

Bench ON and octane requirement (PRF’s)

Surrogate 1
Surrogate 2
Engine
89

Effect of alkenes: 86

Engine Octane Requirement

83
Gasoline without Alkenes
Gasoline containing Alkenes 80
3000 3500 4000 4500 5000
Engine speed (rpm)

Lawrence Livermore National Laboratory

34
 Applications: Reactivity maps
70 -2
Time Scale: 10X
60
Turbo -2.5

50
-3
P [bar]

40
-3.5
30
Carbureted -4
20
10 Surrogate 1 -4.5

600 650 700 750 800 850 900 950 1000 -5

T [K]
70
60
Turbo
Mehl M., T. Faravelli, F. Giavazzi, 50
E. Ranzi, P. Scorletti, A. Tardani,
P [bar]

D. Terna, Energy & Fuels. 20, 40

2391–2398 (2006) 30
20 Carbureted
Andy D. B. Yates, André Swarts and 10 Surrogate 2 (with alkene)
Carl L. Viljoen, SAE 2005-01-2083
600 650 700 750 800 850 900 950 1000
T [K]
Lawrence Livermore National Laboratory
35
 Engine combustion simulation (HCCI)

CFD • Coupled well-mixed reactors represent

different T (and f) regions of the cylinder.
• Typical number of zones N = 10’s to 100’s.
• Allows large kinetic mechanisms to be
Qwall
simulated for the cycle at a relatively low
Zone 1
T1, y11, y12, ... cost.
∆E, ∆m, ∆y
Wall

• Savings comes at the cost of low resolution

Uniform Pressure

Zone 2 of the fluid dynamics.

T2, y21, y22, ...

Zones coupled with

• Transport between zones not captured in
energy, mass and detail (unlike CFD) – only
species transport phenomenological.
Zone N
TN, yN1, yN2, ...
• Most accurate when chemical kinetic effects
dominate behavior (HCCI).

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36
 Multizone example: 1-way coupling with KIVA
Step 2: track the temperature from the partitioned KIVA zones in the
multi-zone (with CHEMKIN) model until main heat release begins

Multizone (overlap): accurate

species production, energy
corrected to match KIVA

KIVA: accurate pressure and

temperature for detailed
cylinder geometry
Lawrence Livermore National Laboratory
37
 Multizone example: 1-way coupling with KIVA
Step 3: complete the remainder of the cycle containing the main heat
release using the multizone model alone

Zone 1 Qwall
T1, y11, y12, ...
Switch at burn
∆E, ∆m, ∆y fraction = 0.1%
Wall
Uniform Pressure

Zone 2
T2, y21, y22, ...

Zones coupled with

energy, mass and
species transport

Zone N
TN, yN1, yN2, ...

Multizone (solo): accurate

species production, chemical
energy released
Lawrence Livermore National Laboratory
38
KIVA3V coupled with an ANN combustion model for fast analysis
of HCCI combustion and emissions

Input
P
τ Ignition
Delay
Variables
φ Time

…
…
EGR

Input Hidden Output

Layer Layers Layer

1 tk
=
Ignition Condition: I (t ) ∫= dt 1
Lawrence Livermore National Laboratory
t (0) τ
39
The ignition integral criterion determines ignition
a two step global mechanism analyzes combustion
Calculate Ignition Integral
in Each Cell
2 tk 1
I (t ) = ∫ dt
t (0) τ
1 3
Yes
Is
Ignition
Turn on global fuel Criterio
conversion mechanism
n met?
C8H18 + 8.5O2→ 8CO +
9H2O
CO + ½O2→CO2 No
4
Lawrence Livermore National Laboratory
40
 Future activities

• Development of detailed kinetic models for new fuels of

interests (alkyl aromatics, more details in PAH formation,
unsaturated bio- esters, …)

• Interactions among fossil and bio-fuels (ethanol, butanol, bio

esters, etc…)

• Validation of the surrogate model in engine conditions

(Sandia)

• Development of effective strategies for the reduction of

mechanism for complex surrogates

Lawrence Livermore National Laboratory

41
 Closing Comments
• In the years to come we will still need combustion for many
applications (liquid hydrocarbons have a very high energy
density)

• Fuels are evolving, and new fuel chemistry models have

become more powerful
• Capability has followed the computer industry and the laser
• Overall system models have developed to the point that they
can be used for practical problems
• The fundamental knowledge we are building up is opening the
way to a more energy efficient design of engine and to a better
insight in fuel effect compositions

Lawrence Livermore National Laboratory

42
 Acknowledgments

LLNL Combustion modeling group : Charles Westbrook, William Pitz,

Marco Mehl…. But many researchers and post docs have contributed
during the years to the development of these mechanisms and models:

• Henry Curran and coworkers, NUI Galway (C1-C5)

• Olivier Herbinet, Nancy (Methyldecanoate)

• Salvador Aceves Group (Slides are courtesy of Matt McNenly)

Some of the activity presented was carried out in Milano:

• Ranzi’s kinetic modeling group

• Onorati’s engine group

Lawrence Livermore National Laboratory

43
 Thanks for your attention!

Lawrence Livermore National Laboratory

44
 We came a long way…

1550 1600 1650 1700 1750 1800 1850 1900 1950

Phlogiston Theory “The Chemical History of a Candle”

J.B. van Helmont, J. Becher M. Faraday

Combustion as Oxidation Chain reaction and thermal ignition (Nobel 1956)

A. Lavoisier , P. S. Laplace Semenov, Hinshelwood

Theory of gas kinetics, free radicals, elementary reactions and reaction mechanisms for
combustion applications Fristrom R. M. (1990)
Lawrence Livermore National Laboratory
45
 Combustion Science Today
Interference-free composite H-
atom LIF image produced with
ps excitation in a Φ=1.2
premixed CH4/O2/ N2 flame.

Molecular-beam flame
sampling and synchrotron-
photoionization mass
spectrometry analysis
[Science - 24 June 2005]
CRF - Sandia
CFD calculations: RANS,
LES, DNS. Coupling of
Ab initio electronic-structure calculations and numerical chemistry and
molecular dynamics simulations fluid dynamics

CRF - Sandia

CRF - Sandia
Lawrence Livermore National Laboratory
46
Toluene
1000
Mittal G. and Sung, C.J. (2007)

Rapid Compression Machine 44 atm

Ignition Delay Times [ms]

100

10
Shock Tube 12 atm

0.1 Shock Tube 55 atm

Vanderover, J. and Oehlschlaeger, M. A. (2008) toluene

0.01
0.7 0.8 0.9 1 1.1
1000K/T
1E-2
Jet Stirred Reactor TOLUENE
CH2O
CH4
Hi T (O and H 1E-3
BENZALDEHYDE
radical formation) Mole Fraction

1E-4
Low T (HO2
radicals,
resonantly 1E-5

stabilized radicals
(P = 1atm, Τ = 0.1s)
and termination 1E-6
reactions 1100 1150 1200 1250 1300 1350 1400
T[K]

Lawrence Livermore National Laboratory

47
Engine Combustion: Homogeneous Charge
Compression Ignition (HCCI)
Typical HCCI Combustion
Temperature and Heat Release Rate
profiles

1st Heat
release stage

The HRR
slows down
(NTC)

Main Heat
Release
HRR

TDC CAD

Lawrence Livermore National Laboratory

48
 Kinetic Modeling
Reaction A n Ea Modified Arrhenius Law:
n
H2+M<=>H+H+M 4.577E+19 -1.40 1.044E+05 A ·T ·exp(-Ea/RT)
O2+M<=>O+O+M 4.420E+17 -0.63 1.189E+05
H2O+M<=>H+OH+M 1.907E+23 -1.83 1.185E+05 Initiation
H2O2+O2<=>HO2+HO2 1.136E+16 -0.34 4.973E+04
H2O2(+M)<=>OH+OH(+M) 2.951E+14 0.00 4.843E+04
H+O2<=>O+OH 3.547E+15 -0.40 1.660E+04 H+O2+H2H+2OH
O+H2<=>H+OH 5.080E+04 2.67 6.292E+03 Chain Branching
OH+H2<=>H+H2O 2.160E+08 1.51 3.430E+03
O+H2O<=>OH+OH 2.970E+06 2.02 1.340E+04
OH+M<=>O+H+M 9.780E+17 -0.74 1.021E+05
H+O2(+M)<=>HO2(+M) 1.475E+12 0.60 0.000E+00
HO2+H<=>OH+OH 7.079E+13 0.00 2.950E+02
HO2+O<=>OH+O2 3.250E+13 0.00 0.000E+00 Propagation
H2O2+H<=>H2O+OH 2.410E+13 0.00 3.970E+03
H2O2+H<=>H2+HO2 2.150E+10 1.00 6.000E+03
H2O2+O<=>OH+HO2 9.550E+06 2.00 3.970E+03
H2O2+OH<=>H2O+HO2 2.000E+12 0.00 4.272E+02
HO2+H<=>H2+O2 1.660E+13 0.00 8.230E+02
Termination
HO2+OH<=>H2O+O2 1.973E+10 0.96 -3.284E+02

This mechanism provide a quantitative explanation of ignition timing,

explosion limits, flame speed, …
Lawrence Livermore National Laboratory
49
Fossil Fuels

Lawrence Livermore National Laboratory

50
Fuel from gasification

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51
Autoignition: Hydrogen

Lawrence Livermore National Laboratory

52
 OH

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53
 Chemical Kinetics
and Soot Production

Charles Westbrook
Lawrence Livermore National Laboratory

CEFRC
June 2010
Diesel engine combustion: A revolution

2
 Early models of Diesel combustion
Liquid core with continuous evaporation
(1976)

3
 Early models of Diesel combustion
Liquid fuel jet shedding droplets, with combustion at
the edge of a stoichiometric shell (diffusion flame)

4
Prior to Laser-Sheet Imaging

 Autoignition and premixed burn

were thought to occur in near-
stoichiometric regions.

 The "quasi-steady" portion of

Diesel combustion was thought to
be adequately described by steady Schematic of group combustion for a fuel spray.
From Kuo, as adapted from H. Chiu and Croke
spray combustion theory.

 Appeared to fit most available

data.

 This "old" description was never

fully developed into a conceptual
model.
A "representative" schematic is given.
Old description of DI Diesel combustion.
The DOE Engine Combustion Research Program
at Sandia’s CRF played a major role in solving the
diesel “mystery”.
 Mission - Develop the science-
base for in-cylinder combustion
and emissions processes.
– Help U.S. manufacturers reduce
emissions & improve performance.

 Approach –
– Strong interaction and
collaboration with industry.
– Optical diagnostics.
– Realistic engine geometries with
optical access through:
> pistons
> cylinder liner
> spacer plates
> exhaust ports
Heavy-Duty Diesel Engine Research

Approach: Investigate the processes

in the cylinder of an operating diesel
engine using advanced optical
diagnostics

Modified heavy-duty truck engine

provides good optical access while
maintaining the basic combustion
characteristics of a production engine.

Data from multiple advanced laser

diagnostics have substantially
improved our understanding of diesel
combustion and emissions formation.
Optical Setup
 Laser-Sheet Imaging Data - 1
Liquid-phase Fuel
 Liquid fuel images show that
all the fuel vaporizes within a
characteristic length (~1 inch)
from the injector.

Vapor-phase Fuel
 Vapor fuel images show that
downstream of the liquid
region, the fuel and air are
uniformly mixed to an
equivalence ratio of 3-4.

Chemiluminescence
 Chemiluminescence images
show autoignition occurring
across the downstream
portion of the fuel jet.

Quiescent Chamber, 1200 rpm, TTDC = 1000 K, ρTDC = 16.6 kg/m3

 Laser-Sheet Imaging Data - 2
PAH Distribution
 PAHs form throughout the
cross-section of the fuel jet
immediately following fuel
breakdown at the start of the
apparent heat release.

Soot Distribution
 LII soot images show that
soot forms throughout the
cross-section of the fuel jet
beginning just downstream
of the liquid-fuel region.

OH PLIF Image
 OH radical images show that
the diffusion flame forms at
the jet periphery subsequent
to an initial fuel-rich
premixed combustion phase.

Quiescent Chamber, 1200 rpm, TTDC = 1000 K, ρTDC = 16.6 kg/m3

 Laser Sheet Imaging is Providing a
New Understanding of DI Diesel Combustion

Old Description New Conceptual Model

 The appearance is significantly different.

– Regimes of Diesel combustion are different than thought.
(flame standoff, upstream mixing, instantaneous vs.
averaged).
 Predicting the soot precursors is one of the keys
to predicting soot emissions from a Diesel engine
Fuel-rich premixed reaction zone

From:
Fuel-Rich Premixed Reaction Zone
John Dec,
SAE paper
970873

12
Steady growth
in molecular
size leads to
visible soot
Correlations between Fuel Structural
Features and Benzene Formation

Hongzhi R. Zhang, Eric G. Eddings, Adel F. Sarofim

The University of Utah

and Charles K. Westbrook

Lawrence Livermore National Lab

presented at
2008 International Combustion Institute Meeting
Montreal, Canada, August 8th, 2008
 Outline
Introduction

Chemistry of Benzene Precursors and

Comparison of Measured and
Predicted Benzene Concentrations

Benzene Formation Potential

Benzene Formation Pathways

 Introduction
Combustion generated benzene is a health concern
Benzene is a major precursor for particulate pollution
Benzene is a known carcinogen
Benzene is a major precursor of PAH, also carcinogens

We want to identify fuel properties that are critical to major benzene

formation pathways and benzene formation potentials for individual fuel
components
Fuel structure: between normal, iso-, and cyclo paraffins
Fuel structure: C3, C4 vs. C12, C16 fuels
Other properties: Equivalence ratio, Hydrogen deficiency,
Combustion temperature

22 premixed flames; C1-C12 fuels; Φ = 1.0-3.06; P = 20-760 torr; Tmax =

1600-2370 K

Benzene concentrations were predicted within 30% of the experimental

data for 15 flames (total of 22 flames)
Major Benzene Formation Pathways Revisited
Class 1: Acetylene addition (Westmoreland et al., 1989;
Frenklach et al., 1985)
R1: C2H2 + CH2CHCHCH = C6H6 + H Natural
R2: C2H2 + HCCHCCH = C6H5 Gas,
Synfuel,
Class 2: C3 combination (Hopf, 1971; Miller-Melius, 1992)
Indicator
R3: H2CCCH + H2CCCH = C6H6
Fuels,
R4: H2CCCH + CH2CCH2 = C6H6 + H
Biofuels
R5: H2CCCH + H2CCCH = C6H5 + H
R6: H2CCCH + CH2CHCH2 = FULVENE + 2H

Class 3: Combination of CH3 and C5H5

R7: C5H5 + CH3 = C-C6H8 = C6H6 + 2H
Liquid
Class 4: Cascading dehydrogenation (Zhang et al., 2007) Fuels
R8: cycloC6-R C-C6H10(–R) C-C6H8(–R) from Oil
C6H6(–R) and Coal
Class 5: De-alkylation
R9: C6H5-R + H = C6H6 + R
Experimental: Benzene from Cyclo-Paraffins

Author Fuel Φ P torr T(Max) in K [C6H6] Max

V C7H16 1.0 760 1843 12 PPM
HSP gasoline 1.0 760 1990 344
LWC C-C6H12 1.0 30 1960 473

Questions:

1. Why gasoline produces more benzene than n-heptane, the

indicator fuel for octane rating?
2. What are the benzene sources in gasoline?
3. How is benzene formed from various chemical classes?
 Outline
Introduction

Chemistry of Benzene Precursors and

Comparison of Measured and
Predicted Benzene Concentrations

Benzene Formation Potential

Benzene Formation Pathways

 Sub-Models Compiled from
Literatures
We took
• Marinov-Westbrook-Pitz’s hydrogen model
• Hwang, Miller et al.’s, and Westbrook’s acetylene oxid. models
• Wang and Frenklach’s acetylene reaction set with vinylic and
aromatic radicals
• Marinov and Malte’s ethylene oxidation sub-model
• Tsang’s propane and propene chemical kinetics
• Pitz and Westbrook’s n-butane sub-model
• Miller and Melius benzene formation sub-model
• Emdee-Brezinsky-Glassman’s toluene and benzene oxidation sub-
model

We have added
• 100 modification steps to the base gas core concerning benzene
chemistry
• Fuel Component Sub-Mechanisms
 Precursor Chemistry
A list of benzene precursors includes
Major precursors: C3H3, C2H2, n-C4H3, n-C4H5
Minor precursors: C-C5H5, C-C6Hx, Ph-R
Bridging Species: a-C3H5, C2H3
Other Related Species: a-C3H4, p-C3H4, C4H6 isomers, C3H5
isomers, C-C5H6, C4H4, C4H2, C2-C4 olefins

New Reactions in the mechanism

Large olefin decomposition: 1-C7H14 = a-C3H5 + C4H9-1
New addition of chemistry of p-C3H4
p-C3H4 has comparable, if not higher, concentrations in
flames, in comparison with those of a-C3H4
It is easier to form C3H3 radicals from p-C3H4 than from a-
C 3H 4
Reactions involving C4 species

Reaction of C2H3=C2H2+H critically examined

 Modeled Benzene
Concentrations
2.E-01 BH 6.E-02 TCB 3.E-04 MPW
C6H6 4.E-02 C6H6 2.E-04 CH4
1.E-01
X

X
2.E-02 1.E-04

0.E+00 0.E+00 0.E+00

0 0.5 1 0 0.2 0.4 0.6 0 0.3 0.6 0.9
HAB (cm) HAB (cm) HAB (cm)

3.E-04 MPW 1.E-03 2.E-03 CBL

2.E-04 C2H6 C4H6
5.E-04 MCM 1.E-03
X

X
1.E-04 C3H8
0.E+00 0.E+00 0.E+00
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8 0 0.5 1 1.5
HAB (cm) HAB (cm) HAB (cm)
 Modeled Benzene
Concentrations
8.E-05 EDV 6.E-04 EDV 8.E-05 DDA
6.E-05 6.E-05
C7H16 4.E-04 C8H18 C10H22
4.E-05 4.E-05
X

X
2.E-04
2.E-05 2.E-05
0.E+00 0.E+00 0.E+00
0 0.2 0.4 0.6 0 0.2 0.4 0.6 0 0.1 0.2 0.3
HAB (cm) HAB (cm) HAB (cm)

6.E-04 HSP Gasoline 2.E-03 DDAKerosene 6.E-04 LWC

4.E-04 4.E-04 C6H12
1.E-03
X

X
2.E-04 2.E-04

0.E+00 0.E+00 0.E+00

0 0.05 0.1 0 0.1 0.2 0.3 0 0.1 0.2 0.3
HAB (cm) HAB (cm) HAB (cm)
 Outline
Introduction

Chemistry of Benzene Precursors and

Comparison of Measured and
Predicted Benzene Concentrations

Benzene Formation Potential

Benzene Formation Pathways

 Benzene Formation Potential
# Fuel Inert Ar, % C/O Eq. P torr T(Max) Exp. Max. Cal. Max. Deviation
Ratio K at cm [C6H6]b at cm [C6H6]b at cm
F1 CH4 0.453 0.626 2.50 760 1605 at 0.4 280 at 0.8 141 at 0.8 -49.6
F2 C2H6 0.453 0.715 2.50 760 1600 at 0.24 230 at 0.8 205 at 0.8 -10.9
F3 C3H8 0.44 0.833 2.78 760 1640 at 0.4 840 at 0.35 922 at 0.32 +9.8
F4 C3H8 0.424 0.54 1.80 30 2190 at 0.95 17.5 at 0.75 72.9 at 0.77 +×4.2e
F5 C2H2 0.05 0.959 2.40 20 1901 at 1.0 40 at 0.37 82.7 at 0.37 +×2.1e
F6 C2H2 0.45 1.00 2.50 19.5 1850 at 1.0 58.9 at 0.6 39.1 at 0.64 -33.6
F7 C2H2 0.55 1.103 2.76 90 1988 at 0.73 140 at 0.6 96.7 at 0.55 -30.9
F8 C2H4 0.5 0.634 1.90 20 2192 at 1.7 33.1 at 0.9 11.4 at 0.77 -×2.9e
F9 C2H4 0 0.80 2.40 760 1815 at 0.1 936 at 0.15 136 at 0.14 -×6.9e
F10 C2H4 0.656 0.92 2.76 760 1600 at 0.3 250 at 0.35 212 at 0.35 -15.2
F11 C2H4 0.578 1.02 3.06 760 1420 at 0.3 575 at 1.0 553 at 1.0 -3.8
F12 C3H6 0.25 0.773 2.32 37.5 2371 at 0.71 1220 at 0.39 927 at 0.39 -24.0
F13 C4H6 0.03 0.874 2.40 20 2310 at 1.65 1300 at 0.85 1490 at 0.85 +14.6
F14 C6H6 0.3 0.717 1.79 20 1905 at 0.2 N/A N/A Good
F15 C6H6 0.752c 0.72 1.80 760 1850 at 0.45 N/A N/A Good
F16 C7H16 0.841c 0.318 1.00 760 1843 at 0.25 12 at 0.08 1.77 at 0.09 -×6.8e
F17 C7H16 0.73c 0.605 1.90 760 1640 at 0.30 75 at 0.225 75.8 at 0.23 +1.1
F18 i-C8H18 0.682c 0.608 1.90 760 1670 at 0.30 292 at 0.21 455 at 0.23 +55.8
F19 C10H22 0.682c 0.558 1.73 760 1688 at 0.20 65 at 0.10 68.5 at 0.10 +5.4
F20 gasoline 0.768c, 0.01d 0.9-1 760 1990 at 0.046 344 at 0.05 330 at 0.05 -4.1
F21 kerosene 0.684c ≈1.7 760 1775 at 0.20 1090 at 0.1 850 at 0.75 -22.0
F22 C-C6H12 0.325 0.333 1.00 30 1960 at 0.6 473 at 0.09 498 at 0.09 +5.3

X means “a Factor of X”
 Benzene Formation Potential
The Highest and Lowest Benzene Producer

Author Fuel Inert C/O P Exp. Max. Cal. Max. Deviati

Ar, % torr Y(C6H6)b Y(C6H6)b on, %
CBL C4H6 0.03 0.874 20 1300 at 0.85 1490 at 0.85 +14.6
AHB C3H6 0.25 0.773 37.5 1220 at 0.39 927 at 0.39 -24.0
DDA kerosene 0.684c φ=1.7 760 1090 at 0.1 850 at 0.75 -22.0
CDB C2H4 0 0.80 760 936 at 0.15 136 at 0.14 -X6.9e
MCM C3H8 0.44 0.833 760 840 at 0.35 922 at 0.32 +9.8

EDA C7H16 0.73c 0.605 760 75 at 0.225 75.8 at 0.23 +1.1

DDA C10H22 0.682c 0.558 760 65 at 0.10 68.5 at 0.10 +5.4
BDR C2H2 0.45 1.00 19.5 58.9 at 0.6 39.1 at 0.64 -33.6
WHL C2H2 0.05 0.959 20 40 at 0.37 82.7 at 0.37 +X2.1e
BW C2H4 0.5 0.634 20 33.1 at 0.9 11.4 at 0.77 -X2.9e
CNT C3H8 0.424 0.54 30 17.5 at 0.75 72.9 at 0.77 +X4.2e
V C7H16 0.841c 0.318 760 12 at 0.08 1.77 at 0.09 -X6.8e
 Benzene Formation Potential
Effects of Carbon Backbone: C3 Species
Author Fuel C/O P T(Max) T(Max), K at Exp. Max. Cal. Max. Deviati
torr K at cm cm, Fitted Y(C6H6)b Y(C6H6)b on, %
AHB C3H6 0.773 37.5 2371 at 0.71 1220 at 0.39 927 at 0.39 -24.0
HW C2H4 0.92 760 1600 at 0.3 250 at 0.35 212 at 0.35 -15.2
CMM C2H4 1.02 760 1420 at 0.3 575 at 1.0 553 at 1.0 -3.8

MCM C3H8 0.833 760 1640 at 0.4 840 at 0.35 922 at 0.32 +9.8
MPW CH4 0.626 760 1605 at 0.4 280 at 0.8 141 at 0.8 -49.6
MPW C2H6 0.715 760 1600 at 0.24 230 at 0.8 205 at 0.8 -10.9

Fuel decomposition
C3H8  C3H6  a-C3H5  C3H4  C3H3
C3H8  C2H4  C2H2  C3H3
Benzene formation
C3H3 + C3H3 = bC6H6
C3H3 + C3H3 = C6H5 + H
C3H3 + a-C3H4 = bC6H6 + H
C3H3 + a-C3H5 = fC6H6 + 2H
 Benzene Formation Potential
Effects of Carbon Backbone: C4 Species
Author Fuel C/O P T(Max) T(Max), K at Exp. Max. Cal. Max. Deviati
torr K at cm cm, Fitted Y(C6H6)b Y(C6H6)b on, %
CBL C4H6 0.874 20 2310 at 1.65 2050 at 1.75 1300 at 0.85 1490 at 0.85 +14.6
WHL C2H2 0.959 20 1901 at 1.0 40 at 0.37 82.7 at 0.37 +X2.1e
BDR C2H2 1.00 19.5 1850 at 1.0 58.9 at 0.6 39.1 at 0.64 -33.6

Fuel decomposition
C 4H 6  C 4H 5  C 4H 4  C 4H 3
C 4H 6  C 2H 3
C 4H 5  C 2H 3 & C 2H 2
C 4H 5 + H  C 3H 3
Benzene formation
C 2H 2 + C 4H 3 = C 6H 5
C 2H 2 + C 4H 5 = bC6H6 + H
C 3H 3 + C 3H 3 = bC6H6
 Benzene Formation Potential
Effects of Carbon Backbone: Cyclohexanes
Author Fuel C/O P T(Max) T(Max), K at Exp. Max. Cal. Max. Deviati
torr K at cm cm, Fitted Y(C6H6)b Y(C6H6)b on, %
DDA kerosene φ=1.7 760 1775 at 0.20 1775 at 0.25 1090 at 0.1 850 at 0.75 -22.0
DDA C10H22 0.558 760 1688 at 0.20 1688 at 0.22 65 at 0.10 68.5 at 0.10 +5.4

LWC C-C6H12 0.333 30 1960 at 0.6 1960 at 0.55 473 at 0.09 498 at 0.09 +5.3
V C7H16 0.318 760 1843 at 0.25 12 at 0.08 1.77 at 0.09 -X6.8e
HSP gasoline φ=1 760 1990 at 0.046 1990 at 0.106 344 at 0.05 330 at 0.05 -4.1

Benzene formation
Cascading dehydrogenation & Interweaving
dehydrogenation

C-C6H12  C-C6H10  C-C6H8  bC6H6

R-C-C6H11  C-C6H10  C-C6H8  bC6H6
R-C-C6H11  R-C-C6H9  C-C6H8  bC6H6
R-C-C6H11  R-C-C6H9  R-C-C6H7  bC6H6
R-C-C6H11  R-C-C6H9  R-C-C6H7  R-C6H5
 Benzene Formation Potential
Effects of Branching: cyclo > iso > normal
paraffins
Author Fuel C/O P T(Max) T(Max), K at Exp. Max. Cal. Max. Devi
torr K at cm cm, Fitted Y(C6H6)b Y(C6H6)b on, %
EDA i-C8H18 0.608 760 1670 at 0.30 1670 at 0.36 292 at 0.21 455 at 0.23 +55.8
EDA C7H16 0.605 760 1640 at 0.30 1640 at 0.40 75 at 0.225 75.8 at 0.23 +1.1
DDA C10H22 0.558 760 1688 at 0.20 1688 at 0.22 65 at 0.10 68.5 at 0.10 +5.4

LWC C-C6H12 0.333 30 1960 at 0.6 1960 at 0.55 473 at 0.09 498 at 0.09 +5.3
V C7H16 0.318 760 1843 at 0.25 12 at 0.08 1.77 at 0.09 -X6.8

Fuel decomposition
i-C8H18  i-C4H8  i-C4H7
i-C4H7  a-C3H4  C3H3
i-C4H8  s-C3H5  p-C3H4  C3H3
Benzene formation
C 3H 3 + C 3H 3 = bC6H6
C 3H 3 + C 3H 3 = C 6H 5 + H
C3H3 + a-C3H4 = bC6H6 + H
 Outline
Introduction

Chemistry of Benzene Precursors and

Comparison of Measured and
Predicted Benzene Concentrations

Benzene Formation Potential

Benzene Formation Pathways

Benzene Formation Pathways
Magnitude

Rates

Precursors
 In a Normal Decane Flame

Contribution of Major Benzene Formation Pathways

51% from C3H3 + C3H3 = bC6H6
13% from C3H3 + a-C3H5 = fC6H6 + 2H
13% from C3H3 + a-C3H4 = bC6H6 + H
12% from C2H3 + C4H3 (C4H5) = C 6H 5
(bC6H6 + H)
11% from C6H5-CH3 + H = C6H6 + CH3
 In an Acetylene Flame

Contribution of Major Benzene Formation Pathways

94% from C3H3 + C3H3 = bC6H6
5% from C6H5-CH3 + H = C6H6 + CH3
Propargyl Radical Formation Pathways
87% 1CH + C 2H 2 = H2CCCH + H
2
11% 3CH + C H = H2CCCH + H
2 2 2
 In a Cyclohexane Flame
C4Hx C3Hx+ C6H5
-8
+C2H2 C3H3 1.00×10

2.49×10-8
9.66×10-9
5.26×10-10 2.72×10-7

C-C6H8 C6H6 C6H5CH3

-6 -9
1.44×10 7.12×10

1.52×10-6
3.19×10-6 2.80×10-5
C-C6H10 C-C6H11 C-C6H12

Contribution of Major Benzene Formation Pathways

100% from cycloC6-R  C-C6H10  C-C6H8  bC6H6
Benzene Formation Pathways: in Butadiene Flames
C5H5 C6H5O C6H5CO C6H5CHO
6.44×10-7 4.21×10-7

3.54×10-8

4.32×10-8
6.15×10-7 7.63×10-8
C6H5C2H
H2CCCH+ 8.71×10-8
C-C6H7 H2CCCH C6H5
6.12×10-7

7.63×10-8
3.29×10-7
H2CCCCH
4.49×10-7
3.54×10-8 -8
+C2H2
3.25×10 2.35×10-7

CH2CHCHCH C6H6 C6H5CH3 C6H5CH2

+C2H2 1.05×10-7 3.42×10-8
2.41×10-8

1.31×10-6
7.33×10-7
-8 -8 -8
3.79×10 8.41×10 6.62×10
-8
7.41×10
CH2CHCCH2 H2CCCH+ C6H5CHO C3Hx+
+C2H2 Fulvene CH2CHCH2 C4Hx

Contribution of Major Benzene Formation Pathways

48% from C3H3 + C3H3 = bC6H6
20% from C2H2 + C4H3 (C4H5) = C6H5 (bC6H6 + H)
12% from C3H3 + a-C3H5 = fC6H6 + 2H
10% from C6H5-CHO + H = C6H6 + CHO
5% from C6H5-CH3 + H = C6H6 + CH3
5% from C5H5 + CH3 = C-C6H8 = C6H6 + 2H
Soot Precursor Production Potential
Contribution from Individual Surrogate Components to the Formation of
Benzene (a kerosene fuel)
Benzene Contributors: Benzene (28%), Toluene (26%) and Methyl
Cyclohexane (40%)
Component Fractions: Benzene (1%), Toluene (10%), Methyl
Cyclohexane (10%), and paraffins (79%)

n-C12H26
i-C8H18
C6H5CH3
C6H6

C6H11CH3 C6H6

i-C8H18
C6H11CH3

n-C12H26
C6H5CH3

a b

Surrogate Distribution Benzene Formation

* Experimental: Doute et al., Combustion Science Technology, 106 (4-6) (1995) 327–344.
* Modeling: Zhang et al., Proceedings of Combustion Institute, (2007) 31, 401-409.
 Concluding Comments
The Utah Surrogate Model Was Validated for 22
Premixed Flames of Various Fuels (C1-C12 fuels; Φ =
1.0-3.06; P = 20-760 torr; T = 1600-2370 K).
Benzene Concentrations Were Predicted within 30% of
the Experimental Data for 15 (out of 22) Flames.
Both Formation Pathways and Formation Potential of
Benzene Were Found to Be Dependent on the Fuel
Structure, and C3, C4 and C-C6 Were among the Most
Productive Fuels.
C3 Combination Was Identified to be the Major Benzene
Formation Pathway for Most Fuels; That Is Replaced
with Dehydrogenation Only for Cyclohexanes.
Acetylene Addition Was Found to Be Important in C4
Flames and Those with Large Paraffinic Fuels.
 Predicting the soot precursors is one of the keys
to predicting soot emissions from a Diesel engine
Fuel-rich premixed reaction zone

From:
Fuel-Rich Premixed Reaction Zone
John Dec,
SAE paper
970873

39
Premixed ignition in Diesel combustion

• Fuel-rich conditions (Φ ≈ 4 )
• Relatively low temperature (T ≈ 850 K )
- Source of cetane ratings in Diesel engines
- Very similar to conditions of engine knock
- Very complex chemical kinetic pathways
• Products are good producers of soot
precursor species
• Ignition kinetics are the same as in engine knock in SI
engines, driven by H2O2 decomposition
Products of rich premixed ignition are mostly
small unsaturated hydrocarbons, especially acetylene and ethene,
which are known precursors to soot
Experimental background

• Addition of oxygenated species reduces soot

- Important possible oxygenates include biodiesel fuels

• Soot production correlates with post-ignition levels of selected

chemical species

• Suggestions that this is due to presence of C - C bonds or total O

concentrations

• Use kinetic model to examine these possibilities

Predicted level of soot precursors correlates well with soot emissions from a
Diesel engine

From:
Flynn, Durrett,
Dec, Westbrook, et
al., SAE paper
1999-01-0509

43
44
Structure of
Tripropylene Glycol Monomethyl Ether (TPGME)
Experiments at Sandia show same trends as
LLNL kinetic models

DBM and TPGME reduce sooting, but DBM is less

effective than TPGME
Models show same soot precursor formation,
but oxygen enhances precursor consumption

Example of C2H3 + O2 breaking C - C bond

Understand and predict emissions from open
burning or detonation of explosives
RDX and HMX are based on non-aromatic rings

C C N
N N N C

C C C N
N N C

Note the absence of C - C bonds or aromatic

rings
Presence of aromatic rings indicates explosive
will lead to soot.

TNT TATB

NH2
CH3
O2N NO2
O2N NO2

H2 N NH2
NO2
NO2

Aromatic rings and lots of C - C bonds

 RDX does not produce soot precursors

O O
O O
+ NO2 N
N
O N N O
O CH2
N N O N
N N.
+
O

N
N N
O
N N CH2
N
O O N.
O O
+
CH2

CH2
+ NO2
.N

No carbon – carbon bonds!

 Soot tendencies depend on molecular structure

From Ree et al, J. Phys. Chem. A, 1996

Oxygen is the main obstacle to soot production

• Goal is to produce C - O bonds

• There are many possible sources of oxygen
- Simplest alternative is air
- Oxygenated hydrocarbon or other molecules
• This is the principle used in diesel engines to reduce soot
production
• This is the explanation for some munitions combustion
observations
Molecular structure of oxygenated fuel additive
determines its soot reduction properties
 Variability in soot precursor production observed computationally

 Before modeling approach was used, all oxygenates were believed to

be equally effective at soot reduction

 Subsequent engine experiments consistent with model results

 Reaction pathways that lead to early CO2 production “waste” available

oxygen atoms in the oxygenate

 Same approach provided sooting estimates for oil sands fuel

 All analysis based on single-component “diesel fuel” surrogate

 Need for more thorough, multicomponent diesel simulations

 Opportunities for designing optimal oxygenated additives

 Kitamura, et al. 2002

Conventional
Diesel path

Higher HCCI
O2

Low Temperature
temperature[K]
62
Multiscale modeling

 Growth of computing capabilities makes it

possible to address a newer class of demanding
computational problems
 Multiscales can refer to wide ranges in spatial
length scales or, more commonly, time scales
 These problems occur in virtually every discipline
 This offers the potential for including fine scale,
short time constant phenomena in practical,
engineering simulations
 Example taken from Violi, Kubota et al., 29th
Symposium
 Nanoparticle Evolution
Young soot growth in flame conditions with assumed constant temperature (1700K) and gas-phase species
profile (H, H2, C8H10, C8H9, C12H8, C12H7) for 10 msec using Violi-Sarofim kinetics.

Violi-Sarofim Mechanism 0x Violi-Sarofim Mechanism Violi-Sarofim Mechanism 100x

Cyclo-Elimination Rates 1x Cyclo-Elimination Rates Cyclo-Elimination Rates

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Cinepak decompressor Cinepak decompressor Cinepak decompressor
are needed to see this picture. are needed to see this picture. are needed to see this picture.

2 nm

Nanoparticles follow different evolutionary paths dependent on the mechanism and

kinetic rates defined by the user.